WO2023235454A1 - High speed wetting agents for thermal control of li-ion hazards - Google Patents

Abstract

A firefighting composition includes a glycol ether, water, and mixture comprising two or more selected from the group consisting of a glycol, an ethoxylated acetylenic diol surfactant, a quaternary silicone surfactant, and an ethoxylated polydimethylsiloxane.

Description

HIGH SPEED WETTING AGENTS FOR

THERMAL CONTROL OF LI-ION HAZARDS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63/348,274, filed on June 2, 2022, the contents of which are incorporated herein by reference in their entirety.

TECHNOLOGY

[0002] The present technology is generally related to firefighting compositions. Specifically, the technology is related to wetting agents for controlling fires in lithium-ion or sodium-ion battery applications.

SUMMARY

[0003] In an aspect, a firefighting composition includes: a glycol ether; water; and two or more of a glycol, an ethoxylated acetylenic diol surfactant, a quaternary silicone surfactant, and an ethoxylated polydimethylsiloxane.

[0004] In some embodiments, the firefighting composition includes: a glycol ether; water; a glycol; and an ethoxylated acetylenic diol surfactant.

[0005] In some embodiments, the glycol ether includes diethylene glycol monobutyl ether (butyl Carbitol™), diethylene glycol monohexyl ether (hexyl Carbitol™), dipropylene glycol n-butyl ether, tripropylene glycol mono n-butyl ether, or a mixture of any two or more thereof.

[0006] In some embodiments, the firefighting composition includes from about 1 wt% to about 35 wt% of the glycol ether. In some embodiments, the firefighting composition includes about 10 wt% of the glycol ether.

[0007] In some embodiments, the glycol includes ethylene glycol, propylene glycol, or butylene glycol. [0008] In some embodiments, the firefighting composition includes from about 1 wt% to about 25 wt% of the glycol. In some embodiments, the firefighting composition includes about 5 wt% of the glycol.

[0009] In some embodiments, the ethoxylated acetylenic diol is ethoxylated 2, 4,7,9- tetramethyl 5 decyn-4,7-diol (Surfynol® 465), ethoxylated 2,5,8, 1 l-tetramethyl-6-dodecyn- 5,8-diol (Dynol 604, Dynol607), a,a'-[l,4-dimethyl-l,4-bis(3-methylbutyl)-2-butyne-l,4- diyl]bis[co-hydroxy-poly(oxy-l,2-ethanediyl) (Dynol 800), or a mixture of any two or more thereof.

[0010] In some embodiments, the firefighting composition includes from about 1 wt% to about 25 wt% of the ethoxylated acetylenic diol. In some embodiments, the firefighting composition includes about 5 wt% of the ethoxylated acetylenic diol.

[0011] In some embodiments, the water is deionized water.

[0012] In some embodiments, the water is present in an amount of the balance after considering the amounts of glycol, glycol ether, and ethoxylated acetylenic diol surfactant.

[0013] In one aspect, a firefighting composition includes: a glycol ether; water; a quaternary silicone surfactant; and an ethoxylated polydimethylsiloxane.

[0014] In some embodiments, the glycol ether includes di ethylene glycol monobutyl ether (butyl Carbitol™), diethylene glycol monohexyl ether (hexyl Carbitol™), dipropylene glycol n-butyl ether, tripropylene glycol mono n-butyl ether, or a mixture of any two or more thereof.

[0015] In some embodiments, the firefighting composition includes from about 1 wt% to about 50 wt% of the glycol ether. In some embodiments, the firefighting composition includes about 25 wt% of the glycol ether.

[0016] In some embodiments, the quaternary silicone surfactant includes N,N-diethyl- 2-hydroxy-N-methyl-3-[3-[l,3,3,3-trimethyl-l-[(trimethylsilyl)oxy]-l-disiloxanyl]propoxy]- 1-propanaminium chloride (1 : 1) (Silqua® A0). [0017] In some embodiments, the firefighting composition includes from about 0.05 wt% to about 5 wt% of the quaternary silicone surfactant. In some embodiments, the firefighting composition includes about 1 wt% of the quaternary silicone surfactant.

[0018] In some embodiments, the ethoxylated poly dimethylsiloxane includes PEG-X- dimethicone, where X is a number of PEG groups and is from 2 to 10.

[0019] In some embodiments, the firefighting composition includes from about 0.05 wt% to about 5 wt% of the ethoxylated polydimethylsiloxane. In some embodiments, the firefighting composition includes about 1 wt% of the ethoxylated polydimethylsiloxane.

[0020] In some embodiments, the water is deionized water.

[0021] In some embodiments, the water is present in an amount of the balance after considering the amounts of glycol ether, quaternary silicone surfactant, and ethoxylated polydimethylsiloxane.

[0022] In one aspect, a firefighting composition includes a glycol, a polyether, an ethoxylated acetylenic diol surfactant, and water.

[0023] In an aspect, a method of extinguishing or abating a fire includes administering any one of the firefighting compositions described herein to the fire.

[0024] In some embodiments, the fire is a lithium-ion battery fire or a sodium-ion battery fire.

[0025] In another aspect, a method is provided for controlling a thermal runaway event associated with a lithium-ion or sodium-ion battery includes administering any one of the firefighting compositions described herein to the lithium-ion or sodium-ion battery.

[0026] In another aspect, a method of fighting a fire includes applying a firefighting composition including a glycol, a polyether, an ethoxylated acetylenic diol surfactant, and water to the fire.

DETAILED DESCRIPTION [0027] 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.

[0028] The use of the terms “a” and “and” 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 can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or illustrative 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.

[0029] For fighting various types of fires, many firefighting agents require intensive amounts of water. However, in some instances, adding just the water to the fire without a wetting agent can be problematic. Herein are firefighting compositions and methods that have the effect of enhanced wetting capability for fires such as those that may be lithium-ion or sodium-ion based fires. The agents allow for cooling of the batteries in a fire or thermal runaway event, to extinguish or abate the fire. Additionally, the compositions assist in cooling and/or controlling thermal runaway events that may occur with lithium-ion or sodium-ion applications.

[0030] As used herein, “wetting” in the context of a firefighting agent means refers to its ability to decrease the surface and/or interfacial tension of the liquid agent such that the fluid may move faster across the surface of the hazard. This is often used to achieve faster coverage of the hazard as well as a more rapid cooling effect in contrast to water alone.

[0031] In an aspect, a firefighting composition includes a glycol ether, water, and a mixture comprising two or more selected from the consisting group of a glycol, an ethoxylated acetylenic diol surfactant, a quaternary silicone surfactant, and an ethoxylated polydimethylsiloxane.

[0032] In an aspect, a firefighting composition includes a glycol ether, water, a glycol, and an ethoxylated acetylenic diol surfactant.

[0033] Illustrative examples of the glycol ether for the firefighting compositions include, but are not limited to, diethylene glycol monobutyl ether (butyl Carbitol™), diethylene glycol monohexyl ether (hexyl Carbitol™), dipropylene glycol n-butyl ether, tripropylene glycol mono n-butyl ether, or a mixture of any two or more thereof. In some embodiments, the firefighting composition includes from about 1 wt% to about 35 wt% of the glycol ether. In some embodiments, the firefighting composition includes the glycol ether at about 10 wt%.

[0034] When included in the firefighting compositions, the glycol may include, but is not necessarily limited to, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, and the like, or a mixture of any two or more thereof. In some embodiments, the firefighting composition includes from about 1 wt% to about 25 wt% of the glycol. In some embodiments, the firefighting composition includes about 5 wt% of the glycol.

[0035] When included in the firefighting compositions, the ethoxylated acetylenic diol may be ethoxylated 2,4,7,9-tetramethyl 5 decyn-4,7-diol (Surfynol® 465), ethoxylated 2,5,8, 1 l-tetramethyl-6-dodecyn-5,8-diol (Dynol 604, Dynol607), a,a'-[l,4-dimethyl-l,4- bis(3-methylbutyl)-2-butyne-l,4-diyl]bis[co-hydroxy-poly(oxy-l,2-ethanediyl) (Dynol 800), or a mixture of any two or more thereof. Other materials that may be used include anionic surfactants, cationic surfactants, zwitterionic surfactants, nonionic surfactants, or nonionic branched dimers known as gemini surfactants (a family of synthetic amphiphilic materials having, in order, a long hydrocarbon chain, an ionic group, a spacer group, a second ionic group, and another hydrocarbon tail), or mixtures of two or more thereof. In some embodiments, the firefighting composition includes from about 0.5 wt% to about 25 wt% of the ethoxylated acetylenic diol. In some embodiments, the firefighting composition includes the ethoxylated acetylenic diol at about 5 wt%. [0036] Illustrative anionic surfactants include an alkyl sulfate surfactant, an alkyl sulfonate surfactant, alkyl ether sulfate surfactant, an alkyl ether sulfonate surfactant, or a combination of two or more thereof. In some embodiments, the anionic surfactant may include an alkyl sulfate surfactant and/or an alkyl sulfonate surfactant. In some embodiments, the alkyl sulfate salt surfactant includes include a Cs-i2-alkyl sulfate salt. Nonlimiting examples of the Cs-i2-alkyl sulfate salt include a dodecyl sulfate salt, a decyl sulfate salt, an octyl sulfate salt, or a combination of any two or more thereof. In some embodiments, the alkyl sulfate salt includes an alkyl sulfate sodium salt, such as a sodium decyl sulfate, sodium octyl sulfate, or a combination thereof. In some embodiments, the alkyl sulfate salt includes an alkyl sulfate ammonium salt, such as an ammonium decyl sulfate, ammonium octyl sulfate, ammonium lauryl sulfate, or a combination thereof. In some embodiments, the anionic surfactant includes a Cs-i4-alkyl sulfate salt and/or a Cs-u-alkyl sulfonate salt. In some embodiments, the firefighting composition further includes an anionic surfactant, which comprises one or more surfactants selected from Cs-n-alkyl sulfate salts and/or a Cs-n-alkyl sulfonate salts. As a non-limiting example, one or more of octyl sulfate salts, decyl sulfate salts, dodecyl sulfate salts and tetradecyl sulfate salts may be used as anionic surfactants in the present firefighting compositions. The anionic surfactant may be a sodium, potassium and/or ammonium salt.

[0037] Illustrative zwitterionic surfactants include an alkylamidoalkyl betaine surfactant, an alkyl betaine surfactant, an alkyl sulfobetaine surfactant, an alkylamidoalkylene hydroxysultaine surfactant, such as an alkylamidopropyl hydroxysultaine surfactant, or a combination of two or more thereof. As a non-limiting example, the firefighting composition further includes a zwitterionic surfactant, which comprises one or more of a Cs-is- alkylamidopropyl hydroxysultaine surfactant, a Cs-is-alkylamidopropyl betaine surfactant, a Cs-is-alkyl sulfobetaine surfactant, a Cx-ix-alkyl betaine surfactant, or a combination of two or more thereof. Non-limiting examples of the alkylamidoalkylene hydroxysultaine surfactant include a Cs-is-alkylamidopropyl hydroxysultaine surfactant, such as a cocamidopropyl hydroxysultaine surfactant, which includes a lauryl amidopropyl hydroxysultaine and a myristyl amidopropyl hydroxysultaine. Non-limiting examples of the alkylamidoalkyl betaine surfactant include a Cs-is-alkylamidoalkyl betaine surfactant, such as a cocamidopropyl betaine, a tallowamidopropyl betaine, a lauryl amidopropyl betaine or a myristyl amidopropyl betaine. In some embodiments, the zwitterionic surfactant includes a Cs- -alkylamidopropyl hydroxysultaine, such as a cocamidopropyl hydroxysultaine. In some embodiments, the zwitterionic surfactant includes lauryl amidopropyl hydroxysultaine and/or my ri sty 1 ami dopropy 1 hydroxy sultaine .

[0038] Illustrative nonionic surfactants include an aliphatic alcohol and/or an aliphatic alcohol ethoxylate. As a non-limiting example, the firefighting composition may include an aliphatic alcohol-based nonionic surfactant including an aliphatic alcohol having 8 to 14 carbon atoms and/or an aliphatic alcohol ethoxylate having 10 to 16 carbon atoms in its alcohol portion. The aliphatic alcohol ethoxylate may has an average degree of polymerization (i.e., the average number of ethylene oxide units) of about 0.7-2.0 and often of no more than about 1.5, no more than about 1.2, or no more than about 1.0. Aliphatic alcohols, which include a linear Cs-i4-aliphatic alcohol, such as a Cs-i4-fatty alcohol, may be used as a nonionic surfactant in the present firefighting compositions. Non-limiting examples of such alcohols include one or more of octyl alcohol, decyl alcohol, lauryl alcohol and myristyl alcohol. The firefighting composition may include an aliphatic alcohol ethoxylate having an average of no more than about 2 ethylene oxide units. In some embodiments, the aliphatic alcohol portion of such ethoxylates has about 10 to 16 carbon atoms. Non-limiting examples include decyl alcohol ethoxylates, lauryl alcohol ethoxylates and/or myristyl alcohol ethoxylates. In some embodiments, the alcohol ethoxylates have an average of no more than about 2 ethylene oxide units, no more than about 1.5 ethylene oxide units, no more than about 1.2 ethylene oxide units and, in some instances, no more than about 1 ethylene oxide units. In some embodiments, the aliphatic alcohol ethoxylate comprises an ethoxylate of a linear Cs-i4-aliphatic alcohol having no more than about 1.2 ethylene oxide units.

[0039] In some embodiments, the water may be deionized water. In some embodiments, the amount of water in the composition is the balance of the composition after considering the amounts of the glycol, the polyether, and the ethoxylated acetylenic diol surfactant.

[0040] In another aspect, a firefighting composition may include a glycol ether, a quaternary silicone surfactant, an ethoxylated polydimethylsiloxane, and water. In any such embodiments, the glycol ether may be an alkyl Carbitol™. Illustrative examples may include, but are not limited to diethylene glycol monobutyl ether (butyl Carbitol™), diethylene glycol monohexyl ether (hexyl Carbitol™), dipropylene glycol n-butyl ether, tripropylene glycol mono n-butyl ether, or a mixture of any two or more thereof. In some embodiments, the firefighting composition includes from about 0.5 wt% to about 50 wt% of the glycol ether. In some embodiments, the firefighting composition includes the glycol ether at about 25 wt%

[0041] When included in the firefighting compositions, the quaternary silicone surfactant may be N,N-diethyl-2-hydroxy-N-methyl-3-[3-[l,3,3,3-trimethyl-l- [(trimethylsilyl)oxy]-l-disiloxanyl]propoxy]-l-propanaminium, chloride (1 : 1) (i.e., Silquat® AO). The compositions may also include polyether siloxanes such as Dynol® 960 or 980, or poly siloxane surfactants having alkyl groups from Ci-Cis, and silicone poly ether fatty acid ester quaternary compounds from C12-C18. In some embodiments, the firefighting composition includes from about 0.1 wt% to about 5 wt% of the quaternary silicone surfactant. In some embodiments, the firefighting composition includes the quaternary silicone surfactant at about 1 wt%. In some embodiments, the compositions may include nonionic polyether siloxane surfactants, multipolymeric siloxane surfactants, linear siloxane surfactants, silicone phosphate surfactants, or a mixture of any two or more thereof.

[0042] When included in the firefighting compositions, the ethoxylated polydimethylsiloxane may be PEG-5 dimethicone (i.e., Silsurf® A004-UP), or others such as PEG-3 dimethicone, PEG-4 dimethicone, or PEG-X dimethicone, where X is from 2 to 10. In some embodiments, the firefighting composition includes from about 0.05 wt% to about 5 wt% of the quaternary silicone surfactant. In some embodiments, the firefighting composition may include the quaternary silicone surfactant at about 1 wt%. As used herein, X in PEG-X is an integer and is the number of polyethylene glycol units, and PEG is an abbreviation for polyethylene glycol. In some embodiments, X may be 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some embodiments, X is 4 or 5.

[0043] In some embodiments, the firefighting composition may further include a sugar component. In some embodiments, the sugar component may include a monosaccharide sugar, a disaccharide sugar, or a sugar alcohol. In some embodiments, the sugar component may include fructose, glucose, galactose, xylose, mannose, sucrose, lactose, maltose, an oligosaccharide, or a mixture of any two or more thereof. In some embodiments, the sugar alcohol may include a four carbon sugar alcohol, such as erythritol, a five carbon alditol, such as xylitol, a six carbon alditol, such as mannitol and/or sorbitol, and other sugar alcohols, such as isomalt. In some embodiments, the monosaccharide may be high fructose corn syrup. In some embodiments, the high fructose corn syrup may additionally contain glucose and/or oligosaccharides. The sugar component may also be a carbonized or caramelized sugar. For example, such carbonized or caramelized sugars may include, but are not limited to, brown sugar or molasses.

[0044] Saccharides for use in the present firefighting compositions are generally simple monosaccharide sugars and may include other carbohydrates, such as common sugar (sucrose/dextrose) derived from sugar cane or sugar beets. Sucrose is a disaccharide composed from the basic, simple sugar molecules glucose and fructose. Mixtures where the majority of the sucrose has been broken down into its monosaccharide components, glucose and fructose (e.g., invert sugar), are suitable for use in the present firefighting compositions. Sucrose is readily available in view of its world production from cane and sugar beet on the order of millions of tons per annum. Those skilled in the art will also be aware that other commercially available simple monosaccharides and related sugar alcohols can be utilized in the present firefighting compositions.

[0045] In some embodiments, the firefighting composition may further include a thickener, such as a polysaccharide thickener. Illustrative thickeners include agar, sodium alginate, carrageenan, gum arabic, gum guaicum, neem gum, pistacia lentiscus, gum chatti, caranna, galactomannan, gum tragacanth, karaya gum, guar gum, welan gum, rhamsam gum, locust bean gum, beta-glucan, cellulose, methylcellulose, chicle gum, kino gum, dammar gum, glucomannan, succinoglycan, mastic gum, spruce gum, tara gum, gellan gum, acacia gum, cassia gum, diutan gum, fenugreek gum, ghatti gum, hydroxyethylcellulose, hydroxypropylmethylcellulose, karaya gum, konjac gum, pectin, propylene glycol alginate, or a mixture of any two or more thereof. In some embodiments, the thickener comprises xanthan gum, diutan gum, rhamsan gum, welan gum, gellan gum, guar gum, konjac gum, tara gum, succinoglycan, methylcellulose, or a combination of two or more thereof. [0046] In some embodiments, the firefighting composition may further include a mixture of xanthan gum and one or more of diutan gum, rhamsan gum, welan gum, gellan gum, guar gum, konjac gum, tara gum, succinoglycan, and methylcellulose. In some embodiments, the firefighting composition may further include a mixture of xanthan gum and one or more of diutan gum, rhamsan gum, welan gum, succinoglycan, and gellan gum as the polysaccharide thickener. In some embodiment, the firefighting composition may further include a mixture of xanthan gum and diutan gum and/or rhamsan gum. In some embodiments, the firefighting composition may further include a mixture of xanthan gum and succinoglycan. In some embodiments, the firefighting composition may further include a mixture of xanthan gum and welan gum. In some embodiments, the firefighting composition further includes welan gum.

[0047] In some embodiments, the firefighting composition may further include one or more chelators or sequestering buffers. Illustrative chelators and sequestering buffers include agents that sequester and chelate metal ions, including polyamminopolycarboxylic acids, ethylenediaminetetraacetic acid, citric acid, tartaric acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid and salts thereof. Illustrative buffers include, but are not limited to, Sorensen's phosphate or Mcllvaine's citrate buffers.

[0048] In some embodiments, the firefighting composition may further include one or more corrosion inhibitors. Illustrative and non-limiting corrosion inhibitors include orthophenylphenol, tolyltri azole, and phosphate ester acids. In some embodiments, the corrosion inhibitor is tolyltri azole.

[0049] In some embodiments, the firefighting composition may further include a metallic salt, such as a metallic salt which includes a multi-valent cation. Illustrative nonlimiting metallic salts include a cation selected from the group consisting of aluminum, calcium, copper, iron, magnesium, potassium, and calcium cations. The counteranion may be a sulfate and/or phosphate anion. In one embodiment, the metallic salt may include magnesium sulfate.

[0050] In some embodiments, the firefighting composition may further include a reducing agent. In some embodiments, the reducing agent may be selected such that it is more readily oxidized compared to other components of the firefighting composition. As a non-limiting example, the reducing agent may be oxidized more readily than the sugar component or polysaccharide components. Illustrative reducing agents include, but are not limited to, sodium sulfite, sodium bisulfite, sodium metabisulfite, or a mixture of any two or more thereof.

[0051] In some embodiments, the firefighting composition may further include a biocide. Illustrative examples include, but are not limited to, Kathon CG/ICP (Rohm & Haas Company), Givgard G-4 40 (Givaudan, Inc.), Dowicil 75 and Dowacide A (Dow Chemical Company).

[0052] In some embodiments, the firefighting composition may further include microfibrous cellulose. The microfibrous cellulose included in the firefighting compositions may include microfibrous cellulose produced by mechanically disrupting/altering cellulose fibers, e.g., cereal, wood, and/or cotton-based cellulose fibers - commonly referred to as microfibrillated cellulose (MFC). Microfibrillated cellulose can be obtained through a fibrillation process of cellulose fibers. In such a process, the mechanical shearing can strip away the outer layer of the cellulose fibers, exposing the fibril bundles. The macroscopic fibers are typically mechanically sheared until the fibrils are released, resulting in separation of the cellulose fibers into a three dimensional network of microfibrils with a very large surface area. The exposed fibrils are much smaller in diameter compared to the original fibers, and can form a network or a web-like structure.

[0053] An illustrative and non-limiting example of microfibrillated cellulose is Exilva™ microfibrillated cellulose (available from Borregaard, Sarpsborg, Norway). Exilva™ microfibrillated cellulose is a pre-activated product, available as a 2% suspension or a 10% paste, that is produced from mechanically disrupting cellulose sourced from Norway spruce. Exilva™ microfibrillated cellulose is reported to be an insoluble microfibrillated cellulose consisting of an entanglement of the cellulose fibers, which has the ability to interact both physically through its extreme surface area and chemically through hydrogen bonding. Other commercial sources of microfibrous cellulose include Celova® microfibrillated cellulose (available from Weidmann Electrical Technology AG (Rapperswil, Switzerland) and Curran® microfibrillated cellulose (available from CelluComp, Fife, Scotland). Curran® microfibrillated cellulose is produced from extraction of nanocellulose fibers from waste streams of root vegetables, primarily carrots and sugar beet pulp.

[0054] Another illustrative and non-limiting example of a source of microfibrillated cellulose for use in the present compositions is microfibrillated cellulose-mineral composite commercially available from FiberLean® Technologies (Par Moor Centre, United Kingdom). The FiberLean® MFC-composite is reportedly produced by fibrillating the cellulose fibers in the presence of one of a number of different minerals, such as calcium carbonate, clay (e.g., kaolin or bentonite), alumina, zirconia, graphite, silicate or talc, to obtain a nano-fibrillar cellulose suspension.

[0055] When included in the firefighting compositions, the microfibrous cellulose may include a fermentation-derived cellulose, such as a microfibrous cellulose derived from a microbial fermentation process. The microfibrous cellulose may include cellulose derived from a bacterial fermentation process, e.g., from fermentation of a Komagataeibacter xylinus strain or an Acetobacter xylinum strain. Fermentation-derived cellulose (FDC) produced by such a method may have an average fiber diameter of about 0.1-0.2 pm. This very small fiber size and diameter means that a given weight of FDC can have up to 200 times more surface area than other common forms of cellulose.

[0056] The microfibrous cellulose employed in the present firefighting compositions may have an average fiber diameter of no more than about 10 pm, no more than about 1 pm, and in some instances about 50 to 300 nm (0.05-0.3 pm). Quite often, the microfibrous cellulose is a derived from microbial fermentation. Prior to inclusion in the present compositions, such microbial fermentation derived cellulose may be activated by combining a powdered microfibrous cellulose and any optional co-agent with water and then mixing with high shear.

[0057] The present firefighting compositions may advantageously be substantially free of any fluorinated compounds. As used herein, the “phrase substantially free of fluorinated compounds” means that the aqueous firefighting composition includes no more than 0.1 wt.% fluorinated compounds. In some embodiments, the firefighting composition includes no more than 0.01 wt.% and, in some instances, no more than about 0.005 wt.% fluorinated compounds. The firefighting compositions of the present disclosure may be substantially free of fluorine in any form. As used herein, the phrase “substantially free of fluorine” means that the firefighting composition has a total concentration of fluorine atoms on a weight percentage basis of no more than about 70 ppt F.

[0058] In any of the above embodiments, the water may be deionized water. The amount of water in the composition is the balance of the composition after considering the amounts of the glycol, the polyether, and the ethoxylated acetylenic diol surfactant.

[0059] In another aspect, a method of fighting a fire includes applying a firefighting composition including a glycol ether, water, and a mixture comprising two or more selected from the consisting group of a glycol, an ethoxylated acetylenic diol surfactant, a quaternary silicone surfactant, and an ethoxylated polydimethylsiloxane to the fire. The methods may be used to completely extinguish the fire. Alternatively, the methods may be used to abate, or contain, the fire for application of other agents or removal of a fuel source. Additionally, methods of controlling thermal runaway events associated with lithium-ion and/or sodium- ion batteries by administering the composition to a battery experiencing a thermal runaway event are provided. The fires may include those where the application of just water may cause further violent and exothermic reactions. For example, the fire may be a lithium-ion fire or a sodium-ion battery fire. As used herein lithium-ion and sodium-ion batteries are those batteries that are rechargeable.

EXAMPLES

[0060] The following examples more specifically illustrate formulations for preparing aqueous firefighting compositions according to various embodiments described above. These examples should in no way be construed as limiting the scope of the present technology.

[0061] Example 1. Propylene glycol (5 wt%), butyl carbitol™ (10 wt%), and Surfynol® 465 (5 wt%) were all mixed in deionized water (80 wt%) to form a firefighting composition. The firefighting composition may be applied to a lithium-based fire to extinguish or abate the fire.

[0062] Example 2. Butyl carbitol™ (25 wt%), Silquat® A0 (1 wt%), and Silsurf® A0004-UP (1 wt%) were all mixed in deionized water (80 wt%) to form a firefighting composition. The firefighting composition may be applied to a lithium-based fire to extinguish or abate the fire.

[0063] While certain embodiments have been illustrated and described, it should be understood that changes and modifications can 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.

[0064] 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.

[0065] The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can 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. [0066] 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.

[0067] 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 can 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 can 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 can 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.

[0068] 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.

[0069] Other embodiments are set forth in the following claims.

Claims

WHAT IS CLAIMED IS:

1. A firefighting composition comprising: a glycol ether; water; and two or more of a glycol, an ethoxylated acetylenic diol surfactant, a quaternary silicone surfactant, and an ethoxylated polydimethylsiloxane.

2. The firefighting composition of claim 1 comprising: a glycol ether; water; a glycol; and an ethoxylated acetylenic diol surfactant.

3. The firefighting composition of claim 1 or claim 2, wherein the glycol ether comprises diethylene glycol monobutyl ether (butyl Carbitol™), diethylene glycol monohexyl ether (hexyl Carbitol™), dipropylene glycol n-butyl ether, tripropylene glycol mono n-butyl ether, or a mixture of any two or more thereof.

4. The firefighting composition of any one of the preceding claims, wherein the firefighting composition comprises from about 1 wt% to about 35 wt% of the glycol ether.

5. The firefighting composition of any one of the preceding claims, wherein the firefighting composition comprises about 10 wt% of the glycol ether.

6. The firefighting composition of any one of claims 1 or 3-5, wherein the glycol comprises ethylene glycol, propylene glycol, or butylene glycol.

7. The firefighting composition of any one of claims 1 or 3-6, wherein the firefighting composition comprises from about 1 wt% to about 25 wt% of the glycol.

8. The firefighting composition of any one of claims 1 or 3-7, wherein the firefighting composition comprises about 5 wt% of the glycol.

9. The firefighting composition of any one of claims 1 or 3-8, wherein the ethoxylated acetylenic diol is ethoxylated 2,4,7,9-tetramethyl 5 decyn-4,7-diol (Surfynol® 465), ethoxylated 2,5,8, 1 l-tetramethyl-6-dodecyn-5,8-diol (Dynol 604, Dynol607), a,a'- [ 1 ,4-dimethyl- 1 ,4-bis(3 -methylbutyl)-2-butyne- 1 ,4-diyl]bis[co-hydroxy-poly(oxy- 1 ,2- ethanediyl) (Dynol 800), or a mixture of any two or more thereof. firefighting composition of any one of claims 1 or 3-9, wherein the firefighting composition comprises from about 1 wt% to about 25 wt% of the ethoxylated acetylenic diol. firefighting composition of any one of claims 1 or 3-10, wherein the firefighting composition comprises about 5 wt% of the ethoxylated acetylenic diol. firefighting composition of any one of the preceding claims, wherein the water is deionized water. firefighting composition of any one of claims 3-12, wherein the water is present in an amount of the balance after considering the amounts of glycol, glycol ether, and ethoxylated acetylenic diol surfactant. firefighting composition of claim 1 comprising: a glycol ether; water; a quaternary silicone surfactant; and an ethoxylated polydimethylsiloxane. firefighting composition of claim 14, wherein the glycol ether comprises diethylene glycol monobutyl ether (butyl Carbitol™), diethylene glycol monohexyl ether (hexyl Carbitol™), dipropylene glycol n-butyl ether, tripropylene glycol mono n-butyl ether, or a mixture of any two or more thereof. firefighting composition of any one of claims 1, 14, or 15, wherein the firefighting composition comprises from about 1 wt% to about 50 wt% of the glycol ether. firefighting composition of any one of claims 1 or 14-16, wherein the firefighting composition comprises about 25 wt% of the glycol ether. firefighting composition of any one of claims 1 or 14-17, wherein the quaternary silicone surfactant comprises N,N-diethyl-2-hydroxy-N-methyl-3-[3-[l, 3,3,3- trimethyl- 1 -[(trimethylsilyl)oxy]-l -disiloxanyl]propoxy]- 1 -propanaminium chloride (1 : 1) (Silquat® AO). firefighting composition of any one of claims 1 or 14-18, wherein the firefighting composition comprises from about 0.05 wt% to about 5 wt% of the quaternary silicone surfactant. firefighting composition of any one of claims 1 or 14-19, wherein the firefighting composition comprises about 1 wt% of the quaternary silicone surfactant. firefighting composition of any one of claims 1 or 14-20, wherein the ethoxylated poly dimethylsiloxane comprises PEG-X-dimethicone, wherein X is a number of PEG groups and is from 2 to 10. firefighting composition of any one of claims 1 or 14-21, wherein the firefighting composition comprises from about 0.05 wt% to about 5 wt% of the ethoxylated polydimethylsiloxane. firefighting composition of any one of claims 1 or 14-22, wherein the firefighting composition comprises about 1 wt% of the ethoxylated polydimethylsiloxane. firefighting composition of any one of claims 14-23, wherein the water is deionized water. firefighting composition of any one of claims 14-24, wherein the water is present in an amount of the balance after considering the amounts of glycol ether, quaternary silicone surfactant, and ethoxylated polydimethylsiloxane. ethod of extinguishing or abating a fire, the method comprising administering the firefighting composition of any of the preceding claims to the fire. method of claim 26, wherein the fire is a lithium-ion battery fire or a sodium-ion battery fire. ethod of controlling a thermal runaway event associated with a lithium-ion or sodium-ion battery, method comprising administering the firefighting composition of any one of claims 1-25 to the lithium-ion or sodium-ion battery.