Patent Application
20230266630
The present technology is generally related to electrochromic devices. More particularly, it is related to redox compounds that are suitable for use in electrochromic devices having a persistent color memory and can provide a current during clearing for a substantial time period after being charged.
Electrochromic devices have been well known for many years. When a sufficient electrical potential is applied across a pair of electrodes, an electrochromic medium, disposed between the electrodes, may become activated, changing its color and/or light transmissivity. Taking advantage of this, devices such as dimmable mirrors and windows have become increasingly popular in industries such as automotive and aviation.
This disclosure addresses phenazine electrochromic materials having improved weathering stability properties for use in electrochromic devices, in particular as the anodic redox species attached or confined to a polymer matrix film.
Provided in one aspect is compound represented by:
In some embodiments, the sterically hindered group is selected from tertiary butyl, isobutyl, isopropyl, 2-ethyl butyl, 2-ethyl hexyl, sec-butyl, isopentyl, and neopentyl.
In some embodiments, R1, R3, R4, R6, R8, and R9 are each independently H. In some embodiments, R1, R3, R4, R6, R7, and R9 are each independently H.
In some embodiments, at least one of R2, R3, R7, and R8 are independently C2-C8 alkyl. In some embodiments, at least one of R2, R3, R7, and R8 are independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. In some embodiments, at least one of R2, R3, R7, and R8 are independently isopropyl, neopentyl or tertiary butyl.
In some embodiments, R2 and R7 or R2 and R8 are each independently C2-C8 alkyl. In some embodiments, R2 and R7 or R2 and R8 are each independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. In some embodiments, R2 and R7 or R2 and R8 are each independently isopropyl, neopentyl or tertiary butyl.
In some embodiments, R3 and R8 or R3 and R7 are each independently C2-C8 alkyl. In some embodiments, R3 and R8 or R3 and R7 are each independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. In some embodiments, R3 and R8 or R3 and R7 are each independently isopropyl, neopentyl, or tertiary butyl.
In some embodiments, at least one of R2, R3, R7, and R8 are independently aryl. In some embodiments, at least one of R2, R3, R7, and R8 are independently phenyl.
In some embodiments, R2 and R7 or R2 and R8 are each independently aryl. In some embodiments, R2 and R7 are each independently phenyl.
In some embodiments, R3 and R8 or R3 and R7 are each independently aryl. In some embodiments, R3 and R8 or R3 and R7 are each independently phenyl.
In some embodiments, at least one of R5 and R10 are independently represented by:
-L1-A-L2-OR14;
In some embodiments,
In some embodiments, at least one of R5 and R10 are independently represented by:
In some embodiments, n is 2 or 4; x is 3; and each R15 is independently C1 alkyl or C2 alkylhydroxyl.
In some embodiments, at least one of R5 and R10 are independently represented by:
-L3-OR16;
In some embodiments, each L3 is independently an C4 or C6 alkylene group; and each R16 is H.
In some embodiments, at least one of R5 and R10 are independently represented by:
In some embodiments, y is 3 or 6.
In some embodiments, the compound is ammonium salt with an anion comprising F−, Cl−, Br−, I−, BF4−, PF6−, SbF6−, AsF6−, ClO4−, SO3CF3−, N(CF3SO2)2−, C(CF3SO2)3−, N(SO2C2F3)2−, Al(OC(CF3)3)4−, BAr4−, or mixtures of anions thereof wherein Ar is an aryl or fluorinated aryl group. In some embodiments, the anion is selected from PF6− and SO3CF3−.
In some embodiments, the compound is selected from:
Provided in another aspect is an energy storage device including:
Provided in another aspect is an energy storage device including:
In some embodiments, the energy storage device further includes an electrolyte comprising a solvent and a metal salt or an 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.
Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and may be practiced with any other embodiment(s).
As used herein, “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, “about” will mean up to plus or minus 10% of the particular term.
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein may be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.
In general, “substituted” refers to an alkyl, alkenyl, aryl, or ether group, as defined below (e.g., an alkyl group) in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to non-hydrogen or non-carbon atoms. Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom are replaced by one or more bonds, including double or triple bonds, to a heteroatom. Thus, a substituted group will be substituted with one or more substituents, unless otherwise specified. In some embodiments, a substituted group is substituted with 1, 2, 3, 4, 5, or 6 substituents. Examples of substituent groups include: halogens (i.e., F, Cl, Br, and I); hydroxyls; alkoxy, alkenoxy, alkynoxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo); carboxyls; 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.
As used herein, “alkyl” groups include straight chain and branched alkyl groups having from 1 to about 20 carbon atoms, and typically from 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms. As employed herein, “alkyl groups” include cycloalkyl groups as defined below. Alkyl groups may be substituted or unsubstituted. An alkyl group may be substituted one or more times. An alkyl group may be substituted two or more times. Examples of straight chain 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, isopentyl groups, and 1-cyclopentyl-4-methylpentyl. Representative substituted alkyl groups may be substituted one 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 is an alkyl group having one or more halo groups. In some embodiments, haloalkyl refers to a per-haloalkyl group.
Cycloalkyl groups are cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, the cycloalkyl group has 3 to 8 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 5, 6, or 7. Cycloalkyl groups may be substituted or unsubstituted. Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl, and the like. Cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined above. Representative substituted cycloalkyl groups may be mono-substituted or substituted more than once, such as, but not limited to: 2,2-; 2,3-; 2,4-; 2,5-; or 2,6-disubstituted cyclohexyl groups or mono-, di-, or tri-substituted norbornyl or cycloheptyl groups, which may be substituted with, for example, alkyl, alkoxy, amino, thio, hydroxy, cyano, and/or halo groups.
Alkenyl groups are straight chain, branched or cyclic alkyl groups having 2 to about 20 carbon atoms, and further including at least one double bond. In some embodiments alkenyl groups have from 1 to 12 carbons, or, typically, from 1 to 8 carbon atoms. Alkenyl groups may be substituted or unsubstituted. Alkenyl groups include, for instance, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl groups among others. Alkenyl groups may be substituted similarly to alkyl groups. Divalent alkenyl groups, i.e., alkenyl groups with two points of attachment, include, but are not limited to, CH—CH═CH2, C═CH2, or C═CHCH3.
As used herein, “aryl”, or “aromatic,” groups are cyclic aromatic hydrocarbons that do not contain heteroatoms. Aryl groups include monocyclic, bicyclic, and polycyclic ring systems. Thus, aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenylenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups. An aryl group with one or more alkyl groups may also be referred to as alkaryl groups. In some embodiments, aryl groups contain 6-14 carbons, and in others from 6 to 12 or even 6-10 carbon atoms in the ring portions of the groups. The phrase “aryl groups” includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, and the like). Aryl groups may be substituted or unsubstituted.
Heterocyclyl or heterocycle refers to both aromatic and nonaromatic ring compounds including monocyclic, bicyclic, and polycyclic ring compounds containing 3 or more ring members of which one or more is a heteroatom such as, but not limited to, N, O, and S. Examples of heterocyclyl groups include, but are not limited to: unsaturated 3 to 8 membered rings containing 1 to 4 nitrogen atoms such as, but not limited to pyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridinyl, dihydropyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazolyl (e.g. 4H-1,2,4-triazolyl, 1H-1,2,3-triazolyl, 2H-1,2,3-triazolyl etc.), tetrazolyl, (e.g. 1H-tetrazolyl, 2H tetrazolyl, etc.); saturated 3 to 8 membered rings containing 1 to 4 nitrogen atoms such as, but not limited to, pyrrolidinyl, imidazolidinyl, piperidinyl, piperazinyl; condensed unsaturated heterocyclic groups containing 1 to 4 nitrogen atoms such as, but not limited to, indolyl, isoindolyl, indolinyl, indolizinyl, benzimidazolyl, quinolyl, isoquinolyl, indazolyl, benzotriazolyl; unsaturated 3 to 8 membered rings containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms such as, but not limited to, oxazolyl, isoxazolyl, oxadiazolyl (e.g. 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, etc.); saturated 3 to 8 membered rings containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms such as, but not limited to, morpholinyl; unsaturated condensed heterocyclic groups containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, for example, benzoxazolyl, benzoxadiazolyl, benzoxazinyl (e.g. 2H-1,4-benzoxazinyl etc.); unsaturated 3 to 8 membered rings containing 1 to 3 sulfur atoms and 1 to 3 nitrogen atoms such as, but not limited to, thiazolyl, isothiazolyl, thiadiazolyl (e.g. 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, etc.); saturated 3 to 8 membered rings containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms such as, but not limited to, thiazolodinyl; saturated and unsaturated 3 to 8 membered rings containing 1 to 2 sulfur atoms such as, but not limited to, thienyl, dihydrodithiinyl, dihydrodithionyl, tetrahydrothiophene, tetrahydrothiopyran; unsaturated condensed heterocyclic rings containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms such as, but not limited to, benzothiazolyl, benzothiadiazolyl, benzothiazinyl (e.g. 2H-1,4-benzothiazinyl, etc.), dihydrobenzothiazinyl (e.g. 2H-3,4-dihydrobenzothiazinyl, etc.), unsaturated 3 to 8 membered rings containing oxygen atoms such as, but not limited to furyl; unsaturated condensed heterocyclic rings containing 1 to 2 oxygen atoms such as benzodioxolyl (e.g., 1,3-benzodioxoyl, etc.); unsaturated 3 to 8 membered rings containing an oxygen atom and 1 to 2 sulfur atoms such as, but not limited to, dihydrooxathiinyl; saturated 3 to 8 membered rings containing 1 to 2 oxygen atoms and 1 to 2 sulfur atoms such as 1,4-oxathiane; unsaturated condensed rings containing 1 to 2 sulfur atoms such as benzothienyl, benzodithiinyl; and unsaturated condensed heterocyclic rings containing an oxygen atom and 1 to 2 oxygen atoms such as benzoxathiinyl. Heterocyclyl group also include those described above in which one or more S atoms in the ring is double-bonded to one or two oxygen atoms (sulfoxides and sulfones). For example, heterocyclyl groups include tetrahydrothiophene oxide and tetrahydrothiophene 1,1-dioxide. Typical heterocyclyl groups contain 5 or 6 ring members. Thus, for example, heterocyclyl groups include morpholinyl, piperazinyl, piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, thiophenyl, thiomorpholinyl, thiomorpholinyl in which the S atom of the thiomorpholinyl is bonded to one or more O atoms, pyrrolyl, pyridinyl homopiperazinyl, oxazolidin-2-onyl, pyrrolidin-2-onyl, oxazolyl, quinuclidinyl, thiazolyl, isoxazolyl, furanyl, dibenzylfuranyl, and tetrahydrofuranyl. Heterocyclyl or heterocycles may be substituted.
Heteroaryl groups are aromatic ring compounds containing 5 or more ring members, of which, one or more is a heteroatom such as, but not limited to, N, O, and S. Heteroaryl groups include, but are not limited to, groups such as pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thiophenyl, benzothiophenyl, furanyl, benzofuranyl, dibenzofuranyl, indolyl, azaindolyl (pyrrolopyridinyl), indazolyl, benzimidazolyl, imidazopyridinyl (azabenzimidazolyl), pyrazolopyridinyl, triazolopyridinyl, benzotriazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups. Heteroaryl groups include fused ring compounds in which all rings are aromatic such as indolyl groups and include fused ring compounds in which only one of the rings is aromatic, such as 2,3-dihydro indolyl groups. Although the phrase “heteroaryl groups” includes fused ring compounds, the phrase does not include heteroaryl groups that have other groups bonded to one of the ring members, such as alkyl groups. Rather, heteroaryl groups with such substitution are referred to as “substituted heteroaryl groups.” Representative substituted heteroaryl groups may be substituted one or more times with various substituents such as those listed above.
As used herein, the prefix “halo” refers to a halogen (i.e. F, Cl, Br, or I) being attached to the group being modified by the “halo” prefix. For example, haloaryls are halogenated aryl groups.
Groups described herein having two or more points of attachment (i.e., divalent, trivalent, or polyvalent) within the compound of the present technology are designated by use of the suffix, “ene.” For example, divalent alkyl groups are alkylene groups, divalent aryl groups are arylene groups, divalent heteroaryl groups are divalent heteroarylene groups, and so forth.
The present disclosure relates to electrochromic devices that incorporate 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 demonstrated in the Examples, the phenazine compounds described herein are thermally stable and have improved weathering durability, for example, electrical cycling while under UV exposure (at about 390 nm or greater). The phenazines described herein are electrochromic.
More broadly, disclosed herein are energy storage devices and/or electrochromic memory devices that include a cathodic material, and an anodic material such that when the cathodic material and anodic material are in an activated state, the devices maintains an activated (i.e. darkened) state for long periods of time at open circuit. When the terms cathodic and anodic material are used herein, at least one of them is electrochromic. The cathodic material/moiety may be associated with a first conductive substrate, or sequestered within a polymer matrix, and the anodic material/moiety may be associated with a second conductive substrate or sequestered within a polymeric matrix. For example, the anodic material may be covalently crosslinked and coated on a second conductive substrate and the cathodic material may be covalently crosslinked and coated on the surface of a first conductive substrate. By coating the anodic and cathodic materials to the substrate, the anodic and cathodic materials are prevented from migration within the device, thus potentially maintaining an activated stated indefinitely.
As noted above, the anodic or cathodic materials may also be part of the polymeric matrix with the anodic or cathodic material being covalently bound to the polymer. This may be accomplished with the presence of a functional group on the anodic or cathodic material that is reacted with the polymer or monomers that make up the polymer. For example, where the anodic or cathodic materials contain a hydroxyl group, the anodic or cathodic material may be bound into a polymer matrix via a condensation reaction or react with isocyanate functionality to form a polyurethane-based polymer matrix. Amines may also react with isocyanate functionalities to form urea and biuret linkages. It can be also anticipated that other cross-linked polymeric matrix can be formed using a multifunctional epoxy or polymers in combination with a curing agent like an amine, alcohol or anhydride or through base or acid catalyzed homopolymerization.
Typical solution-phase electrochromic devices contain at least one anodic (oxidizable) material or species, at least one cathodic (reducible) material or species, and a solvent. Upon applying a sufficient electrical potential to a solution-phase electrochromic device, i.e. activation, of a typical solution-phase devices will undergo a color change (i.e. darkened, or low transmission state). Because the anodic and cathodic materials are capable of free diffusion through the solvent while in the activated state, the electrochromic device will self-erase upon removal of the charging potential. It has now been found that sequestration of an anodic material on the surface of a conductive substrate while sequestrating the cathodic material on the surface of a second conductive substrate results in electrochromic devices that are configured to maintain the charged, i.e. activated, state for prolonged periods of time in comparison to typical solution-phase electrochromic devices, as long as the electrochromic anodic and cathodic films are separated by a ionic conductive electrolyte.
The electrochromic devices 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 joining the first substrate to the second substrate with the first and second conductive surfaces contacting the sealing member. For the surface confinement of the anodic and cathodic materials, the anodic material may be sequestered on one conductive surface and the cathodic material may be sequestered on the other conductive surface. Within the chamber is disposed an electrolyte between the anodic and cathodic layers. The first and second substrates may be off-set to one another to allow for electric contact to be made with the first and second conductive surfaces, as is well established for other solution phase electrochromic devices.
In one aspect, an energy storage or memory device is provided. The energy storage or memory device may include a cathodic material and an anodic material. The cathodic material may be a viologen and the anodic material may be a phenazine as described herein.
In some embodiments, the anodic material comprises a phenazine compound represented as:
A sterically hindered group may be selected from tertiary butyl, isobutyl, isopropyl, 2-ethyl butyl, 2-ethyl hexyl, sec-butyl, isopentyl, and neopentyl. A sterically hindered group may be an alkyl group comprising an isopropyl moiety. In some embodiments, a sterically hindered group is not a methyl group.
In some embodiments, R1, R3, R4, R6, R8, and R9 are each independently H. In some embodiments, R1, R3, R4, R6, R7, and R9 are each independently H.
In some embodiments, at least one of R2, R3, R7, and R8 are independently C2-C8 alkyl. In some embodiments, at least one of R2, R3, R7, and R8 are independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. In some embodiments, at least one of R2, R3, R7, and R8 are independently isopropyl, neopentyl or tertiary butyl.
In some embodiments, R2 and R7 or R2 and R8 are each independently C2-C8 alkyl. In some embodiments, R2 and R7 or R2 and R8 are each independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. In some embodiments, wherein R2 and R7 or R2 and R8 are each independently isopropyl, neopentyl or tertiary butyl.
In some embodiments, R3 and R8 or R3 and R7 are each independently C2-C8 alkyl. In some embodiments, R3 and R8 or R3 and R7 are each independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. In some embodiments, R3 and R8 or R3 and R7 are each independently isopropyl, neopentyl, or tertiary butyl.
In some embodiments, at least one of R2, R3, R7, and R8 are independently aryl. In some embodiments, at least one of R2, R3, R7, and R8 are independently phenyl.
In some embodiments, R2 and R7 or R2 and R8 are each independently aryl. In some embodiments, R2 and R7 are each independently phenyl.
In some embodiments, R3 and R8 or R3 and R7 are each independently aryl. In some embodiments, R3 and R8 or R3 and R7 are each independently phenyl.
In some embodiments, at least one of R5 and R10 are independently represented by:
-L1-A-L2-OR14;
In some embodiments,
In some embodiments, at least one of R5 and R10 are independently represented by:
In some embodiments, n is 2 or 4;
In some embodiments, at least one of R5 and R10 are independently represented by:
-L3-OR16;
In some embodiments, each L3 is independently an C4 or C6 alkylene group; each R16 is H.
In some embodiments, at least one of R5 and R10 are independently represented by:
—(CH2)y—OH
In some embodiments, y is 3 or 6.
In some embodiments, the compound is ammonium salt with an anion comprising 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 mixtures of anions thereof, wherein Ar is an aryl or fluorinated aryl group. In some embodiments, the anion is selected from PF6−, SO3CF3−, and a mixture of anions thereof.
According to various embodiments herein, the phenazine compounds disclosed herein may be any one of the following compounds. As noted, some of the phenazines disclosed has at least one net, positive charge that is electronically balanced by an anion (not shown). The anion may be any of a variety of anions as noted above.
In another aspect, an electrochromic device includes an anodic material coated on to the surface of a first conductive substrate and covalently crosslinked, and a cathodic material coated on to the surface of a second conductive substrate and covalently crosslinked. The electrochromic device exhibits a high transmission state at short circuit and a low transmission state upon application of an electric potential, where the high transmission state is at least 4 times greater than the low transmission state; and the electrochromic device is configured to maintain a transmission percentage within 5% of the low transmission state for at least 8 hours at 20° C. at open circuit after application of a potential sufficient to reach to the low transmissions state. In some embodiments, the electrochromic device is configured to maintain a transmission percentage within 5% of the low transmission state for at least 8, 10, 15, 20, 24, or 48 hours at 20° C. at open circuit after application of a potential sufficient to reach to the low transmissions state. In some embodiments, the device is configured to maintain a transmission percentage within 10% of the low transmission state for at least 2 days, 3 days, 4 days, or 5 days at 20° C. at open circuit after application of a potential sufficient to reach to the low transmissions state. In some embodiments, the device is configured to maintain a transmission percentage within 10% of the low transmission state from 8 hours to 10 days at 20° C. at open circuit after application of a potential sufficient to reach to the low transmissions state. The low transmission state may range from about 0.001% to about 30%. The high transmission state range from about 50% to about 95%. In some embodiments, after 4000 cycles from the high transmission state to the low transmission state, a high transmission value does not vary by more than 5% from an initial high transmission value. As used herein the initial high transmission value is the state of the device prior to the application of an electric potential after device fabrication. In some embodiments, after 4000 cycles from high transmission to low transmission, the low transmission value does not vary by more than 5% from an initial low transmission value. As used herein, the initial low transmission value is the low transmission value achieved upon the first charging of the device at a full voltage application.
In any of the above aspects, the cathodic material may be a viologen, a low-dimerizing viologen or a non-dimerizing viologen. The term low-dimerizing viologen is applied to some viologens that show dimerization characteristics to a lesser extent that dimerizing viologens. The viologen material may be sequestered within the polymer matrix by being physically trapped within, or the viologen material may be functionalized such that it is amenable to being polymerized or reacted with the polymer to be covalently bonded to the polymer. Illustrative viologens include, but are not limited to, methyl viologen, octyl viologen, benzyl viologen, polymeric viologens, and the viologens described in U.S. Pat. Nos. 4,902,108; 6,188,505; 5,998,617; 10,464,900; and 6,710,906. Other viologens may include those of Formula (I), (III), or (IV):
In Formula I, R1 and R2 are individually alkyl, siloxy alkyl, hydroxyalkyl, alkenyl, or aralkyl; R4, R6, R8, and R10 are individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl; R3, R5, R7, and R9 are individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl, and X is an anion. However, Formula (I) may be subject to the proviso that R3 and R5, or R7 and R9, or R3, R5, R7, and R9 are individually secondary alkyl, tertiary alkyl, or aryl.
In Formula (III), R1 and R2 are individually alkyl, siloxyalkyl, hydroxyalkyl, alkenyl, or aralkyl; R4, R6, R8, R10 are individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl; R3, R5, R7, and R9 are individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy or aryl; R19 is (CH2)n′ or arylene, and n′ is from 1 to 12; X is an anion; and wherein R3 and R5, or R7 and R9 are individually secondary alkyl, tertiary alkyl, or aryl.
In Formula (IV), R1 and R1′ are individually alkyl, siloxyalkyl, hydroxyalkyl, alkenyl, or aralkyl; R4, R6, R8, R10, R4′, R6′, R8′, and R10′ are individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl; R7, R9, R7′, and R9′ are individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl; R19 is (CH2)n′ or arylene, and n′ is from 1 to 12; X is an anion; and either R3, R5, R3′, and R5′ are individually secondary alkyl, tertiary alkyl, or aryl; or R7, R9, R7′, and R9′ are individually secondary alkyl, tertiary alkyl, or aryl. For any of the viologens described, the counterion (anion) may be any of a halide, a borate, a fluoroborate, a tetraaryl borate, a hexafluoro metal or metalloid, a sulfate, a sulfonate, a sulfonamide, a carboxylate, a perchlorate, a tetrachloroferrate, or the like, or mixtures of any two or more thereof. Illustrative 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−, wherein Ar is a aryl or a fluorinated aryl or a bis(trifluoromethyl) aryl group. In some embodiments, X is a tetrafluoroborate or a bis(trifluoromethylsulfonyl) imide anion.
In any of the above aspects, the anodic material may be any one or more of the phenazines compounds described herein covalently attached to, or confined within, the second polymer matrix, the second polymer matrix configured to prevent or minimize substantial diffusion of the anodic material in the activated state. As with the viologen, the anodic material may be sequestered within the polymer matrix by being physically trapped within, or the anodic material may be functionalized such that it is amenable to being polymerized or reacted with the polymer to be covalently bonded to the polymer.
Further examples of anodic and cathodic materials may be found in U.S. Pat. Nos. 4,902,108; 5,294,376; 5,998,617; 6,193,912; 10,971,718; and 8,228,590.
Where the devices include an electrolyte, the electrolyte may include a solvent and a salt. The salt may be a metal salt or an ammonium salt. Illustrative solvents for use in the electrolyte may include, but are not limited to, 3-methylsulfolane, dimethyl sulfoxide, dimethyl formamide, tetraglyme 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 beta-propiolactone, gamma-butyrolactone, and gamma-valerolactone; propylene carbonate (PC), ethylene carbonate; and homogenous mixtures of the same. While specific solvents have been disclosed as being associated with the electrolyte, numerous other solvents that would be known to those having ordinary skill in the art having the present disclosure before them are likewise contemplated for use. Illustrative salts include, but are not limited to, metal or ammonium salts, such as but not limited to Li+, Na+, K+, NR′4+, where each R′ is individually H, alkyl, or cycloalkyl, of the following anions 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−, wherein Ar is an aryl or fluorinated aryl group such as, but not limited to, C6H5, 3,5-(CF3)2C6H3]4, or C6F5. Further examples of polymer electrolyte materials used in electrochromic devices can be found in U.S. Pat. Nos. 6,635,194 and 5,940,201.
With regard to the substrates and conductive coatings on the substrates, those typically used in solution-based electrochromic devices may be used. For example, the one or both substrates may be glass, metal, plastic, or ceramic. The conductive coating on one or more of the substrates may be transparent or opaque depending upon the intended use of the device. For example, where the device is a window, both coatings should be substantially transparent, and where the device is a mirror at least one coating is transparent. Illustrative, 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 nano-wire coatings, carbon nanotubes, graphene coatings, wire grids, conductive polymers such as, but not limited to, 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 thereof.
The present invention, thus generally described, will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present invention.
The four step synthesis of the title compound is as follows:
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 three neck 5 L round bottom flask equipped with a dean-stark condenser, a mechanical stirrer, and a thermometer. The mixture was heated to 203° C. for 1 week under a nitrogen atmosphere. The reaction mixture was then cooled to 60° C. The solid was filtered under inert condition to prevent oxidation. The solid was then washed with a mixture of 1:1 acetone and water (4 L). The solid was recrystallized by first partially dissolving in 1 L acetone and then a solution of sodium dithionite in water was added (160 g dissolved in 2 L water). Finally, the solution was cooled to room temperature and the solid was filtered under inert conditions. In vacuo removal of the solvent provided 2,7-di-tert-butyl-5,10-dihydrophenazine in 516 g (72% yield). GC analysis showed 99.8% pure product.
Step 2: To a 12-liter round bottom flask was charged 1,4-dibromobutane (2260 g) and acetone (6 L). The flask was cooled to 5-7° C. The dimethyl amino propanol (1200 g) was slowly added via addition funnel. The reaction was slightly exothermic. Once the addition was complete, the temperature was allowed to rise to room temperature. After stirring at room temperature for 48 hours, the product precipitated out as a white crystal. The solid product was filtered and washed with acetone. Vacuum drying provided 3112 g of the desired product (yield 93%).
Step 3: 240 g of 2,7-di-tert-butyl-5,10-dihydrophenazine, 1154 g of 4-bromo-N-(3-hydroxypropyl)-N,N-dimethylbutan-1-aminium bromide, 280 g of sodium dithionite, 375 g of sodium carbonate, 30 g methyl tributyl ammonium chloride, 30 ml water and 7400 mL of acetonitrile were added to a 12 L round bottom flask. The mixture was heated to reflux under a nitrogen atmosphere for 48 hours, where HPLC analysis showed no dihydrophenazine was present. 3 L of acetonitrile was then distilled off and the reaction mixture was allowed to cool down to room temperature, where the reaction solids were then filtered out and washed with 2.5 L acetone. The solid was redissolved in 1.3 L water, heated, and residual acetone was distilled off at 70° C. 2 L Ethanol was added and the reaction mixture was cooled to room temperature. The solid was filtered and washed with ethanol. The solid was discarded and the filtrate containing the product was concentrated to oil in vacuo. The oil was added to 6 L hot acetone. Upon cooling, the filtrate was decanted, and the gummy solid was washed with additional acetone. The gummy solid was N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium bromide and was taken directly to make the PF6 salt. The product was 99% pure by HPLC and mass ES analysis.
Step 4: Synthesis of: N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium hexafluorophosphate.
First metathesis: The gummy solid of N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium bromide was dissolved in a 900 mL of water and 100 ml triethyl amine mixture by heat to 50° C. 2500 mL of 30% NH4PF6 solution in water was added, and the reaction was allowed to stir at 50° C. for 5 hours. The reaction was cooled to precipitate N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium hexafluorophosphate as a grey solid in 720 g of wet solid.
The second metathesis was repeated by dissolving the solid in 350 ml acetonitrile, 1000 ml water, 150 ml triethylamine and 1000 ml ethanol. The reaction mixture was heated to 65° C. and 1700 ml 30% NH4PF6 solution was added. After continued heating for 3 hours, 1000 ml water was added. 150 ml acetonitrile was distilled off, and the reaction was cooled to room temperature. Upon cooling, the product solidified. The filtrate was decanted, and the product washed with 3 L cold water to give a gummy solid. The solid was dissolved in 1000 ml acetonitrile. The acetonitrile and residual water were completely removed under vacuum to give a brown concentrate. To the brown concentrate was added to a hot solution mixture of 4000 ml ethanol, 100 ml triethylamine, and 10 ml anhydrous hydrazine. After continued heating at 60° C. for 15 minutes, the reaction was cooled to 40° C. and 2000 ml hexane was added. The reaction was cooled to room temperature and then at 0-5° C. for 4 hours. The solid was filtered under inert conditions and washed with 1000 ml cold ethanol and then 1000 ml 1:1 mixture of ethanol and hexane. The solid was vacuum dried to give 494 g (yield 64%) of a off white solid. The product is 99.5% pure by HPLC and mass spectroscopy.
50 g of N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio) butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium bromide was dissolved in 85 mL of hot water and 250 mL of 30% sodium triflate was added. The reaction mixture was heated to 60° C. for 4 hours. 200 ml water was added followed by cooling to room temperature. The product was filtered and washed with 300 ml water under inert conditions.
The second metathesis was done by dissolving the above solid in 150 ml hot water. 20 ml triethylamine was added. The reaction was allowed to stir at 50° C. for 5 hours. The reaction was cooled and filtered to give N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium triflate as a white solid in 50 g (82% yield) after vacuum drying. The product was 99.9% pure by HPLC and mass spectroscopy.
In this Example, Device A was made with the following compound:
In this Example, Device B was made with the following compound:
Device A was prepared by coating an indium tin oxide (ITO) coated piece of 3-inch by 3-inch glass (2.2 mm thickness) with a mixture made by dissolving 0.3518 grams of bis N,N′-(6-hydroxyhexyl) viologen bis [bis trifluoromethanesulfonyl imide] (NTF), 0.0149 grams of octamethyl bis(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), plus 100 ppm of dibutyltin diacetate (DBTDA) catalyst. The mixture was coated directly on the ITO coating with a #16 Mayer rod to control thickness.
Also for device A, second piece of 3-inch by 3-inch ITO coated glass (2.2 mm thickness) was coated with a solution made by dissolving 0.3969 grams of 5,10-bis(n-butyl-N,N-dimethylammonium n-propanol) phenazine triflate, 0.0166 grams of octamethyl bis(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 in propylene carbonate (PC) and 3-methoxypropionitrile (MPN) (35% wt PC, 65% wt MPN), plus 100 ppm of DBTDA catalyst. The second film was made by coating the solution with a #8 Mayer rod to control thickness.
Device B was prepared by coating an indium tin oxide (ITO) coated piece of 3-inch by 3-inch glass (2.2 mm thickness) with a solution made by dissolving 0.3588 grams of bis (6-hydroxyhexyl) viologen bis [bistrifluoromethane sulfonyl imide] (NTF), 0.0149 grams of octamethyl dihexanol 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 in propylene carbonate (PC) and 3-methoxypropionitrile (MPN) (35% PC, 65% MPN) plus 100 ppm of dibutyl tin diacetate (DBTDA) catalyst. This film was made by coating the solution with a #16 Mayer rod to control the thickness.
Also, for device B, a second piece of 3-inch by 3-inch ITO coated glass (2.2 mm thickness) was coated with a solution made by dissolving 0.4112 grams of N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium bis(hexafluorophosphate), 0.0152 grams of octamethyl bis(6-hydroxyhexyl) ferrocene, 0.0006 grams of surfactant (TEGO Glide 410), and 0.1706 grams of HDT-Isocyanurate (Desmodur N3300, Covestro) in a 3 gram solution in propylene carbonate (PC) and 3-methoxypropionitrile (MPN) (35% PC, 65% MPN), plus 100 ppm of DBTA, thereby forming a second film. This second film was made with a #8 Mayer rod.
The films above were allowed to cure under a nitrogen atmosphere overnight in an oven at 60° C. Once the films were cured, the edges of the films were removed (less than a centimeter) to accommodate the epoxy seal and electrical contact to the ITO. The first and second films on their respective ITO coated glass substrates were positioned in a space-apart relationship facing each other, and an epoxy seal was placed around the perimeter and cured to form a cell leaving offsets for attachment of electrical contacts. The distance between the two substrates was about 135 micrometers. The resulting cell was filled with a solution of 0.1 molar tetraethyl ammonium bis-trifluoromethanesulfonimidate (TEANTF) and a cross-linkable polymer matrix precursor in PC to form a gel electrolyte.
The Devices A and B with two different anodic compounds were subjected to a variety of durability tests.
The results of the UV cycling durability test for Devices A and B are shown in
Device B made with phenazine compound with tert butyl groups showed significant improvement in UV cycling durability as shown in
The results of the 85° C. cycling durability testing for Devices A and B are shown in
Para. 1. A compound represented by:
Para. 2. The compound of Para. 1, wherein the sterically hindered group is selected from tertiary butyl, isobutyl, isopropyl, 2-ethyl butyl, 2-ethyl hexyl, sec-butyl, isopentyl, and neopentyl.
Para. 3. The compound of Paras. 1 or 2, wherein R1, R3, R4, R6, R8, and R9 are each independently H.
Para. 4. The compound of Paras. 1 or 2, wherein R1, R3, R4, R6, R7, and R9 are each independently H.
Para. 5. The compound of any one of Paras. 1-4, wherein at least one of R2, R3, R7, and R8 are independently C2-C8 alkyl.
Para. 6. The compound of Para. 5, wherein at least one of R2, R3, R7, and R8 are independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl.
Para. 7. The compound of Para. 6, wherein at least one of R2, R3, R7, and R8 are independently isopropyl, neopentyl or tertiary butyl.
Para. 8. The compound of any one of Paras. 1-4, wherein R2 and R7 or R2 and Re are each independently C2-C8 alkyl.
Para. 9. The compound of Para. 8, wherein R2 and R7 or R2 and R8 are each independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl.
Para. 10. The compound of Para. 9, wherein R2 and R7 or R2 and R8 are each independently isopropyl, neopentyl or tertiary butyl.
Para. 11. The compound of any one of Paras. 1-2, wherein R3 and R8 or R3 and R are each independently C2-C8 alkyl.
Para. 12. The compound of Para. 11, wherein R3 and R8 or R3 and R7 are each independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl.
Para. 13. The compound of Para. 12, wherein R3 and R8 or R3 and R7 are each independently isopropyl, neopentyl, or tertiary butyl.
Para. 14. The compound of any one of Paras. 1-4, wherein at least one of R2, R3, R7, and R8 are independently aryl.
Para. 15. The compound of Para. 14, wherein at least one of R2, R3, R7, and Re are independently phenyl.
Para. 16. The compound of any one of Paras. 1-4, wherein R2 and R7 or R2 and Re are each independently aryl.
Para. 17. The compound of Para. 16, wherein R2 and R7 are each independently phenyl.
Para. 18. The compound of any one of Paras. 1-2, wherein R3 and R8 or R3 and R7 are each independently aryl.
Para. 19. The compound of Para. 18, wherein R3 and R8 or R3 and R7 are each independently phenyl.
Para. 20. The compound of any one of Paras. 1-19, wherein at least one of R5 and R10 are independently represented by:
-L1-A-L2-OR14;
Para. 21. The compound of Para. 20,
Para. 22. The compound of any one of Paras. 1-19, wherein at least one of R5 and R10 are independently represented by:
Para. 23. The compound of Para. 22,
Para. 24. The compound of any one of Paras. 1-19, wherein at least one of R5 and R10 are independently represented by:
-L3-OR16;
Para. 25. The compound of Para. 24,
Para. 26. The compound of any one of Paras. 1-19, wherein at least one of R5 and R10 are independently represented by:
Para. 27. The compound of Para. 26, y is 3 or 6.
Para. 28. The compound of any one of Paras. 1-23, wherein the compound is ammonium salt with an anion comprising 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 mixtures of anions thereof, wherein Ar is an aryl or fluorinated aryl group.
Para. 29. The compound of Para. 28, wherein the anion is selected from PF6− and SO3CF3−.
Para. 30. The compound of Para. 1, wherein the compound is selected from:
Para. 31. An energy storage device comprising:
Para. 32. An energy storage device comprising:
Para. 33. The energy storage device of Paras. 31 or 32 further comprising an electrolyte comprising a solvent and a metal salt or an ammonium salt.
Para. 34. The energy storage device of Paras. 32 or 33, wherein the separator comprises an ion exchange membrane or a size-exclusion membrane.
Para. 35. The energy storage device of any one of Paras. 31-34, wherein the energy storage device is a battery.
While certain embodiments have been illustrated and described, it should be understood that changes and modifications may be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.
The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of” will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of” excludes any element not specified.
The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations may be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds, compositions, or biological systems, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.
As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range may be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein may be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which may be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.
All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.
Other embodiments are set forth in the following claims.
This application claims the benefit of priority to U.S. Provisional Patent Application No. 63/311,694 filed Feb. 18, 2022, which is hereby incorporated by reference, in its entirety for any and all purposes.
| Number | Date | Country | |
|---|---|---|---|
| 63311694 | Feb 2022 | US |
