Fluorinated electrolyte composition for chalcogen batteries

Abstract

The present invention relates to a fluorinated electrolyte composition for chalcogen batteries. The invention also relates to a battery comprising: an anode; a cathode comprising chalcogen elements separated from the anode; and an electrolyte composition in fluid communication with the anode and the cathode, the electrolyte composition comprising a fluorinated solvent comprising: greater than 30% by volume of a fluorinated carbonate for use with a cathode comprising a carbon-chalcogen composite, the carbon-chalcogen composite has at least 50 wt% chalcogen based on the solids weight of the carbon-chalcogen composite; and / or at least 20% by volume of a fluorinated carbonate, and a fluorinated compound different from the fluorinated carbonate, the% by volume based on the electrolyte composition but not the total volume of the salt.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 523,946 filed on June 29, 2023 and U.S. Provisional Patent Application No. 63 / 531,180 filed on August 7, 2023, which are hereby incorporated by reference in their entireties. Technical Field

[0003] The disclosed subject matter generally relates to a fluorinated electrolyte composition for use in chalcogenide cells. Background Art

[0004] In battery applications, an electrolyte composition in fluid communication with a cathode and an anode allows ions to move between the electrodes, thereby enabling the battery to be charged and discharged. In lithium-chalcogenide (e.g., lithium-sulfur) batteries, electrolyte compositions have been developed; however, many of these electrolyte compositions require rich electrolyte conditions (e.g., a ratio of E / S>10) to achieve good performance. There is a lack of electrolyte compositions for such batteries that employ lean electrolyte conditions (e.g., a ratio of E / S≤10). Summary of the invention

[0005] Therefore, the presently disclosed subject matter is directed to providing a battery that overcomes some or all of the above-mentioned disadvantages.

[0006] According to a non-limiting embodiment or aspect, a battery is provided, comprising a cathode; an anode comprising a chalcogen separated from the cathode; and an electrolyte composition in fluid communication with the cathode and the anode, and the electrolyte composition comprises a fluorinated solvent comprising greater than 30 volume % of a fluorinated carbonate and is used with a cathode comprising a carbon-chalcogen composite material having at least 50 weight % of a chalcogen, based on the solid weight of the carbon-chalcogen composite material; and / or a fluorinated carbonate (at least 20 volume %) and a fluorinated compound different from the fluorinated carbonate, the volume % being based on the total volume of the electrolyte composition (but not counting salts).

[0007] In certain non-limiting embodiments or aspects, the electrolyte composition may include at least 40 volume percent of the fluorinated solvent, based on the total volume of the electrolyte composition (but excluding the salt).

[0008] In certain non-limiting embodiments or aspects, the fluorinated carbonate can include fluoroethylene carbonate.

[0009] In certain non-limiting embodiments or aspects, the fluorinated solvent may include fluorinated carbonates and fluorinated compounds, the fluorinated carbonates including fluoroethylene carbonate, the fluoroethylene carbonate comprising at least 20 volume percent, based on the total volume of the electrolyte composition (but not including the salt).

[0010] In certain non-limiting embodiments or aspects, the fluorinated compound may include a fluorinated ester, a fluorinated ether, a secondary fluorinated carbonate, a fluorinated sulfone, a fluorinated epoxy resin, a fluorinated nitrile, a fluorinated (meth)acrylate, a fluorinated silane, a fluorinated (poly)glycerol ether, a fluorinated acetate, a fluorinated propionate and / or any combination thereof.

[0011] In certain non-limiting embodiments or aspects, the fluorinated compound may include a fluorinated ether.

[0012] In certain non-limiting embodiments or aspects, the electrolyte composition can include a plurality of different salts.

[0013] In certain non-limiting embodiments or aspects, the cell can have a salt concentration ranging from 0.2 to 6.0 M of a variety of different salts.

[0014] In certain non-limiting embodiments or aspects, the fluorinated carbonate and / or fluorinated compound can include a cyclic fluorinated carbonate.

[0015] In certain non-limiting embodiments or aspects, the electrolyte composition may further include a nitrile.

[0016] In certain non-limiting embodiments or aspects, the cathode can include lithium and the anode can include sulfur.

[0017] In certain non-limiting embodiments or aspects, the battery may include an electrolyte to sulfur (E / S) ratio of up to 10.

[0018] In certain non-limiting embodiments or aspects, the sulfur cathode can comprise at least 30 weight percent sulfur.

[0019] In some non-limiting embodiments or aspects, the cathode may have a conductivity of 2-100 mg-S / cm 2 load level.

[0020] In some non-limiting embodiments or aspects, the battery may include a secondary battery.

[0021] In some non-limiting embodiments or aspects, the battery can include a coin cell, a cylindrical cell, and / or a pouch cell.

[0022] In some non-limiting embodiments or aspects, the cell can have an activation energy of at least 95 kJ / mol.

[0023] In some non-limiting embodiments or aspects, the electrolyte composition may further include a non-fluorinated solvent having a hybrid atom and a molecular weight of up to 150 g / mol.

[0024] In some non-limiting embodiments or aspects, the cathode can include a carbon-chalcogen composite having at least 50 weight percent chalcogen based on the solid weight of the carbon-chalcogen composite and / or at least 35 weight percent chalcogen based on the total solid weight of the cathode.

[0025] According to a non-limiting embodiment or aspect, there is provided a battery comprising: an anode; a cathode comprising a chalcogen element separated from the anode; and an electrolyte composition in fluid communication with the anode and the cathode, the electrolyte composition comprising a fluorinated solvent comprising: (1) greater than 30 volume % of a fluorinated carbonate; or (2) at least 10 volume % of a fluorinated carbonate, and a fluorinated compound other than the fluorinated carbonate; or (3) at least 2 volume % of a fluorinated carbonate, and a fluorinated compound other than the fluorinated carbonate, the volume % being based on the total volume of the electrolyte composition (excluding salts); the electrolyte composition further comprising a plurality of different salts.

[0026] In some non-limiting embodiments or aspects, the anode can include lithium and the cathode can include sulfur.

[0027] Further embodiments or aspects are listed in the following numbered clauses:

[0028] Item 1. A battery comprising: an anode; a cathode comprising a chalcogen separated from the anode; and an electrolyte composition in fluid communication with the anode and the cathode, the electrolyte composition comprising a fluorinated solvent comprising: greater than 30 volume % of a fluorinated carbonate, for use with a cathode comprising a carbon-chalcogen composite having at least 50 weight % of a chalcogen based on the solid weight of the carbon-chalcogen composite; and / or a fluorinated carbonate (at least 20 volume %) and a fluorinated compound other than the fluorinated carbonate, the volume % being based on the total volume of the electrolyte composition (excluding salts).

[0029] Item 2. The battery of Item 1, wherein the electrolyte composition comprises at least 40 volume % of the fluorinated solvent, based on the total volume of the electrolyte composition (excluding salt).

[0030] Item 3: The battery of Item 1 or 2, wherein the fluorinated carbonate comprises fluoroethylene carbonate.

[0031] Item 4: The battery of any one of Items 1-3, wherein the fluorinated solvent comprises a fluorinated carbonate and a fluorinated compound, the fluorinated carbonate comprises fluoroethylene carbonate, and the fluoroethylene carbonate accounts for at least 20 volume %, based on the total volume of the electrolyte composition (excluding salts).

[0032] Item 5: The battery of any of Items 1-4, wherein the fluorinated compound comprises a fluorinated ester, a fluorinated ether, a secondary fluorinated carbonate, a fluorinated sulfone, a fluorinated epoxy resin, a fluorinated nitrile, a fluorinated (meth)acrylate, a fluorinated silane, a fluorinated (poly)glycol ether, a fluorinated acetate, a fluorinated propionate, and / or any combination thereof.

[0033] Article 6: The battery of Article 5, wherein the fluorinated compound comprises a fluorinated ether.

[0034] Item 7: The battery of any one of Items 1-6, wherein the electrolyte composition comprises a plurality of different salts.

[0035] Article 8: The battery of Article 7, having salt concentrations of a plurality of different salts ranging from 0.2-6.0M.

[0036] Item 9: The battery of any one of Items 1-8, wherein the fluorinated carbonate and / or the fluorinated compound comprises a cyclic fluorinated carbonate.

[0037] Item 10: The battery of any one of Items 1-9, wherein the electrolyte composition further comprises a nitrile.

[0038] Item 11: A battery according to any one of Items 1-10, wherein the anode comprises lithium and the cathode comprises sulfur.

[0039] Item 12: The battery of Item 11, wherein the battery comprises an electrolyte to sulfur (E / S) ratio of at most 10.

[0040] Item 13: The battery of Item 11 or Item 12, wherein the sulfur cathode contains at least 30 weight percent sulfur.

[0041] Item 14: A battery according to any of Items 11-13, wherein the cathode has a loading level of 2-100 mg-S / cm 2 .

[0042] Article 15: A battery as described in any one of Articles 1 to 14, wherein the battery comprises a secondary battery.

[0043] Item 16: The battery of any one of Items 1-15, wherein the battery comprises a coin cell, a cylindrical cell, and / or a pouch cell.

[0044] Article 17: A battery according to any of Articles 1 to 16, having an activation energy of at least 95 kJ / mol.

[0045] Item 18. The battery of items 1-17, wherein the electrolyte composition further comprises a non-fluorinated solvent having hybrid atoms and a molecular weight of up to 150 g / mol.

[0046] Item 19: The battery of any of Items 1-18, wherein the cathode comprises a carbon-chalcogen composite having at least 50 weight percent chalcogen based on the solid weight of the carbon-chalcogen composite and / or at least 35 weight percent chalcogen based on the total solid weight of the cathode.

[0047] Item 20: A battery comprising: an anode; a cathode separated from the anode and comprising a chalcogenide; and an electrolyte composition in fluid communication with the anode and the cathode, the electrolyte composition comprising a fluorinated solvent comprising: (1) greater than 30 volume % of a fluorinated carbonate; or (2) at least 10 volume % of a fluorinated carbonate, and a fluorinated compound other than the fluorinated carbonate; or (3) at least 2 volume % of a fluorinated carbonate, and a fluorinated compound other than the fluorinated carbonate, the volume % being based on the total volume of the electrolyte composition (excluding salts); the electrolyte composition further comprising a plurality of different salts.

[0048] Article 21: The battery of Article 20, wherein the anode comprises lithium and the cathode comprises sulfur.

[0049] These and other features and characteristics of the presently disclosed subject matter, as well as the methods of operation and function of the combination of related elements and parts of the structure and the economy of manufacturing, will become more apparent upon consideration of the following description and appended claims and reference to the accompanying drawings, all of which form a part hereof, wherein like reference numerals indicate corresponding parts in the several figures. It is to be expressly understood, however, that the drawings are for purposes of illustration and description only and are not intended as a definition of the limits of the disclosed subject matter. As used in the specification and claims, the singular forms of "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Additional advantages and details of the disclosed subject matter are explained in more detail below with reference to exemplary embodiments or aspects shown in the accompanying drawings, in which:

[0051] Figure 1 Shown are schematic views of batteries according to some non-limiting embodiments or aspects of the presently disclosed subject matter. DETAILED DESCRIPTION

[0052] For purposes of the description below, the terms "end," "upper," "lower," "right," "left," "vertical," "horizontal," "top," "bottom," "lateral," "longitudinal," and their derivatives shall relate to the disclosed subject matter as the drawings are oriented. However, it shall be understood that the disclosed subject matter may assume various optional variations and step sequences unless expressly specified to the contrary. It shall also be understood that the specific devices and methods shown in the drawings and described in the following specification are merely exemplary embodiments or aspects of the disclosed subject matter. Accordingly, unless otherwise specified, specific dimensions and other physical characteristics related to the embodiments or aspects disclosed herein are not to be considered limiting.

[0053] Any aspect, component, element, structure, behavior, step, function, instruction and / or the like used herein should not be interpreted as critical or essential unless explicitly described as such. In addition, as used herein, the articles "a" and "an" are intended to include one or more items and can be used interchangeably with "one or more" and "at least one". In addition, as used herein, the term "set" is intended to include one or more items (e.g., related items, unrelated items, a combination of related items and unrelated items, and / or the like), and can be used interchangeably with "one or more" or "at least one". When referring to only one item, "one" or similar terms are used. In addition, as used herein, the terms "have", "have", etc. are intended to be open terms.

[0054] As used herein, the term "comprising" (and other similar terms, e.g., "including" and "containing") is "open ended" and open to including unspecified materials. Although described with "comprising", the terms "consisting essentially of" and "consisting of" are also within the scope of the present disclosure.

[0055] Non-limiting embodiments or aspects of the disclosed subject matter are directed to an electrolyte composition for use with a battery. Non-limiting embodiments or aspects of the disclosed subject matter are also directed to a battery comprising: an anode; a cathode; and an electrolyte composition in fluid communication (e.g., contact) with the anode and the cathode, such as the electrolyte composition described herein. The battery can be a chalcogen battery as described herein.

[0056] In some non-limiting embodiments or aspects, electrolyte composition may include fluorinated solvent.Based on the cumulative volume of electrolyte composition (not counting salt), fluorinated solvent may include the carbonate of fluorination greater than 30 volume %, such as at least 35 volume %, at least 40 volume %, at least 45 volume %, at least 50 volume %, at least 55 volume % or at least 60 volume %.Based on the cumulative volume of electrolyte composition (not counting salt), fluorinated solvent may include the carbonate of fluorination of at most 100 volume %, such as at most 95 volume %, at most 80 volume %, at most 75 volume % or at most 70 volume %.

[0057] In some non-limiting embodiments or aspects, electrolyte composition may include fluorinated solvent.Based on the cumulative volume of electrolyte composition (not counting salt), fluorinated solvent may include at least 20 volume % of fluorinated carbonate, and the fluorinated compound different from the carbonate of this fluorination.Based on the cumulative volume of electrolyte composition (not counting salt), fluorinated carbonate may account for at least 25 volume %, at least 30 volume %, at least 35 volume %, at least 40 volume %, at least 45 volume % or at least 50 volume %.Based on the cumulative volume of electrolyte composition (not counting salt), fluorinated compound may account for at least 5 volume %, at least 10 volume %, at least 15 volume %, at least 20 volume % or at least 25 volume %.

[0058] In some non-limiting embodiments or aspects, the electrolyte composition may comprise at least 25 volume % of a fluorinated solvent (e.g., a fluorinated carbonate and / or a fluorinated compound), e.g., at least 30 volume %, at least 35 volume %, at least 40 volume %, at least 45 volume %, at least 50 volume %, at least 55 volume %, at least 60 volume %, at least 65 volume %, at least 70 volume %, based on the total volume of the electrolyte composition (excluding salt).

[0059] Fluorinated carbonates may include fluoroethylene carbonate (FEC) [4-fluoro-1,3-1,3-dioxolane-2-one].

[0060] In some non-limiting embodiments or aspects where the fluorinated solvent comprises a fluorinated carbonate and a fluorinated compound, the fluorinated carbonate can comprise FEC in an amount of at least 20 volume %, e.g., at least 25 volume %, at least 30 volume %, at least 35 volume %, at least 40 volume %, at least 45 volume %, or at least 50 volume %, based on the total volume of the electrolyte composition (excluding the salt).

[0061] The fluorinated compounds used in combination with the fluorinated carbonate (e.g., FEC) may include fluorinated esters, fluorinated ethers, secondary fluorinated carbonates, fluorinated sulfones, fluorinated epoxies, fluorinated nitriles, fluorinated (meth)acrylates, fluorinated silanes, fluorinated acetates, fluorinated propionates, fluorinated phosphates, fluorinated sulfites, fluorinated borates, fluorinated benzenes, fluorinated pyridines, fluorinated diketones, and / or any combination thereof.

[0062] The fluorinated ester may include α-(trifluoromethyl)-γ-valerolactone, 3-(trifluoromethyl)dihydrofuran-2(3H)-one, difluoromethyl 2,2,2-trifluoroethyl ether, 2,2,2-trifluoroethyl formate, 3-acetyl-3-fluorodihydrofuran-2(3H)-one, methyl undecylfluoro-2-methyl-3-oxahexanoate, methyl 2,2,2-trifluoroethyl carbonate (FEMC), and / or any combination thereof.

[0063] The fluorinated ethers may include 3,3,4,4-tetrafluoro-1-oxacyclopentane, 1,1-difluoro-2-(2-fluoroethoxy)ethane, 1-fluoro-2-(2-fluoroethoxy)ethane, hexafluoroisopropyl methyl ether, 3,3,4,4-tetrafluorotetrahydrofuran, bis(2,2-difluoroethyl)ether, 1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether, bis(2,2-difluoroethyl)ether, 1 , 1,2,2,-tetrafluoroethyl 2,2,2-trifluoroethyl ether, 1,2-(1,1,2,2,-tetrafluoroethoxy)ethane (TFEE), methoxyperfluorobutane, bis(2,2,2-trifluoroethyl) ether, 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether, 2,2,3,3,3-pentafluoropropyl 1,1,2,2-tetrafluoroethyl ether, and / or any combination thereof.

[0064] The second fluorinated carbonate (different from the fluorinated carbonate) can include 4-(trifluoromethyl)-1,3-dioxolane, 4-(fluoromethyl)-1,3-dioxolane-2-one, fluoromethyl methyl carbonate, 2,2-difluoroethyl methyl carbonate, 2,2-difluoroethyl 2,2,2-trifluoroethyl carbonate, ethyl (2,2,2-trifluoroethyl) carbonate, bis (2,2,2-trifluoroethyl) carbonate, 3,3,3-trifluoropropylene carbonate, trans-4,5-difluoroethylene carbonate / trans-4,5-difluoro-1,3-dioxolane-2-one, bis (pentafluorophenyl) carbonate, trans-4,5-difluoroethylene carbonate, 4-fluoro-1,3-dioxolane-2-one, and / or any combination thereof.

[0065] The fluorinated sulfone may include 4-fluorophenylmethylsulfone, bis(4-fluorophenyl)sulfone, phenyldifluoromethylsulfone, fluoromethylphenylsulfone, phenyltrifluoromethylsulfone, and / or any combination thereof.

[0066] The fluorinated epoxy resin may include 1,1,1-trifluoro-2,3-butylene oxide, 1,2-epoxy-3,3,3-trifluoropropane, epifluoropropane, and / or any combination thereof.

[0067] The fluorinated nitrile may comprise fluoroacetonitrile.

[0068] The fluorinated (meth)acrylate may include hexafluoroisopropyl acrylate, 2,2,2-trifluoroethyl acrylate, methyl 2-fluoroacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, and / or any combination thereof.

[0069] The fluorinated silane may include (3,3,3-trifluoropropyl)methyldimethoxysilane, (3,3,3-trifluoropropyl)trimethoxysilane, trifluoromethyltrimethylsilane, and / or any combination thereof.

[0070] The fluorinated acetate may include ethyl fluoroacetate, 2,2,2-trifluoroethyl acetate, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate, methyl trifluoroacetate, methyl fluoroacetate, methyl difluoroacetate, 2,2,2-trifluoroethyl trifluoroacetate, and / or any combination thereof.

[0071] The fluorinated propionate may include methyl 2-fluoro-2-methylpropionate, methyl 2-fluoropropionate, methyl perfluoro-2,5-dimethyl-3,6-dioxane heptanoate, methyl 2,2,3,3-tetrafluoro-3-(methoxy)propionate, methyl 3,3,3-trifluoropropionate, ethyl 3,3,3-trifluoropyruvate, and / or any combination thereof.

[0072] The fluorinated phosphate ester may include bis(2,2,2-trifluoroethyl)methylphosphonate, tris(2,2,2-trifluoroethyl)phosphate, and / or any combination thereof.

[0073] The fluorinated sulfite may include bis(2,2,2-trifluoroethyl)sulfite, trifluoromethanesulfonylmethane, bis(trifluoromethanesulfonyl)methane, tris(trifluoromethanesulfonyl)methane, and / or any combination thereof.

[0074] The fluorinated borate ester may comprise tris(2,2,2-trifluoroethyl)borate.

[0075] The fluorinated benzene may include a,a,a-trifluorotoluene, fluorobenzene, and / or any combination thereof.

[0076] The fluorinated pyridine may comprise 2-fluoropyridine.

[0077] The fluorinated diketone may comprise hexafluoroacetylacetone.

[0078] In some non-limiting embodiments or aspects, the fluorinated compound can comprise a fluorinated ether.

[0079] In some non-limiting embodiments or aspects, one or both of the fluorinated carbonate and the fluorinated compound can comprise a cyclic fluorinated compound, such as a cyclic fluorinated carbonate.

[0080] In some non-limiting embodiments or aspects, the electrolyte composition may further comprise a non-fluorinated solvent. Based on the total volume of the electrolyte composition (excluding salt), the non-fluorinated solvent may account for up to 50 volume %, such as up to 40 volume %, up to 30 volume % or up to 20 volume %.

[0081] The molecular weight of the non-fluorinated solvent may be up to 150 g / mol, for example up to 100 g / mol.

[0082] The non-fluorinated solvent may have at least one hybrid atom. At least one hybrid atom may include atoms from IIIA group (B, Al, Ga, In, Tl), IVA group (C, Si, Ge, Sn, Pb), VA group (N, P, As, Sb, Bi), VIA group (O, S, Se, Te), VIIA group (F, Cl, Br, I) and / or any combination thereof. At least one hybrid atom may include at least one of the following atoms: B, Al, Si, N, P, O, S, Se, F, Cl, Br, I and / or any combination thereof. At least one hybrid atom may include at least one of the following atoms: N, P, O, S and / or any combination thereof. The compound comprising the hybrid atom may be in the solid phase at room temperature and may be dissolved in and / or compatible with other electrolyte components.

[0083] Non-limiting examples of non-fluorinated solvents having at least one hybrid atom include: ethers (e.g., dimethoxyethane, dimethoxymethane (DME), 15 crown 5-ether, (R)-(-)-glycidyl ester methyl ether, tetraethylene glycol dimethyl ether, poly(ethylene glycol) dimethyl ether MW 250, poly(propylene glycol) diglycidyl ether (Mn 380), trimethylpropane triglycidyl ether, 2-methyltetrahydrofuran, 1,3-dioxolane, and / or any combination thereof), acrylates (e.g., methyl trans-3-methoxyacrylate, methyl methacrylate, containing ≤30 ppm MEHQ as inhibitor, 99%, and / or any combination thereof); sulfones (e.g., divinyl sulfone, phenyl vinyl sulfone, methyl vinyl sulfone, ethyl vinyl sulfone, cyclopentane, and / or any combination thereof), carbonates (e.g., diethyl carbonate (DEC), ethyl methyl carbonate, ethylene carbonate (EC), vinylene carbonate, propylene carbonate, and / or any combination thereof), epoxies (e.g., 1,2-butylene oxide, cis-2,3-butylene oxide, and / or any combination thereof), silanes (e.g., tetrakis(methoxyethoxy)silane, methyltris(methoxyethoxy)silane, tetraisopropoxysilane, and / or any combination thereof), esters: acetates (e.g., , ethyl acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, and / or any combination thereof for HPLC m≥99.7%)), esters: propionates (e.g., ethyl propionate, propyl propionate, propylene glycol monomethyl ether propionate, and / or any combination thereof), ionic liquids (e.g., 1-ethyl-3-methylimidazolium di(fluorosulfonyl)imide), lactones (e.g., β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and / or any combination thereof), formamides (e.g., dimethylformamide, and / or any combination thereof), tetrahydrofuran (THF), tetrahydropyran (THP), and / or any combination thereof.

[0084] The compound comprising a hybrid atom may comprise at least one oxygen atom, such as an ester, an ether, a carbonate, an epoxy resin and / or any combination thereof. The compound may have a molecular weight of up to 500 g / mol, such as up to 250 g / mol or up to 150 g / mol.

[0085] In some non-limiting embodiments or aspects, the electrolyte composition may include at least one salt. In some non-limiting embodiments or aspects, the electrolyte composition may include a variety of different salts. It has been found that including a variety of different salts rather than a single salt can improve the capacity of a battery using the electrolyte composition.

[0086] Non-limiting examples of the salt and / or salts may include: lithium bis(trifluoromethane)sulfonyl imide (LiTFSI), lithium hexafluorophosphate (LiPF6), lithium iodide, ultra dry lithium (Li I), lithium bis(fluorosulfonyl)amide (LiFSI), lithium carbonate, ACS (Li2CO3), anhydrous lithium nitrate (LiNO3), lithium chloride (LiCl), lithium perchlorate (LiClO4), lithium phosphate (Li3PO4), lithium tetraborate (LiBF4), monobasic lithium phosphate (H2LiO4P), lithium fluoride (LiF), lithium bromide (LiBr), lithium bis(oxalate)borate (LiBOB), lithium nitride (LiNO3), lithium bis(pentafluoroethanesulfonyl)imide (LiPTFSI), lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl imide (LiHDF), lithium difluoro(oxalate)borate (LiODFB), lithium tetrafluoroborate (LiBF4), lithium hexafluoroarsonic acid (V) (LiAsF6), lithium difluoro(dioxalate)phosphate (LiODFP), lithium difluoride phosphate (LiPO2F2), and / or any combination thereof.

[0087] The salt may have a gas phase acidity value (at 25° C.) of at most 370 kJ / mol, for example at most 350 kJ / mol, at most 330 kJ / mol, at most 315 kJ / mol, or at most 295 kJ / mol or at most 275 kJ / mol of anion, as determined using HSC Chemistry 9 software (e.g., for determining ΔG values, H values, S values, Cp values, etc.). The electrolyte salt may be a salt of a superacid. The stronger the acidity, the more likely the anion is to associate with a cation (e.g., H + The weaker the coordination of cations, Li ions). Gas phase acidity can be calculate.

[0088] The electrolyte composition may have a salt concentration of from 0.2-6.0 M, such as from 0.4-5.0 M, from 0.6-4.5 M, from 0.8-2 M, from 0.8-1.2 M, or from 1.0-3.0 M (salt and / or multiple salts). The electrolyte composition may have a salt concentration of at least 0.2 M, such as at least 0.4 M, at least 0.6 M, or at least 0.8 M. The electrolyte composition may have a salt concentration of up to 6.0 M, such as up to 5.0 M, up to 4.5 M, up to 3.0 M, up to 2.0 M.

[0089] In some non-limiting embodiments or aspects, the electrolyte composition may further include a nitrile. The nitrile may include cyclopentanedinitrile, propionitrile, valeronitrile, acetonitrile, benzonitrile, butyronitrile and / or any combination thereof.

[0090] The electrolyte composition may comprise up to 50 volume %, eg, up to 40 volume %, up to 30 volume %, or up to 20 volume %, of the nitrile, based on the total volume of the electrolyte composition (excluding salt).

[0091] In some non-limiting embodiments or aspects, the electrolyte composition may include a variety of different salts. The electrolyte composition may also include a fluorinated solvent, which includes: (1) a fluorinated carbonate greater than 30% by volume (e.g., at least 35% by volume or at least 40% by volume); or (2) at least 10% by volume of a fluorinated carbonate (e.g., at least 15% by volume or at least 20% by volume), and a fluorinated compound different from the fluorinated carbonate; or (3) at least 2% by volume (e.g., at least 4% by volume or at least 6% by volume or at least 8% by volume) of a fluorinated carbonate, and a fluorinated compound different from the fluorinated carbonate (e.g., at least 22% by volume, at least 24% by volume, at least 26% by volume or at least 28% by volume), and the volume % is based on the total volume of the electrolyte composition (not counting salt). A variety of different salts, fluorinated carbonates and fluorinated compounds can be as described above.

[0092] refer to Figure 1 , a battery 100 is shown according to a non-limiting embodiment or aspect. Figure 1 The battery 100 in the embodiment may include a battery that has undergone a series of discharges (see Figure 1 , below the dashed line) and recharging (see Figure 1 , above the dotted line) step of a secondary (rechargeable) battery.

[0093] The cell 100 can include an anode 102 separated from a cathode 104. An electrolyte composition 106 (eg, an electrolyte composition as described above) can be in fluid communication with the anode 102 and the cathode 104.

[0094] During discharge, electron flow may flow from anode 102 to cathode 104, and current may flow from cathode 104 to anode 102. Ionic material 108 may flow from anode 102 to cathode 104 through electrolyte composition 106. In some non-limiting examples, ionic material 108 may include lithium ions.

[0095] During recharging, electrons may flow from the cathode 104 to the anode 102, and current may flow from the anode 102 to the cathode 104. Ionic material 108 may flow from the cathode 104 to the anode 102 via the electrolyte composition 106.

[0096] The battery 100 may include a separator (not shown) between the anode 102 and the cathode 104, which may be configured to allow ions to pass therethrough (e.g., the ionic material 108) during charging and / or discharging of the battery 100. The battery 100 may include a charger 109 configured to recharge the battery 100 after it has been at least partially discharged.

[0097] The battery 100 may include one or more current collectors (not shown). The anode 102 and / or the cathode 104 may include a current collector as an electrode support. The current collector may serve as a current conductor between the electrode and any external circuit. The current collector may be made of any suitable material, such as aluminum, copper, nickel, titanium, stainless steel, and / or any combination thereof. For example, the current collector for the anode 102 may be made of copper. For example, the current collector (not shown) of the cathode 104 may be made of aluminum. The current collector may take any form, such as a foil, mesh, foam, and / or carbon-coated current collector.

[0098] Continue to refer to Figure 1 In some non-limiting embodiments or aspects, cathode 104 may include at least one of the following: at least one material including a chalcogenide (e.g., S, Se, O, and Te), a fluoride, at least one intercalation cathode material (e.g., LiCoO2, LiMnO2, LiNiO2, LiCo x Ni y Mn 1-x-y O2) and LiFePO4, which may include various dopants such as Ni, Mg, Al, Cr, Zn, Ti, Fe, Co, Ni, Cu, Nd and La, at least one supercapacitor material (e.g., metal oxide / hydroxide), a conductive polymer or some combination thereof. Cathode 104 may include a chalcogen element. Cathode 104 may include sulfur.

[0099] In some non-limiting embodiments or aspects, cathode 104 may include a substrate coated with a coating containing a carbon-chalcogen composite material. The coating may further include a binder and a conductive carbon. The binder may include a polymer material. Non-limiting examples of suitable polymer materials include carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), polyethylene glycol dimethyl ether (PEGDME), conductive polymers (such as poly (3,4-ethylenedioxythiophene) (PEDOT)), polyacrylic acid (PAA), polyethyleneimine (PEI), latex polymers, acrylates, polyurethanes, polyurethane acrylates, etc.

[0100] The carbon-chalcogen composite material may include at least 50% by weight of chalcogen, such as at least 60% by weight of chalcogen, based on the solid weight of the carbon-chalcogen composite material. The carbon-chalcogen composite material may include a carbon-sulfur composite material having a sulfur:carbon weight ratio of at least 50:50, such as at least 55:45, at least 60:40, such as 64:36. The carbon-chalcogen composite material may include at least 35% by weight of chalcogen, based on the solid weight of the cathode.

[0101] The coating comprising the carbon-chalcogen composite material may comprise at least 60 wt % of the carbon-chalcogen composite material, such as at least 70 wt % or at least 80 wt %. The coating comprising the carbon-chalcogen composite material may comprise up to 20 wt % of conductive carbon, such as up to 15 wt % or up to 10 wt %. The coating comprising the carbon-chalcogen composite material may comprise up to 20 wt % of a binder, such as up to 15 wt % or up to 10 wt %.

[0102] In some non-limiting embodiments or aspects, a battery comprising an electrolyte composition having greater than 30% by volume fluorinated carbonate and no other fluorinated compounds can be used with a cathode formed using a coating having a carbon-chalcogen composite material as described herein. It should be understood that a cathode formed using a coating having a carbon-chalcogen composite material as described herein can be used with other electrolyte compositions described herein, such as electrolyte compositions comprising a plurality of fluorinated compounds and / or a plurality of different salts.

[0103] In some non-limiting embodiments or aspects, cathode 104 may include at least 30 wt% sulfur (and / or other active materials, such as chalcogen materials), such as at least 35 wt%, at least 40 wt%, at least 45 wt%, or at least 50 wt%, based on the total weight of the overall cathode 104 (which includes active materials and inactive materials (e.g., binders, conductive carbon, etc.). In some non-limiting embodiments or aspects, cathode 104 may include up to 90 wt% sulfur, such as up to 85 wt%, up to 80 wt%, or up to 75 wt%, based on the total weight of the entire cathode 104.

[0104] In some non-limiting embodiments or aspects, cathode 104 may have a conductivity of 2-100 mg-S / cm 2 Loading level, for example 2-80 mg-S / cm 2 or 2-50mg-S / cm 2 The cathode 104 may have a conductivity of at least 2 mg-S / cm 2 The cathode 104 may have a loading level of up to 100 mg-S / cm 2 The loading level is, for example, up to 80 mg-S / cm 2 or up to 50 mg-S / cm 2 The loading level can be determined by measuring the coating weight and the coating surface area.

[0105] Continue to refer to Figure 1In some non-limiting embodiments or aspects, the anode 102 may include at least one of the following: at least one element from Group IVA (e.g., C, Si, Sn), at least one element from Group IIIA (e.g., Al), at least one transition metal from Group IB-VIIIB (e.g., Zn, Cd, Ag), at least one alkaline earth metal from Group IIA (e.g., Mg, Ca), at least one alkali metal from Group IA (e.g., Li, Na, K), at least one compound (e.g., Li x Si y , Li x Ge y 、LiAl、Li x Sn y , LTO, NiO, SiO x ), or some combination thereof. Anode 102 may include at least one of an alkali metal from Group IA, an alkaline earth metal from Group IIA, an element from Group IIIA, and / or some combination thereof. Anode 102 may include lithium and / or sodium, such as lithium.

[0106] In some non-limiting embodiments or aspects, the battery 100 can include a chalcogen-containing cathode 104 and a lithium-containing anode 102, such as a sulfur cathode 104 and a lithium anode 102 (eg, a lithium-chalcogen and / or lithium-sulfur battery).

[0107] In some non-limiting embodiments or aspects, the battery 100 may include an electrolyte composition 106. The electrolyte composition 106 may be a liquid, solid, or gel material. The electrolyte composition 106 may be located between the cathode 104 and the anode 102 (electrode). The electrolyte may wet or soak the electrode.

[0108] In some non-limiting embodiments or aspects, the cell 100 may include an electrolyte to sulfur (E / S) ratio of at most 10, such as at most 7, at most 5, at most 4, at most 3, at most 2.5, or at most 2 (e.g., a cell 100 having a lean electrolyte condition). The E / S ratio may be determined by dividing the electrolyte volume (mL) by the cathode active material (g). Such a cell 100 may include an electrolyte composition 106 and a sulfur cathode 104.

[0109] Cell 100 may have an activation energy of at least 95 kJ / mol as determined by TGA following the procedure described in ASTM method E1641-16.

[0110] At more than 0.8 mA / cm 2 (e.g. at least 1.0 mA / cm 2 or at least 1.2mA / cm 2), the battery may have a high midpoint voltage (Mid-V) of at least 1.70 V, such as at least 1.74 V or at least 1.78 V. The midpoint voltage may be the voltage when the battery is discharged to 50% capacity at a specified current density.

[0111] In some non-limiting embodiments or aspects, the battery 100 is a primary battery.

[0112] In some non-limiting embodiments or aspects where the battery 100 is a secondary battery, the secondary battery can be cycled in the following manner: The battery 100 is provided in the form of a secondary battery as described herein. The secondary battery can be at least partially discharged and then at least partially charged. The secondary battery can be discharged and charged in a cycle as described herein, and the cycle can be repeated at least until the secondary battery exhibits a parasitic state during the charging step.

[0113] In some non-limiting embodiments or aspects, the secondary battery can provide at least 30 cycles, such as at least 50 cycles, at least 75 cycles, or at least 100 cycles in the charging step before exhibiting a parasitic state.

[0114] The battery 100 can be used in any suitable application. In some non-limiting embodiments, the battery 100 can be used in consumer electronics, vehicles (eg, electric vehicles), and the like.

[0115] The battery 100 may include a coin cell battery, a cylindrical battery, and / or a pouch cell battery.

[0116] In some non-limiting embodiments or aspects, the battery 100 may have a capacity retention of at least 50% at 0°C, such as at least 60% or at least 70%, compared to room temperature (e.g., 20°C). The capacity retention after storage at 45°C for one month and testing at room temperature may be at least 80%, at least 85%, or at least 90%. The battery 100 may be at least 6 mA / cm 2 , for example at least 7 mA / cm 2 or at least 8mA / cm 2 The device has a 5 second pulse at a current density of 1000 nm and a 10% capacity interval at 3, 4 or 5 pulses.

[0117] The present disclosure also relates to a method for producing a rechargeable battery, namely the rechargeable battery described in the present disclosure. Figure 1 , the method may include placing the electrolyte composition 106 in contact with the anode 102 and the cathode 104 of the battery 100 to form a rechargeable battery.

[0118] Example

[0119] The following examples are given to demonstrate the general principles of the present disclosure. The present disclosure should not be considered limited to the specific examples set forth.

[0120] Examples 1-7

[0121] Preparation of electrolyte composition

[0122] The electrolyte composition was prepared according to Table 1 below.

[0123] Table 1

[0124]

[0125]

[0126] Such electrolyte compositions as in Table 1 are included in a coin cell battery having a lithium anode and a chalcogen (sulfur) cathode, wherein the cathode is a carbon-chalcogen composite having at least 50 weight percent sulfur based on the solid weight of the carbon-chalcogen composite and at least 35 weight percent sulfur based on the total solid weight of the cathode. 2 At a current density of at least 1.0 mA / cm 2 or at least 1.2mA / cm 2 Next, determine the Mid-V of the coin cell battery.

[0127] Compared to Comparative Example 1, Examples 2-7 showed improved Mid-V at the 3rd cycle.

[0128] Although the disclosed subject matter has been described in detail for purposes of illustration based on what are presently considered to be the most practical and preferred embodiments or aspects, it should be understood that the details are provided for that purpose only and that the disclosed subject matter is not limited to the disclosed embodiments or aspects, but rather is intended to cover modifications and equivalent arrangements within the spirit and scope of the appended claims. For example, it should be understood that the presently disclosed subject matter contemplates that, to the extent possible, one or more features of any embodiment or aspect may be combined with one or more features of any other embodiment or aspect.

Claims

1. Battery, including: anode; a cathode comprising a chalcogen element separated from the anode; and an electrolyte composition in fluid communication with the anode and the cathode, the electrolyte composition comprising a fluorinated solvent comprising: Greater than 30 volume percent of a fluorinated carbonate, used with a cathode comprising a carbon-chalcogen composite having at least 50 weight percent chalcogen based on the weight of the solids of the carbon-chalcogen composite; and / or at least 20% by volume of a fluorinated carbonate; and a fluorinated compound other than the fluorinated carbonate, Volume % is based on the total volume of the electrolyte composition excluding salts.

2. The battery of claim 1, wherein the electrolyte composition comprises at least 40 volume % of the fluorinated solvent, based on the total volume of the electrolyte composition excluding the salt.

3. The battery of claim 1, wherein the fluorinated carbonate comprises fluoroethylene carbonate.

4. The battery of claim 1, wherein the fluorinated solvent comprises a fluorinated carbonate and a fluorinated compound, the fluorinated carbonate comprising fluoroethylene carbonate, the fluoroethylene carbonate comprising at least 20 volume percent, based on the total volume of the electrolyte composition excluding the salt.

5. The battery of claim 1, wherein the fluorinated compound comprises a fluorinated ester, a fluorinated ether, a secondary fluorinated carbonate, a fluorinated sulfone, a fluorinated epoxy, a fluorinated nitrile, a fluorinated (meth)acrylate, a fluorinated silane, a fluorinated (poly)glycol ether, a fluorinated acetate, a fluorinated propionate and / or any combination thereof.

6. The battery of claim 5, wherein the fluorinated compound comprises a fluorinated ether.

7. The battery of claim 1, wherein the electrolyte composition comprises a plurality of different salts.

8. The battery of claim 7, having a salt concentration of the plurality of different salts ranging from 0.2-6.0M.

9. The battery of claim 1, wherein the fluorinated carbonate and / or fluorinated compound comprises a cyclic fluorinated carbonate.

10. The battery of claim 1, wherein the electrolyte composition further comprises a nitrile.

11. The battery of claim 1, wherein the anode comprises lithium and the cathode comprises sulfur.

12. The battery of claim 11, wherein the battery has an electrolyte to sulfur (E / S) ratio of at most 10.

13. The battery of claim 11, wherein the sulfur cathode comprises at least 30 weight percent sulfur.

14. The battery of claim 11, wherein the cathode has a conductivity of from 2 to 100 mg-S / cm 2 load level.

15. The battery of claim 1, wherein the battery comprises a secondary battery.

16. The battery of claim 1, wherein the battery comprises a coin cell, a cylindrical cell and / or a pouch cell.

17. The battery of claim 1 having an activation energy of at least 95 kJ / mol.

18. The battery of claim 1, wherein the electrolyte composition further comprises a non-fluorinated solvent having hybrid atoms and a molecular weight of at most 150 g / mol.

19. The battery of claim 1, wherein the cathode comprises a carbon-chalcogen composite having at least 50 weight percent chalcogen based on the solids weight of the carbon-chalcogen composite and / or at least 35 weight percent chalcogen based on the total solids weight of the cathode.

20. Batteries, including: anode; a cathode comprising a chalcogen element separated from the anode; and an electrolyte composition in fluid communication with the anode and the cathode, the electrolyte composition comprising a fluorinated solvent comprising: (1) greater than 30% by volume of a fluorinated carbonate; or (2) at least 10% by volume of a fluorinated carbonate and a fluorinated compound other than the fluorinated carbonate; or (3) at least 2% by volume of a fluorinated carbonate and a fluorinated compound other than the fluorinated carbonate, Volume % is based on the total volume of the electrolyte composition but not including the salt; The electrolyte composition also includes a variety of different salts.

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