Compositions and methods for fluorosurfactants in metal-ion batteries

Abstract

The present disclosure provides compositions and methods for improving the performance of, among other things, metal-ion batteries. In some embodiments, the present disclosure provides electrolytes containing fluorosurfactant additives that are effective in improving battery life, initial capacity, capacity fade, wetting time, and dendrite formation in metal-ion batteries. In some embodiments, the present disclosure provides perfluoroalkyl group-terminated oligomers derived from perfluoroalkyl mercaptans and hydrophilic and / or hydrophobic monomers polymerized by free radical reactions, and their use to improve MIB performance.

Description

[Technical Field]

[0001] background A metal-ion battery (MIB) consists of an anode and a cathode separated from each other by a semipermeable membrane known as a separator. The battery is completed by filling it with an electrolyte solution containing metal ions. During battery discharge, metal ions migrate from the anode (negative electrode) through the electrolyte solution to the cathode (positive electrode). During battery charging, lithium ions migrate in the opposite direction, from the battery's cathode to the anode. [Background technology]

[0002] Lithium-ion batteries (LIBs) are a popular 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 capable of accommodating lithium ions. A typical liquid electrolyte consists of a carbonate, such as propylene carbonate or ethylene carbonate, dissolving a lithium hexafluorophosphate salt.

[0003] While LIB performance is exceptional, there is room for improvement. Improvements to MIBs are also needed in general. For example, when adding electrolyte to a battery, the time it takes to completely wet the complex structure of the electrodes and separator determines how long it takes to fabricate the battery. Currently, more rapid wetting times are needed to reduce the time it takes to fabricate MIBs. Furthermore, it is desirable to maximize the initial capacity of the battery and ensure that this capacity remains as high as possible during cycling. Therefore, there is a current need to improve the initial capacity (and maintain capacity) of MIBs. Furthermore, in some MIBs, dendrite formation can sometimes cause catastrophic events, resulting in battery failure and, in some cases, fires that are extremely difficult to extinguish. Therefore, these catastrophic events must be mitigated and / or eliminated for improved safety and economics (e.g., longer battery life). Finally, MIB operation at low temperatures is not optimal with current technology. Therefore, there is a need to improve MIB performance at low temperatures.

[0004] To address these and other needs, the present disclosure provides, among other things, electrolyte additives that can control and tailor the properties of MIBs. In some embodiments, the present disclosure provides perfluoroalkyl sulfide-terminated oligomers (R) that are effective in improving battery performance. f -oligomer). Summary of the Invention [Means for solving the problem]

[0005] Disclosure Overview According to some aspects, the present disclosure provides perfluoroalkyl sulfide-terminated oligomers and their use in improving the performance of MIBs. In some embodiments, the perfluoroalkyl sulfide-terminated oligomers have a backbone composed of oligomeric moieties with varying numbers of carbon atoms, made from hydrophilic (or mixed hydrophilic and hydrophobic) monomers. In some embodiments, the perfluoroalkyl sulfide-terminated oligomers disclosed herein are added to metal-ion batteries to provide multiple improvements, including, but not limited to, improvements in the wetting time of the electrolyte into the battery, the initial capacity of the battery, capacity fade with battery cycling, and reduced dendrimer formation and extended battery life. In some embodiments, the perfluoroalkyl sulfide-terminated oligomers disclosed herein have been previously used in firefighting foams and are described in U.S. Patent Nos. 4,460,480, 4,439,329, and 4,089,804, each of which is incorporated herein by reference in its entirety.

[0006] According to some embodiments, the present disclosure provides a method for preparing a compound comprising: an electrolyte salt; a solvent; and a compound of formula I:R f -E n -S-[M1] x [M2] y H [wherein, R f is a linear or branched perfluoroalkyl group having 4 to 18 carbon atoms, a perfluoroalkyloxyalkylene group having 5 to 19 carbon atoms, or a mixture thereof; E nis a straight or branched alkylene having 1 to 12 carbon atoms, -CON(R')-E'-, -SON(R')-E'-, -E''-CON(R')-E'-, -E''-S-E'-, -E''-N(R')-E'-, or -E''-SON(R')-E'-, where R' is hydrogen or alkyl having 1 to 6 carbon atoms, E' is alkylene having 2 to 8 carbon atoms, E'' is alkylene having 1 to 4 carbon atoms, and [M1] is a hydrophilic monomer of type M1 disclosed herein. wherein [M2] represents a hydrophilic monomer unit derived from an M2-type hydrophobic monomer disclosed herein, the sum of x and y is between 1 and about 500, and x / (x+y) is between 1 and 0.5; and in some embodiments, there is more than one type of --M1- unit and more than one type of --M2- unit in the fluorocarbon surfactant; and n is 0 or 1.

[0007] In some embodiments, the at least one fluorocarbon surfactant according to Formula I comprises about 0.1% to about 5% by weight of the electrolyte. In some embodiments, M1 is an acrylamide unit. In some embodiments, the electrolyte salt is an electrolyte lithium salt. In some embodiments, the electrolyte lithium salt is selected from LiClO4, LiPF6, LiBF4, LiCF3SO3, LiN(CF3SO2)2, or a combination thereof. In some embodiments, the solvent includes one or more of dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate. In some embodiments, the electrolyte includes one or more of the compounds according to Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, 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, Example 21, Example 22, Example 23, Example 24, and Example 25. In some embodiments, the electrolyte includes one or more of DX1080 and DX1090.

[0008] In some embodiments, the at least one fluorocarbon surfactant is [ka] [wherein n is an integer of 1 to 30].

[0009] In some embodiments, the at least one fluorocarbon surfactant is [ka] Includes.

[0010] In some embodiments, the at least one fluorocarbon surfactant is [ka] Includes.

[0011] According to some aspects, the present disclosure provides an ion battery comprising: a housing including an electric core; and an electrolyte disposed within the housing, wherein the electric core is in contact with the electrolyte, and the electrolyte is an ion battery electrolyte disclosed herein. In some embodiments, the ion battery is a lithium-ion battery. In some embodiments, the lithium salt is selected from LiClO, LiPF, LiBF, LiCFSO, LiN(CFSO), or a combination thereof. In some embodiments, the electrolyte comprises a solvent selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and a combination thereof.

[0012] According to some aspects, the present disclosure provides a method for improving the performance of a metal-ion battery, the method comprising contacting the metal-ion battery with a metal-ion battery electrolyte disclosed herein. In some embodiments, the improved performance includes improved charge capacity of the metal-ion battery and reduced capacity fade during charge and discharge cycling. 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 extended life of the metal-ion battery during charge and discharge cycling under a high cutoff voltage. In some embodiments, the improved performance includes extended life of the metal-ion battery. In some embodiments, the metal-ion battery is a lithium-ion battery.

[0013] According to some aspects, the present disclosure provides a method for reducing the time required to wet an electrode of a metal-ion battery, the method comprising contacting the electrode with a metal-ion battery electrolyte disclosed herein. In some embodiments, the metal-ion battery is a lithium-ion battery. In some embodiments, the electrolyte salt is selected from LiClO, LiPF, LiBF, LiCFSO, LiN(CFSO), or combinations thereof. In some embodiments, the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and combinations thereof. [Brief explanation of the drawings]

[0014] [Figure 1] Figure 1 shows data on the internal resistance change during standing of batteries containing different surfactants according to some embodiments disclosed herein. Figure 1 shows that electrolytes without additives generally require wetting times of more than 4 hours, while electrolytes containing Rf-oligomers according to some embodiments disclosed herein reduce the wetting time to about 2 hours.

[0015] [Figure 2]2 shows initial capacity data for batteries containing different Rf-oligomers according to some embodiments disclosed herein, which have the same functional groups but different backbone lengths (backbone lengths increase from left to right).

[0016] [Figure 3] FIG. 3 shows cycling performance data with and without the Rf-oligomers disclosed herein, according to certain embodiments disclosed herein.

[0017] [Figure 4] FIG. 4 shows cycling performance data with and without the Rf-oligomers disclosed herein, according to certain embodiments disclosed herein.

[0018] [Figure 5] Figure 5 shows the cycling performance of an NMC 532 battery at a high cutoff voltage of 4.35 V and a rate of 0.5 C, according to some embodiments disclosed herein. (A) shows the capacity retention over cycles. (B) shows the coulombic efficiency over cycles. The blue dashed circle at approximately cycle 70 in (A) and (B) indicates the initiation of dendrites in the battery without Rf-oligomer, followed by the appearance of dendrites on subsequent cycles. The Rf-oligomer used here was derived from DX1080.

[0019] [Figure 6] Figure 6 shows graphite anodes and separators after 140 cycles of overcharge according to certain embodiments disclosed herein. (A) shows the electrolyte without DX1080 additive, and (B) shows the electrolyte with DX1080 additive. (C) shows a comparison of the separators after cycling. Top: surfactant DX1080; bottom: no surfactant. (D) and (E). SEM images of graphite anodes after cycling. (D) without DX1080 additive, and (E) with DX1080 additive. DETAILED DESCRIPTION OF THE INVENTION

[0020] Detailed Description According to some aspects, the present disclosure provides perfluoroalkyl group-terminated oligomers derived from perfluoroalkyl mercaptans and hydrophilic and / or hydrophobic monomers polymerized by free radical reactions, and their use to improve MIB performance.

[0021] According to one particular embodiment, the perfluoroalkyl-terminated oligomer (Rf-oligomer) is represented by the following formula I: R f -E n -S-[M1] x [M2] y H (I) is expressed by

[0022] In the formula, R f is a linear or branched perfluoroalkyl group having 4 to 18 carbon atoms, a perfluoroalkyloxyalkylene group having 5 to 19 carbon atoms, or a mixture thereof; E n is a straight or branched alkylene having 1 to 12 carbon atoms, -CON(R')-E'-, -SON(R')-E'-, -E''-CON(R')-E'-, -E''-S-E'-, -E''-N(R')-E'-, or -E''-SON(R')-E'-, wherein R' is hydrogen or alkyl having 1 to 6 carbon atoms, E' is alkylene having 2 to 8 carbon atoms, E'' is alkylene having 1 to 4 carbon atoms, [M1] represents a hydrophilic monomer unit derived from a hydrophilic monomer of type M1 as defined herein, and [M2] represents a hydrophobic monomer unit derived from a hydrophobic monomer of type M2 as defined herein. The sum of x and y is between 1 and about 500, x / (x+y) is between 1 and 0.5, and in some embodiments, more than one type of --M1- unit and more than one type of --M2- unit is present in the fluorocarbon surfactant; and n is 0 or 1.

[0023] In some embodiments, the oligomeric units can be randomly distributed, and therefore the above formula does not depict the actual arrangement of the oligomeric units.

[0024] In some embodiments, the oligomers disclosed herein have Formula II R f -E n -SH (II) [In the formula, R f and E n R is as disclosed herein. f -mercaptan, by polymerizing one or more hydrophilic monomers of type M1 with or without one or more hydrophobic monomers of type M2.

[0025] R in Formula II f Mercaptans 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 Patent Application No. 36868 filed April 24, 1968, each of which is incorporated by reference as if fully set forth herein.

[0026] Suitable R f Mercaptans can alternatively be f Acid halides, such as R f SO2Cl or R f COCl can be readily prepared by reacting it with an aminomercaptan, such as HN(R')-E'-SH, in an inert solvent.

[0027] In some embodiments, acrylic and methacrylic acids and their salts, as well as their hydroxyalkyl esters, such as hydrophilic group-containing derivatives, for example, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, or 2,3-hydroxypropyl esters, and also ethoxylated and polyethoxylated hydroxyalkyl esters, for example, HO-C m H 2m -O-(CH2-CH2-O) n -R1 Hydrophilic monomers of type M1 containing at least one hydrophilic group, such as esters of alcohols of the formula: wherein R1 is hydrogen or methyl, m is 2 to 5, and n is 1 to 20, or esters of similar alcohols in which some of the ethylene oxide units have been replaced by propylene oxide units, are known and commercially available. Further suitable esters are dialkylaminoalkyl acrylates and methacrylates, such as 2-(dimethylamino)-ethyl-, 2-(diethylamino)-ethyl-, and 3-(dimethylamino)-2-hydroxypropyl esters. Another class of hydrophilic monomers are acrylamides and methacrylamides, 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 methacrylimides, for example trimethylamine methacrylimide and dimethyl-(2-hydroxypropyl)amine methacrylimide, and the corresponding derivatives of acrylic acid; monoolefin sulfonic acids and their salts, such as sodium ethylene sulfonate, sodium styrene sulfonate, and 2-acrylamido-2-methylpropane sulfonic acid;N-[2-(dimethylamino)-ethyl]-acrylamide and -methacrylamide, N-[3-(dimethylamino)-2-hydroxypropyl]methacrylamide, or monoolefin 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-methyl-2-methyl-2-pyrrolidone, 2 ... 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-vinylpiperidine, 2- and 4-vinylquinoline, 2,4-dimethyl-6-vinyl-s-triazine, 4-acrylyl-morpholine, and the quaternized derivatives of the above pyridines;

[0028] In some embodiments, the hydrophilic monomers of type M1 listed above can be used alone or in combination with each other and with suitable hydrophobic monomers of type M2.

[0029] In some embodiments, hydrophilic monomers of type M1 that require a comonomer for polymerization are maleates, fumarates, and vinyl ethers; for example, the following combinations of monomers are useful: di(hydroxyalkyl)maleates, such as di(2-hydroxyethyl)maleate, and ethoxylated hydroxyalkylmaleates, hydroxyalkylmonomaleates, such as 2-hydroxyethylmonomaleate, and hydroxylated hydroxyalkylmonomaleates with vinyl ethers, vinyl esters, styrene, or generally any monomer that readily copolymerizes with maleates or fumarates; hydroxyalkylvinylethers, such as 2-hydroxyethylvinylether, 4-hydroxybutylvinylether with maleates, fumarates, or virtually any monomer that readily copolymerizes with vinyl ethers.

[0030] In some embodiments, hydrophilic monomers of type M1 are acrylic acid, methacrylic acid, acrylamide, diacetone acrylamide, acrylamidopropanesulfonic acid and salts thereof, and hydroxyethyl methacrylate.

[0031] In some embodiments, the hydrophobic monomers of type M2 that are actually copolymerized with the hydrophilic monomers of type M1 are known and include: acrylates, methacrylates, maleates, fumarates and itaconates having 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;

[0032] Vinyl esters with 1 to 18 carbons in the ester group, such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl 2-ethylhexanoate, and vinyl benzoate; vinyl acetate chloride and isopropenyl acetate, vinyl carbonate derivatives;

[0033] Styrene and substituted styrenes such as o- and p-methyl, 3,4-dimethyl, 3,4-diethyl, and p-chlorostyrene; alpha olefins, including straight-chain and branched-chain substituted alpha olefins having up to 18 carbon atoms in the side chain, including ethylene, propylene, and butylene;

[0034] 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;

[0035] Vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, methacrylonitrile, tetrafluoroethylene, trifluorochloroethylene, hexafluoropropylene;

[0036] Dienes, in particular 1,3-butadiene, isoprene, and chloroprene, 2-fluorobutadiene, 1,1,3-trifluorobutadiene, 1,1,2,3-tetrafluorobutadiene, 1,1,2-trifluoro-3,4-dichlorobutadiene, and tri- and pentafluorobutadiene and isoprene.

[0037] In some embodiments, the hydrophobic monomer of type M2 is a fluorinated monomer.

[0038] In some embodiments, mercaptans act as so-called chain transfer agents in free radical polymerization and copolymerization reactions. The hydrophilic monomers of type M1 and hydrophobic monomers of type M2 already listed homopolymerize and / or copolymerize in the presence of a free radical initiator, and thus R of formula II f -mercaptan, and the R f - Formation of oligomers in high yields.

[0039] In some embodiments, the polymerization reaction is carried out in an essentially water-free reaction medium, preferably a lower alcohol such as methanol or isopropanol, or acetone or a lower cellosolve, which dissolves the reactants and catalyst.

[0040] In some embodiments, the oligomerization temperature is maintained between 20°C and 60°C, although temperatures up to 100°C may be used. The optimum temperature can be readily determined for each oligomerization and depends on the reaction, the relative reactivities of the monomers, and the particular feed-radical initiator used. In some embodiments, an oxygen-free atmosphere is desirable to promote the propagation of free radicals necessary for effective catalytic reaction, and the oligomerization is carried out under nitrogen.

[0041] In some embodiments, the catalyst used should be a free radical initiator such as peroxide, persulfate or azo compound.In some embodiments, organic peroxide and hydroperoxide, hydrogen peroxide, azo catalyst and water-soluble persulfate are used.Specific examples include ammonium persulfate, lauroyl peroxide, tert-butyl peroxide, and especially azo catalyst 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).

[0042] In some embodiments, depending on the particular initiator and monomer system, a catalytic amount of initiator between 0.01-0.5% by weight of monomer is used, and in some embodiments, 0.01-0.2% by weight of azo catalyst per weight of monomer is used.

[0043] In some embodiments, R from M and M type monomers f -oligomers are synthesized by the one-step polymerization reaction described above. fIt is also possible to synthesize the -oligomers in a two-step synthesis. In this alternative synthesis, a hydrolyzable hydrophobic monomer of type M2 is substituted with R f -mercaptan, and R containing -M2- monomer units f In the second step, such R f The -oligomer is hydrolyzed with a base, preferably an alcoholic solution of sodium hydroxide or potassium hydroxide. This hydrolysis process converts selected -M2- monomer units 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 maleate units. Similarly, R containing maleic anhydride monomer units are f The oligomers can be hydrolyzed or amidated.

[0044] In some embodiments, Formula I R f -E n -S-[M1] x [M2] y H (I) R f -oligomers are R in oligomers f The oligomers are synthesized to balance the oleophobic and hydrophobic properties of the -ES segments with the hydrophilic properties of the -M1- and hydrophobic properties of the -M2- monomer units. In some embodiments, there is more than one type of -M1- and more than one type of -M2- unit in the oligomer to achieve the desired balance of properties. In some embodiments, it is not necessary to incorporate hydrophobic -M2- monomer units to achieve the appropriate balance of oleophobic / hydrophobic and hydrophilic properties.

[0045] Further, in some embodiments, R f The chain length of the group and the nature and ratio of the M1 and M2 monomer units are varied to achieve desired properties. f -oligomers are prepared by dissolving at least 0.01% by weight of R in water or water-solvent mixtures. f-Achieving oligomer solubility.

[0046] In some embodiments, M1 and M2 type monomers are selected from the group consisting of a degree of polymerization, i.e., R f --E--S segment and-[M1] x [M2] y R formed by H f -oligomeric segments are selected by varying the weight ratio of R f The R -oligomers reduce the surface tension of aqueous systems to any desired extent, down to as low as 16 dynes / cm. In some embodiments, R -oligomers provide any desired surface tension between 76 dynes / cm and about 16 dynes / cm in water. f -oligomeric compositions can be prepared. Thus, in some embodiments, R f - The oligomers can be used in applications requiring improved wetting and spreading of liquids on substrates that are difficult to wet or that are contaminated with oil or silicone.

[0047] In some embodiments, Formula I R f -E n -S-[M1] x [M2] y H (I) R f The oligomer has the formula II R f -E n -SH (II) A wide variety of R f -mercaptans, as well as a vast number of commercially available monomers of type M1 and M2 as defined herein.

[0048] In some embodiments, R f is a perfluoroalkyl group having 6 to 14 carbon atoms,

[0049] E is alkylene, preferably ethylene; [ka] and

[0050] In the formula, T1 is --COOMe; --CONH2; --CONHR2; --CONH2R3; --CONH--E1--NR2R3; --CONH--E1--NR2R3R4X; --CONHCH2OH; --CONHCH2OR2; --CONHE2OH; --CO(OE1) n OR1;--COOCH2CHOHCH2OH;--CONH--E2--SO3Me;--CON(E1OH)2,

[0051] T2 is --OH, --OE2OR1, --(OE1) nOR1 , --SO3Me, --C6H4SO3Me, [ka] pyridinium halide, --NHCOR1, --NH2, and T3 and T4 are independently --COOMe, --CONH2, --CO(OE1) n OR1, --CONH--E1, --OH, --CON(E1--OH)2,

[0052] R1 is hydrogen or methyl;

[0053] R2, R3, and R4 are independently alkyl having 1 to 6 carbon atoms;

[0054] E1 is alkylene having 2 or 3 carbon atoms,

[0055] E2 is alkylene having 2 to 6 carbon atoms,

[0056] Me is hydrogen or an alkali metal;

[0057] X is a halide,

[0058] n is 1 to 20, [ka] and

[0059] In the formula, G1 is --COOR5, --OCOR2, --CN, --OR5, --C6H5, --C6H4X;

[0060] G2 is --H, R2 or halide;

[0061] G3 and G4 may independently be --COOR5 or together be --CO--O--CO--;

[0062] R1, R2, and X are as previously defined.

[0063] R5 is alkyl having 1 to 18 carbon atoms, or cycloalkyl, aryl, or alkenyl having 6 to 18 carbon atoms;

[0064] The sum of x and y is between 4 and about 500, and x / (x+y) is between 0.5 and 1.

[0065] 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 between about 0.5 and 1.

[0066] In some embodiments, R f -oligomers have the structure R f --ES-[M1] x H, wherein R f is a linear perfluoroalkyl group having 6 to 12 carbon atoms,

[0067] E is --CH2CH2-, [ka] and

[0068] x is between 4 and 50.

[0069] In some embodiments, R is used as an electrolyte additive. f -oligomers having the structure R listed abovef -ES-[M1] x H, wherein -M1- is [ka] and

[0070] x varies from 10 to 50.

[0071] According to some embodiments, the electrolyte additive comprises one or more of the compounds according to Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, 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, Example 21, Example 22, Example 23, Example 24, or Example 25. According to some embodiments, the electrolyte additive comprises one or more commercially available products, such as DX1080 or DX1090 (Dynax). In some embodiments, the commercially available products, such as DX1080 or DX1090, are added to the electrolyte in a dry state. Drying consists in heating the product in a vacuum oven until a constant weight is achieved.

[0072] In some embodiments, the electrolyte additive disclosed herein is represented by a structure having repeating units, and the integer represents the number of repeating units. See Examples. Those skilled in the art will understand that the integer is an average value determined by the stoichiometry between the mercaptan and the polymerizable monomer. The resulting oligomer does not consist of a single defined molecular weight, but rather consists of a molecular weight distribution centered around an average value.

[0073] In some embodiments, the electrolyte additive is

[0074] [ka] [wherein n is an integer between 1 and 40].

[0075] In some embodiments, the electrolyte additive comprises one or more of the following:

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086]

change

[0087]

change

[0088]

change

[0089]

change

[0090]

change

[0091]

change

[0092]

change

[0093]

change

[0094]

change

[0095]

change

[0096]

change

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka] R disclosed herein f -Use of oligomeric MIB in electrolytes

[0101] According to some embodiments, the R disclosed herein f The R-oligomers are useful as additives to electrolytes for MIBs, such as lithium ion batteries. f -oligomer is present in the electrolyte in an 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. f The R -oligomer is present in the electrolyte in an amount of about 0.001% to 5% by weight of the electrolyte. f The R -oligomer is present in the electrolyte in an amount of about 0.01% to 2% by weight of the electrolyte. f The oligomer is present in the electrolyte in an amount of about 0.05% to 1% by weight of the electrolyte.

[0102] In some embodiments, the R disclosed herein added to the electrolyte f The class of oligomer is selected from the group consisting of polyethylene oxide, amphoteric / zwitterionic, anionic, cationic, nonionic, acrylamide oligomer, acrylamide co-oligomer, N-vinylpyrrolidone oligomer, phosphate, sulfonate, and combinations thereof. In some embodiments, the R disclosed herein added to the electrolyte is f In some such embodiments, the oligomer comprises a PEG-containing unit, a PPG-containing unit, a polyacrylic acid-containing unit, a polyacrylamide-containing unit, and a PVA-containing unit. f the oligomer comprises at least 1 unit, at least 2 units, at least 3 units, at least 4 units, at least 5 units, at least 6 units, at least 7 units, at least 8 units, at least 9 units, at least 10 units, at least 11 units, at least 12 units, at least 13 units, at least 14 units, at least 15 units, at least 16 units, at least 17 units, at least 18 units, at least 19 units, at least 20 units, at least 21 units, at least 22 units, at least 23 units, at least 24 units, at least 25 units, at least 26 units, at least 27 units, at least 28 units, at least 29 units, or at least 30 units per molecule.

[0103] In some embodiments, the R disclosed herein added to the electrolyte f In some embodiments, the R oligomer disclosed herein is added to the electrolyte. fthe oligomer comprises 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

[0104] In some embodiments, the electrolytes disclosed herein include a salt that is readily dissolved or dissociated in a solvent. In some embodiments, the electrolyte includes a lithium salt. In some embodiments, the lithium salt is selected from LiClO4, LiPF6, LiBF4, LiCF3SO3, LiN(CF3SO2)2, or a combination thereof. In some embodiments, the electrolyte includes 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-)2 (where R can be methyl, alkyl, methyl halide, and ethyl); Mg(B(C2O4)2); Mg(BOB)2; magnesium titanate@superoxomagnesium titanate; magnesium titanate (MgTiO3); magnesium dititanate (MgTi2O5); [Mg(L x[Al(ORF)4]2 (where x=3, 6, L=MeCN (acetonitrile), DME (1,2-dimethoxyethane), and 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 the same as those described herein for magnesium salts, except that magnesium is replaced with trivalent aluminum. In some embodiments, the aluminum salt is selected from the group consisting of Al(L)3 (where L=halogen), (Al(TFSI)3), (Al(ClO4)3), (Al(OTF)3), Al-Zn / Al(OTF)3, or combinations thereof. Electrolyte Solvent

[0105] In some embodiments, the electrolyte comprises an organic solvent having high solubility for one or more salts and low viscosity to facilitate ion migration. In some embodiments, the electrolyte comprises an organic solvent having high solubility for lithium salts and low viscosity to facilitate lithium ion migration. Such solvents include, for example, cyclic carbonate solvents, linear 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 solvent comprises ethylene carbonate, propylene carbonate, and combinations thereof. In some embodiments, the solvent comprises a pyrocarbonate, such as a dialkylpyrocarbonate, used directly or added to a dialkyl carbonate mixture to better control CO2 evolution. In some embodiments, the solvent comprises an ether solvent. 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, i.e., 1 M LiPF in ethylene carbonate (EC)-ethyl methyl carbonate (EMC) (v / v=1:1). Other additives

[0106] In some embodiments, the electrolyte is a R fIn addition to the oligomer, the electrolyte contains an additive. In some embodiments, the additive is a substance that protects the cathode and / or anode. In some embodiments, the cathode additive is included to stabilize the cathode structure and protect the surface to retard battery aging. In some embodiments, the anode additive is included to stabilize the anode structure and protect the surface to retard battery aging. In some embodiments, the electrolyte contains a surfactant, an SEI-forming additive, a material for adjusting viscosity, a material that aids in salt solubilization, and combinations thereof. In some embodiments, the electrolyte contains a cathode protectant such as butylamine, N,N'-dicyclohexylcarbodiimide (DCI), lithium bis(oxalato)boronate (LiBOB), and combinations thereof. In some embodiments, the electrolyte contains a LIPF6 salt stabilizer additive, such as tris(2,2,2-trifluoroethylphosphite) (TTFP), 1-methyl-2-pyrrolidinone, hexamethyl-phosphoramide, and combinations thereof. In some embodiments, the electrolyte includes an overcharge protection additive, such as bipyridyl carbonate, diphenyl carbonate, difluoroanisole, thianthrene, 2,7-diacetylthianthrene, and combinations thereof. In some embodiments, the electrolyte includes a flame retardant additive, such as trimethyl phosphate. In some embodiments, the electrolyte includes a lithium deposition improver, such as cetyltrimethylammonium chloride. In some embodiments, the electrolyte includes an ionic solvation promoter, such as tris(pentafluorophenyl)borane (TPFPB). In some embodiments, the electrolyte includes an Al corrosion inhibitor, such as lithium bis(oxalate)boronate (LiBOB). battery

[0107] According to some aspects, the present disclosure provides an ion battery comprising a housing and an electric core. The electric core comprises an anode, a cathode, and a separator, each of which is in contact with an electrolyte. In some embodiments, the negative electrode (anode) is made of graphitic carbon, and the positive electrode (cathode) is made of a layered oxide (e.g., lithium cobalt oxide), a polyanion (e.g., lithium iron phosphate), or a spinel (e.g., lithium manganate). In some embodiments disclosed herein, the cathode electrode is made of polycrystalline LiNi 0.5 Mn 0.3 Co 0.2 O2 (NMC 532) or single crystal LiNi 0.5 Mn 0.3 Co 0.2 O2 (NMC 721). In some embodiments, the anode electrode comprises one or more of graphite, lithium, magnesium, and aluminum. In some embodiments, the electrode is baked in a vacuum at 80°C for 48 hours to remove moisture. In some embodiments, the housing is a rigid or semi-rigid structure effective to prevent atmospheric air and / or moisture from contacting the electrical core / electrolyte. R disclosed herein f -Effect of oligomers on battery performance

[0108] According to some embodiments, the R disclosed herein f -oligomers are added to the electrolyte to improve one or more of the following battery performance issues: dendrite formation, battery life, initial capacity, capacity fade, and wetting time. In some embodiments, the R f The oligomers can also have a positive effect on the performance of the battery both above and below room temperature. Wetting Time:

[0109] According to some embodiments, the R disclosed herein f In some embodiments, the R-oligomers disclosed herein are effective in reducing the wetting time of the electrolyte when in contact with battery components. f- The wetting time of the electrolyte containing the oligomer is R f -A reduction of about 1% to about 80% when compared to the wetting time of the same electrolyte without the oligomer. In some embodiments, the wetting time is reduced by at least 10%, at least 20%, at least 30%, at least 40%, or at least 50%. The wetting time is defined as the time after electrolyte injection until the electrolyte resistance reaches a plateau. See, for example, Figure 1. Initial capacity:

[0110] In some embodiments, the R f The R-oligomers, when added to an electrolyte, are effective in increasing the initial capacity of a battery. The initial capacity is defined as the capacity at the first cycle. In some embodiments, the R-oligomers disclosed herein f -oligomers are effective in increasing the initial capacity of MIB by about 1% to about 50%. In some embodiments, the R f The oligomer is effective to increase the initial capacity of the MIB by at least 1%, at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, or at least 30%.

[0111] In some embodiments, the R f -oligomers are effective in increasing the initial capacity of MIBs containing highly porous and / or less porous electrodes. f The R-oligomers are effective in increasing the initial capacity of MIBs, including single-crystal electrodes and polycrystalline electrodes. f -oligomers are polycrystalline LiNi 0.5 Mn 0.3 Co 0.2 In some embodiments, the R disclosed herein is effective in increasing the initial capacity of a battery that includes an O electrode. f -oligomers are polycrystalline LiNi 0.5 Mn 0.3 Co 0.2In some embodiments, the R disclosed herein is effective in increasing the initial capacity of a battery containing an O electrode from 4.75 Ah to about 5.25 Ah. f -oligomers are single crystal LiNi 0.5 Mn 0.3 Co 0.2 It is effective in increasing the initial capacity of a battery containing an O2 electrode from 4.2 Ah to 5.0 Ah. Cycling stability / battery life:

[0112] In some embodiments, the R f When included in the electrolyte, the R-oligomers are effective in improving cycling stability and battery life. As used herein, the term "cycling" refers to the process of charging and discharging a battery to determine how well it retains its charge capacity over a number of cycles. In some embodiments, cycling stability is evaluated using a charge / discharge rate of 0.5C. In some embodiments, the R-oligomers disclosed herein are effective in improving cycling stability and battery life. f -oligomers are effective to maintain at least 90% of their initial capacity after at least 100 cycles, at least 200 cycles, at least 300 cycles, at least 400 cycles, or at least 500 cycles. f The oligomer is effective to retain at least 95% of the 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:

[0113] In some embodiments, the R f The R-oligomers, when added to an electrolyte, are effective in reducing dendrite formation. f The R-oligomers, when added to the electrolyte, are effective in reducing dendrite formation when the battery is operating under overcharge conditions. f-oligomers are effective in reducing dendrite formation. [Example]

[0114] Battery Testing To test for improvements in the identified target performance areas, battery testing was performed using the following procedure. Electrodes and electrolytes used:

[0115] The cathode electrode used in this experiment was polycrystalline LiNi 0.5 Mn 0.3 Co 0.2 O2 (NMC 532) or single crystal LiNi 0.5 Mn 0.3 Co 0.2 The cathodes were either 02 (NMC 721) or 02 (NMC 721). Two types of cathodes were tested. The anode electrode used in this experiment was graphite in all cells. Before assembling the cells, all electrodes were baked in a vacuum at 80°C for 48 hours to remove moisture.

[0116] An electrolyte solution containing the fluorosurfactant disclosed herein was mixed in a glove box and then added to the blank battery, which was then sealed, removed from the glove box, and cycled under constant pressure.

[0117] The final battery typically had a capacity of about 5 Ah. The electrolyte used was standard LP50 electrolyte, i.e., 1 M LiPF6 in ethylene carbonate (EC)-ethyl methyl carbonate (EMC) (v / v = 1:1), and the amount used per battery was about 20 mL. The surfactant used in this study was 0.5 wt% of the active components of the electrolyte unless otherwise indicated. All surfactants were soluble after stirring at 50 °C for 48 hours. All batteries were sealed in pouches using a vacuum sealer at a pressure of -970 mBar and a temperature of 180 °C. Wetting Time:

[0118] All batteries underwent the same wetting procedure. After assembly, the batteries were left at room temperature for 10 hours, during which the voltage and internal resistance fluctuations were monitored. A steady voltage and stable internal resistance indicated that the wetting had reached a stable or metastable state. The batteries were then further treated at elevated temperature (40°C) for 48 hours to achieve better wetting, and then aged at a current of 0.05C for 4 hours, followed by 4 hours at a current of 0.1C. After aging, the pouch cells were cut open to release the gas formed during aging, and approximately 3 mL of electrolyte was added to replenish the electrolyte consumed during aging. Finally, the cells were resealed and left at room temperature for 6 hours before undergoing cycle testing. Initial capacity:

[0119] After the resting and aging protocols, all cells were cycled at a rate of 0.5C. The initial capacity is defined as the capacity on the first cycle. These data reflect the wetting state of the electrode, since better wetting results in more electrode material reaction and therefore increased capacity. As discussed below, the results demonstrate that the surfactants disclosed herein can significantly improve wetting. Polycrystalline LiNi 0.5 Mn 0.3 Co 0.2 For the O2 electrode, the initial capacity can be improved from 4.75 Ah to approximately 5.25 Ah, and the single-crystal LiNi 0.5 Mn 0.3 Co 0.2 In the case of the O2 electrode, the monocrystalline NMC721 electrode has a much higher cathode density and therefore is less porous, making it less wettable than the polycrystalline electrode. Therefore, the improvement is more significant, with the initial capacity improving from 4.2 Ah to 5.0 Ah. Cycling stability / battery life:

[0120] The cycling stability is evaluated using a charge / discharge rate of 0.5C. In batteries, electrolyte consumption and uneven distribution during cycling are the main causes of capacity fade, so wetting is very important for cycling performance. The results show that when surfactants are used, significant improvements in cycling stability are achieved. Detailed results are disclosed below. Dendrite suppression:

[0121] Dendrites typically do not readily form in lithium-ion batteries under normal operating conditions, but they readily form when operated under overcharge conditions. To avoid dendrite formation, the anode / cathode capacity ratio is typically set to approximately 1.1, which was a typical value for the battery tests disclosed herein. To evaluate the dendrite suppression effect, the upper cutoff voltage of the polyNMC532 battery was set to 4.35 V, which contributed nearly 20% extra capacity and promoted dendrite formation. Test Overview:

[0122] In the tests, between 0.1 and 5 wt.% of various oligomers were added to selected electrolytes and battery configurations. Battery performance was then evaluated for its ability to overcome various issues associated with metal-ion batteries. Results were compared to blank samples that did not contain the various oligomers.

[0123] The surfactants disclosed herein have been discovered to address issues such as dendrite suppression, battery life, initial capacity, capacity fade, wetting time, and low / high temperature operation. Preparation of surfactants

[0124] R disclosed herein f Some representative examples of the synthesis of oligomers are given below. Example 1

[0125] Perfluoromercapto-(AA)4 oligomer [ka]

[0126] A 500 mL glass bottle was charged with 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, 0.12 mol), and 2-propanol (300 mL) as a solvent at room temperature. 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 another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80-85 °C. The reaction medium was maintained at 80-85 °C for 2 hours. The reaction medium was removed from the water bath and transferred to a 1 L crystallization dish. The solvent was evaporated at room temperature in a fume hood for 2-3 days, and then dried overnight (17 hours) at 50 °C in an oven to obtain a white powder (49.1 g, 63.2%). Example 2

[0127] Perfluoromercapto-(AA)6 oligomer [ka]

[0128] A 500 mL glass bottle was charged with 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 a solvent at room temperature. 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 another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80-85 °C. The reaction medium was maintained at 80-85 °C for 2 hours. The reaction medium was removed from the water bath and transferred to a 1 L crystallization dish. The solvent was evaporated at room temperature in a fume hood for 2-3 days, and then dried in an oven at 50 °C overnight (17 hours) to obtain a white powder (71.4 g, 74%).

[0129] The following oligomers were made using the procedures outlined in Examples 1 and 2, varying only the acrylamide stoichiometry. [Table 4] Example 9

[0130] To prepare Example 9, the procedure outlined in Examples 1 and 2 was used, except that the starting thiol was 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanethiol and the stoichiometry of acrylamide to the thiol was 15 to 1. [ka]

[0131] A 500 mL glass bottle was charged with acrylamide (24.4 g, 0.34 mol), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanethiol (11.0 g, 0.02 mol), and 2-propanol (200 mL) as a solvent at room temperature. The mixture was stirred to dissolve the mixture, and then the solution was purged with nitrogen for 10 minutes. Vazo-52 (0.3 g, 0.001 mol) was added to the mixture, and then the solution was purged with nitrogen for another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80-85 °C. The reaction medium was maintained at 80-85 °C for 2 hours. The reaction medium was removed from the water bath and transferred to a 1 L crystallization dish, and the solvent was allowed to evaporate in a fume hood at room temperature for 2–3 days, followed by drying in an oven at 50 °C overnight (17 h) to give a white powder (31.6 g, 89.2%). Example 10

[0132] Dodecanethiol Hydrocarbon Acrylamide Oligomer [ka]

[0133] A 500 mL glass bottle was charged with acrylamide (74.6 g, 1.05 mol), dodecanethiol (14.2 g, 0.07 mol), and 2-propanol (200 mL) as a solvent at room temperature. 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 another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80-85 °C. The reaction medium was maintained at 80-85 °C for 2 hours. The reaction medium was removed from the water bath and transferred to a 1 L crystallization dish. The solvent was evaporated at room temperature in a fume hood for 2-3 days, and then dried in an oven at 50 °C overnight (17 hours) to obtain a white powder (76.9 g, 85.4%). Example 11

[0134] Preparation of perfluoromercapto-acrylamide (AA) acrylic acid (GAA) co-oligomers

[0135] Perfluoromercapto-(AA)4(GAA)4 co-oligomer [ka]

[0136] A 250 mL glass bottle was charged with acrylamide (6.86 g, 0.10 mol), acrylic acid (6.96 g, 0.10 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (1) (9.20 g, 0.02 mol), and methanol (200 mL) as a solvent at room temperature. 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 another 10 minutes. The glass bottle was sealed and transferred to a 70-75 °C water bath. The reaction was maintained at 80-85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1 L crystallization dish, and the solvent was allowed to evaporate at room temperature in a fume hood for 2–3 days, followed by drying in an oven at 50 °C overnight (17 h) to yield a white powder (21.5 g, 94%). Example 12

[0137] Preparation of perfluoromercapto-acrylamide (AA) acrylic acid (GAA) co-oligomers

[0138] Perfluoromercapto-(AA)8(GAA)1 co-oligomer [ka]

[0139] A 500 mL glass bottle was charged with acrylamide (54.9 g, 0.84 mol), acrylic acid (7.6 g, 0.01 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (1) (4.0 g, 0.1 mol), and 2-propanol (250 mL) as a solvent at room temperature. 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 another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80-85 °C. The reaction was held at 80-85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1 L crystallization dish, and the solvent was allowed to evaporate at room temperature in a fume hood for 2–3 days, followed by drying in an oven at 50 °C overnight (17 h) to yield a white powder (67.2 g, 94%). Example 13

[0140] Preparation of perfluoromercapto-acrylamide (AA) acrylic acid (GAA) co-oligomers

[0141] Perfluoromercapto (AA) 14 (GAA)1 co-oligomer [ka]

[0142] A 500 mL glass bottle was charged with acrylamide (73.3 g, 1.03 mol), acrylic acid (5.3 g, 0.07 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (1) (28 g, 0.07 mol), and 2-propanol (250 mL) as a solvent at room temperature. 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 another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80-85 °C. The reaction was held at 80-85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1 L crystallization dish, and the solvent was allowed to evaporate in a fume hood at room temperature for 2–3 days, followed by drying in an oven at 50 °C overnight (17 h) to yield a white powder (100.2 g, 94%). Example 14

[0143] Preparation of perfluoromercapto-acrylamide (AA) acrylic acid (GAA) co-oligomers

[0144] Perfluoromercapto-(AA)4(GAA)1 co-oligomer [ka]

[0145] A 500 mL glass bottle was charged with acrylamide (22.45 g, 0.32 mol), acrylic acid (5.69 g, 0.08 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (1) (30 g, 0.08 mol), and 2-propanol (250 mL) as a solvent at room temperature. The mixture was stirred to dissolve the mixture, and then the solution was purged with nitrogen for 10 minutes. Vazo-52 (0.4 g, 0.002 mol) was added to the mixture, and then the solution was purged with nitrogen for another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80-85 °C. The reaction was held at 80-85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1 L crystallization dish, and the solvent was allowed to evaporate in a fume hood at room temperature for 2–3 days, followed by drying in an oven at 50 °C overnight (17 h) to yield a white powder (43.4 g, 73%). Example 15

[0146] Preparation of perfluoromercapto-acrylamide (AA) acrylate (GAA) co-oligomers

[0147] Perfluoromercapto-(AA)4(MA)1 co-oligomer [ka]

[0148] A 500 mL glass bottle was charged with acrylamide (22.45 g, 0.32 mol), methyl acrylate (6.8 g, 0.08 mol, MA), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (1) (30 g, 0.08 mol), and 2-propanol (250 mL) as a solvent at room temperature. The mixture was stirred to dissolve the mixture, and then the solution was purged with nitrogen for 10 minutes. Vazo-52 (0.4 g, 0.002 mol) was added to the mixture, and then the solution was purged with nitrogen for another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80–85 °C. The reaction was held at 80–85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1 L crystallization dish, and the solvent was allowed to evaporate in a fume hood at room temperature for 2–3 days, followed by drying in an oven at 50 °C overnight (17 h) to yield a white powder (49.9 g, 73%). Example 16

[0149] Preparation of perfluoromercapto-acrylamide (AA) acrylate (GAA) co-oligomers

[0150] Perfluoromercapto-(AA)4(BA)1 co-oligomer [ka]

[0151] A 500 mL glass bottle was charged with acrylamide (22.45 g, 0.32 mol), butyl acrylate (10.12 g, 0.08 mol, BA), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (1) (30 g, 0.08 mol), and 2-propanol (250 mL) as a solvent at room temperature. The mixture was stirred to dissolve the mixture, and then the solution was purged with nitrogen for 10 minutes. Vazo-52 (0.4 g, 0.002 mol) was added to the mixture, and then the solution was purged with nitrogen for another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80-85 °C. The reaction was held at 80-85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1 L crystallization dish, and the solvent was allowed to evaporate at room temperature in a fume hood for 2–3 days, followed by drying in an oven at 50 °C overnight (17 h) to yield a white powder (43.1 g, 68%). Example 17

[0152] Preparation of perfluoromercapto-acrylamide (AA) perfluoromethacrylate (PFMA) co-oligomers

[0153] Perfluoromercapto-(AA)4(PFMA)1 co-oligomer [ka]

[0154] A 500 mL glass bottle was charged with acrylamide (8.23 g, 0.12 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl-2-methacrylate (12.5 g, 0.03 mol, PFMA), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (1) (11 g, 0.03 mol), and 2-propanol (200 mL) as solvent at room temperature. The mixture was stirred to dissolve the mixture, and then the solution was purged with nitrogen for 10 minutes. Vazo-52 (0.4 g, 0.002 mol) was added to the mixture, and then the solution was purged with nitrogen for another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80–85 °C. The reaction was held at 80–85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1 L crystallization dish, and the solvent was allowed to evaporate at room temperature in a fume hood for 2–3 days, followed by drying in an oven at 50 °C overnight (17 h) to yield a white powder (22.2 g, 70%). Example 18

[0155] Preparation of perfluoromercapto-acrylamide (AA) perfluoromethacrylate (PFMA) co-oligomers

[0156] Perfluoromercapto (AA) 14 (PFMA)1 co-oligomer [ka]

[0157] A 500 mL glass bottle was charged with acrylamide (28.81 g, 0.12 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl-2-methacrylate (12.5 g, 0.03 mol, PFMA), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (1) (11.0 g, 0.03 mol), and 2-propanol (200 mL) as solvent at room temperature. The mixture was stirred to dissolve the mixture, and then the solution was purged with nitrogen for 10 minutes. Vazo-52 (0.4 g, 0.002 mol) was added to the mixture, and then the solution was purged with nitrogen for another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80–85 °C. The reaction was held at 80–85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1 L crystallization dish, and the solvent was allowed to evaporate at room temperature in a fume hood for 2–3 days, followed by drying in an oven at 50 °C overnight (17 h) to yield a white powder (42.7 g, 82%). Example 19

[0158] Preparation of perfluoromercapto-poly-N-vinyl-2-pyrollidinone (PV2P) oligomers

[0159] Perfluoromercapto-(PV2P)4 oligomer [ka]

[0160] A 500 mL glass bottle was charged with n-vinyl-2-pyrrolidinone (58.5 g, 0.53 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (1) (50 g, 0.13 mol), and 2-propanol (300 mL) as a solvent at room temperature. The mixture was stirred to dissolve the mixture, and then the solution was purged with nitrogen for 10 minutes. Vazo-52 (0.4 g, 0.002 mol) was added to the mixture, and then the solution was purged with nitrogen for another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80-85 °C. The reaction was held at 80-85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1 L crystallization dish, and the solvent was allowed to evaporate at room temperature in a fume hood for 2–3 days, followed by drying in an oven at 50 °C overnight (17 h) to yield a white powder (101.8 g, 94%).

[0161] Using these conditions, the following series of N-vinyl-2-pyrollidinoine oligomers were prepared: [Table 5] Example 24

[0162] Preparation of perfluoromercapto-poly(1-propanesulfonic acid), 2-methyl-2-[(1-oxo-2-propen-1-yl)amino]-, sodium salt (AMPS) oligomer

[0163] Perfluoromercapto-(AMPS)4 oligomer [ka]

[0164] A 500 mL glass bottle was charged with 50% aqueous sodium 2-methyl-2-[(1-oxo-2-propen-1-yl)amino]-1-propanesulfonate (154 g, 0.34 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (1) (32 g, 0.08 mol), and 2-propanol (300 mL) as solvent at room temperature. The mixture was stirred to obtain two phases. The reaction mixture was then purged with nitrogen for 10 minutes. Vazo-52 (0.4 g, 0.002 mol) was added to the mixture, and the solution was then purged with nitrogen for another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80-85 °C. The reaction was maintained at 80-85 °C for 2 hours. A portion of the reaction mixture was removed from the water bath and transferred to a 1 L crystallization dish, and the solvent was allowed to evaporate at room temperature in a fume hood for 5–6 days, followed by drying in an oven at 50 °C overnight (48 h) to yield a white powder (17.5 g, 17.4%). Example 25

[0165] Preparation of perfluoromercapto-poly(1-propanesulfonic acid), 2-methyl-2-[(1-oxo-2-propen-1-yl)amino]-, sodium salt (AMPS) oligomer

[0166] Perfluoromercapto (AMPS) 14 Oligomer [ka]

[0167] A 500 mL glass bottle was charged with 50% aqueous sodium 2-methyl-2-[(1-oxo-2-propen-1-yl)amino]-1-propanesulfonate (154 g, 0.34 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol (1) (32 g, 0.08 mol), and 2-propanol (300 mL) as solvent at room temperature. The mixture was stirred to obtain two phases. The reaction mixture was then purged with nitrogen for 10 minutes. Vazo-52 (0.4 g, 0.002 mol) was added to the mixture, and the solution was then purged with nitrogen for another 10 minutes. The glass bottle was sealed and transferred to a water bath at 80-85 °C. The reaction was maintained at 80-85 °C for 2 hours. A portion of the reaction mixture was removed from the water bath and transferred to a 1 L crystallization dish, and the solvent was allowed to evaporate at room temperature in a fume hood for 5–6 days, followed by drying in an oven at 50 °C overnight (48 h) to yield a white powder (27.1 g, 10%). Tested battery

[0168] For battery evaluation, polycrystalline LiNi 0.5 Mn 0.3 Co 0.2 O2 (NMC 532) or single crystal LiNi 0.5 Mn 0.3 Co 0.2 One of two cathodes was used: O2 (NMC 721). The anode was unchanged (anode name and type: lithium intercalated graphite) and the common electrolyte was the same (LD50 from Gotion).

[0169] The R disclosed herein tested f -List of all classes / families of oligomers Polyethylene oxide R f -oligomeric lithium salts Zwitterionic Acrylamide Oligomer Acrylamide Co-oligomer N-vinylpyrrolidone oligomer phosphate sulfonates Cationic Anionic, cationic, and nonionic blends

[0170] List of four performance parameters evaluated Wetting Time initial capacity Capacity retention Dendrite suppression Wetting time in LIB

[0171] Electrochemical impedance spectroscopy (EIS) was used to examine the change in the internal resistance of the battery. After the electrolyte was injected, the internal resistance changed with the penetration of the electrolyte. Once the electrodes were completely wetted, the resistance reached an equilibrium state.

[0172] As shown in Figure 1, the effect of several electrolyte formulations on their ability to reduce wetting time was tested. LP50 electrolyte alone (black squares) was used as a control and compared with LP50 in combination with DuPont Zonyl FSA (red circles), 3M FC-4430 (blue triangles), the compound from Example 2 (1%), and the compound from Example 6 (1%). The data show that the radius of curvature for the LP50 control is much larger than when mixed with either the compound from Example 2 or 6. This is evident in the shape of the curves from 0 to approximately 240 minutes after injection. As can be seen, when the electrolyte contains the compound from Example 2 or 6, the electrolyte resistance plateaus significantly more quickly, and a decrease in radius of curvature is observed. Furthermore, the observed radius of curvature for Examples 2 and 6 (containing acrylamide oligomers) was also significantly smaller than the electrolytes containing DuPont Zonyl FSA and 3M FC-4430 (non-acrylamide). Specifically, the observed electrolyte resistance plateaued for Examples 2 and 6 at approximately 2 hours after injection, while the observed electrolyte resistance plateaued for 3M FC-4430 at approximately 4 hours. initial capacity

[0173] As shown in Figure 2, in a battery containing a nickel, manganese, and cobalt polycrystalline cathode (NMC 532 cell), various R ions containing acrylamide units with the same functional group but different backbone lengths were tested. f -oligomers were tested. All surfactants showed significantly improved initial capacity (approximately 5.2 Ah), indicating that the better wettability provided by the surfactants resulted in more electrode material being activated. f - The battery without oligomer has a capacity of about 4.75 Ah (Figure 2). The surfactant exhibits a "smile" curve, indicating that molecules with shorter backbone lengths and molecules with longer backbone lengths have better performance (Figure 2). Table 1 below shows the R f -oligomers and the corresponding target number of acrylamide units per molecule. [Table 1] Cycle stability / battery life

[0174] As shown in Figures 3 and 4, the electrolyte LP50 was tested for cycling stability over 500 cycles, either alone or in combination with the compounds of Examples 1 or 6. After 500 cycles, the R f The R-oligomers of Example 1 were able to significantly improve the battery capacity retention. As shown in Figure 4, the battery with LP50 electrolyte alone showed a capacity decrease from 4.32 Ah to 3.66 Ah over 500 cycles, which is equivalent to 85% capacity preservation. In contrast, the R-oligomers of Example 1 f The battery with the electrolyte containing the R-oligomer showed a capacity drop from 5 Ah to 4.75 Ah, which is equivalent to 95% capacity conservation. f The battery with the electrolyte containing the R-oligomer showed a capacity drop from 4.86 Ah to 4.44 Ah, which is equivalent to a 91% capacity conservation. fThe R-oligomers were effective in maintaining 95-91% of the initial battery capacity, while the control was only able to maintain 85% of its initial capacity. f It is also noted that the initial battery capacity increases when the -oligomer is used. The data in Figures 3 and 4 are summarized in Table 2 below. [Table 2]

[0175] Additional examples were tested for volume retention compared to the LP50 control according to the protocol above, and the results are summarized below. [Table 6]

[0176] Examples with "average" capacity retention had similar capacity retention compared to electrolyte alone after 500 cycles. Examples with "good" capacity retention had higher capacity retention compared to electrolyte alone after 500 cycles, but were not as beneficial as Example 1. Dendrite suppression

[0177] The dendrite suppression performance was evaluated based on electrochemical data and SEM photographs, as shown in Figure 5. This evaluation was performed using the R f This was done by using dried DX1080 consisting of -oligomers. The DX1080 was dried by heating in a vacuum oven until a constant weight was achieved. Battery cycle performance

[0178] NMC 532 polycrystalline batteries were tested at a high cutoff voltage of 4.35 V and a 0.5 C rate. In the control group, the battery exhibited typical dendrite formation behavior, with a rapid decline in capacity after approximately 70 cycles (Figure 5A). Such a dramatic capacity fade can be attributed to the formation of dendrite growth, which typically results in dead lithium and the loss of a significant amount of lithium ions. Correspondingly, the coulombic efficiency (defined as the ratio of the battery's charge output to its charge input) began to fluctuate around the 70th cycle and was observed to fall below 100% (Figure 5B). This evidence indicates the formation of lithium dendrites on the graphite anode during cycling under overcharge conditions.

[0179] In comparison, the surfactant-containing battery exhibited steady cycling: capacity retention was 86.4% and 75.6% after 67 and 140 cycles, respectively, significantly higher than the control's 84.1% and 50.46% (Table 3). [Table 3]

[0180] More importantly, the Coulombic efficiency remains steady at approximately 100%, showing no formation of dead lithium even at such a high cutoff voltage. This result indicates that the surfactant can effectively prevent the formation of lithium dendrites under overcharge conditions. Characterization of graphite anodes

[0181] To further confirm that surfactants can suppress dendrite growth, we characterized the graphite anode after cycling. As shown in Figure 6A, without surfactants, a large amount of dead lithium is found deposited on the separator and graphite. Dead lithium is also highly flammable and can spontaneously combust when exposed to air, indicating that the dead lithium spots are the cause of capacity fade. In contrast, with surfactants, the graphite electrode and separator are significantly cleaner, indicating that dead lithium / lithium dendrites are mitigated under overcharge conditions (Figures 6B-C). These results are further verified by SEM images, which show that the electrode with surfactants exhibits a much smoother surface (Figure 6E) than the electrode without surfactants (Figure 6D).

[0182] These electrochemical results and characterizations indicate that the Rf-oligomers present in DX1080 can effectively inhibit dendrite growth.

[0183] All documents cited in this application are incorporated herein by reference as if fully recited herein.

[0184] Although illustrative embodiments of the present disclosure have been described herein, it should be understood that the present disclosure is not limited to what has been described, and that various other changes or modifications can be made by those skilled in the art without departing from the scope or spirit of the invention.

Claims

1. Electrolyte salts, a solvent, and Formula I R ｆ -E ｎ -S-[M １ ] ｘ [M ２ ] ｙ H (I) [In the formula, R ｆ is a linear or branched perfluoroalkyl group having 4 to 18 carbon atoms, a perfluoroalkyloxyalkylene group having 5 to 19 carbon atoms, or a mixture thereof; E ｎ represents a straight or branched chain alkylene having 1 to 12 carbon atoms, —CON(R′)-E′—, —SO ２ N(R')-E'-, -E''-CON(R')-E'-, -E''-S-E'-, -E''-N(R')-E'-, or -E''-SO ２ N(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; [M １ ]is M １ represents a hydrophilic monomer unit derived from a hydrophilic monomer of the type [M ２ ]is M ２ represents a hydrophobic monomer unit derived from a hydrophobic monomer of the type M １ is optionally more than one monomer, M ２ is optionally more than one monomer, 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. At least one fluorocarbon surfactant according to 1. An ionic battery electrolyte comprising:

2. 10. The ionic battery electrolyte of claim 1, wherein said at least one fluorocarbon surfactant according to Formula I comprises from about 0.1% to about 5% by weight of said electrolyte.

3. M １ 10. The ionic battery electrolyte of claim 1, wherein is an acrylamide unit.

4. 10. The ionic battery electrolyte of claim 1, wherein the electrolyte salt is a lithium electrolyte salt.

5. The electrolyte lithium salt is LiClO ４ , LiPF ６ , LiBF ４ , LiCF ３ SO ３ , LiN(CF ３ SO ２ ) ２ 5. The ionic battery electrolyte of claim 4, wherein the ionic battery electrolyte is selected from the group consisting of:

6. 10. The ionic battery electrolyte of claim 1, wherein the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate.

7. 10. The ionic battery electrolyte of claim 1, wherein the electrolyte comprises one or more of the compounds according to Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, 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, Example 21, Example 22, Example 23, Example 24, and Example 25.

8. 10. The ionic battery electrolyte of claim 1, wherein the electrolyte comprises one or more of DX1080 and DX1090.

9. a housing containing an electrical core; and An electrolyte disposed within the housing An ion battery comprising: the electrical core is in contact with the electrolyte; The ion battery, wherein the electrolyte is the ion battery electrolyte of claim 1.

10. 10. The ion battery of claim 9, wherein the ion battery is a lithium ion battery.

11. The lithium salt is LiClO ４ , LiPF ６ , LiBF ４ , LiCF ３ SO ３ , LiN(CF ３ SO ２ ) ２ 11. The ion battery of claim 10, wherein the ionic conductivity is selected from the group consisting of:

12. 10. The ion battery of claim 9, wherein the electrolyte comprises a solvent selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and combinations thereof.

13. 10. A method for improving the performance of a metal ion battery, comprising contacting the metal ion battery with the ion battery electrolyte of claim 1.

14. 14. The method of claim 13, wherein the improved performance includes improved charge capacity and fade during charge and discharge cycling of the metal ion battery.

15. 14. The method of claim 13, wherein the improved performance includes reduced dendrite formation during charge and discharge cycling of the metal ion battery.

16. 14. The method of claim 13, wherein the improved performance comprises an increased lifespan of the metal-ion battery.

17. 14. The method of claim 13, wherein the metal ion battery is a lithium ion battery.

18. 10. A method of reducing the time required to wet an electrode of a metal-ion battery, comprising contacting the electrode with the ion battery electrolyte of claim 1.

19. 20. The method of claim 18, wherein the metal ion battery is a lithium ion battery.

20. The electrolyte salt is LiClO ４ , LiPF ６ , LiBF ４ , LiCF ３ SO ３ , LiN(CF ３ SO ２ ) ２ 19. The method of claim 18, wherein the compound is selected from the group consisting of:

21. 20. The method of claim 18, wherein the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and combinations thereof.

22. the at least one fluorocarbon surfactant [Transformation 50] [wherein n is an integer from 1 to 30] 10. The ionic battery electrolyte of claim 1, comprising:

23. the at least one fluorocarbon surfactant 【Chemistry 51】 10. The ionic battery electrolyte of claim 1, comprising:

24. the at least one fluorocarbon surfactant 【Chemistry 52】 10. The ionic battery electrolyte of claim 1, comprising:

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