Compositions and methods for fluorous surfactants in metal ion batteries

Abstract

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

Description

Background Technology

[0001] A metal-ion battery (MIB) consists of an anode and a cathode separated from each other by a semi-permeable membrane called a separator. The battery is completed by filling it with an electrolyte solution containing metal ions. During discharge, metal ions move from the anode (negative electrode) to the cathode (positive electrode) via the electrolyte solution. When the battery is charging, lithium ions move in the reverse direction, from the cathode to the anode.

[0002] Lithium-ion batteries (LIBs) are a common type of metal-ion battery. Typically, the anode is lithium-intercalated graphite, and the cathode is made of a variety of materials, including lithium iron phosphate (LFP), nickel manganese cobalt (NMC), and many others capable of holding lithium ions. The typical liquid electrolyte consists of carbonates such as propylene carbonate and ethylene carbonate, which dissolve lithium hexafluorophosphate salts.

[0003] While LIBs offer exceptional performance, areas for improvement exist. There is also a general need for improvement in MIBs. For example, the time required to fully wet the complex structure of the electrodes and separators when the electrolyte is added to the battery determines the overall battery manufacturing time. There is currently a need for faster wetting times to reduce the time spent manufacturing the MIB. Furthermore, it is desirable for the battery to have the maximum initial capacity and maintain that capacity as high as possible during cycling. Therefore, there is a need to improve the initial capacity (and capacity retention) of the MIB. Additionally, catastrophic events occasionally occur due to dendrite formation in some MIBs, leading to battery failure and, in some cases, fires that are very difficult to extinguish. Therefore, there is a need to mitigate and / or eliminate these catastrophic events for improved safety and improved economics (e.g., longer battery life). Finally, operating MIBs at low temperatures using current technology is suboptimal. Therefore, there is a need to improve the performance of MIBs at low temperatures.

[0004] To address these and other needs, this disclosure specifically provides electrolyte additives that allow for the controllability and regulation of MIB performance. In some embodiments, this disclosure provides oligomers (R...) comprising perfluoroalkyl sulfide-terminated ends. f Additives (such as oligomers) that effectively improve battery performance. Summary of the Invention

[0005] According to several aspects, this disclosure provides perfluoroalkyl sulfide-terminated oligomers and their use in improving the performance of metal-ion batteries (MIBs). In some embodiments, the perfluoroalkyl sulfide-terminated oligomers have a backbone comprising oligomeric structural portions having different carbon numbers, said oligomeric structural portions being made of hydrophilic (or a mixture of hydrophilic and hydrophobic) monomers. In some embodiments, the perfluoroalkyl sulfide-terminated oligomers disclosed herein are added to metal-ion batteries to provide improvements in several aspects, including, but not limited to, improved electrolyte wetting time into the battery, initial battery capacity, capacity decay with battery cycling, reduced dendrite formation, and increased battery life. In some embodiments, the perfluoroalkyl sulfide-terminated oligomers disclosed herein are those previously used in fire-extinguishing foams and 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 aspects, this disclosure provides an ion battery electrolyte comprising: an electrolyte salt; a solvent; and at least one fluorocarbon surfactant according to Formula I: R f -E n -S-[M1] x [M2] y H, where R f It is a straight-chain or branched perfluoroalkyl group with 4-18 carbon atoms, a perfluoroalkoxyalkylene group with 5-19 carbon atoms, or a mixture thereof; E n It is a straight-chain or branched alkylene group with 1-12 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 an alkyl group with 1-6 carbon atoms, E' is an alkylene group with 2-8 carbon atoms and E” is an alkylene group with 1-4 carbon atoms; [M1 [M1] represents a hydrophilic monomer unit derived from a hydrophilic monomer of type M1 disclosed herein; and [M2] represents a hydrophobic monomer unit derived from a hydrophobic monomer of type M2 disclosed herein; wherein the sum of x and y is between 1 and about 500; x / (x+y) is between 1 and 0.5; in some embodiments, the fluorocarbon surfactant contains more than one type of -M1-unit and more than one type of -M2-unit; and n is 0 or 1.

[0007] In some embodiments, at least one fluorocarbon surfactant according to Formula I comprises about 0.1% to about 5% by weight of an 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 combinations thereof. In some embodiments, the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate. In some embodiments, the electrolyte comprises one or more of the compounds according to Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, and 25. In some embodiments, the electrolyte comprises one or more of DX1080 and DX1090.

[0008] In some embodiments, at least one fluorocarbon surfactant comprises:

[0009]

[0010] Where n is an integer from 1 to 30.

[0011] In some embodiments, at least one fluorocarbon surfactant comprises:

[0012]

[0013] In some embodiments, at least one fluorocarbon surfactant comprises:

[0014]

[0015] According to some aspects, this disclosure provides an ion battery comprising: a housing containing a battery cell; and an electrolyte disposed in the housing, wherein the battery cell is in contact with the electrolyte; wherein the electrolyte is an ion battery electrolyte 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.

[0016] According to some aspects, this disclosure provides a method for improving the performance of a metal-ion battery, the method comprising the step of contacting the metal-ion battery with an ion battery electrolyte as described herein. In some embodiments, the improved performance includes improved charge capacity of the metal-ion battery and reduced capacity decay during charge and discharge cycles. In some embodiments, the improved performance includes reduced dendrite formation during charge and discharge cycles of the metal-ion battery. In some embodiments, the improved performance includes increased lifetime of the metal-ion battery during charge and discharge cycles at high cutoff voltages. In some embodiments, the improved performance includes increased lifetime of the metal-ion battery. In some embodiments, the metal-ion battery is a lithium-ion battery.

[0017] According to some aspects, this disclosure provides a method for reducing the time required to wet the electrodes of a metal-ion battery, the method comprising the step of contacting the electrodes with an electrolyte for the ion battery as described herein. In some embodiments, the metal-ion battery is a lithium-ion battery. In some embodiments, the electrolyte salt is selected from LiClO4, LiPF6, LiBF4, LiCF3SO3, LiN(CF3SO2)2, or combinations thereof. In some embodiments, the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and combinations thereof. Attached Figure Description

[0018] Figure 1 Data on the changes in internal resistance of batteries with different surfactants during resting are shown according to some embodiments disclosed herein. Figure 1 The results show that additive-free electrolytes typically require wetting times exceeding 4 hours, and using R according to some embodiments disclosed herein... f -Oligomers, wetting time shortened to ～ 2 hours.

[0019] Figure 2 Different Rs are shown according to some embodiments disclosed herein. f - Data on the initial capacity of oligomer batteries. R f -Oligomers have the same functional groups, but different backbone lengths (backbone length increases from left to right).

[0020] Figure 3 The following diagram illustrates embodiments of the invention having and not having R as disclosed herein. f - Data on the cycling performance of oligomers.

[0021] Figure 4 The following diagram illustrates embodiments of the invention having and not having R as disclosed herein. f - Data on the cycling performance of oligomers.

[0022] Figure 5 The cycling performance of NMC 532 batteries at a high cutoff voltage of 4.35 V and a rate of 0.5 C according to some embodiments disclosed herein is shown. (A) shows the capacity retention during cycling. (B) shows the coulombic efficiency during cycling. The blue dashed circles at ~70 cycles in (A) and (B) indicate the absence of R f - The oligomer initiates dendrite formation in the battery, followed by dendrite formation in subsequent cycles. The R used here... f - The oligomers are from DX1080.

[0023] Figure 6 The graphite anode and separator after 140 overcharge cycles are shown according to some embodiments disclosed herein. (A) shows the electrolyte without DX1080 additive, (B) shows the electrolyte with DX1080 additive. (C) shows a comparison of the separators after cycling. Top image: surfactant DX1080; Bottom image: without surfactant. (D) and (E). SEM images of the graphite anode after cycling. (D) without DX1080 additive, (E) with DX1080 additive. Detailed Implementation

[0024] According to some aspects, this disclosure provides oligomers with perfluoroalkyl groups terminated by perfluoroalkyl thiols and hydrophilic and / or hydrophobic monomers polymerized via free radical reactions, and their use in improving MIB performance.

[0025] According to some implementation schemes, perfluoroalkyl-terminated oligomers (R... f -Oligomers) are represented by the following formula I:

[0026] R f -E n -S-[M1] x [M2] y H(I)

[0027] Where R f It is a straight-chain or branched perfluoroalkyl group with 4-18 carbon atoms, a perfluoroalkoxyalkylene group with 5-19 carbon atoms, or a mixture thereof; E nIt is a straight-chain or branched alkylene group with 1-12 carbon atoms, -CON(R')-E'-, -SO2N(R')-E'-, -E”-CON(R')-E'-, -E”-S-E'-, -E”-N(R')-E'- or -E”-SO2N(R')-E'-, wherein R' is hydrogen or an alkyl group with 1-6 carbon atoms, E' is an alkylene group with 2-8 carbon atoms and E” is an alkylene group with 1-4 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; in some embodiments, the fluorocarbon surfactant contains more than one type of -M1-unit and more than one type of -M2-unit; and n is 0 or 1.

[0028] In some implementations, the above formula does not depict the actual sequence of oligomer units, because these units can be randomly distributed.

[0029] In some implementations, by using R in Formula II f - The oligomers disclosed herein are synthesized by polymerizing one or more hydrophilic monomers of type M1 in the presence or absence of one or more hydrophobic monomers of type M2 in the presence of thiols.

[0030] R f -E n -SH (II)

[0031] Where R f and E n As disclosed in this article.

[0032] R of Formula II f Thiols are particularly described in U.S. Patent 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 April 24, 1968, each of which is incorporated herein by reference as if set forth herein in its entirety.

[0033] Alternatively, a suitable R f Thiols can be used to make R f Acid halides such as R f SO2Cl or R f COCl can be readily prepared by reacting aminothiols, such as HN(R')-E'-SH, in an inert solvent.

[0034] In some embodiments, hydrophilic monomers of type M1 containing at least one hydrophilic group are known and commercially available, such as acrylic acid and methacrylic acid and their salts, as well as derivatives containing hydrophilic groups, such as their hydroxyalkyl esters, for example 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, or 2,3-hydroxypropyl esters; and ethoxylated and polyethoxylated hydroxyalkyl esters, such as those of formula HO-C m H 2m -O-(CH2-CH2-O) nEsters of alcohols with -R1, where R1 represents hydrogen or methyl, m represents 2-5 and n represents 1-20, or esters similar to alcohols in which a portion of the ethylene oxide unit is replaced by a propylene oxide unit. 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 with 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. Amines; hydrophilic monomers of further interest are hydrazine derivatives, such as trialkylamine methacryloimides, such as trimethylamine-methacryloimide and dimethyl-(2-hydroxypropyl)amine-methacryloimide, and corresponding derivatives of acrylic acid; monoolefin sulfonic acids and their salts, such as sodium vinyl sulfonate, sodium styrene sulfonate, and 2-acrylamido-2-methylpropanesulfonic acid; N-[2-(dimethylamino)-ethyl]acrylamide and methylacrylamide, N-[3-(dimethylamino)-2-hydroxypropyl] ]-Methacrylamide, or monoolefin derivatives of heterocyclic nitrogen-containing monomers such as N-vinylpyrrole, N-vinyl-succinimide, 1-vinyl-2-pyrrolidone, 1-vinyl-imidazolium, 1-vinyl-indole, 2-vinyl-imidazolium, 4(5)-vinyl-imidazolium, 2-vinyl-1-methyl-imidazolium, 5-vinyl-pyrazoline, 3-methyl-5-isopropenyl, 5-methylene-hydantoin, 3-vinyl-2-oxazolidinone, 3-methacrylamide 2-oxazolidinone, 3-methacryloyl-5-methyl-2-oxazolidinone, 3-vinyl-5-methyl-2-oxazolidinone, 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-acryloyl-morpholine, and quaternized derivatives of the above-mentioned pyridines.

[0035] In some implementations, the hydrophilic monomers of type M1 described above can be used alone or in combination with each other, as well as in combination with suitable hydrophobic monomers of type M2.

[0036] In some embodiments, the hydrophilic monomers required for the type M1 of polymerization are maleate, fumarate, and vinyl ether; for example, the following monomer combinations are useful: di(hydroxyalkyl)maleate, such as di(2-hydroxyethyl)maleate and ethoxylated hydroxyalkyl maleate; hydroxyalkyl monomaleate, such as 2-hydroxyethyl monomaleate and hydroxylated hydroxyalkyl monomaleate, with vinyl ether, vinyl ester, styrene, or generally any monomer that will readily copolymerize with maleate or fumarate; hydroxyalkyl vinyl ether, such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, with maleate, fumarate, or generally any monomer that will readily copolymerize with vinyl ether.

[0037] In some embodiments, the hydrophilic monomer of type M1 is acrylic acid, methacrylic acid, acrylamide, diethyl ketone acrylamide, acrylamide propanesulfonic acid and their salts, and hydroxyethyl methacrylate.

[0038] In some embodiments, the hydrophobic monomer of type M2 copolymerized with the hydrophilic monomer of type M1 is known and includes: acrylate, methacrylate, maleate, fumarate and itaconic acid, wherein the ester group has one or more carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, octadecyl, cyclohexyl, phenyl, benzyl and 2-ethoxyethyl;

[0039] Vinyl esters having 1 to 18 carbon atoms in their ester groups, such as vinyl acetate, butyrate, laurate, stearate, 2-ethylhexanoate, and benzoate; vinyl chloride acetate and isopropylene acetate, vinyl carbonate derivatives;

[0040] Styrene and substituted styrene such as o- and p-methyl, 3,4-dimethyl, 3,4-diethyl and p-chlorostyrene; α-olefins, including straight-chain and branched substituted α-olefins having up to 18 carbon atoms in the side chain, including ethylene, propylene and butene.

[0041] Methyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, 2-methoxyethyl vinyl ether, n-propyl vinyl ether, tert-butyl vinyl ether, isopentyl 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 ether;

[0042] Vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, methacrylonitrile, tetrafluoroethylene, trifluorochloroethylene, hexafluoropropylene;

[0043] Dienes, particularly 1,3-butadiene, isoprene and chlorobutadiene, 2-fluorobutadiene, 1,1,3-trifluorobutadiene, 1,1,2,3-tetrafluorobutadiene, 1,1,2-trifluoro-3,4-dichlorobutadiene and trifluoro and pentafluorobutadiene and isoprene.

[0044] In some implementations, the hydrophobic monomer of type M2 is a fluorinated monomer.

[0045] In some embodiments, thiols act as so-called chain transfer agents in free radical polymerization and copolymerization reactions. The previously listed hydrophilic monomers of type M1 and hydrophobic monomers of type M2 will homopolymerize and / or copolymerize in the presence of a free radical initiator, and thus readily react with R of formula II. f -Thiol reaction to form R of formula I in high yield. f -Oligomers.

[0046] In some embodiments, the polymerization reaction is carried out in a substantially anhydrous reaction medium, preferably in a lower alcohol such as methanol or isopropanol, or acetone or a lower cellosol, which dissolves the reactants and catalyst.

[0047] In some embodiments, the oligomerization reaction temperature is maintained between 20°C and 60°C, but temperatures up to 100°C can be used. The optimal temperature can be readily determined for each oligomerization reaction and will depend on the reaction, the relative reactivity of the monomers, and the specific feed-radical initiator used. In some embodiments, an oxygen-free atmosphere is desired to promote the free radical propagation required for efficient catalytic reaction, and the oligomerization reaction is carried out under nitrogen.

[0048] In some embodiments, the catalyst used must be a free radical initiator, such as a peroxide, persulfate, or azo compound. In some embodiments, organic peroxides and hydroperoxides, hydrogen peroxide, azo catalysts, and water-soluble persulfates are used. Specific examples include ammonium persulfate, lauroyl peroxide, tert-butyl peroxide, and especially azo catalysts 2,2'-azobis(isobutyronitrile); 2,2'-azobis(2,4-dimethylpentanonitrile); 2-tert-butylazo-2-cyanopropane; 1-tert-butylazo-1-cyanocyclohexane; and 2,2'-azobis(2,4-dimethyl-4-methoxypentanonitrile).

[0049] In some embodiments, a catalytic amount of initiator is used, i.e., depending on the specific initiator and monomer system, ranging from 0.01% to 0.5% by weight of the monomer. In some embodiments, an azo catalyst is used, comprising 0.01 to 0.2% by weight of the azo catalyst per monomer.

[0050] In some embodiments, R is synthesized from monomers of types M1 and M2 in the one-step polymerization reaction described above.f -Oligomers. However, R can also be synthesized in a two-step synthesis. f -Oligomers. In this alternative synthetic method, a hydrolyzable hydrophobic monomer of type M2 is made in the R of formula II. f Polymerization in the presence of thiols yields R containing -M2- monomer units. f -Oligomers. In the second step, this type of R... f - The oligomer is hydrolyzed with an alkali (preferably an alcohol-based sodium hydroxide or potassium hydroxide solution). During this hydrolysis, the selected -M2- monomer unit is converted into a hydrophilic -M1- monomer unit. In this way, the vinyl acetate monomer unit is converted into a vinyl alcohol monomer unit, or the maleate ester unit is converted into a maleate salt unit. Similarly, R containing maleic anhydride monomer units... f -Oligomers can be hydrolyzed or amidated.

[0051] In some implementations, the R of compound I f -Oligomers

[0052] R f -E n -S-[M1] x [M2] y H(I)

[0053] To balance R f The oleophobicity and hydrophobicity of the -ES- segment correspond to the hydrophilicity of the -M1- monomer unit and the hydrophobicity of the -M2- monomer unit in the oligomer. In some embodiments, more than one type of -M1- unit and more than one type of -M2- unit are present in the oligomer to achieve the desired performance balance. In some embodiments, it is not necessary to introduce hydrophobic -M2- monomer units to achieve a proper balance between oleophobic / hydrophobic and hydrophilic properties.

[0054] Furthermore, in some implementation schemes, R is changed f - The chain length of the group and the properties and ratio of the M1 and M2 monomer units are determined to achieve the desired performance. In some embodiments, R f - The oligomer achieves at least 0.01% by weight of R in water or a water-solvent mixture. f - Solubility of oligomers.

[0055] In some implementations, by changing the degree of polymerization, i.e., R f -ES segment and -[M1] x [M2] y The weight ratio of H-formed segments is used to select M1 and M2 type monomers. R f- The oligomer reduces the surface tension of aqueous systems to any desired level, down to 16 dynes / cm. In some implementations, R can be customized. f - An oligomer composition that provides any desired surface tension in water between 76 dynes / cm and about 16 dynes / cm. In some embodiments, this allows R to be used in applications requiring improved wettability and spreadability of liquids on difficult-to-wet substrates or substrates contaminated with oil or silicone. f -Oligomers.

[0056] In some implementations, R of Formula I f -Oligomers

[0057] R f -E n -S-[M1] x [M2] y H(I)

[0058] R of various forms II f -Thiols

[0059] R f -E n -SH(II)

[0060] Preparation of a large number of commercially available monomers of the M1 and M2 types as defined in this paper.

[0061] In some implementation schemes, R f It is a perfluoroalkyl group having 6-14 carbon atoms.

[0062] E is an alkylene group, preferably an ethylene group.

[0063]

[0064] Where 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;

[0065] T2 is -OH; -OE2OR1; -(OE1) n OR1; -SO3Me; -C6H4SO3Me;

[0066]

[0067] Pyridium halides, -NHCOR1, -NH2

[0068] T3 and T4 are independently -COOMe; -CONH2; -CO(OE1). n OR1;-CONH-E1-OH;-CON(E1-OH)2

[0069] R1 is hydrogen or methyl

[0070] R2, R3, and R4 are independently alkyl groups having 1-6 carbon atoms.

[0071] E1 is an alkylene group having 2 or 3 carbons.

[0072] E2 is an alkylene group having 2-6 carbon atoms.

[0073] Me is hydrogen or an alkali metal.

[0074] X is a halogen and

[0075] n is 1-20

[0076]

[0077] Where G1 is -COOR5; -OCOR2; -CN; -OR5; -C6H5; -C6H4X

[0078] G2 is -H, R2, or a halogen.

[0079] G3 and G4 are independently -COOR5 or can be combined to form -CO-O-CO-

[0080] R1, R2, and X are as defined above.

[0081] R5 is an alkyl or cycloalkyl group having 1-18 carbons, an aryl group, or an alkenyl group having 6-18 carbons.

[0082] The sum of x and y is between 4 and approximately 500; and x / (x+y) is between 0.5 and 1.

[0083] In some implementations, 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 0.5-1.

[0084] In some implementation schemes, R f -Oligomers have a structure R f -ES-[M1] x H, where R f It is a straight-chain perfluoroalkyl group with 6-12 carbon atoms.

[0085] E is -CH2CH2-

[0086]

[0087] And x is 4-50.

[0088] In some implementations, R is used as an electrolyte additive. f - The oligomer has the structure listed above. f -ES-[M1] x H, where -M1- is

[0089]

[0090] And x changes from 10 to 50.

[0091] According to some embodiments, the electrolyte additive comprises one or more compounds selected from Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25. According to some embodiments, the electrolyte additive comprises one or more commercial products, such as DX1080 or DX1090 (Dynax). In some embodiments, the commercial product, such as DX1080 or DX1090, is added to the electrolyte after drying. Drying includes heating the product in a vacuum oven until a constant weight is reached.

[0092] In some embodiments, the electrolyte additives disclosed herein are represented by a structure having repeating units, where an integer represents the number of repeating units. See Examples. Those skilled in the art will understand that this integer is an average value determined by the stoichiometry between the thiol and the polymerizable monomer. The resulting oligomers are not composed of a single, defined molecular weight, but rather a molecular weight distribution centered around the average value.

[0093] In some implementations, the electrolyte additive comprises:

[0094]

[0095] Where n is an integer between 1 and 40;

[0096] In some implementations, the electrolyte additive includes one or more of the following:

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] The R disclosed in this article f - Uses of oligomers in the electrolyte of MIB

[0103] According to some aspects, the R disclosed in this article f -Oligomers can be used as additives in the electrolyte of MIBs (e.g., lithium-ion batteries). In some embodiments, R f - The 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. In some embodiments, R f - The oligomer is present in the electrolyte in an amount of about 0.001% to 5% by weight of the electrolyte. In some embodiments, R f - The oligomer is present in the electrolyte in an amount of about 0.01% to 2% by weight of the electrolyte. In some embodiments, R f - The oligomers are present in the electrolyte in an amount of about 0.05% to 1% by weight of the electrolyte.

[0104] In some implementations, the R disclosed herein is added to the electrolyte. f - The oligomers are selected from the following groups: polyethylene oxide, amphoteric / amphoionic, anionic, cationic, nonionic, acrylamide oligomers, acrylamide co-oligomers, N-vinylpyrrolidone oligomers, phosphates, sulfonates, and combinations thereof. In some embodiments, the R disclosed herein is added to the electrolyte. f -Oligomers include PEG-containing units, PPG-containing units, polyacrylic acid-containing units, polyacrylamide-containing units, and PVA-containing units. In some such embodiments, the R disclosed herein is added to the electrolyte. f - Each oligomer molecule 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 units.

[0105] In some implementations, the R disclosed herein is added to the electrolyte. f - The oligomer includes acrylamide units. In some embodiments, the R disclosed herein is added to the electrolyte. f - Each molecule of the oligomer includes 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.

[0106] Electrolyte salts

[0107] In some embodiments, the electrolytes disclosed herein comprise salts that readily dissolve or dissociate 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-)2, where R can be methyl, alkyl, halomethyl, or ethyl; Mg(B(C2O4)2)2; Mg(BOB)2; magnesium titanate@superoxide magnesium titanate; magnesium titanate (MgTiO3); magnesium disitinate (MgTi2O5), [Mg(L... x [Al(ORF)4]2x = 3, 6L = (L = MeCN (acetonitrile), DME (1,2-dimethoxyethane), (ORF = OCCF3); Mg[B(hfip)4]2, Mg[B(tftb)4]2, wherein hexafluorotertiary isopropoxy is (hfip) and trifluorotertiary 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 described herein for magnesium salts, but magnesium is replaced by trivalent aluminum. In some embodiments, the aluminum salt is 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.

[0108] Electrolyte solvent

[0109] In some embodiments, the electrolyte comprises an organic solvent having high solubility and low viscosity for one or more salts to facilitate ion movement. In some embodiments, the electrolyte comprises an organic solvent having high solubility and low viscosity for lithium salts to facilitate lithium ion movement. 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 solvent comprises ethylene carbonate, propylene carbonate, and combinations thereof. In some embodiments, the solvent comprises pyrocarbonate, such as dialkyl pyrocarbonate used directly or added to a mixture of dialkyl carbonates to better control CO2 evolution. In some embodiments, the solvent comprises an ether solvent. In some embodiments, the solvent comprises one or more of the following: 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 an LP50 electrolyte: 1M LiPF6 in ethylene carbonate (EC)-ethyl methyl carbonate (EMC) (v / v = 1:1).

[0110] Other additives

[0111] In some implementations, the electrolyte, in addition to R disclosed herein, fIn addition to oligomers, additives are also included. In some embodiments, the additives are substances that protect 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 includes surfactants, SEI-forming additives, viscosity-modifying materials, materials that help dissolve salts, and combinations thereof. In some embodiments, the electrolyte includes cathodic protection agents, such as butylamine, N,N'-dicyclohexylcarbodiimide (DCI), lithium bis(oxalate-based)borate (LiBOB), and combinations thereof. In some embodiments, the electrolyte includes LIPF6 salt stabilizer additives, such as tris(2,2,2-trifluoroethyl phosphite) (TTFP), 1-methyl-2-pyrrolidone, hexamethylphosphoramide, and combinations thereof. In some embodiments, the electrolyte includes overcharge protection additives, such as bipyridyl carbonate, diphenyl carbonate, difluoroanisole, thiathracene, 2,7-diacetylthiathracene, and combinations thereof. In some embodiments, the electrolyte contains a flame-retardant additive, such as trimethyl phosphate. In some embodiments, the electrolyte contains a lithium deposition modifier, such as hexadecyltrimethylammonium chloride. In some embodiments, the electrolyte contains an ion solvation enhancer, such as tris(pentafluorophenyl)borane (TPFPB). In some embodiments, the electrolyte contains an Al corrosion inhibitor, such as lithium bis(oxalate-based)borate (LiBOB).

[0112] Battery

[0113] According to some aspects, the present invention provides an ion battery comprising a casing and a cell. The cell includes an anode, a cathode, and a separator, each in contact with an electrolyte. In some embodiments, the negative electrode (anode) is made of graphite carbon, and the positive electrode (cathode) is made of layered oxides (e.g., lithium cobalt oxide), polyanionic oxides (e.g., lithium iron phosphate), or spinel (e.g., lithium manganese oxide). In some embodiments disclosed herein, the cathode electrode is polycrystalline LiNi. 0.5 Mn 0.3 Co 0.2 O2 (NMC532) 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 that effectively prevents atmospheric and / or moisture from contacting the cell / electrolyte.

[0114] The R disclosed in this article f - The impact of oligomers on battery performance

[0115] According to some implementation schemes, the R disclosed in this article will be... f - Oligomers are added to the electrolyte to improve one or more of the following issues related to battery performance: dendrite formation, battery life, initial capacity, capacity decay, and wetting time. In some embodiments, the R disclosed herein... f - Oligomers can also have a positive impact on battery performance at temperatures above or below room temperature.

[0116] Wetting time:

[0117] According to some implementation schemes, the R disclosed in this paper f -Oligomers effectively reduce the wetting time of the electrolyte when in contact with battery components. In some embodiments, with no R f -The wetting time of the oligomer with the same electrolyte, compared to that of the R disclosed herein. f - The wetting time of the oligomer electrolyte is reduced by about 1% to about 80%. 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%. Wetting time is defined as the time it takes for the electrolyte resistance to plateau after electrolyte injection. See, for example... Figure 1 .

[0118] Initial capacity:

[0119] In some implementations, the R disclosed herein f -Oligomers effectively increase the initial capacity of the battery when added to the electrolyte. Initial capacity is defined as the capacity during the first cycle. In some embodiments, the R disclosed herein... f -Oligomers effectively increase the initial capacity of MIBs by about 1% to about 50%. In some embodiments, the R disclosed herein... f - The oligomer effectively increases 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%.

[0120] In some implementations, the R disclosed herein f -Oligomers effectively increase the initial capacity of MIBs comprising high-porosity and / or low-porosity electrodes. In some embodiments, the R disclosed herein... f -Oligomers effectively increase the initial capacity of MIBs comprising both monocrystalline and polycrystalline electrodes. In some embodiments, the R disclosed herein... f -Oligomers effectively increase the content of polycrystalline LiNi 0.5 Mn 0.3 Co 0.2 The initial capacity of the battery with an O2 electrode. In some embodiments, the R disclosed herein... f-Oligomers effectively enable the inclusion of polycrystalline LiNi 0.5 Mn 0.3 Co 0.2 The initial capacity of the battery with the O2 electrode increased from 4.75 Ah to approximately 5.25 Ah. In some embodiments, the R disclosed herein... f -Oligomers effectively enable the inclusion of single-crystal LiNi 0.5 Mn 0.3 Co 0.2 The initial capacity of the battery with the O2 electrode increased from 4.2 Ah to 5.0 Ah.

[0121] Cycle stability / battery life:

[0122] In some implementations, when contained in an electrolyte, the R disclosed herein f -Oligomers effectively improve cycle stability and battery life. As used herein, the term "cycle" refers to the process of charging and discharging a battery to determine how well it retains its charge capacity throughout a number of cycles. In some embodiments, a charge-discharge rate of 0.5C is used to evaluate cycle stability. In some embodiments, the R disclosed herein... f - The oligomer effectively maintains at least 90% of its 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 R disclosed herein... f - The oligomers effectively maintain at least 95% 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.

[0123] Dendrite suppression:

[0124] In some implementations, when added to the electrolyte, the R disclosed herein... f -Oligomers effectively reduce dendrite formation. In some embodiments, when the battery is operating under overcharge conditions, the R disclosed herein, when added to the electrolyte, f -Oligomers effectively reduce dendrite formation. In some embodiments, the R disclosed herein... f -Oligomers effectively reduce dendrite formation.

[0125] Example

[0126] Battery test

[0127] Battery testing was conducted using the following procedure to test improvements in the identified target performance areas:

[0128] Electrodes and electrolytes used:

[0129] The positive electrode used in this experiment is 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). Two types of positive electrodes were tested here. The anode electrode used in this experiment was graphite for all batteries. Before assembling the batteries, all electrodes were baked in a vacuum at 80°C for 48 hours to remove moisture.

[0130] An electrolyte solution containing a fluorinated surfactant as disclosed herein is mixed in a glove box and then added to a blank battery. The battery is then sealed and removed from the glove box for cycling at constant pressure.

[0131] The final batteries typically have a capacity of approximately 5 Ah. The electrolyte used is a standard LP50 electrolyte: 1 M LiPF6 in ethylene carbonate (EC)-ethyl methyl carbonate (EMC) (v / v = 1:1), and approximately 20 mL is used per battery. Unless otherwise specified, the surfactants used in this test are 0.5 wt% of the electrolyte activity. All surfactants were dissolved after stirring at 50°C for 48 hours. All batteries were vacuum-sealed in bags at a pressure of -970 mbar and a temperature of 180°C.

[0132] Wetting time:

[0133] All batteries undergo the same wetting procedure. After assembly, the batteries are left to stand at room temperature for 10 hours to monitor voltage and internal resistance fluctuations. Stable voltage and stable internal resistance indicate that wetting has reached a stable or metastable state. The batteries are then treated with an elevated temperature (40°C) for 48 hours to achieve better wetting, followed by aging at 0.05C for 4 hours, and then at 0.1C for 4 hours. After aging, the pouch cells are cut open to release the gas formed during aging, and ~3 mL of electrolyte is added to replenish the electrolyte consumed during aging. Finally, the batteries are resealed and left to stand at room temperature for 6 hours before cycle testing.

[0134] Initial capacity:

[0135] After a resting and aging process, all cells were cycled at 0.5C. Initial capacity is defined as the capacity of the first cycle. These data reflect the electrode wetting condition, as better wetting leads to more electrode material reaction and thus greater capacity. As described below, the results show that the surfactants disclosed herein can significantly improve wetting conditions. For polycrystalline LiNi 0.5 Mn 0.3 Co 0.2The initial capacity of the O2 electrode can be increased from 4.75 Ah to ~5.25 Ah; for single-crystal LiNi... 0.5 Mn 0.3 Co 0.2 O2 wetting is more difficult than with polycrystalline materials because monocrystalline NMC721 electrodes have a much higher cathode density and therefore lower porosity. Therefore, the improvement is more significant: the initial capacity increases from 4.2 Ah to 5.0 Ah.

[0136] Cycle stability / battery life:

[0137] Cycle stability was evaluated using a charge / discharge rate of 0.5C. Wetting is crucial for cycle performance in batteries because induced electrolyte consumption and uneven distribution during cycling are major causes of capacity decay. The results show that significantly improved cycle stability was achieved when a surfactant was used. Detailed results are presented below.

[0138] Dendrite suppression:

[0139] Under normal operating conditions, dendrites are generally not prone to form in lithium-ion batteries, but they are more likely to form under overcharge conditions. To avoid dendrite formation, the anode / cathode capacity ratio is typically set to ~1.1. This is typical for the battery tests disclosed herein. To evaluate the dendrite suppression effect, an upper cutoff voltage of 4.35V was set for a poly NMC532 battery, which contributed nearly 20% additional capacity and promoted dendrite formation.

[0140] Test Summary:

[0141] For testing, various oligomers between 0.1% and 5% by weight are added to selected electrolytes and battery devices. Battery performance is then evaluated to assess its ability to overcome problems associated with metal-ion batteries. The results are compared to blank samples containing none of the various oligomers.

[0142] The surfactants disclosed herein have been found to address the following issues: dendrite suppression, battery life, initial capacity, capacity decay, wetting time, and low / high temperature operation.

[0143] Preparation of surfactants

[0144] The following provides the R disclosed in this article. f - Some representative examples of oligomer synthesis.

[0145] Example 1

[0146] Perfluorothiol-(AA)4 oligomers

[0147]

[0148] At room temperature, acrylamide (33.7 g, 0.47 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluorooctane-1-thiol (45.0 g, 0.12 mol), and 2-propanol (300 mL) as solvent were added to a 500 mL glass vial. The mixture was stirred to dissolve, 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 the solution was purged with nitrogen again for 10 minutes. The vial 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 crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2–3 days, and then dried overnight (17 h) in an oven at 50 °C to obtain a white powder (49.1 g, 63.2%).

[0149] Example 2

[0150] Perfluorothiol-(AA)6 oligomers

[0151]

[0152] At room temperature, acrylamide (50.5 g, 0.71 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluorooctane-1-thiol (1) (45.0 g, 0.12 mol), and 2-propanol (300 mL) as solvent were added to a 500 mL glass bottle. The mixture was stirred to dissolve it, 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 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 1L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2-3 days, and then dried overnight (17h) in an oven at 50°C to obtain a white powder (71.4g, 74%).

[0153] Using the procedures outlined in Examples 1 and 2, with only the stoichiometry of acrylamide differing, the following oligomers were prepared:

[0154] Example # monomer Oligomeric (n) Yield (%) 3 <![CDATA[CH2CHCONH2]]> 8 84.9 4 <![CDATA[CH2CHCONH2]]> 9 85.3 5 <![CDATA[CH2CHCONH2]]> 12 86.0 6 <![CDATA[CH2CHCONH2]]> 15 88.6 7 <![CDATA[CH2CHCONH2]]> 20 91.5 8 <![CDATA[CH2CHCONH2]]> 30 93.6

[0155] Example 9

[0156] 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-heptadecanethiol, and the stoichiometric ratio of acrylamide to the above thiol was 15:1.

[0157]

[0158] At room temperature, acrylamide (24.4 g, 0.34 mol), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecanethiol (11.0 g, 0.02 mol), and 2-propanol (200 mL) as a solvent were added to a 500 mL glass vial. The mixture was stirred to dissolve, 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 the solution was purged with nitrogen again for 10 minutes. The vial 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 1L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2-3 days, and then dried overnight (17h) in an oven at 50°C to obtain a white powder (31.6g, 89.2%).

[0159] Example 10

[0160] dodecylthiol hydrocarbon acrylamide oligomer

[0161]

[0162] At room temperature, acrylamide (74.6 g, 1.05 mol), dodecyl mercaptan (14.2 g, 0.07 mol), and 2-propanol (200 mL) as solvent were added to a 500 mL glass vial. The mixture was stirred to dissolve, and then purged with nitrogen for 10 minutes. Vazo-52 (0.6 g, 0.002 mol) was added to the mixture, and the solution was purged with nitrogen again for 10 minutes. The vial 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 crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2–3 days, and then dried overnight (17 h) in an oven at 50 °C to obtain a white powder (76.9 g, 85.4%).

[0163] Example 11

[0164] Preparation of perfluorothiol-acrylamide (AA)-acrylic acid (GAA) coolidomers

[0165] Perfluorothiol-(AA)4(GAA)4 coolidomer

[0166]

[0167] To a 250 mL glass bottle at room temperature, add 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-tridecylfluorooctane-1-thiol (1) (9.20 g, 0.02 mol), and methanol (200 mL) as solvent. Stir the mixture to dissolve it, then purge the solution with nitrogen for 10 minutes. Add Vazo-52 (0.6 g, 0.002 mol) to the mixture, then purge the solution with nitrogen for another 10 minutes. Seal the glass bottle and transfer it to a water bath at 70–75 °C. Maintain the reaction at 80–85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2-3 days, and then dried overnight (17h) in an oven at 50°C to obtain a white powder (21.5g, 94%).

[0168] Example 12

[0169] Preparation of perfluorothiol-acrylamide (AA)-acrylic acid (GAA) coolidomers

[0170] Perfluorothiol-(AA)8(GAA)1 coolidomer

[0171]

[0172] At room temperature, 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-tridecylfluorooctane-1-thiol (1) (4.0 g, 0.1 mol), and 2-propanol (250 mL) as solvent were added to a 500 mL glass bottle. The mixture was stirred to dissolve it, 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 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 maintained at 80–85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2-3 days, and then dried overnight (17h) in an oven at 50°C to obtain a white powder (67.2g, 94%).

[0173] Example 13

[0174] Preparation of perfluorothiol-acrylamide (AA)-acrylic acid (GAA) coolidomers

[0175] Perfluorothiol-(AA) 14 (GAA)1 coolidomers

[0176]

[0177] At room temperature, 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-tridecylfluorooctane-1-thiol (1) (28 g, 0.07 mol), and 2-propanol (250 mL) as a solvent were added to a 500 mL glass bottle. The mixture was stirred to dissolve it, 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 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 maintained at 80–85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2-3 days, and then dried overnight (17h) in an oven at 50°C to obtain a white powder (100.2g, 94%).

[0178] Example 14

[0179] Preparation of perfluorothiol-acrylamide (AA)-acrylic acid (GAA) coolidomers

[0180] Perfluorothiol-(AA)4(GAA)1 coolimer

[0181]

[0182] At room temperature, 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-tridecylfluorooctane-1-thiol (1) (30 g, 0.08 mol), and 2-propanol (250 mL) as a solvent were added to a 500 mL glass bottle. The mixture was stirred to dissolve it, 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 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 maintained at 80–85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2-3 days, and then dried overnight (17h) in an oven at 50°C to obtain a white powder (43.4g, 73%).

[0183] Example 15

[0184] Preparation of perfluorothiol-acrylamide (AA)-acrylate (GAA) coolidomers

[0185] Perfluorothiol-(AA)4(MA)1 coolimer

[0186]

[0187] At room temperature, 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-tridecylfluorooctane-1-thiol (1) (30 g, 0.08 mol), and 2-propanol (250 mL) as solvent were added to a 500 mL glass bottle. The mixture was stirred to dissolve it, 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 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 maintained at 80–85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2-3 days, and then dried overnight (17h) in an oven at 50°C to obtain a white powder (49.9g, 73%).

[0188] Example 16

[0189] Preparation of perfluorothiol-acrylamide (AA)-acrylate (GAA) coolidomers

[0190] Perfluorothiol-(AA)4(BA)1 coolimer

[0191]

[0192] At room temperature, 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-tridecylfluorooctane-1-thiol (1) (30 g, 0.08 mol) and 2-propanol (250 mL) as solvent were added to a 500 mL glass bottle. The mixture was stirred to dissolve it, 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 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 maintained at 80–85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2-3 days, and then dried overnight (17h) in an oven at 50°C to obtain a white powder (43.1g, 68%).

[0193] Example 17

[0194] Preparation of perfluorothio-acrylamide (AA)-perfluoromethacrylate (PFMA) coolidomers

[0195] Perfluorothiol-(AA)4(PFMA)1 coolidomer

[0196]

[0197] At room temperature, acrylamide (8.23 g, 0.12 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluorooctyl-2-methacrylate (12.5 g, 0.03 mol, PFMA), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluorooctane-1-thiol (1) (11 g, 0.03 mol) and 2-propanol (200 mL) as solvent were added to a 500 mL glass bottle. The mixture was stirred to dissolve it, 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 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 maintained at 80–85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2-3 days, and then dried overnight (17h) in an oven at 50°C to obtain a white powder (22.2g, 70%).

[0198] Example 18

[0199] Preparation of perfluorothioacrylamide (AA)-perfluoromethacrylate (PFMA) coolidomers

[0200] Perfluorothiol-(AA) 14 (PFMA)1 coolidomer

[0201]

[0202] At room temperature, acrylamide (28.81 g, 0.12 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluorooctyl-2-methacrylate (12.5 g, 0.03 mol, PFMA), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluorooctane-1-thiol (1) (11.0 g, 0.03 mol) and 2-propanol (200 mL) as solvent were added to a 500 mL glass bottle. The mixture was stirred to dissolve it, 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 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 maintained at 80–85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1 L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2-3 days, and then dried overnight (17 h) in an oven at 50 °C to obtain a white powder (42.7 g, 82%).

[0203] Example 19

[0204] Preparation of perfluorothiol-based poly(N-vinyl-2-pyrrolidone) (PV2P) oligomers

[0205] Perfluorothiol-(PV2P)4 oligomers

[0206]

[0207] At room temperature, N-vinyl-2-pyrrolidone (58.5 g, 0.53 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluorooctane-1-thiol (1) (50 g, 0.13 mol), and 2-propanol (300 mL) as solvent were added to a 500 mL glass bottle. The mixture was stirred to dissolve it, 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 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 maintained at 80–85 °C for 2 hours. The reaction mixture was removed from the water bath and transferred to a 1L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 2-3 days, and then dried overnight (17h) in an oven at 50°C to obtain a white powder (101.8g, 94%).

[0208] Using these conditions, the following series of N-vinyl-2-pyrrolidone oligomers were prepared.

[0209] Example # monomer Oligomeric (n) Quantity (g) Yield (%) 20 N-Vinyl-2-pyrrolidone 8 61.4 92.0 21 N-Vinyl-2-pyrrolidone 14 102 99.9 22 N-Vinyl-2-pyrrolidone 30 68.2 87.2 23 N-Vinyl-2-pyrrolidone 40 67.5 88.6

[0210] Example 24

[0211] Preparation of oligomers of perfluorothiol poly(1-propanesulfonic acid), 2-methyl-2-[(1-oxo-2-propen-1-yl)amino]-, sodium salt (AMPS)

[0212] Perfluorothiol-(AMPS)4 oligomers

[0213]

[0214] At room temperature, 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-tridecylfluorooctane-1-thiol (1) (32 g, 0.08 mol), and 2-propanol (300 mL) as solvent were added to a 500 mL glass bottle. 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 purged with nitrogen again for 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 1L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 5-6 days, and then dried overnight (48h) in an oven at 50°C to obtain a white powder (17.5g, 17.4%).

[0215] Example 25

[0216] Preparation of oligomers of perfluorothiol poly(1-propanesulfonic acid), 2-methyl-2-[(1-oxo-2-propen-1-yl)amino]-, sodium salt (AMPS)

[0217] Perfluorothiol-(AMPS) 14 oligomers

[0218]

[0219] At room temperature, 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-tridecylfluorooctane-1-thiol (1) (32 g, 0.08 mol), and 2-propanol (300 mL) as solvent were added to a 500 mL glass bottle. 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 purged with nitrogen again for 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 1L crystallizing dish to allow the solvent to evaporate in a fume hood at room temperature for 5-6 days, and then dried overnight (48h) in an oven at 50°C to obtain a white powder (27.1g, 10%).

[0220] Tested battery

[0221] Two types of cathodes were used 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 O2 (NMC 721). The anode remains unchanged (anode name and type: lithium-intercalated graphite), the same as the general electrolyte (LD50 from Gotion).

[0222] The following are the tested R versions disclosed in this paper. f - A list of all categories / families of oligomers:

[0223] Polyethylene oxide

[0224] R f -Lithium salts of oligomers

[0225] Amphoteric / Amphoteric Ions

[0226] Acrylamide oligomers

[0227] Acrylamide co-oligomers

[0228] N-vinylpyrrolidone oligomers

[0229] phosphate

[0230] sulfonates

[0231] cation

[0232] Blend of anionic, cationic, and nonionic compounds

[0233] The following is a list of the four performance parameters used for evaluation:

[0234] Wetting time

[0235] Initial capacity

[0236] Capacity retention

[0237] Dendrite suppression

[0238] Wetting time in LIB

[0239] Electrochemical impedance spectroscopy (EIS) is used to test changes in the internal resistance of a battery. After electrolyte is injected, the internal resistance changes as the electrolyte permeates. When the electrodes are completely wetted, the resistance reaches equilibrium.

[0240] like Figure 1 As shown, the effects of several electrolyte formulations on reducing wetting time were tested. LP50 electrolyte alone (black square) was used as a control, and it and LP50 were compared with combinations of DuPont Zonyl FSA (red circle), 3MFC-4430 (blue triangle), the compound according to Example 2 (1%), and the compound according to Example 6 (1%). The data showed that the radius of curvature of the LP50 control was much larger than when mixed with the compounds according to Examples 2 or 6. This is evident in the shape of the curves from 0 min to ~240 min after injection. It can be seen that when the electrolyte includes the compounds of Examples 2 or 6, the electrolyte resistance reaches a plateau significantly faster, resulting in a reduced observed radius of curvature. Furthermore, the observed radii of curvature of Examples 2 and 6 (containing acrylamide oligomers) were also significantly smaller than those of the electrolytes containing DuPont Zonyl FSA and 3MFC-4430 (non-acrylamide). Specifically, for Examples 2 and 6, the observed electrolyte resistance plateaued approximately 2 hours after injection, while for 3M FC-4430, the observed electrolyte resistance plateaued approximately 4 hours later.

[0241] Initial capacity

[0242] like Figure 2 As shown, different R values ​​with the same functional groups but different skeleton lengths were tested. f -Oligomers, the R f - The oligomers contain acrylamide units, and the tests were conducted in a cell (NMC 532 cell) containing a nickel, manganese, and cobalt polycrystalline cathode. All surfactants showed significantly improved initial capacity (~5.2 Ah), indicating that the better wetting provided by the surfactants activated more electrode material. For comparison, no R... f - The oligomer battery has a capacity of ~4.75Ah ( Figure 2 Surfactants exhibit a "smile" curve, indicating that molecules with shorter and longer backbone lengths have better properties. Figure 2 Table 1 below will... Figure 2 R referenced in the graph f - The oligomer is associated with the number of target acrylamide units per molecule.

[0243] Table 1

[0244] Number of target acrylamide units per molecule fluorosurfactant reference in graphics 4 Example 1 6 Example 2 8 Example 3 9 Example 4 12 Example 5 15 Example 6 20 Example 7 30 Example 8

[0245] Cycle stability / battery life

[0246] like Figure 3 and Figure 4 As shown, the cycling stability of electrolyte LP50 alone or in combination with the compounds of Examples 1 or 6 was tested for 500 cycles. After 500 cycles, the R... f -Oligomers can significantly improve the maintenance of battery capacity. For example... Figure 4 As shown, the battery with only LP50 electrolyte experienced a capacity decrease from 4.32 Ah to 3.66 Ah after 500 cycles, equivalent to retaining 85% of its capacity. In contrast, the R battery with the electrolyte from Example 1... f The battery capacity of the oligomeric electrolyte decreased from 5 Ah to 4.75 Ah, equivalent to retaining 95% of the capacity. Similarly, R with Example 6... f The capacity of the battery with the oligomeric electrolyte decreased from 4.86 Ah to 4.44 Ah, representing a retention of 91% of the capacity. Therefore, the R disclosed herein... f - The oligomer effectively maintained 95-91% of the initial battery capacity, while the control only maintained 85% of its initial capacity. It was also noted that when R from Examples 1 and 6 was present... f - When oligomers are used, the initial battery capacity increases. Figure 3 and Figure 4 The data is summarized in Table 2 below.

[0247] Table 2

[0248]

[0249] The capacity retention of other embodiments relative to the LP50 control was tested according to the above scheme, and the results are summarized as follows:

[0250] Example # Capacity retention Solubility in electrolytes Example 14 average soluble Example 15 average soluble Example 16 average soluble Example 17 average soluble Example 18 average soluble Example 20 Good (but lower than Example 1) Poor solubility Example 22 Good (but lower than Example 1) Poor solubility Example 23 Good (but lower than Example 1) Poor solubility

[0251] Examples with “average” capacity retention have similar capacity retention after 500 cycles compared to electrolyte-only. Examples with “good” capacity retention have higher capacity retention after 500 cycles compared to electrolyte-only, but are not as advantageous as Example 1.

[0252] Dendrite suppression

[0253] like Figure 5 As shown, dendrite suppression performance was evaluated based on electrochemical data and SEM images. This was achieved using R... f The evaluation was performed using dried DX1080 composed of oligomers. The DX1080 was dried by heating in a vacuum oven until a constant weight was reached.

[0254] Battery cycle performance

[0255] NMC 532 polycrystalline cells were tested using a high cutoff voltage of 4.35V and a rate of 0.5C. In the control group, the cells exhibited typical dendrite formation behavior and a sharp capacity drop after approximately 70 cycles. Figure 5 A). This sharp capacity decay can be attributed to the formation of dendrites, which typically leads to dead lithium and significant lithium-ion loss. Correspondingly, the coulombic efficiency (defined as the ratio of battery charge output to charge input) is observed to begin fluctuating around 70 cycles and fall below 100%. Figure 5 B). This evidence suggests that lithium dendrites formed on the graphite anode during cycling under overcharge conditions.

[0256] In contrast, the batteries with surfactants exhibited stable cycling performance. Capacity retention after 67 and 140 cycles was 86.4% and 75.6%, respectively, significantly higher than the control group's 84.1% and 50.46% (Table 3).

[0257] Table 3. Comparison of battery cycles with and without surfactants.

[0258]

[0259] More importantly, the coulombic efficiency remained stable at around 100%, indicating that no dead lithium formed under this high cutoff voltage. This result demonstrates that surfactants can effectively prevent the formation of lithium dendrites under overcharge conditions.

[0260] Characterization of graphite anode

[0261] To further confirm that the surfactant can inhibit dendrite growth, the graphite anode was characterized after cycling. Figure 6 As shown in Figure A, without the use of surfactants, a significant amount of dead lithium was found deposited on the separator and graphite. Dead lithium is also highly flammable and can spontaneously combust when exposed to air, indicating that point-like dead lithium is responsible for capacity decay. Conversely, with the use of surfactants, the graphite electrodes and separator were much cleaner, indicating that dead lithium / lithium dendrites were mitigated under overcharge conditions. Figure 6 These results were further validated by SEM images, in which the electrode with surfactant showed better performance than the electrode without surfactant (BC). Figure 6 D) A much flatter surface Figure 6 E).

[0262] These electrochemical results and characterizations demonstrate that the Rf-oligomers present in DX1080 can effectively suppress dendrite growth.

[0263] All references cited in this application are incorporated herein by reference as if they were recorded in their entirety herein.

[0264] Although exemplary embodiments of the present disclosure have been described herein, it should be understood that the present disclosure is not limited to those described, and 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. An electrolyte for an ion battery, comprising: Electrolyte salts; Solvent; and At least one fluorocarbon surfactant according to Formula I: R f -E n -S-[M1] x [M2] y H(I) Where R f It is a straight-chain or branched perfluoroalkyl group with 4-18 carbon atoms, a perfluoroalkoxyalkylene group with 5-19 carbon atoms, or a mixture thereof; E n It is a straight-chain or branched alkylene group with 1-12 carbon atoms, -CON(R')-E'-, -SO2N(R')-E'-, -E”-CON(R')-E'-, -E”-S-E'-, -E”-N(R')-E'- or -E”-SO2N(R')-E'-, wherein R' is hydrogen or an alkyl group with 1-6 carbon atoms, E' is an alkylene group with 2-8 carbon atoms and E” is an alkylene group with 1-4 carbon atoms; [M1] represents a hydrophilic monomer unit derived from a hydrophilic monomer of type M1; and [M2] represents a hydrophobic monomer unit derived from a hydrophobic monomer of type M2; Wherein M1 is optionally a monomer of more than one type and M2 is optionally a monomer of more than one type; The sum of x and y is between 1 and approximately 500; x / (x+y) is between 1 and 0.5; and n is 0 or 1.

2. The ion battery electrolyte according to claim 1, wherein the at least one fluorocarbon surfactant according to formula I constitutes about 0.1 wt% to about 5 wt% of the electrolyte.

3. The ion battery electrolyte according to claim 1, wherein M1 is an acrylamide unit.

4. The ion battery electrolyte according to claim 1, wherein the electrolyte salt is an electrolyte lithium salt.

5. The ion battery electrolyte according to claim 4, wherein the electrolyte lithium salt is selected from LiClO4, LiPF6, LiBF4, LiCF3SO3, LiN(CF3SO2)2 or a combination thereof.

6. The ion battery electrolyte according to claim 1, wherein the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.

7. The ion battery electrolyte according to claim 1, wherein the electrolyte comprises one or more compounds selected from the compounds of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 and 25.

8. The ion battery electrolyte according to claim 1, wherein the electrolyte comprises one or more of DX1080 and DX1090.

9. An ion battery, comprising: The casing, which contains the battery cell; and An electrolyte is disposed in the housing, wherein the battery cell is in contact with the electrolyte; The electrolyte is the ion battery electrolyte according to claim 1.

10. The ion battery according to claim 9, wherein the ion battery is a lithium-ion battery.

11. The ion battery according to claim 10, wherein the lithium salt is selected from LiClO4, LiPF6, LiBF4, LiCF3SO3, LiN(CF3SO2)2 or a combination thereof.

12. 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. A method for improving the performance of a metal-ion battery, comprising the step of contacting the metal-ion battery with an ion battery electrolyte according to claim 1.

14. The method of claim 13, wherein the improved performance includes improved charge capacity of the metal-ion battery and reduced degradation during charge and discharge cycles.

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

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

17. The method according to claim 13, wherein the metal-ion battery is a lithium-ion battery.

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

19. The method according to claim 18, wherein the metal-ion battery is a lithium-ion battery.

20. The method according to claim 18, wherein the electrolyte salt is selected from LiClO4, LiPF6, LiBF4, LiCF3SO3, LiN(CF3SO2)2 or a combination thereof.

21. 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 ion battery electrolyte according to claim 1, wherein the at least one fluorocarbon surfactant comprises: Where n is an integer from 1 to 30.

23. The ion battery electrolyte according to claim 1, wherein the at least one fluorocarbon surfactant comprises:

24. The ion battery electrolyte according to claim 1, wherein the at least one fluorocarbon surfactant comprises:

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