Compositions and methods for twin tailed fluorosurfactants in metal ion batteries

Abstract

The present disclosure provides, inter alia, compositions and methods for improving metal ion battery performance. In some aspects, the present disclosure provides an electrolyte comprising a twin tailed fluorosurfactant additive that is effective to improve one or more of battery lifetime, initial capacity, capacity fade, wetting time, and dendrite formation in a metal ion battery.

Description

COMPOSITIONS AND METHODS FOR TWIN TAILED FLUOROSURFACTANTS IN METAL ION BATTERIES CROSS REFERENCE TO RELATED APPLICATION

[0001] The present application claims benefit of U.S. Provisional Patent Application Serial No. 63 / 595,569, filed on November 2, 2023, which is incorporated by reference herein in its entirety. BACKGROUND

[0002] Metal Ion Batteries (MIBs) consist of an anode and a cathode that are kept apart from each other via a semipermeable membrane known as a separator. The battery is completed by filling it with an electrolyte solution containing metal ions. During discharge of the battery, the metal ions move from the anode (negative electrode) through the electrolyte solution to the cathode (positive electrode). When the battery is being charged the lithium ions move in reverse, from the cathode to the anode of the battery.

[0003] Lithium Ion Batteries (LIBs) are a ubiquitous type of metal ion battery. Typically, the anode is lithium intercalated graphite and the cathode is a variety of materials including lithium iron phosphate (LFP), nickel manganese cobalt (NMC) and many other materials with the ability to host lithium ions. Typical liquid electrolytes are comprised of carbonates such as propylene and ethylene carbonate, which dissolve the lithium hexafluorophosphate salt.

[0004] While the performance of LIBs is extraordinary, there are areas where improvement is needed. There is also a need for improvement for MIBs generally. For example, when the electrolyte is added to the battery, the time it takes to completely wet the complex structures of the electrodes and separator dictates how much time it takes to manufacture batteries. There currently exists a need for faster wetting times to reduce time spent in manufacturing MIBs. Furthermore, it is desirable to have the greatest initial capacity for abattery and for that capacity to stay as high as possible during cycling. Thus, there currently exists a need to improve the initial capacity (and to maintain capacity) of MIBs. Moreover, there are occasionally catastrophic events caused by dendrite formation in some MIBs that cause failure of the battery and, in some cases, cause fires that are extremely challenging to extinguish. Thus, there exists a need to mitigate and / or eliminate these catastrophic events for improved safety and for improved economics (e.g., longer battery lifetime). Finally, the operation of MIBs at low temperature is suboptimal with current technology. Thus, there exists a need to improve performance of MIBs at low temperatures. SUMMARY OF THE DISCLOSURE

[0005] To address these and other needs, the present disclosure provides, inter alia, electrolyte additives that can control and modulate the properties of MIBs. In some embodiments, the present disclosure provides additives comprising perfluoroalkyl sulfide terminated compounds (Rf-compounds), which are effective to improve battery performance.

[0006] According to some aspects, the present disclosure provides perfluoroalkyl sulfide terminated compounds and their use in improving the performance of MIBs. In some embodiments, the perfluoroalkyl sulfide terminated compounds comprise a perfluorinated chain region, a spacer region, and an oligomer region. In some embodiments, the perfluoroalkyl sulfide terminated compounds comprise two perfluorinated chains. See, e.g., FIG. 1. In some embodiments, the oligomeric moieties comprise a varying number of carbons that are made up of hydrophilic (or mixtures of hydrophilic and hydrophobic) monomers. In some embodiments, the perfluoroalkyl sulfide terminated compounds disclosed herein are added to metal ion batteries to provide improvement in manifold ways, including, but not limited to, improved wetting time of the electrolyte into the battery, initial capacity of the battery, capacity fade with cycling of the battery, as wells as reduced dendrimer formation and increased battery lifetime relative to MIBs without the perfluoroalkyl sulfide terminated compounds. In someembodiments, mixtures of perfluoroalkyl sulfide terminated compounds with single perflourinated chains and two perflourinated chains are added to the electrolyte of a battery. In some embodiments, the single chain perfluoroalkyl sulfide terminated compounds disclosed herein are those previously used in firefighting foam, and are disclosed, e.g., in U.S. Pat. Nos. 4,460,480, 4,439,329, 4,089,804, each of which is incorporated by reference herein in its entirety.

[0007] According to some aspects, the present disclosure provides a fluorocarbon surfactant according to Formula I:

[0008] perfluoroalkyl of 4 to 18 carbon atoms, perfluoroalkyloxyalkylene of 5 to 19 carbon atoms, or mixtures thereof; X is independently, strait or branched chain alkylene of 1 to 12 carbon atoms, alkyleneoxyalkylene of up to 6 carbon atoms, alkylene–NH-alkylene of up to 6 carbon atoms, or alkylene-N(lower alkyl)-alkylene, where the alkylene groups have a total of up to 6 carbon atoms, —CON(R') —E'—, —SO2N(R') —E'—, —E"—CON(R') —E'—, —E''—S—E'—, — E''—N(R') —E'—; or —E''—SO2N(R') —E'-, where R' is hydrogen or alkyl of 1 to 6 carbon atoms, E' is alkylene of 2 to 8 carbon atoms and E'' is alkylene of 1 to 4 carbon atoms; R1is selected from the group consisting of H, CH3, CO2H, Ph, CH2CH2CO2H, CH3CH2; Q is selected from —CH2CH2—,—CH2—, —CHCH3—, —CH(CH2CO2H)—, — CH(CH2CH2CO2H)—, —CH2CH2CH2—, —CH2CH2CH2CH2—, a covalent bond, and — CH(R'')CH(R'')—; R'' is hydrogen, lower alkyl, aryl, or aryl substituted lower alkyl; Z is selected from the group consisting of an alkyl having 2 to 18 carbon atoms (optionallysubstituted with one or more of an alkyl, aryl, amine, thiol, cyclic / heterocyclic rings, cysteine ethyl ester, –CH(CO2C2H5)CH2–, –CH2CH2– ; A is independently –S–, –SO–, or –SO2–; [M1] represents a hydrophilic monomer unit derived from a hydrophilic monomer of the type M1; and [M2] represents a hydrophobic monomer unit derived from hydrophobic monomers of the type M2; wherein M1is optionally more than one type of monomer and M2is optionally more than one type of monomer; wherein the sum of x and y is between 1 and about 500; and x / (x+y) is between 1 and 0.5.

[0009] In some embodiments, the fluorocarbon surfactant disclosed herein has the structure: .surfactant disclosed herein has the structure: ,

[0014] In some embodiments, the fluorocarbon surfactant disclosed herein has the structure: ,

[0016] wherein n is 1 to 250.

[0017] In some embodiments, the fluorocarbon surfactant disclosed herein has the structure: ,

[0020] In some embodiments, the fluorocarbon surfactant disclosed herein has the structure: ,

[0023] In some embodiments, the fluorocarbon surfactant disclosed herein has the structure: ,

[0026] In some embodiments, the fluorocarbon surfactant disclosed herein has the structure:,

[0029] In some embodiments, the fluorocarbon surfactant disclosed herein has the structure: .surfactant disclosed herein has the structure: .surfactant disclosed herein has the structure: .surfactant disclosed herein has the structure:er monovalent cations. a fluorocarbon surfactant according to Formula IC : wherein Rf is a4 to 18 carbon atoms, perfluoroalkyloxyalkylene of 5 to 19 carbon atoms, or mixtures thereof; X is independently, strait or branched chain alkylene of 1 to 12 carbon atoms, alkyleneoxyalkylene of up to 6 carbon atoms, alkylene–NH-alkylene of up to 6 carbon atoms, or alkylene-N(lower alkyl)- alkylene, where the alkylene groups have a total of up to 6 carbon atoms, —CON(R’) —E'— , —SO2N(R') —E'—, —E"—CON(R') —E'—, —E''—S—E'—, —E''—N(R') —E'—; or — E''—SO2N(R') —E'-, where R' is hydrogen or alkyl of 1 to 6 carbon atoms, E' is alkylene of 2 to 8 carbon atoms and E'' is alkylene of 1 to 4 carbon atoms; R1is selected from the group consisting of H, CH3, CO2H, Ph, CH2CH2CO2H, CH3CH2; Q is selected from —CH2CH2—,—CH2—, —CHCH3—, —CH(CH2CO2H)—, —CH(CH2CH2CO2H)—, —CH2CH2CH2—, — CH2CH2CH2CH2—, a covalent bond, and —CH(R'')CH(R'')— wherein R'' is hydrogen, lower alkyl, aryl, or aryl substituted lower alkyl.

[0038] In some embodiments, the fluorocarbon surfactant as disclosed herein has the structure:

[0039] , or salt of other monovalent cations.

[0040] some the present disclosure provides an ion battery electrolyte comprising an electrolyte salt, a solvent, and at least one fluorocarbon surfactant as disclosed herein. In some embodiments, the at least one fluorocarbon surfactant comprises about 0.1% to about 5% by weight of the electrolyte. In some embodiments, the electrolyte salt is an electrolyte lithium salt. In some embodiments, the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate. In some embodiments, the ion battery electrolyte further comprises at least one fluorocarbon surfactant according to Formula IV: Rf–En–S–[M1]x[M2]yH; wherein Rf is a straight or branched chain perfluoroalkyl of 4 to 18 carbon atoms, perfluoroalkyloxyalkylene of 5 to 19 carbon atoms, or mixtures thereof; En is a straight or branched chain alkylene of 1 to 12 carbon atoms, —CON(R’) —E'—, —SO2N(R') —E'—, —E"—CON(R') —E'—, —E''—S—E'—, —E''—N(R') —E'—; or —E''—SO2N(R') —E'-, where R' is hydrogen or alkyl of 1 to 6 carbon atoms, E' is alkylene of 2 to 8 carbon atoms and E'' is alkylene of 1 to 4 carbon atoms; [M1] represents a hydrophilic monomer unit derived from a hydrophilic monomer of the type M1; and [M2] represents a hydrophobic monomer unit derived from hydrophobic monomers of the type M2; wherein M1is optionally more than one type of monomer and M2is optionally more than one type of monomer; wherein the sum of x and y is between 1 and about 500; x / (x+y) is between 1 and 0.5; and n is 0 or 1.

[0041] In some embodiments, the ion battery electrolyte disclosed herein further comprises one or more of the fluorocarbon surfactants according to compounds that are eithera single tail acrylamide oligomers or a fluorocarbon surfactant with an hydrophilic group having a general structure shown on Figure 1A. Particular but non-limiting compounds are described in Examples 13 to 20.

[0042] According to some aspects, the present disclosure provides an ion battery comprising: a housing comprising an electric core, and an electrolyte disposed in said housing, wherein the electric core is in contact with the electrolyte and the electrolyte comprises at least one fluorocarbon surfactant as disclosed herein. In some embodiments, the ion battery is a lithium ion battery. In some embodiments, the lithium salt is selected from LiClO4, LiPF6, LiBF4, LiCF3SO3, LiN(CF3SO2)2, or combinations thereof. In some embodiments, the electrolyte comprises a solvent selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and combinations thereof.

[0043] According to some aspects, the present disclosure provides a method for improving performance of a metal ion battery comprising the step of contacting the metal ion battery with the ion battery electrolyte as disclosed herein. In some embodiments, the improved performance includes improved charge capacity, fade during charge, and discharge cycling of the metal ion battery. In some embodiments, the improved performance includes reduced dendrite formation during charge and discharge cycling of the metal ion battery. In some embodiments, the improved performance includes an increased lifetime of the metal ion battery. In some embodiments, the metal ion battery is a lithium ion battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] FIG. 1A shows a cartoon illustration of some embodiments of the single tail perfluoroalkyl sulfide terminated compounds as disclosed herein. FIG. 1B shows a cartoon illustration of some embodiments of the twin tailed perfluoroalkyl sulfide terminated compounds as disclosed herein.

[0045] FIG. 2 shows cycling performance of a lithium-ion battery using electrolyte comprising twin tailed Rf-compounds as disclosed herein.

[0046] FIG. 3 shows cycling performance of a lithium-ion battery using electrolyte comprising 0.5 wt% (FIG. 3A) and 1 wt% (FIG. 3B) twin tailed Rf-compounds as disclosed herein.

[0047] FIG. 4 shows cycling performance of a lithium-ion battery using electrolyte comprising 0.5 wt% (FIG. 4A) and 1 wt% (FIG. 4B) twin tailed Rf-compounds as disclosed herein.

[0048] FIG.5 shows comparative data of cycling performance using Rf-compounds as disclosed herein.

[0049] FIG. 6 shows comparative data of cycling performance using no electrolyte additive (FIG. 6A), a twin tailed Rf-compounds as disclosed herein (FIG. 6B), and a combination of single tail and twin tailed Rf-compounds as disclosed herein (FIG.6C). DETAILED DESCRIPTION Twin –tailed Rf-compounds

[0050] According to some aspects, the present disclosure provides a fluorocarbon surfactant according to Formula I (“twin-tailed” Rf compounds as depicted in FIG.1B): (I) wherein Rfof 4 to 18 carbon atoms, perfluoroalkyloxyalkylene of 5 to 19 carbon atoms, or mixtures thereof; X is independently, strait or branched chain alkylene of 1 to 12 carbon atoms, alkyleneoxyalkylene of up to 6 carbon atoms, alkylene–NH-alkylene of up to 6 carbon atoms, or alkylene-N(lower alkyl)-alkylene, where the alkylene groups have a total of up to 6 carbon atoms, —CON(R') —E'—, —SO2N(R') —E'—, —E"—CON(R') —E'—, —E''—S—E'—, —E''—N(R') —E'—; or — E''—SO2N(R') —E'-, where R' is hydrogen or alkyl of 1 to 6 carbon atoms, E' is alkylene of 2 to 8 carbon atoms and E'' is alkylene of 1 to 4 carbon atoms; R1 is selected from the group consisting of H, CH3, CO2H, Ph, CH2CH2CO2H, CH3CH2; Q is selected from —CH2CH2—,—CH2—, —CHCH3—, —CH(CH2CO2H)—, —CH(CH2CH2CO2H)—, —CH2CH2CH2—, — CH2CH2CH2CH2—, a covalent bond, and —CH(R'')CH(R'')—; R'' is hydrogen, lower alkyl, aryl, or aryl substituted lower alkyl; Z is selected from the group consisting of an alkyl having 2 to 18 carbon atoms (optionally substituted with one or more of an alkyl, aryl, amine, thiol, cyclic / heterocyclic rings, cysteine ethyl ester, –CH(CO2C2H5)CH2–, –CH2CH2–; A is –S–, – SO–, or –SO2–; [M1] represents a hydrophilic monomer unit derived from a hydrophilic monomer of the type M1; and [M2] represents a hydrophobic monomer unit derived from hydrophobic monomers of the type M2; wherein M1is optionally more than one type of monomer and M2 is optionally more than one type of monomer; wherein the sum of x and y is between 1 and about 500; and x / (x+y) is between 1 and 0.5. As used herein, the term “lower” in regard to organic molecules is meant those having 1 to 6 carbon atoms.

[0051] In some embodiments, the formula above does not depict the actual sequence of the oligomer units M1 and M2 because the units can be randomly distributed.

[0052] In some embodiments, the compounds disclosed herein are synthesized by polymerizing a hydrophilic monomer or monomers of the type M1 with or without a hydrophobic monomer or monomers of the type M2 in the presence of a twin tailed Rf - mercaptan of Formula IIFormula II

[0053] wherein Rf, R1, X osed herein.

[0054] In some embodiments, the compounds disclosed herein are synthesized from a perfluoroalykyl acid (Rf-acid) having the general structure of Formula III: Formula III

[0055] wherein Rf, R1, X,herein. In some embodiments, the Rf- acids containing sulfide linkage are obtained by the acid catalyzed addition of Rf-thiols to aldehydo or keto acids. In some embodiments, Rf-acids containing sulfoxide or sulfone linkages are obtained by oxidizing Rf-acids with sulfide linkages to the desired oxidation state. In some embodiments, perfluoroalkyl thiols useful herein are have been described in a number of U.S. Patents including U.S. Pat. Nos. 2,894,991; 2,961,470; 2,965,677; 3,088,849; 3,172,190, 3,544,663, 3,655,732, and 4,239,915 each of which are incorporated by reference as if recited in full herein.

[0056] In some embodiments, the Rf-acids are made by reacting a perfluoroalkyl- alkylmercaptan of the formula Rf-En-SH (Formula IV) with a lactone:

[0057] where R1 and R'' are as defined herein, in the presence of a catalytic amount of a Lewis acid, to form a perfluoroalkyl-alkylthio lactone of the formula

[0058] and reacting saidor without isolation thereof, with additional perfluoroalkyl-alkylmercaptan of the formula Rf-En-SH (Formula IV) in the presence of a catalytic amount of a Lewis acid, to obtain a bis(perfluoroalkyl-alkylthio)alkanoic acid (Rf-acid).

[0059] The lactones disclosed herein belong to a known class of compounds, and may be prepared by the dehydration of the corresponding keto acids by a variety of techniques, including slow dehydration, or by dehydration in the presence of an acidic dehydrating agent, such as H3PO4, acetyl chloride, acetic anhydride-sulfuric acid mixtures, acetic anhydride, and the like. See, e.g., U.S. Pat No. 4,485,251, which is incorporated by reference as if recited in full herein.

[0060] As stated above, the reactions between the mercaptan and the lactone, and the reaction between the mercaptan and the substituted lactone, are advantageously conducted in the presence of a catalytic amount of a Lewis acid. Suitable Lewis acids include, e.g., the mineral acids, such as HCl and H2SO4, organic acids such as acetic acid, para toluene sulfonic acid and the like, acid clays and resins, and boron trifluoride, or the diethyl ether complex thereof. The amount by weight of catalyst based on the total weight of the starting materials can vary between broad limits, e.g. between about 0.005% to about 10% by weight, preferably between about 0.01% to about 2% by weight.

[0061] In some embodiments, the perfluoroalkyl-alkylthio lactone may be then separated from the reaction mixture by conventional techniques, such as precipitation and filtration. For example, if the reaction is conducted in the presence of an inert solvent, such as benzene, toluene, chlorobenzene, methoxybenzene or the like, the reaction mixture may be cooled, and optionally a substantial non solvent for the compound, such as an alkane, e.g. heptane added, to promote precipitation. The precipitated compound may then be isolated by separation from the liquid mixture, such as by filtration, decantation, and the like. [M1] and [M2]

[0062] In some embodiments, hydrophilic monomers of the type M1which contain at least one hydrophilic group are commercially available, such as acrylic and methacrylic acid and salts thereof as well as hydrophilic groups containing derivatives such as their hydroxyalkyl esters, e.g., 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl or 2,3- hydroxypropyl esters; also ethoxylated and polyethoxylated hydroxyalkyl esters, such as esters of alcohols of the formula HO-Cm H2m -O-(CH2 -CH2 -O)n -R1

[0063] wherein R1 represents H, CH3, CO2H, Ph, CH2CH2CO2H, or CH3CH2, each m independently represents 2 to 5 and n represents 1 to 20 or esters of analogous alcohols, wherein a part of the ethylene oxide units is replaced by propylene oxide units. Further suitable esters are dialkylaminoalkyl acrylates and methacrylates, such as the 2-(dimethylamino)-ethyl-, 2- (diethylamino)-ethyl- and 3-(dimethylamino) -2-hydroxypropyl esters. Another class of hydrophilic monomers are acrylamide and methacrylamide as well as amides substituted by lower hydroxyalkyl, lower oxaalkyl- or lower dialkylaminoalkyl groups such as N- (hydroxymethyl)-acrylamide and -methacrylamide, N-(3-hydroxypropyl)-acrylamide, N-(2- hydroxyethyl)-methacrylamide, N-(1,1-dimethyl-3-oxabutyl)-acrylamide and N-[1,1- dimethyl-2-(hydroxymethyl)-3-oxabutyl)]-acrylamide; further hydrophilic monomers ofinterest are hydrazine derivatives, such as trialkylamine methacrylimide, e.g., trimethylamine- methacrylimide and dimethyl-(2-hydroxypropyl)amine methacrylimide and the corresponding derivatives of acrylic acid; mono-olefinic sulfonic acids and their salts, such as sodium ethylene sulfonate, sodium styrene sulfonate and 2-acrylamido-2-methylpropanesulfonic acid; N-[2- (dimethylamino)-ethyl]-acrylamide and -methacrylamide, N-[3-(dimethylamino)-2- hydroxypropyl]-methacrylamide, or mono-olefinic derivatives of heterocyclic nitrogen- containing monomers, such as N-vinyl-pyrrole, N-vinyl-succinimide, 1-vinyl-2-pyrrolidone, 1-vinyl-imidazole, 1-vinyl-indole, 2-vinyl-imidazole, 4(5)-vinyl-imidazole, 2-vinyl-1-methyl- imidazole, 5-vinyl-pyrazoline, 3-methyl-5-isopropenyl, 5-methylene-hydantoin, 3-vinyl-2- oxazolidone, 3-methacrylyl-2-oxazolidone, 3-methacrylyl-5-me-2-oxazolidone, 3-vinyl-5- methyl-2-oxazolidone, 2- and 4-vinyl-pyridine, 5-vinyl-2-methyl-pyridine, 2-vinyl-pyridine-1- oxide, 3-isopropenyl-pyridine, 2- and 4-vinyl-piperidine, 2- and 4-vinyl-quinoline, 2, 4- dimethyl-6-vinyl-s-triazine, 4-acrylyl-morpholine as well as the quaternized derivatives of the above pyridines.

[0064] In some embodiments, the above listed hydrophilic monomers of type M1 can be used alone or in combination with each other as well as in combination with suitable hydrophobic monomers of type M2.

[0065] In some embodiments, hydrophilic monomers of type M1 which require a comonomer for polymerization are maleates, fumarates and vinylethers; the following monomer combinations are, for instance, useful in the present disclosure: di(hydroxyalkyl) maleates, such as di(2-hydroxyethyl) maleate, and ethoxylated hydroxyalkyl maleates, hydroxyalkyl monomaleates, such as 2-hydroxyethyl monomaleate and hydroxylated hydroxyalkyl monomaleate with vinyl ethers, vinyl esters, styrene or generally any monomer which will easily copolymerize with maleates or fumarates; hydroxyalkyl vinyl ethers, such as2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, with maleates, fumarates, or generally all monomers which will easily copolymerize with vinyl ethers.

[0066] In some embodiments, the hydrophilic monomers of type M1 are acrylic acid, methacrylic acid, acrylamide, diacetone acrylamide, acrylamidopropane sulfonic acid and salts thereof, and hydroxyethyl methacrylate.

[0067] In some embodiments, hydrophobic monomers of the type M2 which copolymerize with hydrophilic monomers of type M1include: acrylates, methacrylates, maleates, fumarates and itaconates with one or more carbons in the ester group, such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, octadecyl, cyclohexyl, phenyl, benzyl and 2-ethoxyethyl;

[0068] Vinyl esters with 1 to 18 carbons in the ester group, such as vinyl acetate, butyrate, laurate, stearate, 2-ethyl-hexanoate and benzoate; vinyl chloracetate and isopropenyl acetate, vinyl carbonate derivatives;

[0069] Styrene and substituted styrenes such as o- and p-methyl, 3,4-dimethyl, 3,4- diethyl and p-chlorostyrene; alpha olefins which include substituted alpha olefins both straight and branched with up to 18 carbon atoms in the side chain including ethylene, propylene and butylene;

[0070] Methyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, 2-methoxyethyl vinyl ether, n-propyl vinyl ether, t-butyl vinyl ether, isoamyl vinyl ether, n-hexyl vinyl ether, 2-ethylbutyl vinyl ether, diisopropylmethyl vinyl ether, 1-methylheptyl vinyl ether, n-decyl vinyl ether, n-tetradecyl vinyl ether, and n-octadecyl vinyl;

[0071] Vinyl chloride, vinylidene chloride, vinyl fluoride, vinyldene fluoride, acrylonitrile, methacrylonitrile, tetrafluoroethylene, trifluorochloroethylene, hexafluoropropylene;

[0072] Dienes particularly 1,3-butadiene, isoprene, and chloroprene, 2-fluoro- butadiene, 1,1,3-trifluorobutadiene, 1,1,2,3-tetrafluorobutadiene, 1,1,2-trifluoro-3,4- dichlorobutadiene and tri- and pentafluorobutadiene and isoprene.

[0073] In some embodiments, the hydrophobic monomer of the type M2 is a fluorinated monomer.

[0074] In some embodiments, the mercaptans act as so-called chain transfer agents in free-radical polymerization and copolymerization reaction. The previously listed hydrophilic monomers of type M1and hydrophobic monomers of type M2will either homopolymerize and / or copolymerize in the presence of a free-radical initiator and therefore readily react with the twin tailed Rf-mercaptans of formula II forming the instant Rf-compounds of formula I in high yield.

[0075] In some embodiments, the polymerization reaction is performed in an essentially water free reaction medium, preferably in a lower alcohol such as methanol or isopropanol, or acetone or a lower cellosolve which dissolve the reactants and catalyst.

[0076] In some embodiments, the oligomerization temperature is maintained at a temperature between 20° - 60° C, but temperatures up to 100° C may be used. Optimum temperature may be readily determined for each oligomerization and will depend on the reaction, the relative reactivity of the monomers and the specific feed-radical initiator used. In some embodiments, in order to facilitate the free-radical propagation necessary for an effective catalyst reaction an oxygen-free atmosphere is desirable, and the oligomerizations are carried out under nitrogen.

[0077] In some embodiments, the catalyst employed may be a free-radical initiator, such as the peroxides, persulfates or azo compounds. In some embodiments, organic peroxides and hydroperoxides, hydrogen peroxides, azo catalysts and water soluble persulfates are used. Specific examples include ammonium persulfate, lauroyl peroxide, tertbutyl peroxide andparticularly the azo catalysts 2,2'-azobis(isobutyronitrile); 2,2'-azobis(2,4- dimethylvaleronitrile); 2-tert-butylazo-2-cyanopropane; 1-tert-butylazo-1-cyanocyclohexane; and 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile).

[0078] In some embodiments, catalytic amounts of initiator are used, that is between 0.01 and 0.5% by weight of monomers depending on the particular initiator and monomer system. In some embodiments, an azo catalyst from 0.01 to 0.2% by weight of monomers is used.

[0079] In some embodiments, the twin tailed Rf-compounds from monomers of type M1and M2are synthesized in a one step polymerization reaction described above. However, it is also possible to synthesize the Rf-compounds in a two-step synthesis. In this synthesis method, hydrolyzable hydrophobic monomers of type M2are polymerized in the presence of an Rf-mercaptan of formula II yielding an Rf-compound containing –M2– monomer units. In a second step, the Rf-compounds are hydrolyzed with a base, preferably alcoholic sodium or potassium hydroxide solution. In this hydrolysis process, selected –M2– monomer units are converted into hydrophilic –M1– monomer units. In this way, vinyl acetate monomer units are converted into vinyl alcohol monomer units or maleate ester units are converted into maleic acid salt units. Similarly, an Rf-compound containing maleic anhydride monomer units can be hydrolyzed or amidized.

[0080] In some embodiments, Rf -compounds of Formula Iare synthesized to of the Rf-X-A-segment versus the hydrophilic properties of the -M1- monomer units and the hydrophobic properties of the -M2- monomer units in the oligomer. In some embodiments, to achieve a desired balanceof properties more than one type of -M1- units and more than one type of -M2- units are present in the oligomer. In some embodiments, the incorporation of hydrophobic -M2- monomer units is not necessary to achieve the proper balance of oleophobic / hydrophobic versus hydrophilic properties.

[0081] Further, in some embodiments the chain length of the Rf-group and the nature and ratio of the M1 and M2 monomer units is varied to achieve a desired property. In some embodiments, the Rf-compounds achieve a solubility in water or water-solvent mixtures of at least 0.01% by weight of Rf-compound.

[0082] In some embodiments, the Rf-compounds of Formula I

[0083] are preparedV Rf -X-SH (V)

[0084] and a vast number of commercially available monomers of type M1and M2as defined herein.

[0085] In some embodiments, Rfis a perfluoroalkyl group with 6 to 14 carbon atoms,

[0086] X is alkylene, preferably ethylene,

[0087] - ; ; R3; –CONH–E1– NR2R3; –CONH–E1–NR2R3R4X1; –CONHCH2OH; –CONHCH2OR2; –CONHE2OH; – CO(OE1)nOR1; –COOCH2CHOHCH2OH; –CONH–E2–SO3Me; –CON(E1OH)2;

[0088] T2 is –OH; –OE2 OR1 ; –(OE1)n OR1 ; –SO3 Me; –C6 H4 SO3 Me;pyridinium halide, –NHCOR1, –NH e independently –COOMe; –CONH2; – CO(OE1)nOR1; –CONH–E1–OH; –CON(E1–OH)2

[0089] R1is H, CH3, CO2H, Ph, CH2CH2CO2H, CH3CH2;

[0090] R2, R3, R4are independently alkyl with 1 to 6 carbons;

[0091] E1is alkylene with 2 or 3 carbons;

[0092] E2 is alkylene with 2 to 6 carbons;

[0093] Me is hydrogen or alkali metal;

[0094] X1 is halide and;

[0095] n is 1 to 20;

[0096] –C6H4X1

[0097] G2is –H, R2or halide;

[0098] G3and G4are independently –COOR5or combined can be –CO–O–CO–;

[0099] R1, R2, X1are as previously defined;

[0100] R5is alkyl with 1 to 18 carbons or cycloalkyl, aryl, alkenyl with 6 to 18 carbons;

[0101] The sum of x and y is between 4 and about 500; and x / (x+y) is between 0.5 and 1.

[0102] In some embodiments, the sum of x and y is between 10 and about 200, most preferably between 10 and about 100 and x / (x+y) is about 0.5 to 1.

[0103] According to some embodiments, Rf compounds include those described generally above, and are further illustrated by the classes, subclasses, and species disclosed herein. Substructures

[0104] In some embodiments, the fluorocarbon surfactants disclosed herein have the structure according to Formula IA: ,In some embodiments, the fluorocarbon surfactants as disclosed herein, have the structure according to Formula IB:of repeating units.

[0109] A person of ordinary skill in the art would understand that n is an average value determined by the stoichiometry between the mercaptan and the polymerizable monomers. The resulting oligomer is not constituted of one defined molecular weight but rather a molecular weight distribution centered around an average value.

[0110] In some embodiments, the fluorocarbon surfactant has the structure according to Formula IB:, 50, 1 to 40, or 1 to 30.

[0113] In some embodiments, the fluorocarbon surfactant as disclosed herein has the structure: .surfactant as disclosed herein has the structure: .surfactant as disclosed herein has the structure: .

[0116] In some embodiments, the fluorocarbon surfactant as disclosed herein has the structure:er monovalent cations. ctant as disclosed herein has the structure: …surfactant as disclosed herein has the structure: .surfactant as disclosed herein has the Formula IC :wherein Rfindepende l of 4 to 18 carbon atoms, perfluoroalkyloxyalkylene of 5 to 19 carbon atoms, or mixtures thereof; X is independently, strait or branched chain alkylene of 1 to 12 carbon atoms, alkyleneoxyalkylene of up to 6 carbon atoms, alkylene–NH-alkylene of up to 6 carbon atoms, or alkylene-N(lower alkyl)- alkylene, where the alkylene groups have a total of up to 6 carbon atoms, —CON(R') —E'—, —SO2N(R') —E'—, —E"—CON(R') —E'—, —E''—S—E'—, —E''—N(R') —E'—; or — E''—SO2N(R') —E'-, where R' is hydrogen or alkyl of 1 to 6 carbon atoms, E' is alkylene of 2 to 8 carbon atoms and E'' is alkylene of 1 to 4 carbon atoms; R1 is selected from the group consisting of H, CH3, CO2H, Ph, CH2CH2CO2H, CH3CH2; Q is selected from —CH2CH2—, —CH2—, —CHCH3—, —CH(CH2CO2H)—, —CH(CH2CH2CO2H)—, —CH2CH2CH2—, — CH2CH2CH2CH2—, a covalent bond, and —CH(R'')CH(R'')— wherein R'' is hydrogen, lower alkyl, aryl, or aryl substituted lower alkyl.

[0120] In some embodiments, the fluorocarbon surfactant as disclosed herein has the structure:

[0121] In some embodiments, the fluorocarbon surfactant as disclosed herein has the structure:C6F13C6F13salt of other monovalent cations.

[0122] In some embodiments, the fluorocarbon surfactant as disclosed herein has the structure: C6F13.surfactant as disclosed herein has the structure: C6F13.General Methods of Preparing Twin Tailed Rf-Compounds

[0124] In some embodiments, the compounds disclosed herein may be prepared or isolated by synthetic methods known to those skilled in the art for analogous compounds and as illustrated in general schemes I and II, below, and the preparative examples that follow: Scheme I: Rf R'' XASH Formula IIIFormula VI

[0125] Scheme I above depicts a general method for preparing the compounds as disclosed herein. This scheme shows the functionalization of gem-perfluoroalkylthio acids (i.e., twin-tailed mercaptans) with aminothiols derived from cysteamine. In some embodiments, the synthesis of the twin-tailed mercaptan (Formula II) is derived from levulinic acid. It is formed in a two-step sequence starting with activation of the twin-tailed carboxylic acid (Formula III). The Q substituent consists of a group that links the twin-tailed Rfportion of the molecule to the carboxylic acid functionality. In some embodiments, it consists of 0 to 5 carbons (substituted or unsubstituted; saturated or unsaturated; with or without heteroatoms) (e.g. methylene groups) or could consist of substituted alkyl or aryl substituents. This activation of Formula III can be accomplished in a number of ways including (1) treatment with oxalyl chloride to form the acid chloride or (2) treatment with a combination of a carbodiimide reagent [such as N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC) or N,N'- Dicyclohexylcarbodiimide (DCC) and an effective leaving group (such as an NHS alcohol or a chloride group). The activated ester is then reacted with the amino functionality of an amino,thiol containing molecule (Formula VI). This structure can vary by the Z-group that links the amino group to the thiol group. In some embodiments, the Z-group consists of 2 to 5 carbon atoms (substituted or unsubstituted; saturated or unsaturated; with or without heteroatoms) (e.g. methylene groups) or could consist of substituted alkyl or aryl substituents. For Formula VI, the R’’ substituent could be an alkyl group of any length, an aryl group, aryl substituted lower alkyl, or a proton. Formula VI can be either the free base or the protonated amine salt. If the latter is used, then a base such as a trialkylamine (triethylamine) is required in the reaction scheme.

[0126] Variations of the gem-perfluororalkyl thiol acids (twin tailed mercaptans) are disclosed in Table 1 below. Table 1 Aldehyde and keto acids Substituent R1 Substituent Substituent / esters Q R2

[0127] The starting material of Formula 1 can be synthesized using the reactions as shown and described in U.S. Patent Nos. 4,485,251, 4,239,915, and 4,460,480, each of which is incorporated by reference as if recited in full herein. Scheme II:

[0128] Scheme II shows radical oligomerization using radical initiators such as Vazo- 52 to form twin-tail mercapto-polyacrylamides according to some embodiments disclosed herein. In some embodiments, the reactions of Scheme II are performed in methanol or isopropanol using as the starting mercaptan of Formula II. In some embodiments, Formula II and acrylamide are reacted in a solvent (e.g., methanol or isopropanol) and a free radical initiator (e.g. Vazo-52) to produce the product of Formula I. Single Tail Compounds

[0129] According to some aspects, the present disclosure provides perfluoroalkyl group terminated oligomers derived from perfluoroalkyl mercaptans and hydrophilic and / or hydrophobic monomers that are polymerized through free radical reactions, and their use to improve MIB performance.

[0130] According to certain embodiments, the perfluoroalkyl group terminated oligomers (Rf-oligomer) are represented by the following Formula VII: Rf–En–S–[M1]x[M2]yH (VII)

[0131] wherein Rf is a straight or branched chain perfluoroalkyl of 4 to 18 carbon atoms, perfluoroalkyloxyalkylene of 5 to 19 carbon atoms, or mixtures thereof; En is a straight or branched chain alkylene of 1 to 12 carbon atoms, —CON(R’) —E'—, —SO2N(R') —E'—, — E"—CON(R') —E'—, —E''—S—E'—, —E''—N(R') —E'—; or —E''—SO2N(R') —E'-, where R' is hydrogen or alkyl of 1 to 6 carbon atoms, E' is alkylene of 2 to 8 carbon atoms and E'' is alkylene of 1 to 4 carbon atoms; [M1] represents a hydrophilic monomer unit derived from a hydrophilic monomer of the type M1as defined herein, and [M2] represents a hydrophobic monomer unit derived from hydrophobic monomers of the type M2as defined herein. The sum of x and y is between 1 and about 500; x / (x+y) is between 1 and 0.5; in some embodiments, more than one type of – M1– units and more than one type of –M2– units are present in the fluorocarbon surfactant; and n is 0 or 1.

[0132] In some embodiments, the formula above does not depict the actual sequence of the oligomer units, since the units can be randomly distributed.

[0133] In some embodiments, the oligomers disclosed herein are synthesized by polymerizing a hydrophilic monomer or monomers of the type M1 with or without a hydrophobic monomer or monomers of the type M2 in the presence of an Rf -mercaptan of Formula IV Rf -En-SH (IV) wherein Rf and En are as disclosed herein.

[0134] Rf mercaptans of Formula IV are described inter alia in U.S. Pat. Nos. 2,894,991; 2,961,470; 2,965,677; 3,088,849; 3,172,910; 3,554,663; 3,655,732; 3,686,283; 3,883,596; 3,886,201 and 3,935,277; and Australian Application No. 36868; filed Apr. 24, 1968, each of which are incorporated by reference as if recited in full herein.

[0135] Suitable Rf mercaptans can, alternatively, be easily prepared by reacting an Rf acid halide, e.g., Rf SO2 Cl or Rf COCl with an amino mercaptan, e.g., H-N(R')-E'-SH, in an inert solvent.

[0136] In some embodiments, hydrophilic monomers of the type M1 which contain at least one hydrophilic group are known and are commercially available, such as acrylic and methacrylic acid and salts thereof as well as hydrophilic groups containing derivatives such as their hydroxyalkyl esters, e.g., 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl or 2,3- hydroxypropyl esters; also ethoxylated and polyethoxylated hydroxyalkyl esters, such as esters of alcohols of the formula HO-CmH2m-O-(CH2-CH2-O)n-R1wherein R1represents H, CH3, CO2H, Ph, CH2CH2CO2H, or CH3CH2, m represents 2 to 5 and n represents 1 to 20 or esters of analogous alcohols, wherein a part of the ethylene oxide units is replaced by propylene oxide units. Further suitable esters are dialkylaminoalkyl acrylates and methacrylates, such as the 2-(dimethylamino)-ethyl-, 2-(diethylamino)-ethyl- and 3- (dimethylamino) -2-hydroxypropyl esters. Another class of hydrophilic monomers are acrylamide and methacrylamide as well as amides substituted by lower hydroxyalkyl, lower oxaalkyl- or lower dialkylaminoalkyl groups such as N-(hydroxymethyl)-acrylamide and - methacrylamide, N-(3-hydroxypropyl)-acrylamide, N-(2-hydroxyethyl)-methacrylamide, N- (1,1-dimethyl-3-oxabutyl)-acrylamide and N-[1,1-dimethyl-2-(hydroxymethyl)-3-oxabutyl)]- acrylamide; further hydrophilic monomers of interest are hydrazine derivatives, such as trialkylamine methacrylimide, e.g., trimethylamine-methacrylimide and dimethyl-(2- hydroxypropyl)amine methacrylimide and the corresponding derivatives of acrylic acid; mono- olefinic sulfonic acids and their salts, such as sodium ethylene sulfonate, sodium styrene sulfonate and 2-acrylamido-2-methylpropanesulfonic acid; N-[2-(dimethylamino)-ethyl]- acrylamide and -methacrylamide, N-[3-(dimethylamino)-2-hydroxypropyl]-methacrylamide,or mono-olefinic derivatives of heterocyclic nitrogen-containing monomers, such as N-vinyl- pyrrole, N-vinyl-succinimide, 1-vinyl-2-pyrrolidone, 1-vinyl-imidazole, 1-vinyl-indole, 2- vinyl-imidazole, 4(5)-vinyl-imidazole, 2-vinyl-1-methyl-imidazole, 5-vinyl-pyrazoline, 3- methyl-5-isopropenyl, 5-methylene-hydantoin, 3-vinyl-2-oxazolidone, 3-methacrylyl-2- oxazolidone, 3-methacrylyl-5-me-2-oxazolidone, 3-vinyl-5-methyl-2-oxazolidone, 2- and 4- vinyl-pyridine, 5-vinyl-2-methyl-pyridine, 2-vinyl-pyridine-1-oxide, 3-isopropenyl-pyridine, 2- and 4-vinyl-piperidine, 2- and 4-vinyl-quinoline, 2, 4-dimethyl-6-vinyl-s-triazine, 4-acrylyl- morpholine as well as the quaternized derivatives of the above pyridines.

[0137] In some embodiments, the above listed hydrophilic monomers of type M1can be used alone or in combination with each other as well as in combination with suitable hydrophobic monomers of type M2.

[0138] In some embodiments, hydrophilic monomers of type M1which require a comonomer for polymerization are maleates, fumarates and vinylethers; the following monomer combinations are, for instance, useful: di(hydroxyalkyl) maleates, such as di(2- hydroxyethyl) maleate, and ethoxylated hydroxyalkyl maleates, hydroxyalkyl monomaleates, such as 2-hydroxyethyl monomaleate and hydroxylated hydroxyalkyl monomaleate with vinyl ethers, vinyl esters, styrene or generally any monomer which will easily copolymerize with maleates or fumarates; hydroxyalkyl vinyl ethers, such as 2-hydroxyethyl vinyl ether, 4- hydroxybutyl vinyl ether, with maleates, fumarates, or generally all monomers which will easily copolymerize with vinyl ethers.

[0139] In some embodiments, the hydrophilic monomers of type M1 are acrylic acid, methacrylic acid, acrylamide, diacetone acrylamide, acrylamidopropane sulfonic acid and salts thereof, and hydroxyethyl methacrylate.

[0140] In some embodiments, hydrophobic monomers of the type M2which do copolymerize with hydrophilic monomers of type M1are known and include: acrylates,methacrylates, maleates, fumarates and itaconates with one or more carbons in the ester group, such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, octadecyl, cyclohexyl, phenyl, benzyl and 2-ethoxyethyl;

[0141] Vinyl esters with 1 to 18 carbons in the ester group, such as vinyl acetate, butyrate, laurate, stearate, 2-ethyl-hexanoate and benzoate; vinyl chloracetate and isopropenyl acetate, vinyl carbonate derivatives;

[0142] Styrene and substituted styrenes such as o- and p-methyl, 3,4-dimethyl, 3,4- diethyl and p-chlorostyrene; alpha olefins which include substituted alpha olefins both straight and branched with up to 18 carbon atoms in the side chain including ethylene, propylene and butylene;

[0143] Methyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, 2-methoxyethyl vinyl ether, n-propyl vinyl ether, t-butyl vinyl ether, isoamyl vinyl ether, n-hexyl vinyl ether, 2-ethylbutyl vinyl ether, diisopropylmethyl vinyl ether, 1-methylheptyl vinyl ether, n-decyl vinyl ether, n-tetradecyl vinyl ether, and n-octadecyl vinyl;

[0144] Vinyl chloride, vinylidene chloride, vinyl fluoride, vinyldene fluoride, acrylonitrile, methacrylonitrile, tetrafluoroethylene, trifluorochloroethylene, hexafluoropropylene;

[0145] Dienes particularly 1,3-butadiene, isoprene, and chloroprene, 2-fluoro- butadiene, 1,1,3-trifluorobutadiene, 1,1,2,3-tetrafluorobutadiene, 1,1,2-trifluoro-3,4- dichlorobutadiene and tri- and pentafluorobutadiene and isoprene.

[0146] In some embodiments, the hydrophobic monomer of the type M2 is a fluorinated monomer.

[0147] In some embodiments, the mercaptans act as so-called chain transfer agents in free-radical polymerization and copolymerization reaction. The previously listed hydrophilic monomers of type M1and hydrophobic monomers of type M2will either homopolymerizeand / or copolymerize in the presence of a free-radical initiator and therefore readily react with Rf -mercaptans of Formula IV forming the instant Rf -oligomers of formula IV in high yield.

[0148] In some embodiments, the polymerization reaction is performed in an essentially water free reaction medium, preferably in a lower alcohol such as methanol or isopropanol, or acetone or a lower cellosolve which dissolve the reactants and catalyst.

[0149] In some embodiments, the oligomerization temperature is maintained at a temperature between 20 degree and 60 degrees C., but temperatures up to 100 degrees C. may be used. Optimum temperature may be readily determined for each oligomerization and will depend on the reaction, the relative reactivity of the monomers and the specific feed-radical initiator used. In some embodiments, in order to facilitate the free-radical propagation necessary for an effective catalyst reaction an oxygen-free atmosphere is desirable, and the oligomerizations are carried out under nitrogen.

[0150] In some embodiments, the catalyst employed must be a free-radical initiator, such as the peroxides, persulfates or azo compounds. In some embodiments, organic peroxides and hydroperoxides, hydrogen peroxides, azo catalysts and water soluble persulfates are used. Specific examples include ammonium persulfate, lauroyl peroxide, tertbutyl peroxide and particularly the azo catalysts 2,2'-azobis(isobutyronitrile); 2,2'-azobis(2,4- dimethylvaleronitrile); 2-tert-butylazo-2-cyanopropane; 1-tert-butylazo-1-cyanocyclohexane; and 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile).

[0151] In some embodiments, catalytic amounts of initiator are used, that is between 0.01 and 0.5% by weight of monomers depending on the particular initiator and monomer system. In some embodiments, azo catalyst from 0.01 to 0.2% by weight of azocatalyst per weight of monomers are used.

[0152] In some embodiments, the Rf-oligomers from monomers of type M1and M2are synthesized in a one step polymerization reaction described above. However, it is also possibleto synthesize the Rf -oligomers in a two step synthesis. In this alternate synthesis method, hydrolyzable hydrophobic monomers of type M2 are polymerized in the presence of an Rf - mercaptan of Formula IV yielding an Rf -oligomer containing –M2– monomer units. In a second step, such Rf -oligomers are hydrolyzed with a base, preferably alcoholic sodium or potassium hydroxide solution. In this hydrolysis process, selected –M2– monomer units are converted into hydrophilic –M1 – monomer units. In this way, vinyl acetate monomer units are converted into vinyl alcohol monomer units or maleate ester units are converted into maleic acid salt units. Similarly, an Rf-oligomer containing maleic anhydride monomer units can be hydrolyzed or amidized.

[0153] In some embodiments, Rf-oligomers of Formula VII Rf–En–S–[M1]x[M2]yH (VII) are synthesized to balance the oleophobic and hydrophobic properties of the Rf-E-S-segment versus the hydrophilic properties of the -M1- monomer units and the hydrophobic properties of the -M2- monomer units in the oligomer. In some embodiments, to achieve a desired balance of properties more than one type of –M1 – units and more than one type of –M2 – units are present in the oligomer. In some embodiments, the incorporation of hydrophobic –M2– monomer units is not necessary to achieve the proper balance of oleophobic / hydrophobic versus hydrophilic properties.

[0154] Further, in some embodiments the chain length of the Rf -group and the nature and ratio of the M1 and M2 monomer units is varied to achieve a desired property. In some embodiments, the Rf -oligomers achieve a solubility in water or water-solvent mixtures of at least 0.01% by weight of Rf -oligomer.

[0155] In some embodiments, M1 and M2 type monomers are selected by varying the degree of polymerization, i.e. the weight ratio of the Rf–E–S segment versus the segment formed by –[M1]x[M2]yH, Rf–oligomers, which reduce the surface tension of aqueoussystems to any desirable degree and as low as 16 dynes / cm. In some embodiments, it is possible to tailor Rf -oligomer compositions which provide any desirable surface tension in water between 76 dynes / cm and about 16 dynes / cm. In some embodiments, the Rf-oligomers can therefore be used in applications where improved wetting and spreading of liquids on difficult to wet substrates or substrates contaminated with oil or silicones is required.

[0156] In some embodiments, Rf -oligomers of Formula VII Rf–En–S–[M1]x[M2]yH (VII) are prepared from a wide variety of Rf-mercaptans of Formula IV Rf-En-SH (IV) and a vast number of commercially available monomers of type M1and M2as defined herein.

[0157] In some embodiments, Rfis a perfluoroalkyl group with 6 to 14 carbon atoms,

[0158] E is alkylene, preferably ethylene,

[0159] R3 ; –CONH–E1 – NR2 R3 ; –CONH–E1 –NR2 R3 R4 X; –CONHCH2 OH; –CONHCH2 OR2 ; –CONHE2 OH; – CO(OE1)n OR1 ; –COOCH2 CHOHCH2 OH; –CONH–E2 –SO3 Me; –CON(E1 OH)2;

[0160] T2 is –OH; –OE2 OR1 ; –(OE1)n OR1 ; –SO3 Me; –C6 H4 SO3 Me;pyridinium halide, –NHCOR1, –NH2T3& T4are independently –COOMe; –CONH2; – CO(OE1)nOR1; –CONH–E1–OH; –CON(E1–OH)2

[0161] R1is H, CH3, CO2H, Ph, CH2CH2CO2H, CH3CH2

[0162] R2, R3, R4 are independently alkyl with 1 to 6 carbons

[0163] E1 is alkylene with 2 or 3 carbons

[0164] E2 is alkylene with 2 to 6 carbons

[0165] Me is hydrogen or alkali metal

[0166] X is halide and

[0167] n is 1 to 20

[0168] –C6 H4 X

[0169] G2 is –H, R2 or halide

[0170] G3 and G4 are independently –COOR5 or combined can be –CO–O–CO–

[0171] R1, R2, X are as previously defined

[0172] R5 is alkyl with 1 to 18 carbons or cycloalkyl, aryl, alkenyl with 6 to 18 carbons

[0173] The sum of x and y is between 4 and about 500; and x / (x+y) is between 0.5 and 1.

[0174] In some embodiments, the sum of x and y is between 10 and about 200, most preferably between 10 and about 100 and x / (x+y) is about 0.5 to 1.

[0175] In some embodiments, Rf-oligomers have the structure Rf–E—S—[M1]xH, wherein Rfis linear perfluoroalkyl with 6 to 12 carbon atoms

[0176] E is –CH2CH2–

[0177] and x

[0178] In some embodiments, Rf -oligomers used as electrolyte additives have the above listed structure Rf -E-S-[M1 ]x H wherein -M1- is

[0179] and x varies from 10 to 50.

[0180] According to some embodiments, electrolyte additives comprise one or more of the compounds according to Example 7, Example 8, Example 9, Example 10, Example 11, Example 12, Example 13, Example 14, Example 15, Example 16, Example 17, Example 18, Example 19, Example 20, and Example 21. According to some embodiments, electrolyte additives comprise one or more commercial products, such as DX1080 or DX1090 (Dynax). In some embodiments, the commercial products, such as DX1030, DX1080 or DX1090, are added dry to the electrolyte. Drying consists in heating the product in a vacuum oven until constant weight is achieved. Use of Rf-compounds disclosed herein in electrolyte of MIBs

[0181] According to some aspects, the Rf-oligomers and twin tailed Rf-compounds disclosed herein (referred to together as the “disclosed compounds”) are useful as additives to an electrolyte for a MIB, such as a lithium-ion battery. In some embodiments, the disclosed compounds are present in the electrolyte in the amount of about 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.2%, 0.3%, 0.4%, 0.1%, 0.5%, 0.6%, 0.7%, 0.8% 0.9%, 1%, 1.5%, 2%, 2.5%, 3%,3.5%, 4%, 4.5%, or 5% by weight of the electrolyte. In some embodiments, the disclosed compounds are present in the electrolyte in the amount of about 0.001% to 5% by weight of the electrolyte. In some embodiments, the disclosed compounds are present in the electrolyte in the amount of about 0.01% to 2% by weight of the electrolyte. In some embodiments, the disclosed compounds are present in the electrolyte in the amount of about 0.05% to 1% by weight of the electrolyte.

[0182] In some embodiments, the classes of the disclosed compounds disclosed herein added to the electrolyte are selected from the group consisting of: polyethylene oxide, Amphoteric / Zwiterionic, anionic, cationic, non-ionic, Acrylamide oligomers, Acrylamide co- oligomers, N-Vinyl Pyrrolidone oligomers, Phosphate, Sulfonate, and combinations thereof. In some embodiments, the disclosed compounds disclosed herein added to the electrolyte comprise PEG containing units, PPG containing units, polyacrylic acid containing units, polyacrylamide containing units, and PVA containing units. In some such embodiments, the compounds disclosed herein added to the electrolyte comprise at least 1, at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11, at least 12, at least 13, at least 14, at least 15, at least 16, at least 17, at least 18, at least 19, at least 20, at least 21, at least 22, at least 23, at least 24, at least 25, at least 26, at least 27, at least 28, at least 29, or at least 30 units per molecule.

[0183] In some embodiments, the disclosed compounds disclosed herein added to the electrolyte comprise acrylamide units. In some embodiments, the disclosed compounds added to the electrolyte comprise at least 1, at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11, at least 12, at least 13, at least 14, at least 15, at least 16, at least 17, at least 18, at least 19, at least 20, at least 21, at least 22, at least 23, at least 24, at least 25, at least 26, at least 27, at least 28, at least 29, or at least 30 acrylamide units per molecule.Electrolyte salts

[0184] In some embodiments, the electrolytes disclosed herein comprise a salt that is easily dissolved or dissociated in a solvent. In some embodiments, the electrolyte comprises a lithium salt. In some embodiments, the lithium salt is selected from LiClO4, LiPF6, LiBF4, LiCF3SO3, LiN(CF3SO2)2, or combinations thereof. In some embodiments, the electrolyte comprises a magnesium salt. In some embodiments, the magnesium salt is selected from Mg(TFSI)2; MgSO4; MgX2, where X = halogen; Mg(trifoliate)2; Mg(RCO2-)2where R can be methyl, alkyl, halogenated methyl and ethyl; Mg(B(C2O4)2)2; Mg(BOB)2; magnesium titanate@superoxomagnesium titanate; magnesium titanate (MgTiO3); Magnesium dititanate (MgTi2O5), [Mg(L)x] [Al(ORF)4]2x=3, 6 L= (L=MeCN (acetonitrile), DME (1,2- dimethoxyethane), (ORF= OCCF3); Mg[B(hfip)4]2, Mg[B(tftb)4]2, where hexafluoro-tert- isopropoxy is (hfip) and trifluoro-tert-butoxy is (tftb); and the like or combinations thereof. In some embodiments, the electrolyte comprises an aluminum salt. In some embodiments, the aluminum salt is as recited herein for magnesium salts, but the magnesium is substituted with aluminum trivalent. In some embodiments, the aluminum salts are selected from the group consisting of Al(L)3, L= halogen; (Al(TFSI)3); (Al(ClO4)3); (Al(OTF)3); Al-Zn / Al(OTF)3; or combinations thereof. Electrolyte solvents

[0185] In some embodiments, the electrolyte comprises an organic solvent that has a high solubility for one or more salts and low viscosity to aid in movement of ions. In some embodiments, the electrolyte comprises an organic solvent that has a high solubility for lithium salt and low viscosity to aid in movement of lithium ions. Such solvents include, for example, cyclic carbonate solvents, chain carbonate solvents, and combinations thereof. In some embodiments, the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and combinations thereof. In some embodiments, the solventcomprises ethylene carbonate, propylene carbonate, and combinations thereof. In some embodiments, the solvent comprises pyrocarbonates such as dialkyl pyrocarbonates used directly or added to a dialkyl carbonate mix to better control CO2 evolution. In some embodiments, the solvent comprises ethereal solvents. In some embodiments, the solvent comprises one or more of Tert-Amyl ethyl ether; Cyclopentyl methyl ether; Di-tert-butyl ether; Di(propylene glycol) methyl ether; Dibutyl ether; Diethyl ether; Diisopropyl ether; Dimethoxyethane; Dimethoxymethane; 1,4-Dioxane; Ethyl tert-butyl ether; Methoxyethane; 2-(2-Methoxyethoxy)ethanol; Methyl tert-butyl ether; 2-Methyltetrahydrofuran; Morpholine; Polyethylene glycol; Propylene glycol methyl ether; Tetrahydrofuran; Tetrahydrofurfuryl alcohol; Tetrahydropyran; 2,2,5,5-Tetramethyltetrahydrofuran, and combinations thereof. In some embodiments, the electrolyte is LP50 electrolyte: 1 M LiPF6in ethylene carbonate (EC)– ethyl methyl carbonate (EMC) (v / v=1:1). Other additives

[0186] In some embodiments, the electrolytes comprise additives in addition to the compounds disclosed herein. In some embodiments, the additive is a substance that protects the cathode and / or anode. In some embodiments, cathode additives are included to stabilize the cathode structure and protect the surface to slow battery aging. In some embodiments, anode additives are included to stabilize the anode structure and protect the surface to slow battery aging. In some embodiments, the electrolyte comprises surfactants, SEI forming additives, materials to adjust viscosity, materials to help solubilize salts, and combinations thereof. In some embodiments, the electrolyte comprises cathode protection agents, such as Butylamine, N,N’-dicyclohexylcarbodimide (DCI), Lithium bis(oxalate)boronate (LiBOB), and combinations thereof. In some embodiments, the electrolyte comprises LIPF6 salt stabilizer additives, such as Tris(2,2,2-trifluroethylphosphite (TTFP), 1-methyl2-pyrrolidinone, hexamethyl-phosphoramide, and combinations thereof. In some embodiments, the electrolytecomprises overcharge protector additives, such as Bipyridyl carbonate, Diphenyl carbonate, difluororanisole, thianthrene, 2,7-diacetyl thianthrene, and combinations thereof. In some embodiments, the electrolyte comprises a fire retardant additive, such as Trimethyl phosphate. In some embodiments, the electrolyte comprises a lithium deposition improver, such as Cetyltrimethylammonium chloride. In some embodiments, the electrolyte comprises an ionic salvation enhancer, such as tris(pentafluorophenyl)borane (TPFPB). In some embodiments, the electrolyte comprises an Al corrosion inhibitor, such as Lithium bis(oxalate)boronate (LiBOB). Batteries

[0187] According to some aspects, the present disclosure provides ion batteries comprising a housing and an electric core. The electric core comprises the anode, cathode, and separator, each of which is in contact with an electrolyte. In some embodiments, the negative electrode (anode) is made from a graphite carbon and the positive electrode (cathode) is made from a layered oxide (e.g., lithium cobalt oxide), a polyanion (e.g., lithium iron phosphate) or a spinel (e.g., lithium manganese oxide). In some embodiments disclosed herein, the cathode electrodes are either polycrystalline LiNi0.5Mn0.3Co0.2O2 (NMC 532) or single crystalline LiNi0.5Mn0.3Co0.2O2 (NMC 721). In some embodiments, the anode electrodes comprise one or more of graphite, lithium, magnesium, and aluminum. In some embodiments, the electrodes are baked in a vacuum under 80oC for 48 hours to remove moisture. In some embodiments, the housing is a rigid or semi-rigid structure that is effective to prevent the atmosphere and / or moisture from contacting the electric core / electrolyte. Effects of the disclosed compounds on battery performance

[0188] According to some embodiments, the disclosed compounds disclosed herein are added to an electrolyte to improve one or more of the following issues relating to battery performance: dendrite formation, battery lifetime, initial capacity, capacity fade, and wettingtime. In some embodiments, the Disclosed compounds disclosed herein disclosed herein may also have a positive effect on a battery’s performance when above or below room temperature. Initial Capacity:

[0189] In some embodiments, the disclosed compounds herein are effective to increase initial capacity of a battery when added to the electrolyte. The initial capacity is defined as the capacity of the first cycle. In some embodiments, the disclosed compounds are effective to increase the initial capacity of a MIB by about 1% to about 50%. In some embodiments, the disclosed compounds are effective to increase the initial capacity of a MIB by at least 1%, at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, or at least 30%.

[0190] In some embodiments, the disclosed compounds herein are effective to increase the initial capacity of MIBs comprising high porosity and / or low porosity electrodes. In some embodiments, the disclosed compounds are effective to increase the initial capacity of MIBs comprising single crystal and polycrystalline electrodes. In some embodiments, the disclosed compounds are effective to increase the initial capacity of a battery comprising a polycrystalline LiNi0.5Mn0.3Co0.2O2 electrode. In some embodiments, the disclosed compounds are effective to increase the initial capacity from 4.75 Ah to about 5.25 Ah for a battery comprising a polycrystalline LiNi0.5Mn0.3Co0.2O2 electrode. In some embodiments, the disclosed compounds are effective to increase the initial capacity from 4.2 Ah to 5.0 Ah for a battery comprising single-crystalline LiNi0.5Mn0.3Co0.2O2 electrode. Cycling stability / Battery lifetime:

[0191] In some embodiments, the disclosed compounds herein are effective to improve cycling stability and battery life when included in the electrolyte. As used herein, the term “cycling” means the process where a battery is charged and discharged to determine how well it holds its charge capacity over many cycles. In some embodiments, the cycling stability is evaluated using a charging / discharging rate of 0.5 C. In some embodiments, the disclosedcompounds are effective to maintain at least 90% of initial capacity after at least 100 cycles, at least 200 cycles, at least 300 cycles, at least 400 cycles, or at least 500 cycles. In some embodiments, the disclosed compounds are effective to maintain at least 95% of initial capacity after at least 100 cycles, at least 200 cycles, at least 300 cycles, at least 400 cycles, or at least 500 cycles. Dendrite Suppression:

[0192] In some embodiments, the disclosed compounds are effective to decrease dendrite formation when added to an electrolyte. In some embodiments, the disclosed compounds are effective to decrease dendrite formation when added to an electrolyte when the battery is operated under overcharging conditions. In some embodiments, the disclosed compounds are effective to decrease dendrite formation. EXAMPLES

[0193] The following examples are provided to further illustrate the compositions and methods of the present disclosure. These examples are illustrative only and are not intended to limit the scope of the disclosure in any way. Preparation of Twin Tail Rf-compounds Example 1

[0194] Synthesis of twin-tailed levulinic acid derivative:

[0195] Briefly, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (76 g, 0.02 mol, 2 mol equiv.) and alpha-angelica lactone (9.8 g, 0.01 mol, 1 mol equiv.) were charged to a 1L flask containing toluene (280 mL) under a nitrogen atmosphere, and the mixture was heated to 40°C. Boron trifluoride etherate (1.15g, 1 mL, 8.1 mmol, 8 mol%) was added dropwise using an addition funnel under a nitrogen atmosphere. The reaction mixture was then maintained at 40-45°C for 2 hours. The mixture was then cooled with an ice -water bath to maintain the temperature in the range of 0-5°C for one hour. During cooling an off-white suspension was formed. The product was obtained by adding heptanes (100 mL) to the flask and the slurry formed was filtered and dried under vacuum to afford the product (Compound 3) as a white solid (15.44g, 90%), m.p.112-115°C, this melting point data was consistent with that reported in the literature. Example 2

[0196] Synthesis of twin-tailed glyoxylic acid derivative:

[0197] Briefly, using a Dean-Stark reactor setup, glyoxylic acid-monohydrate (1.85 g, 20.1 mmol, 1 equiv.), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (16.8 g, 44.2 mmol, 2.2 equiv. p-toluenesulfonic acid monohydrate (0.38 g, 2.00 mmol, 10 mol%, PTSA) were combined with toluene (40 mL) in a 100 mL round bottom flask. The reaction was refluxed in an oil bath at 125°C overnight (18 hr). The reaction was removed from the heat source, cooled to room temperature, whereupon a gelatinous solid was formed. The solid was collected bygravity filtration, washed with 50 mL hexane, dried under vacuum to afford 12.8 g of product (Compound 5) (15.7 mmol, 78% yield).1H NMR (500 MHz, CDCl3): δ 6.38 (br, s, 1H), 4.42 (s, 1H), 3.03-2.98 (m, 4H), 2.50-2.36 (m, 4H).19F NMR (376 MHz, CDCl3) δ -80.87, -114.30, -121.92, -122.90, 123.46, 126.13-126.21. HRMS (ESI-) calculated m / z for [C13H10F26NO2S2- H]+814.9623; found 814.9629. Preparation of Twin Tail Mercaptans Example 3

[0198] Levulinic acid with cysteamine hydrochloride (activated ester route); Synthesis of Compound 6 (R1= Me, R2= H, RF= C6F13, and Q, X, Z =–CH2CH2– from Scheme I).

[0199] This example discloses the synthesis of a twin-tailed mercaptan according to Scheme I disclosed herein.

[0200] Activation step: Briefly, a reaction vessel is charged with 4,4 Bis- [(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoroctyl)sulfanyl]pentanoic acid1(500 mg, 0.58 mmol, 1.00 equiv.) and toluene (1.4 mL) under a flow of nitrogen gas. To this reaction mixture are added N-hydroxysuccinimide NHS (68 mg, 0.59 mmol, 1 equiv.) followed by dicyclohexylcarbodiimide (DCC, 121 mg, 0.59 mmol, 1 equiv.). The reaction was sealed and heated at 45 °C for 12 h. It was cooled to room temperature, diluted with 2 mL toluene, filtered through a fritted syringe, and the solids were washed with an additional 3 mL of toluene. The solvent was removed under vacuum to yield the crude activated ester, that was used without further purification.

[0201] Amidation step: A reaction vessel was charged with the activated NHS-ester from step 1 (500 mg, 0.52 mmol, 1 equiv.) and toluene (4 mL) under a nitrogen atmosphere. After 15 minutes, triethylamine (0.45 ml, 3.23 mmol, 6.2 equiv.) was added followed by the1See R. A Falk, US Patent No.4,239,915, Dec 16, 1980, and Robert Falk, US Patent No.4,485,251, Nov 27, 1984, which are incorporated by reference as if recited in full herein.addition of cysteamine•HCl 2 (500 mg, 4.40 mmol, 8.4 equiv.). The reaction mixture was stirred at room temperature for 24 h, after which the reaction mixture was quenched with 2N HCl (10 mL) and extracted with CH2Cl2 (2 x 20 mL). The combined organic extracts were dried over anhydrous MgSO4 and concentrated under vacuum to afford 462 mg of Compound 6 (0.50 mmol, 87% yield):Spectroscopic data for Compound 6:1H NMR (500 MHz, CDCl3): δ 5.95 (br, 1H), 3.43 (q, J=6.1 Hz, 2H), 2.86-2.83 (m, 4H),(q, J=6.3 Hz, 2H), 2.42-2.36 (m, 6H), 2.17-2.14 (m, 2H), 1.56 (s, 3H), 1.35 (t, J=8.4 Hz, 1H).13C NMR (100 MHz, CDCl3): δ 171.64, 60.47, 42.38, 36.16, 31.58, 31.46, 31.25, 31.03, 27.05, 24.62, 20.41.19F NMR (376 MHz, CDCl3) δ -79.94, -79.97, -79.00, -113.31, -113.36, -113.40, -120.99, -121.99, -122.60, -125.22, -125.24, -125.27, -125.28, -125.30, -125.32. IR (ATR-ZnSe) [cm–1] 3294, 2925, 1645, 1551, 1366, 1187, 1141, 705. HRMS (ESI-) calculated m / z for [C23H21F26NOS3+Na]+940.0268; found 940.0273.

[0202] Recrystallization of Example 3: To a 250 mL round bottomed flask at ambient temperature containing a magnetic stir bar was added ethyl acetate (125g, ~140 mL) followed by Compound 6 crude product (150 g, 0.25 mol). The mixture was stirred for 30 minutes and formed a yellow solution with a small quantity of gray solids. The mixture was filtered to afford ~0.5 g of solid residue. The filtrate was then placed in a freezer at -18°C for 17 hrs. The precipitate was filtered, washed with ice-cold ethyl acetate (5 mL) to afford an off-white solid which on drying in a vacuum oven at 30°C for 17-hr afforded pure Compound 6 (99.4g, 66% yield). Example 4

[0203] Synthesis of Compound 6 (R1 = Me, R2 = H, RF = C6F13, and Q, X, Z =– CH2CH2– from Scheme 1) via direct amidation. This Example provides the same final product as disclosed in Example 3, but uses a different synthetic route.

[0204] Levulinic acid reacting with cysteamine: Briefly, to a 1L 3-necked flask equipped with a Dean-Stark trap and condenser under a nitrogen atmosphere were added Compound 3 (100.0g, 0.117 mol, 1.0 equiv.) and toluene (400g to flask and 25g in Dean-Stark trap). The mixture was heated to 50°C, then boric acid (1.44g, 0.023 mol, 0.20 equiv.), cysteamine•HCl (26.5g, 0.233 mol, 2 equiv) and triethylamine (23.5g, 0.233 mol, 2 equiv.) were added while stirring. The reaction temperature was raised to reflux (114°C) and heating continued overnight (18 hr.). After which no additional water was collected in the Dean Stark trap and TLC analysis (50% ethyl acetate / hexanes) indicated no residual Compound 3 was present. The reaction was cooled to 60°C and hot filtered and the solids washed with hot toluene (30mL, 60°C). The filtrate was allowed to cool to ambient temperature with stirring. Additional solids precipitated and were filtered. The combined solids were charged to a flask with water (40mL) and toluene (30g) and 6N hydrochloric acid was added until the aqueous phase was pH 2. The mixture was filtered, and the solids washed with toluene (2 x 25mL). The solids were dried at 50°C overnight to afford the product of Compound 6 as a white solid (90.2g, 85% yield).

[0205] 1H NMR and IR analysis indicated that this material was equivalent to that produced by the above described 2 step procedure in Example 3. Example 5

[0206] Synthesis of Compound 7 (R1 = H, R2 = H, RF = C6F13, and X, Z = –CH2CH2– from Scheme 2).

[0207] 2,2-Bis[(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfanyl]acetic acid (3.0 g, 3.67 mmol, 1.00 equiv.) prepared in example 2 was dissolved in THF. N-hydroxysuccinimide (464 mg, 4.03 mmol, 1.10 equiv.) was then added as one solid portion to the stirring solution, followed by addition of DCC (830 mg, 4.02 mmol, 1.10 equiv.). The reaction was left under nitrogen overnight (20 hr). The solution was gravity filtered, the solid was washed with THF (15 mL), and the combined filtrate was concentrated to give a white solid. The crude product was combined with cysteamine•HCl (860 mg, 7.57 mmol, 2.1 equiv.) in DCM (12 mL) under nitrogen. Et3N (1.1 mL, 7.89 mmol, 2.15 equiv.) was added. The reaction was left to stir at room temperature overnight (19 hr.). The reaction mixture was poured into 50 mL 1N HCl in a separatory funnel, and extracted with equal volume DCM. The organic layer was dried over MgSO4, filtered, and concentrated to a light-yellow oil. Example 5 crude product was extracted with saturated sodium bicarbonate / DCM Silica gel column purification (100% hexane to 10% ethyl acetate / hexane to 20% ethyl acetate / hexane isolated as a pale-yellow oil solidifies in a fridge at 5°C. (2.50g, 78%) to produce Compound 7.

[0208] 1H NMR (500 MHz, CDCl3) ^ 6.82-6.78 (m, 1H), 4.42 (s, 1H), 3.52-3.48 (m, 2H), 2.99-2.89 (m, 4H), 2.75-2.67 (m, 2H), 2.48-2.40 (m, 4H), 1.38 (t, J=8.4 Hz, 1H)13C NMR (125 MHz, CDCl3) ^ 167.82, 53.32, 42.76, 31.62, 31.39, 31.17, 24.31, 22.75,19F NMR (470 MHz, CDCl3) ^ -80.86, -114.23, -121.90, -122.88, -123.38, -126.18. IR (ATR, ZnSe) 3291.9, 3078.2, 2940.5, 1643.4, 1551.9, 1231.6, 1185.6, 1142.0. HRMS (ESI) calculated [C20H15F26NOS3+H]+875.9901, found 875.9979. Example 6

[0209] Synthesis of Compound 9 (R1 = Me, R2 = H, RF = C6F13, X, Q= –CH2CH2–, Z = – CH(CO2C2H5)CH2– from Scheme 1)

[0210] In a round bottom flask equipped with a magnetic stir bar, L-cysteine- ethylester•HCl (60 mg, 0.32 mmol, 1.52 equiv) and the NHS ester described for the synthesis of Example 3 above (200 mg, 0.21 mmol, 1.00 equiv) was combined, placed under nitrogen flow. Dichloromethane (4 mL) was added, followed by triethylamine (0.10 mL, 0.72 mmol, 3.43 equiv). The reaction was left to stir at 20°C overnight (18 hr) then poured into separatory funnel, diluted with 5 mL DCM, and extracted twice with 10 mL 10% citric acid. The DCM phase was dried over magnesium sulfate, gravity filtered and concentrated under reduced pressure to give an oily residue. The crude reaction mixture was purified by column chromatography on silica gel using a gradient of 100% hexane to 50% ethyl acetate / hexane to isolate 176 mg product as an opaque oil (0.18 mmol, 86% yield) of Compound 9. DATA:1H NMR (500 MHz, CDCl3) ^ 6.36 (d, J = 7.2 Hz, 1H), 4.86-4.85 (m, 1H), 4.28-4.23 (m, 2H), 3.04-2.83 (m, 2H), 2.50 (t, J = 7.8 Hz, 4H), 2.39 (t, J = 6.3 Hz, 2H), 2.37-2.35 (m, 4H), 2.18- 2.17 (m, 2H), 1.57 (s, 3H), 1.33-1.30 (m, 4H).13C NMR (125 MHz, CDCl3) ^ 171.39, 170.03, 62.09, 60.43, 53.54, 35.93, 31.37, 26.98, 26.81, 20.40, 14.11.19F NMR (470 MHz, CDCl3) ^ -80.17, -113.55, -121.16, -122.16, -122.76, -125.47. IR (ATR, ZnSe) 3305.5, 2937.7, 1741.6, 1651.2, 1532.7, 1233.1, 1187.6, 1142.7. HRMS (ESI) calculated [C26H25F26NO3S3+Na]+1012.0479, found 1012.0468.Example 7

[0211] Preparation of Compound 11

[0212] Twin-tail mercaptans such as the one prepared in Examples 3 or 5 can undergo a Michael addition reaction with acrylamides such as the sodium salt of 2-Acrylamido-2- methyl-1-propanesulfonic acid (AMPS) to form anionic fluorosurfactants.Acrylamido-2-methyl-1-propanesulfonic acid (4.99 g, 0.01 mol available commercially as a 50% aqueous), deionized water (1.9 g), Hexylene glycol (2.4 g) and N-(2-sulfanylethyl)-2,2- bis[3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfanyl]acetamide (10.0 g, 0.01 mol). The reaction mixture was stirred with a nitrogen purge during which THF (20 g) was added to increase solubility and 2 liquid layers were formed. To the reaction mixture, at room temperature, was charged 50% aqueous sodium hydroxide (0.03 g, 0.75 mmol) and the reaction mixture became a single phase within 5 minutes. The mixture was stirred at ambient temperature for 2 hours and then quenched with acetic acid (0.02, 0.3 mmol), The solvents were allowed to evaporate at room temperature in a fume hood for 2 to 3 days to afford the product as a white hygroscopic powder (10.9 g, 95%) of Compound 11. Example 8

[0214] Preparation of compound 12

[0215] This substance was prepared by reacting the substance of Compound 7 (from Example 5) with 2-Acrylamido-2-methyl-1-propanesulfonic acid (AMPS) in the same manner as Example 6.Glyoxylic plus AMPS C6F13C6F13S O H Sodium C6F13SO3~Na+Preparation of twin-tail Acrylamide (AA) Oligomers

[0216] Twin-tail mercaptans such as Formula III (shown below) can also undergo radical oligomerization using radical initiators such as Vazo-52 to form twin-tail mercapto- polyacrylamides of Formula VIII (see, e.g., Examples 9-10, below). Scheme 3 H Rf H Rf H n

[0217] Some representative examples of these oligomeric transformations are discussed below. Solids Filtrates Filtered (from ) %Compounxamp e 9

[0218] To a stirred 500mL flask at ambient temperature was added N-(2-sulfanylethyl)- 2,2-bis-[3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfanyl]acetamide (9.17g, 10 mmol) and acrylamide (3.56g, 50 mmol) in methanol (200 g, 250 mL). The mixture was purged with nitrogen for 10 minutes. The flask was transferred to a water bath at 60 – 65°C. When the reaction mixture started to reflux (60-65°C), Vazo-52 (0.20 g, 0.80 mmol) was added and then the reaction mixture was stirred for 30 minutes then an additional charge of Vazo-52 (0.05 g, 0.20 mmol) was added and held at temperature for an additional 1-hr during which the reaction mixture became a turbid white suspension. The reaction was then cooled to ambient temperature. On cooling the precipitates were filtered and dried to afford an off white solid (2.9 g, 22.7%, Compound 13). The filtrate was concentrated under vacuo to afford an off white solid, which on further drying afforded an additional (9.8 g, 77%, Compound 13A). Example 10

[0219] To a stirred 500mL flask at ambient temperature was added N-(2-sulfanylethyl)- 2,2-bis-[3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfanyl]acetamide (9.17g, 10 mmol) and acrylamide (7.11g, 100 mmol) in methanol (200 g, 250 mL). The mixture was purged with nitrogen for 10 minutes. The flask was transferred to a water bath at 60 – 65°C. When the reaction mixture started to reflux (60-65°C), Vazo-52 (0.15 g, 0.60 mmol) was added and then the reaction mixture was stirred for 2 hr, during which the reaction mixture became a turbid white suspension. An additional charge of Vazo-52 (0.05 g, 0.20 mmol) was added and held at temperature for an additional 1-hr. The reaction was then cooled to ambient temperature. On cooling the precipitates were filtered and dried to afford an off white solid (4.7g, 28.9%, Compound 14). The remaining filtrate was lost during the removal of the solvent under vacuo and did not afford any additional material. Preparation of Single Tail Rf-oligomer surfactants

[0220] Some representative examples of the synthesis of the Rf-oligomers disclosed herein are provided below. Example 11

[0221] Perfluoromercapto -(AA)4Oligomer

[0222] To a 500 mL glass bottle, at room temperature, were charged acrylamide (33.7 g, 0.47 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol, (45.0 g, 0.12mol) and 2- propanol (300 mL) as solvent. The mixture was stirred to dissolve the mixture and then the solution was purged with nitrogen for 10 minutes. Vazo-52 (0.6 g, 0.002 mol) was added to the mixture and then the solution was purged with nitrogen for an additional 10 minutes The glass bottle was sealed and transferred to a water bath at 80 – 85°C. The reaction medium was held at 80 – 85°C for 2 hours. The reaction medium was removed from the water bath and transferred to a 1L crystallizing dish to allow the solvent to evaporate at room temperature in a fume hood for 2 to 3 days and then dried in an oven at 50°C overnight (17 h) to afford a white powder (49.1 g, 63.2%). Example 12

[0223] Perfluoromercapto -(AA)6Oligomer

[0224] To a 500 mL glass bottle, at room temperature, were charged acrylamide (50.5 g, 0.71 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol, (1) (45.0 g, 0.12 mol) and 2- propanol (300 mL) as solvent. The mixture was stirred to dissolve the mixture and then the solution was purged with nitrogen for 10 minutes. Vazo-52 (0.6 g, 0.002 mol) was added to the mixture and then the solution was purged with nitrogen for an additional 10 minutes The glass bottle was sealed and transferred to a water bath at 80 – 85°C. The reaction medium was held at 80 – 85°C for 2 hours. The reaction medium was removed from the water bath and transferred to a 1L crystallizing dish to allow the solvent to evaporate at room temperature in a fume hoodfor 2 to 3 days and then dried in an oven at 50°C overnight (17 h) to afford a white powder (71.4 g, 74%).

[0225] Using the procedure outlined in Examples 11 and 12, differing only in the stoichiometry of acrylamide the following oligomers were made: Example # Monomer Oligomerization (n) Yield (%) 13 CH2CHCONH2 8 84.9Battery Testing

[0226] Battery testing was performed using the following procedures to test for improvements in the identified target performance areas: Electrodes and electrolytes used:

[0227] The cathode electrodes used in this experiment were either polycrystalline NMC111, polycrystalline LiNi0.5Mn0.3Co0.2O2 (NMC 532) or single crystalline LiNi0.5Mn0.3Co0.2O2 (NMC 721). Two kinds of cathodes were tested here. The anode electrodes used in this experiment were graphite for all batteries. Before the assembly of batteries, all electrodes are baked in a vacuum under 80oC for 48 hours to remove moisture.

[0228] The electrolyte solutions comprising fluorosurfactants as disclosed herein were mixed in a glove box and then then added to a blank battery. The battery was then sealed and taken out of the glovebox to be cycled under constant pressure.

[0229] The final batteries typically had capacities around 5 Ah. The electrolyte used was standard LP50 electrolyte: 1 M LiPF6 in ethylene carbonate (EC)–ethyl methyl carbonate (EMC) (v / v=1:1), and the amount used for each battery was around 20 mL. The surfactants used in this test were 0.5 wt% in active of electrolyte unless otherwise indicated. All surfactantscould be dissolved after being stirred at 50oC for 48 hours. All batteries were sealed in pouches using the vacuum sealer with a pressure of -970 mBar and a temperature of 180oC. Initial Capacity:

[0230] After the resting and aging protocols, all batteries were cycled at a rate of 0.5 C. The initial capacity is defined as the capacity of the first cycle. These data reflect the wetting conditions of electrodes since better wetting results in the reactions of more electrode materials, hence more capacity. As discussed below, the results show that the surfactant as disclosed herein can significantly improve the wetting condition. For polycrystalline LiNi0.5Mn0.3Co0.2O2electrode, the initial capacity can be improved from 4.75 Ah to ~5.25 Ah; for single-crystalline LiNi0.5Mn0.3Co0.2O2, the wetting is more difficult than the polycrystalline one because the single crystalline NMC721 electrodes have a much higher cathode density and thereby less porosity. Therefore, the improvement is more obvious: the initial capacity is improved from 4.2 Ah to 5.0 Ah. Cycling stability / Battery lifetime:

[0231] The cycling stability is evaluated using a charging / discharging rate of 0.5 C. In batteries, wetting is critical for cycling performance, since the consumption and non-uniform distribution of electrolytes induced during cycling is a major cause for capacity fading. The results show that a significantly improved cycling stability is achieved when the surfactants are used. Detailed results are disclosed below. Dendrite Suppression:

[0232] Dendrites are usually not easy to form in lithium-ion batteries under normal working conditions, but they are easy to form when working in the conditions of overcharge. To avoid the dendrite formation, the anode / cathode capacity ratio is usually set to ~1.1. This was typical for the battery testing disclosed herein. To evaluate dendrite suppression effects,the upper cut-off voltage was set as 4.35 V for poly NMC532 batteries, which would contribute nearly 20 % extra capacity and encourage dendrite formation. Summary of testing:

[0233] For the testing, between 0.1 to 5% by weight of the various oligomers were added to the electrolyte of choice and the battery setup. The battery performance was then evaluated for the ability to overcome the various problems associated with metal ion batteries. The results were compared to blank samples that do not contain the various oligomers.

[0234] It was discovered that surfactants as disclosed herein address the following issues: dendrite suppression, battery lifetime, initial capacity, capacity fade, wetting time, and low / high temperature operation. Example 19

[0235] Initial testing: The additives were tested in 6.5 Ah pouch cells from MTI, with a cathode material that was polycrystalline NMC111. We conducted an initial screening of all the surfactants and concluded as follows:

[0236] Figure 2 shows an example of Compound 13 of Example 9 at 1 wt%. This additive shows a capacity retention of 89.3% after 137 cycles. Compound 7 [(JRS16-157, Glyoxalate)] was used to prepare an n = 5 acrylamide oligomer and evaluated in the same battery type. It was not able to complete cycling and caused the cells to outgas badly. Any of the glyoxylic acid derived twin tail compounds were abandoned.

[0237] Example 7, Compound 11 and Example 10, Compound 14 are both twin tail molecules but with a different non-fluorinated part. For that reason, they appear on two different Figures: Figure 3A / Figure 3B and Figure 4A / Figure 4B respectively. Figure 4A shows testing of Example 10, Compound 140.5 wt.%. Capacity at First cycle: 6.576 Ah; 152 cycle: 6.403 Ah; Capacity retention: 97.3%. Figure 4B shows testing of Example 10, Compound 14 (1 wt.%). Capacity at First cycle: 6.255 Ah; 157 cycle: 5.892 Ah; Capacity retention: 94.2%.

[0238] Figure 5 provides summary data showing how Example 12, Compound 16 compares to Example 7, Compound 11 and to the blank with no additive. Figure 5 shows data for 275 cycles. Example 20

[0239] Overcharge test with twin-tail surfactants: Overcharge tests were performed on a NMC 532 polycrystalline cells. The overcharge test using Example 7, Compound 11 showed that it had some capacity to help with respect to overcharging (dendrite formation). Example 8, Compound 12 also had some ability in this regard, but outgassing was problematic. The root cause of this outgassing has not been investigated, but could be due to a degradation of the molecule or to the presence of residual solvent in the tested sample. Example 21

[0240] Synergism of Example 10, Compound 14 with other fluorosurfactants: long lifetime batteries

[0241] Example 10, Compound 14 is unique. Its solubility in the electrolyte is very low, and its ability to enhance capacity retention is also limited. It lowers the initial capacity of the batteries slightly. Therefore, on its own, it is not a very effective additive. However, when combined with other additives, it shows an improvement in capacity retention and the long-term cycling of lithium-ion batteries. In the experiments that follow it is used as a co- additive it as a co-additive at a ratio of only 0.1 wt.% due to its solubility.

[0242] The following data was taken with NMC 532 polycrystalline cells. Figure 6 shows a comparison of the NMC control (Figure 6A), a sample with 0.4% of a compound prepared according to Example 11, compound 15 (Figure 6B), and a third sample with 0.1% of a compound prepared according to Example 10, Compound 14 added to 0.4% of a compound prepared according to Example 11, compound 15 (Figure 6C). These samples were run in triplicate and Table 2 summarizes the average capacity retention over 500 and 1000 cycles. Itis clear from this data that the twin tail Compound 14 from Example 10 has a profound effect on the long life of the batteries.

[0243] As shown in Figure 6, the extended capacity retention demonstrates that twin tail diminishes the dendrite formation and other cycling failures that occur with extended use. Figure 6A shows NMC control (over 500 cycles). Figure 6B shows data testing the use of 0.4% of the single tail acrylamide oligomer (n=4) prepared according to Example 11 Compound 15 (over 1000 cycles). Figure 6C shows data testing the use of 0.4% of the single tail acrylamide oligomer (n=4) prepared according to Example 13, compound 15 with 0.1% of twin tail Acrylamide oligomer n=10, Example 10, Compound 14 over 1000 cycles. Average capacity retention after 500 and 1000 cycles (average of 3 samples each) was as follows (control was not ran beyond 500 cycles as it reached the 80% capacity retention range at that number of cycles): Table 2 Control (500 0.4% of the single tail 0.4% of the single tail acrylamide c cles) acr lamide oli omer (n=4) oli omer (n=4) re ared accordin to

[0244] All documents cited in this application are hereby incorporated by reference as if recited in full herein.

[0245] Although illustrative embodiments of the present disclosure have been described herein, it should be understood that the disclosure is not limited to those described,and that various other changes or modification may be made by one of ordinary skill in the art without departing from the scope or spirit of the invention.

Claims

What is claimed is:

1. A fluorocarbon surfactant according to Formula I: wherein Rfis4 to 18 carbon atoms, perfluoroalkyloxyalkylene of 5 to 19 carbon atoms, or mixtures thereof; X is independently, strait or branched chain alkylene of 1 to 12 carbon atoms, alkyleneoxyalkylene of up to 6 carbon atoms, alkylene–NH-alkylene of up to 6 carbon atoms, or alkylene-N(lower alkyl)-alkylene, where the alkylene groups have a total of up to 6 carbon atoms, —CON(R’) —E'—, —SO2N(R') —E'—, —E"—CON(R') —E'—, —E''—S—E'—, —E''—N(R') —E'—; or —E''—SO2N(R') —E'-, where R' is hydrogen or alkyl of 1 to 6 carbon atoms, E' is alkylene of 2 to 8 carbon atoms and E'' is alkylene of 1 to 4 carbon atoms; R1is selected from the group consisting of H, CH3, CO2H, Ph, CH2CH2CO2H, CH3CH2; Q is selected from —CH2CH2—, —CH2—, CHCH3—, —CH(CH2CO2H)—, — CH(CH2CH2CO2H)—, —CH2CH2CH2—, —CH2CH2CH2CH2—, a covalent bond, and — CH(R'')CH(R'') —; R'' is hydrogen, lower alkyl, aryl, or aryl substituted lower alkyl; Z is selected from the group consisting of an alkyl having 2 to 18 carbon atoms (optionally substituted with one or more of an alkyl, aryl, amine, thiol, cyclic / heterocyclic rings, cysteine ethyl ester, –CH(CO2C2H5)CH2–, –CH2CH2– );A is –S–, –SO–, or –SO2–; [M1] represents a hydrophilic monomer unit derived from a hydrophilic monomer of the type M1; and [M2] represents a hydrophobic monomer unit derived from hydrophobic monomers of the type M2; wherein M1 is optionally more than one type of monomer and M2 is optionally more than one type of monomer; wherein the sum of x and y is between 1 and about 500; and x / (x+y) is between 1 and 0.

5.

2. The fluorocarbon surfactant of claim 1, having the structure: .

3. The fluorocarbon,wherein n is 1 4. The fluorocarbon surfactant of claim 1, having the structure:, wherein n is 1 to 5. The fluorocarbon surfactant of claim 1, having the structure: , wherein n is 16. The fluorocarbon surfactant of claim 1, having the structure: ,wherein n is 1 7. The fluorocarbon surfactant of claim 1, having the structure: ,wherein n is 1 to 40.

8. The fluorocarbon surfactant of claim 1, having the structure: , wherein n is 19. The fluorocarbon surfactant of claim 1, having the structure: .

10. The fluorocarbon surfactant of claim 1, having the structure: .

11. The fluorocarbon surfactant of claim 1, having the structure: .

2. The fluorocarbon surfactant of claim 1, having the structure: .

13. The fluorocarbon surfactant of claim 1, having the structure: .1, having the structure: .

15. A fluorocarbon surfactant according to Formula IC :wherein Rfindependen yl of 4 to 18 carbon atoms, perfluoroalkyloxyalkylene of 5 to 19 carbon atoms, or mixtures thereof; X is independently, strait or branched chain alkylene of 1 to 12 carbon atoms, alkyleneoxyalkylene of up to 6 carbon atoms, alkylene–NH-alkylene of up to 6 carbon atoms, or alkylene-N(lower alkyl)-alkylene, where the alkylene groups have a total of up to 6 carbon atoms, —CON(R') —E'—, —SO2N(R') —E'—, — E"—CON(R') —E'—, —E''—S—E'—, —E''—N(R') —E'—; or —E''—SO2N(R') —E'-, where R' is hydrogen or alkyl of 1 to 6 carbon atoms, E' is alkylene of 2 to 8 carbon atoms and E'' is alkylene of 1 to 4 carbon atoms; R1is selected from the group consisting of H, CH3, CO2H, Ph, CH2CH2CO2H, CH3CH2; Q is selected from —CH2CH2—, —CH2—, —CHCH3—, — CH(CH2CO2H)—, —CH(CH2CH2CO2H)—, —CH2CH2CH2—, —CH2CH2CH2CH2—, a covalent bond, and —CH(R'')CH(R'')— wherein R'' is hydrogen, lower alkyl, aryl, or aryl substituted lower alkyl.

16. The fluorocarbon surfactant of claim 15 having the structure: .

17. An ion battery electrolyte comprising an electrolyte salt, a solvent, and at least one fluorocarbon surfactant according to any one of claims 1-16.

18. The ion battery electrolyte of claim 17, wherein the at least one fluorocarbon surfactant comprises about 0.1% to about 5% by weight of the electrolyte.

19. The ion battery electrolyte of claim 17, wherein the electrolyte salt is an electrolyte lithium salt.

20. The ion battery electrolyte of claim 17, wherein the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate.

21. The ion battery electrolyte of claim 17, further comprising at least one fluorocarbon surfactant according to Formula VII: Rf–En–S–[M1]x[M2]yH (VII) wherein Rf is a straight or branched chain perfluoroalkyl of 4 to 18 carbon atoms, perfluoroalkyloxyalkylene of 5 to 19 carbon atoms, or mixtures thereof; Enis a straight or branched chain alkylene of 1 to 12 carbon atoms, —CON(R') —E'—, —SO2N(R') —E'—, —E"—CON(R') —E'—, —E''—S—E'—, —E''—N(R') —E'—; or —E''—SO2N(R') —E'-, where R' is hydrogenor alkyl of 1 to 6 carbon atoms, E' is alkylene of 2 to 8 carbon atoms and E'' is alkylene of 1 to 4 carbon atoms; [M1] represents a hydrophilic monomer unit derived from a hydrophilic monomer of the type M1; and [M2] represents a hydrophobic monomer unit derived from hydrophobic monomers of the type M2; wherein M1is optionally more than one type of monomer and M2is optionally more than one type of monomer; wherein the sum of x and y is between 1 and about 500; x / (x+y) is between 1 and 0.5; and n is 0 or 1.

22. The ion battery electrolyte of claim 21 comprising one or more of the fluorocarbon surfactants according to Example 11, Example 12, Example 13, Example 14, Example 15, Example 16, Example 17, and Example 18.

23. An ion battery comprising: a housing comprising an electric core, and an electrolyte disposed in said housing, wherein the electric core is in contact with the electrolyte and the electrolyte comprises at least one fluorocarbon surfactant according to any one of claims 1-5.

24. The ion battery of claim 23, wherein the ion battery is a lithium ion battery comprising a lithium salt.

25. The ion battery of claim 23, wherein the lithium salt is selected from LiClO4, LiPF6, LiBF4, LiCF3SO3, LiN(CF3SO2)2, or combinations thereof.

26. The ion battery of claim 23, wherein the electrolyte comprises a solvent selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and combinations thereof.

27. A method for improving performance of a metal ion battery comprising the step of contacting the metal ion battery with the ion battery electrolyte of claim 17.

28. The method of claim 27, wherein the improved performance includes improved charge capacity, fade during charge, and discharge cycling of the metal ion battery relative to a metal ion battery without fluorocarbon surfactant.

29. The method of claim 27, wherein the improved performance includes reduced dendrite formation during charge and discharge cycling of the metal ion battery relative to a metal ion battery without fluorocarbon surfactant.

30. The method of claim 27, wherein the improved performance includes an increased lifetime of the metal ion battery relative to a metal ion battery without fluorocarbon surfactant.

31. The method of claim 27, wherein the metal ion battery is a lithium ion battery.

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