Fluorinated sulfone preparation method, electrolyte, secondary battery and electric device

Abstract

The invention discloses a preparation method of fluorosulfone, an electrolyte, a secondary battery and an electric device. The preparation method comprises the following steps: mixing sulfinate with a structure as shown in a formula I and alkyl halide in a solvent, and carrying out alkylation reaction to prepare fluorosulfone with a structure as shown in a formula II; wherein the solvent can be used for dissolving the sulfinate and the alkyl halide; wherein the structural formula of alkyl halide comprises R2-X, R1 comprises a C1-C6 alkyl group containing at least one fluorine atom, R2 comprises any one of a C1-C6 alkyl group and a substituted or unsubstituted C6-C12 aryl group, M comprises an alkali metal element, and X comprises halogen. The preparation conditions are mild, and the product yield is high.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of batteries, in particular to a preparation method of fluorosulfone, an electrolyte, a secondary battery and an electric device. BACKGROUND

[0002] Fluorosulfone compounds have the possibility of being applied in secondary battery electrolytes due to their strong oxidative stability, suitable viscosity and suitable separator wetting. However, the harsh preparation conditions and low yield of traditional fluorosulfone compounds limit the application of fluorosulfone compounds. SUMMARY

[0003] The present application is carried out in view of the above-mentioned problems, and aims to provide a preparation method of fluorosulfone, an electrolyte, a secondary battery and an electric device, so as to make the preparation conditions of fluorosulfone compounds mild and the yield of products higher.

[0004] In order to achieve the above-mentioned purpose, the present application provides a preparation method of fluorosulfone, an electrolyte, a secondary battery and an electric device.

[0005] In a first aspect, the present application provides a preparation method of fluorosulfone, comprising the following steps:

[0006] Mixing a sulfinate salt comprising a structure shown in Formula I with an alkyl halide in a solvent to occur an alkylation reaction to prepare fluorosulfone comprising a structure shown in Formula II; wherein the solvent can dissolve the sulfinate salt and the alkyl halide;

[0007]

[0008] wherein the structural formula of the alkyl halide comprises R2-X, R1 comprises C1-C6 alkyl containing at least one fluorine atom, R2 comprises any one of C1-C6 alkyl, substituted or unsubstituted C6-C12 aryl, M comprises an alkali metal element, and X comprises halogen.

[0009] In the technical solution of the present application, a solvent capable of dissolving the sulfinate salt and the alkyl halide at the same time is used, so that the alkylation reaction of the sulfinate salt and the alkyl halide is a homogeneous reaction. Without the need for a phase transfer catalyst, the sulfinate salt and the alkyl halide can react. The preparation process is simple, the preparation conditions are mild, the yield of the product is good, and the purity is high.

[0010] In any embodiment, R1 comprises C1-C3 alkyl containing at least one fluorine atom; and / or, R2 comprises C1-C5 alkyl.

[0011] In the case of smaller volume of the above-mentioned substituent, the steric hindrance is smaller, which can further improve the efficiency of the substitution reaction.

[0012] In any embodiment, the sulfinic acid salt comprising the structure of Formula I includes at least one of sodium trifluoromethylsulfinates, potassium trifluoromethylsulfinates, sodium trifluoroethylsulfinates, and sodium 3,3,3-trifluoropropyl-1-sulfinates. The above-mentioned sulfinic acid salt raw materials are readily available, which is conducive to controlling the production cost.

[0013] In any embodiment, R2 includes any one of methyl, ethyl, isopropyl, and n-butyl, and X includes chlorine, bromine, or iodine. The above-mentioned halogenated alkyl raw materials are readily available, which is conducive to controlling the production cost.

[0014] In any embodiment, the solvent includes any one of polyethylene glycol, ethanol, a mixture of water and acetonitrile, and a mixture of polyethylene glycol and acetonitrile. The above-mentioned solvent can simultaneously dissolve the sulfinic acid salt comprising the structure of Formula I and the halogenated alkyl, so that the alkylation reaction of the sulfinic acid salt comprising the structure of Formula I and the halogenated alkyl is a homogeneous reaction.

[0015] In any embodiment, the number average molecular weight of the polyethylene glycol is 200-400. The molecular weight of the polyethylene glycol is within a suitable range, which is conducive to simultaneously dissolving the sulfinic acid salt comprising the structure of Formula I and the halogenated alkyl, and can make the viscosity of the solvent using the polyethylene glycol more suitable.

[0016] In any embodiment, the volume ratio of the polyethylene glycol to acetonitrile in the mixture of polyethylene glycol and acetonitrile is (1-10):1; and / or, the volume ratio of water to acetonitrile in the mixture of water and acetonitrile is (1-10):1. The volume ratio of the polyethylene glycol to acetonitrile in the mixture of polyethylene glycol and acetonitrile is within a suitable range, which is conducive to simultaneously dissolving the sulfinic acid salt comprising the structure of Formula I and the halogenated alkyl, and the sulfinic acid salt comprising the structure of Formula I and the halogenated alkyl are more conducive to being simultaneously dissolved when the proportion of the polyethylene glycol is more. The volume ratio of water to acetonitrile in the mixture of water and acetonitrile is within a suitable range, which is conducive to simultaneously dissolving the sulfinic acid salt comprising the structure of Formula I and the halogenated alkyl.

[0017] In any embodiment, the molar ratio of the sulfinic acid salt comprising the structure of Formula I to the halogenated alkyl is 1:(1-3). The molar ratio of the sulfinic acid salt comprising the structure of Formula I to the halogenated alkyl is within a suitable range, which is further conducive to improving the conversion rate and yield of the alkylation reaction. Excess halogenated alkyl is conducive to more complete reaction of the sulfinic acid salt.

[0018] In any embodiment, the mass ratio of the sulfinic acid salt comprising the structure of Formula I to the solvent is 1:(20-50). The mass ratio of the sulfinic acid salt comprising the structure of Formula I to the solvent is within a suitable range, on the one hand, which is conducive to the sulfinic acid salt comprising the structure of Formula I and the halogenated alkyl being sufficiently dissolved in the solvent, and on the other hand, which is conducive to the reaction raw materials being reacted at a suitable concentration, so as to further improve the conversion rate and yield of the alkylation reaction.

[0019] In any embodiment, the reaction temperature of the alkylation reaction is 40-80℃. At a suitable temperature, it is beneficial to maintain a high reaction activity.

[0020] In any embodiment, the reaction time of the alkylation reaction is 3-6h. At a suitable reaction time, it is beneficial to the full occurrence of the reaction.

[0021] In any embodiment, the step of preparing the fluorosulfone comprising the structure shown in Formula II by mixing the sulfinate salt comprising the structure shown in Formula I with the haloalkane in a solvent to occur the alkylation reaction comprises:

[0022] dissolving the sulfinate salt comprising the structure shown in Formula I into a solvent to obtain a mixture;

[0023] dropping the haloalkane into the mixture to occur the alkylation reaction to prepare the fluorosulfone comprising the structure shown in Formula II.

[0024] Dropping the haloalkane into the mixture in which the sulfinate salt comprising the structure shown in Formula I is dissolved in a dropping manner is beneficial to promote the full contact of raw materials, further promote the occurrence of the alkylation reaction, and further beneficial to improve the conversion rate and yield of the alkylation reaction.

[0025] In any embodiment, the preparation method further comprises subjecting the product of the alkylation reaction to a distillation treatment to prepare the fluorosulfone comprising the structure shown in Formula II.

[0026] In the technical solution of the present application, since the boiling points of the solvent and the raw materials and the product, i.e., the fluorosulfone comprising the structure shown in Formula II, are not similar, the target product, i.e., the fluorosulfone comprising the structure shown in Formula II, can be purified by a simple distillation treatment, and the purification treatment step is simple and efficient.

[0027] In a second aspect, the present application provides an electrolyte comprising the fluorosulfone prepared by the preparation method according to the first aspect of the present application.

[0028] In a third aspect, the present application provides a secondary battery comprising a positive electrode sheet, a negative electrode sheet, a separator, and the electrolyte according to the second aspect of the present application.

[0029] In a fourth aspect, the present application provides an electric device comprising the secondary battery according to the third aspect of the present application. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 is a schematic diagram of a secondary battery according to an embodiment of the present application.

[0031] Figure 2 is a schematic diagram of a secondary battery according to an embodiment of the present application. Figure 1 is an exploded view of the secondary battery according to an embodiment of the present application.

[0032] Figure 3 is a schematic view of a battery module according to an embodiment of the present application.

[0033] Figure 4 is a schematic view of a battery pack according to an embodiment of the present application.

[0034] Figure 5 is a schematic view of a battery pack according to an embodiment of the present application. Figure 4 is an exploded view of a battery pack according to an embodiment of the present application.

[0035] Figure 6 is a schematic view of an electric device using a secondary battery as a power source according to an embodiment of the present application.

[0036] Figure 7 is a 1H NMR chart of the fluoro-sulfone prepared in Example 1 of the present application.

[0037] Figure 8 is a 19F NMR chart of the fluoro-sulfone prepared in Example 1 of the present application.

[0038] BRIEF DESCRIPTION OF DRAWINGS

[0039] 1 battery pack; 2 upper case; 3 lower case; 4 battery module; 5 secondary battery; 51 case; 52 electrode assembly; 53 top cap assembly. DETAILED DESCRIPTION

[0040] Hereinafter, embodiments of the present application, in which a method for preparing a fluoro-sulfone, an electrolyte, a battery, and an electric device are specifically disclosed, will be explained in detail with appropriate reference to the accompanying drawings. However, there will be cases where unnecessary detailed explanation is omitted. For example, there will be cases where detailed explanation of matters which are well known, repeated explanation of substantially identical structures are omitted. This is to avoid the following explanation from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. In addition, the accompanying drawings and the following explanation are provided so that those skilled in the art can fully understand the present application, and are not intended to limit the subject matter recited in the claims.

[0041] The ranges disclosed herein are intended to be "open" ranges, i.e., the upper and lower limits of the range are not included. The ranges are also intended to include any and all sub-ranges of the range, i.e., all combinations of any two of the range limits, unless otherwise indicated. For example, a range of "1 to 10" is intended to include any number from 1 to 10, including the integers 1 and 10. Unless otherwise indicated, the use of "or" in the disclosed aspects herein is the inclusive, and not the exclusive use. Only the context, and not the number of times an item is used, can determine that it is the exclusive use. For example, the phrase "A uses B or C" means that A can use B, or A can use C, or A can use both B and C. Also, the use of the term "one" or "a" or "the" is intended to be singular as well as plural, unless only the singular form is used. For example, the phrase "one or more of A, B, and C" means that A, B, or C can be present, and that one of A, B, and C can be present, and that two of A, B, and C can be present, and that all of A, B, and C can be present.

[0042] All embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions, unless otherwise specified.

[0043] All technical features and optional technical features of the present application can be combined with each other to form new technical solutions, unless otherwise specified.

[0044] Unless otherwise specified, all steps of the present application can be performed in sequence or randomly, and preferably in sequence. For example, the method comprises steps (a) and (b), which means that the method can comprise steps (a) and (b) in sequence, or steps (b) and (a) in sequence. For example, the method also comprises step (c), which means that step (c) can be added to the method in any order, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0045] Unless otherwise specified, the "includes" and "contains" mentioned in the present application are open-ended, and can also be closed. For example, the "includes" and "contains" can mean that other components not listed can also be included or contained, or only the listed components can be included or contained.

[0046] Fluorosulfone compounds have the possibility of being applied in secondary battery electrolyte due to their strong oxidative stability, suitable viscosity and suitable separator wetting. However, the harsh preparation conditions and low yield of traditional fluorosulfone compounds limit the application of fluorosulfone compounds. For example, the preparation of traditional fluorosulfone compounds usually requires the reaction of trifluoromethylsulfonyl fluoride or trifluoromethylsulfonic anhydride with alkyl Grignard reagent at a temperature of minus 20 °C in the presence of anhydrous environment, which is harsh.

[0047] Based on this, the embodiments of the present application propose a preparation method of fluorosulfone, an electrolyte, a secondary battery and an electric device.

[0048] In a first aspect, the embodiments of the present application provide a preparation method of fluorosulfone, comprising the following steps:

[0049] Mixing a sulfinate salt comprising a structure shown in Formula I with a haloalkane in a solvent to occur an alkylation reaction to prepare a fluorosulfone comprising a structure shown in Formula II; wherein the solvent can dissolve the sulfinate salt and the haloalkane;

[0050]

[0051] wherein the structural formula of haloalkane comprises R2-X, R1 comprises C1-C6 alkyl containing at least one fluorine atom, R2 comprises any one of C1-C6 alkyl, substituted or unsubstituted C6-C12 aryl, M comprises an alkali metal element, and X comprises halogen.

[0052] Herein, "C1-C6 alkyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, no unsaturation in the group, having from 1 to 6 carbon atoms, and attached to the rest of the molecule by a single bond. Suitable examples include, but are not limited to: methyl (-CH3), ethyl (-CH2CH3), 1-propyl (-CH2CH2CH3), 2-propyl (-CH(CH3)2), 1-butyl (-CH2CH2CH2CH3).

[0053] Herein, "C1-C6 alkyl containing at least one fluorine atom" refers to that at least one hydrogen atom in "C1-C6 alkyl" is replaced by a fluorine atom.

[0054] Herein, "aryl" refers to an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring compound. C6-C12 aryl refers to an aryl group comprising 6-12 carbon atoms, and suitable examples include, but are not limited to: phenyl, tolyl and xylyl.

[0055] As used herein, "substituted" means that at least one hydrogen atom of the compound or chemical moiety is replaced with another chemical moiety, wherein the substituent can be independently selected from the group consisting of hydroxyl, thiol, amino, cyano, nitro, aldehyde, halogen atom, alkenyl, alkynyl, aryl, heteroaryl, C1-C6 alkyl, C1-C6 alkoxy.

[0056] As used herein, "alkali metal element" refers to lithium element, sodium element, potassium element, rubidium element, cesium element, and francium element.

[0057] As used herein, "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), and

[0058] (Ts).

[0059] In the technical solution of the present application, the solvent capable of dissolving both the sulfinate and the halogenated alkane is used, which can make the alkylation reaction of the sulfinate and the halogenated alkane a homogeneous reaction, and the sulfinate and the halogenated alkane can react without the need for a phase transfer catalyst. The preparation process is simple, the preparation conditions are mild, the yield of the product is good, and the purity is high.

[0060] In some embodiments, R1 includes a C1-C3 alkyl group containing at least one fluorine atom; and / or, R2 includes a C1-C5 alkyl group.

[0061] Similarly, "C1-C3 alkyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, the group is free of unsaturation, has from 1 to 6 carbon atoms, and is attached to the rest of the molecule by a single bond. "C1-C5 alkyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, the group is free of unsaturation, has from 1 to 5 carbon atoms, and is attached to the rest of the molecule by a single bond.

[0062] "C1-C3 alkyl group containing at least one fluorine atom" refers to at least one hydrogen atom in "C1-C3 alkyl" is replaced by a fluorine atom.

[0063] In the case of smaller volume of the above-mentioned substituent, the reaction steric hindrance is smaller, which can further improve the efficiency of the substitution reaction.

[0064] In some embodiments, the sulfinate containing the structure shown in Formula I includes at least one of sodium trifluoromethylsulfinate, potassium trifluoromethylsulfinate, sodium trifluoroethylsulfinate, and sodium 3,3,3-trifluoropropyl-1-sulfinate. The above-mentioned sulfinate raw materials are easy to obtain, which is conducive to controlling the production cost.

[0065] In some embodiments, R2 includes any one of methyl, ethyl, isopropyl, and n-butyl, and X includes chlorine, bromine, or iodine. The above-mentioned halogenated alkane raw materials are easy to obtain, which is conducive to controlling the production cost.

[0066] In some embodiments, the solvent comprises any one of polyethylene glycol, ethanol, a mixture of water and acetonitrile, a mixture of polyethylene glycol and acetonitrile. The solvent can dissolve both the sulfinic acid salt comprising the structure of Formula I and the haloalkane, so that the alkylation reaction of the sulfinic acid salt comprising the structure of Formula I and the haloalkane is a homogeneous reaction.

[0067] In some embodiments, the number average molecular weight of the polyethylene glycol is 200-400. The molecular weight of the polyethylene glycol is in a suitable range, which is conducive to dissolving both the sulfinic acid salt comprising the structure of Formula I and the haloalkane, and can make the viscosity of the solvent using the polyethylene glycol more suitable. The molecular weight of the polyethylene glycol can be 200, 300, 400, or a range formed by any two numerical values.

[0068] In some embodiments, the volume ratio of polyethylene glycol to acetonitrile in the mixture of polyethylene glycol and acetonitrile is (1-10):1; the volume ratio of the two in the mixture of polyethylene glycol and acetonitrile is in a suitable range, which is conducive to dissolving both the sulfinic acid salt comprising the structure of Formula I and the haloalkane, and when the proportion of polyethylene glycol is larger, it is more conducive to dissolving both the sulfinic acid salt comprising the structure of Formula I and the haloalkane. The volume ratio of water to acetonitrile in the mixture of water and acetonitrile is (1-10):1; the volume ratio of the two in the mixture of water and acetonitrile is in a suitable range, which is conducive to dissolving both the sulfinic acid salt comprising the structure of Formula I and the haloalkane.

[0069] The volume ratio of polyethylene glycol to acetonitrile in the mixture of polyethylene glycol and acetonitrile includes the minimum and maximum values of the above range, and every value between such minimum and maximum values, and specific examples include but are not limited to the point values in the examples and the following point values: 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or a range formed by any two numerical values. The volume ratio of water to acetonitrile in the mixture of water and acetonitrile includes the minimum and maximum values of the above range, and every value between such minimum and maximum values, and specific examples include but are not limited to the point values in the examples and the following point values: 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or a range formed by any two numerical values.

[0070] In some embodiments, the molar ratio of the sulfinate salt comprising the structure shown in Formula I to the halogenated alkane is 1:(1-3). The molar ratio of the sulfinate salt comprising the structure shown in Formula I to the halogenated alkane within this suitable range is further advantageous for improving the conversion and yield of the alkylation reaction. Among them, the excess of halogenated alkane is advantageous for the more complete reaction of the sulfinate salt. The molar ratio of the sulfinate salt comprising the structure shown in Formula I to the halogenated alkane includes the minimum and maximum values of the above-mentioned range, and every value between such minimum and maximum values, and specific examples include but are not limited to the point values in the examples and the following point values: 1:1, 1:2, 1:3, or a range composed of any two numerical values.

[0071] In some embodiments, the mass ratio of the sulfinate salt comprising the structure shown in Formula I to the solvent is 1:(20-50). The mass ratio of the sulfinate salt comprising the structure shown in Formula I to the solvent within this suitable range is advantageous for, on the one hand, the sulfinate salt comprising the structure shown in Formula I and the halogenated alkane to be sufficiently dissolved in the solvent, and on the other hand, the reaction raw materials to be reacted at a suitable concentration, so as to further improve the conversion and yield of the alkylation reaction. The mass ratio of the sulfinate salt comprising the structure shown in Formula I to the solvent includes the minimum and maximum values of the above-mentioned range, and every value between such minimum and maximum values, and specific examples include but are not limited to the point values in the examples and the following point values: 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, 1:31, 1:32, 1:33, 1:34, 1:35, 1:36, 1:37, 1:38, 1:39, 1:40, 1:41, 1:42, 1:43, 1:44, 1:45, 1:46, 1:47, 1:48, 1:49, 1:50, or a range composed of any two numerical values.

[0072] In some embodiments, the reaction temperature of the alkylation reaction is 40-80°C. At a suitable temperature, it is advantageous to maintain a high reaction activity. The temperature value includes the minimum and maximum values of the range, and every value between such minimum and maximum values, and specific examples include but are not limited to the point values in the examples and the following point values: 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, or a range composed of any two numerical values.

[0073] In some embodiments, the reaction time of the alkylation reaction is 3-6h. At a suitable reaction time, it is advantageous for the reaction to occur sufficiently. The reaction time of the alkylation reaction can be 3h, 4h, 5h, 6h, or a range composed of any two numerical values.

[0074] In some embodiments, the step of preparing the fluorosulfone comprising the structure shown in Formula II by mixing the sulfinic acid salt comprising the structure shown in Formula I with the haloalkane in a solvent to cause an alkylation reaction comprises:

[0075] dissolving the sulfinic acid salt comprising the structure shown in Formula I in a solvent to obtain a mixture;

[0076] adding the haloalkane dropwise to the mixture to cause an alkylation reaction to prepare the fluorosulfone comprising the structure shown in Formula II.

[0077] The step of adding the haloalkane dropwise to the mixture in which the sulfinic acid salt comprising the structure shown in Formula I is dissolved facilitates the full contact of the raw materials and further facilitates the alkylation reaction to occur, thereby further facilitating the improvement of the conversion rate and yield of the alkylation reaction.

[0078] In some embodiments, the preparation method further comprises subjecting the product of the alkylation reaction to a distillation treatment to prepare the fluorosulfone comprising the structure shown in Formula II.

[0079] In the technical solution of the present application, the solvent used has a boiling point that is not close to that of the raw materials and the product (the fluorosulfone comprising the structure shown in Formula II), so that the target product (the fluorosulfone comprising the structure shown in Formula II) can be purified by simple distillation treatment, and the purification treatment step is simple and efficient.

[0080] In a second aspect, the embodiments of the present application provide an electrolyte comprising the fluorosulfone prepared by the preparation method according to the first aspect of the present application.

[0081] In a third aspect, the present application provides a secondary battery comprising: a positive electrode sheet, a negative electrode sheet, a separator, and the electrolyte according to the second aspect of the present application.

[0082] Generally, a secondary battery comprises a positive electrode sheet, a negative electrode sheet, an electrolyte, and a separator. During the charging and discharging of the battery, active ions are inserted and extracted between the positive electrode sheet and the negative electrode sheet. The electrolyte plays a role in conducting ions between the positive electrode sheet and the negative electrode sheet. The separator is arranged between the positive electrode sheet and the negative electrode sheet, mainly to prevent short circuiting of the positive and negative electrodes, while allowing ions to pass through.

[0083] The positive electrode sheet comprises a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector, and the positive electrode film layer comprises a positive electrode active material.

[0084] By way of example, the positive electrode current collector has two opposite surfaces in the thickness direction thereof, and the positive electrode film layer is arranged on either one or both of the two opposite surfaces of the positive electrode current collector.

[0085] In some embodiments, the cathode current collector can employ a metal foil or a composite current collector. For example, as a metal foil, an aluminum foil can be employed. The composite current collector can include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector can be formed by forming a metal material (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, silver alloy, etc.) on a polymer material base material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).

[0086] In some embodiments, when the secondary battery is a sodium ion battery, the cathode active material can further include a cathode active material for a sodium ion battery known in the art. For example, the cathode active material is selected from one or more of a layered transition metal oxide, a polyanionic compound, and a Prussian blue analog.

[0087] In the layered transition metal oxide, the transition metal can be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr, and Ce. The layered transition metal oxide is, for example, Na x MO2, where M is one or more of Ti, V, Mn, Co, Ni, Fe, Cr, and Cu, and 0 < x ≤ 1.

[0088] The polyanionic compound can be a compound having a sodium ion, a transition metal ion, and a tetrahedral (YO4) n- anion unit. The transition metal can be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr, and Ce; Y can be at least one of P, S, and Si; and n represents the valence of (YO4) n- .

[0089] The polyanionic compound can be a compound having a sodium ion, a transition metal ion, a tetrahedral (YO4) n- anion unit, and a halogen anion. The transition metal can be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr, and Ce; Y can be at least one of P, S, and Si; n represents the valence of (YO4) n- ; and the halogen can be at least one of F, Cl, and Br.

[0090] The polyanionic compound can be a compound having a sodium ion, a tetrahedral (YO4) n- anion unit, a polyhedral unit (ZO y ) m+ , and an optional halogen anion. Y can be at least one of P, S, and Si; and n represents the valence of (YO4)n- valence; Z represents a transition metal, which can be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr, and Ce, and m represents (ZO y m+ valence; halogen can be at least one of F, CI, and Br.

[0091] In some embodiments, the polyanionic compound is, for example, NaFePO4, Na3V2(PO4)3, NaM’PO4F (M’ is one or more of V, Fe, Mn, and Ni), and Na3(VO y )2(PO4)2F 3-2y (0≤y≤1) at least one.

[0092] In some embodiments, the Prussian blue analog can be a class of compounds having sodium ions, transition metal ions, and cyanide ions (CN - )6, where Me and Me’ are each independently at least one of Ni, Cu, Fe, Mn, Co, and Zn, 0 a Me b Me’ c (CN)6, where Me and Me’ are each independently at least one of Ni, Cu, Fe, Mn, Co, and Zn, 0

[0093] In some embodiments, the specific positive active material is, for example, NaNi 1 / 3 Fe 1 / 3 Mn 1 / 3 O2, Na4Fe3(PO4)2P2O7, NaFePO4, Na3V2(PO4)3, NaMnFe(CN)6, but is not particularly limited, and thus a positive active material conventionally used for sodium-ion batteries can be selected.

[0094] In some embodiments, the positive electrode film layer can further optionally include a binder. As an example, the binder can include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluorine-containing acrylate resin.

[0095] In some embodiments, the positive electrode film layer can further optionally include a conductive agent. As an example, the conductive agent can include at least one of super P carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

[0096] ​In some embodiments, the positive electrode sheet can be prepared by dispersing the above-mentioned components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder, and any other components, in a solvent (e.g., N-methylpyrrolidone) to form a positive electrode slurry; coating the positive electrode slurry on a positive electrode current collector; and subjecting the same to a drying, cold-pressing, or the like process to obtain the positive electrode sheet.

[0097] The negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, the negative electrode film layer including a negative electrode active material.

[0098] As an example, the negative electrode current collector has two surfaces opposite in the thickness direction thereof, and the negative electrode film layer is disposed on either one or both of the two surfaces of the negative electrode current collector.

[0099] In some embodiments, the negative electrode current collector can employ a metal foil or a composite current collector. As a metal foil, for example, a copper foil can be employed. The composite current collector can include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector can be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, silver alloy, etc.) on a polymer material base layer (e.g., a base layer of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).

[0100] In some embodiments, the negative electrode active material can employ a negative electrode active material for a battery known in the art. As an example, the negative electrode active material can include at least one of artificial graphite, natural graphite, soft carbon, hard carbon, a silicon-based material, a tin-based material, sodium titanate, etc. The silicon-based material can be selected from at least one of elemental silicon, a silicon oxide compound, a silicon-carbon composite, a silicon-nitrogen composite, and a silicon alloy. The tin-based material can be selected from at least one of elemental tin, a tin oxide compound, and a tin alloy. However, the present application is not limited to these materials, and other conventional materials that can be used as a negative electrode active material for a battery can also be used. These negative electrode active materials can be used alone or in combination of two or more.

[0101] In some embodiments, the negative electrode film layer can also optionally include a binder. The binder can be selected from at least one of styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).

[0102] In some embodiments, the negative electrode film layer can also optionally include a conductive agent. The conductive agent can be selected from at least one of super-P, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

[0103] In some embodiments, the negative electrode film layer can also optionally include other additives, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), etc.

[0104] In some embodiments, the negative electrode sheet can be prepared by dispersing the above-mentioned components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the binder, and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry; coating the negative electrode slurry on a negative electrode current collector, and after processes such as drying, cold pressing, etc., the negative electrode sheet can be obtained.

[0105] The electrolyte plays a role of conducting ions between the positive electrode sheet and the negative electrode sheet. The type of electrolyte is not specifically limited in the present application and can be selected as needed. For example, the electrolyte can be liquid, gel, or all-solid-state.

[0106] In some embodiments, the electrolyte uses an electrolyte solution. The electrolyte solution includes the electrolyte solution provided in the first aspect of the present application. The electrolyte solution includes an electrolyte salt and a solvent.

[0107] In some embodiments, the electrolyte salt can be selected from at least one of sodium hexafluorophosphate (NaPF6), sodium difluoro oxalate borate (NaDFOB), sodium tetrafluoroborate (NaBF4), sodium bis(oxalato)borate (NaBOB), sodium perchlorate, sodium hexafluoroarsenate, sodium bis(fluorosulfonyl)imide (NaFSI), sodium trifluoromethylsulfonate, sodium bis(trifluoromethylsulfonyl)imide (NaTFSI).

[0108] In some embodiments, the solvent can be selected from at least one of ethylene carbonate, propylene carbonate, methyl ethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone, and diethyl sulfone.

[0109] In some embodiments, the electrolyte solution can also optionally include an additive. For example, the additive can include a negative electrode film-forming additive, a positive electrode film-forming additive, and can also include an additive capable of improving certain properties of the battery, such as an additive for improving the overcharge performance of the battery, an additive for improving the high-temperature or low-temperature performance of the battery, etc.

[0110] In some embodiments, the material of the separator film base film can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene, and polyvinylidene fluoride. The separator film base film can be a single layer film or a multi-layer composite film, and is not particularly limited. When the separator film base film is a multi-layer composite film, the materials of the respective layers can be the same or different, and are not particularly limited.

[0111] In some embodiments, the positive electrode tab, the negative electrode tab, and the separator film can be made into an electrode assembly through a winding process or a stacking process.

[0112] In some embodiments, the secondary battery can include an outer package. The outer package can be used to package the electrode assembly and the electrolyte described above.

[0113] In some embodiments, the outer package of the secondary battery can be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The outer package of the secondary battery can also be a soft package, such as a pouch-type soft package. The material of the soft package can be plastic, and as plastic, polypropylene, polybutylene terephthalate, polybutylene succinate, or the like can be listed.

[0114] The shape of the secondary battery is not particularly limited in the present application, and can be cylindrical, square, or any other shape. For example, Figure 1 is a square structure of a secondary battery 5 as an example.

[0115] In some embodiments, referring to Figure 2 , the outer package can include a shell 51 and a cover plate 53. The shell 51 can include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity. The shell 51 has an opening communicating with the receiving cavity, and the cover plate 53 can be provided on the opening to close the receiving cavity. The positive electrode tab, the negative electrode tab, and the separator film can be made into an electrode assembly 52 through a winding process or a stacking process. The electrode assembly 52 is packaged in the receiving cavity. The electrolyte is impregnated in the electrode assembly 52. The number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and a person skilled in the art can select according to the specific actual needs.

[0116] In some embodiments, the secondary battery can be assembled into a battery module, and the number of secondary batteries contained in the battery module can be one or more, and the specific number can be selected by a person skilled in the art according to the application and capacity of the battery module.

[0117] Figure 3 is a battery module 4 as an example. Referring to Figure 3 , in the battery module 4, a plurality of secondary batteries 5 can be arranged in sequence along the length direction of the battery module 4. Of course, other arbitrary arrangements can also be made. Further, the plurality of secondary batteries 5 can be fixed by fasteners.

[0118] Optionally, the battery module 4 can further include a housing having an accommodation space, and the plurality of secondary batteries 5 are accommodated in the accommodation space.

[0119] In some embodiments, the above-described battery module can be assembled into a battery pack, and the number of battery modules contained in the battery pack can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.

[0120] Figure 4 and Figure 5 is a battery pack 1 as an example. Referring to Figure 4 and Figure 5 In the battery pack 1, a battery box and a plurality of battery modules 4 disposed in the battery box can be included. The battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 and form a closed space for accommodating the battery modules 4. The plurality of battery modules 4 can be arranged in the battery box in any manner.

[0121] In a fourth aspect, the present application provides a power utilization device including the secondary battery of the third aspect of the present application.

[0122] In addition, the present application also provides a power utilization device including at least one of the secondary battery, the battery module, or the battery pack provided by the present application. The secondary battery, the battery module, or the battery pack can be used as a power supply of the power utilization device, and can also be used as an energy storage unit of the power utilization device. The power utilization device can include a mobile device (such as a mobile phone, a notebook computer, etc.), an electric vehicle (such as a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a ship and a satellite, an energy storage system, etc., but is not limited thereto.

[0123] As the power utilization device, the secondary battery, the battery module, or the battery pack can be selected according to the use requirements thereof.

[0124] Figure 6 is a power utilization device as an example. The power utilization device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc. In order to meet the high power and high energy density requirements of the secondary battery for the power utilization device, a battery pack or a battery module can be used.

[0125] As another example of the device, it can be a mobile phone, a tablet computer, a notebook computer, etc. The device usually requires thinning, and a secondary battery can be used as a power supply.

[0126] Embodiments

[0127] Hereinafter, the examples of the present application will be described. The examples described below are illustrative and are intended to explain the present application, and are not to be understood as limiting the present application. In the examples, the specific techniques or conditions not mentioned are performed according to the techniques or conditions described in the literature in the art or according to the product manual. The reagents or instruments not mentioned by the manufacturer are all conventional products that can be obtained commercially.

[0128] Example 1

[0129] In a dry 1000ml three-necked flask, 500ml of polyethylene glycol 400, 15.6g (100mmol) of sodium trifluoromethylsulfinic acid were added, stirred for 30min under nitrogen protection, 13.8g (100mmol) of methyl iodide was slowly added dropwise, after the addition was completed, the reaction was kept at 40℃ for 4h. The excess methyl iodide was recovered by distillation at 80℃, and further heated to 160℃ to obtain colorless transparent liquid trifluoromethyl methyl sulfone 12.6g.

[0130] The differences between Examples 1-18 and Comparative Examples 1-4 of the present application and Example 1 are shown in Table 1. Among them, the preparation process of Examples 18 and Comparative Example 4 is shown as follows.

[0131] Example 18

[0132] Sodium trifluoroethylsulfinic acid was prepared by the following steps: 3.6g (30mmol) of CF3CH2Cl was added to a 100ml sealed tube under dry ice cooling, then 30ml of (CH3)2SO, 7.9g (45mmol) of Na2S2O4 and 7.6g (90mmol) of NaHCO3 were added, and the reaction was carried out at 80℃ for 12h. After the organic solvent was extracted with ethanol under reduced pressure, 4.1g of white solid CF3CH2SO2Na was obtained.19F NMR δ[D2O]: 17.6ppm (t, J = 12Hz), H NMR 8[D2O]: 3.23ppm (q, J = 12Hz).

[0133] In a dry 1000ml three-necked flask, 500ml of polyethylene glycol 400, 16.2g (100mmol) of sodium trifluoroethylsulfinic acid were added, stirred for 30min under nitrogen protection, 27.5g (200mmol) of methyl iodide was slowly added dropwise, after the addition was completed, the reaction was kept at 40℃ for 4h. The excess methyl iodide was recovered by distillation at 80℃, and colorless transparent liquid trifluoroethyl methyl sulfone 15.2g was obtained by distillation under reduced pressure at 80℃.

[0134] Comparative Example 4

[0135] In a 1000 ml three-necked flask, a mixed solution of iodomethane (27.5 g: 200 mmol), sodium trifluoromethanesulfinate (15.6 g: 100 mmol), propionitrile (250 ml) and tetrabutylammonium iodide (7.4 g: 20 mmol) was added and reacted at 40 °C for 4 h. The excess iodomethane was recovered by distillation at 80 °C and further distilled at 160 °C to obtain colorless transparent liquid trifluoromethyl methyl sulfone 7.2 g.

[0136] Performance test:

[0137] The products prepared in Examples 1-18 and Comparative Examples 1-4 were tested for yield and purity.

[0138] (1) Yield refers to the ratio of the actual production of product obtained from a unit quantity of raw material to the theoretically calculated product yield in a chemical reaction.

[0139] Yield = Actual amount of product generated / Theoretical amount of product generated x 100%.

[0140] Taking Example 1 as an example, the yield of the product (trifluoromethyl methyl sulfone) = actual amount of product (trifluoromethyl methyl sulfone) generated / theoretical amount of product (trifluoromethyl methyl sulfone) generated x 100%.

[0141] In the formula, the actual amount refers to the mass of the product obtained in the experiment, and the theoretical amount is the theoretical mass of the product calculated according to the amount of reactants and the chemical equation of the reaction. 100 mmol of sodium trifluoromethyl sulfinate theoretically generates 100 mmol of product (trifluoromethyl methyl sulfone). For ease of calculation, the above formula can be converted to molar yield:

[0142] Yield of product Y = moles of product (trifluoromethyl methyl sulfone) / moles of raw material (sodium trifluoromethyl sulfinate) x 100%.

[0143] In the formula, the moles of product (trifluoromethyl methyl sulfone) refer to the mass of the product obtained in the experiment / the molar mass of the product.

[0144] (2) Purity: Gas chromatography was used to test the purity.

[0145] Equipment model: Agilent 8860 gas chromatograph.

[0146] Detector type: FID.

[0147] Column type: HP-5.

[0148] Test method: Temperature program: initial temperature 50 °C, hold for 1 min, rate 15 °C / min, up to 240 °C, hold for 5 min.

[0149] Detector temperature: 280 °C, injection temperature: 280 °C, column flow: 1 ml / min.

[0150]

[0151]

[0152] From the results of Table 1, compared with Comparative Examples 1-4, the solvent capable of simultaneously dissolving the sulfinic acid salt and the haloalkane is used in the present application, which can make the alkylation reaction of the sulfinic acid salt and the haloalkane be a homogeneous reaction, and the sulfinic acid salt and the haloalkane can react without the phase transfer catalyst, and the yield of the product is better. The solvent used in Comparative Examples 1-3 cannot simultaneously dissolve the sulfinic acid salt and the haloalkane, and cannot realize the homogeneous reaction, and the yield of the product is lower. The solvent used in Comparative Example 4 cannot simultaneously dissolve the sulfinic acid salt and the haloalkane, and a phase transfer catalyst tetrabutylammonium iodide is used, but the yield of the target product is still not as good as that of the present application.

[0153] From Examples 1-4, it can be seen that adjusting the molar ratio between the sulfinic acid salt and the haloalkane can better promote the alkylation reaction, and the molar ratio between the sulfinic acid salt and the haloalkane of 1:(1-3) is more conducive to improving the yield of the target product.

[0154] From Examples 2, 5-6, it can be seen that adjusting the mass ratio of the sulfinic acid salt to the solvent can better play the role of the solvent, thereby being conducive to improving the yield of the target product.

[0155] From Examples 2, 7-9, it can be seen that adjusting the reaction temperature and the reaction time, the reaction conditions are mild, and the yield of the target product can be further improved.

[0156] From Examples 2, 10-16, it can be seen that different solvents capable of simultaneously dissolving the sulfinic acid salt and the haloalkane are used, which can make the alkylation reaction of the sulfinic acid salt and the haloalkane be a homogeneous reaction, and the sulfinic acid salt and the haloalkane can react without the phase transfer catalyst, thereby improving the yield of the product. Among them, the solvent containing polyethylene glycol can better simultaneously dissolve the sulfinic acid salt and the haloalkane, and the viscosity of the solvent is more suitable, or the temperature in the reaction process is more suitable, thereby further improving the yield of the product.

[0157] From Examples 2, 17, 18, it can be seen that different sulfinic acid salts and haloalkanes are used, and the solvent capable of simultaneously dissolving the sulfinic acid salt and the haloalkane is used, which can make the alkylation reaction of the sulfinic acid salt and the haloalkane be a homogeneous reaction, thereby improving the yield of the product.

[0158] The fluorosulfone prepared in Example 1 is analyzed by nuclear magnetic resonance spectroscopy, Figure 7The1H spectrum of the product prepared in Example 1, Figure 8 The19F spectrum of the fluoro-sulfone prepared in Example 1, from Figure 7 It is known that 1 H-NMR (CDCI3): δ = 3.15 (s, 3H, CH3). From Figure 8 It is known that 19 F-NMR (CDCI3): δ = -82.30 (s, 3F, CF3).

[0159] In combination with Figures 7-8 It is known that the product prepared in Example 1 is trifluoromethyl methyl sulfone.

[0160] Note that the present application is not limited to the above-described embodiments. The above-described embodiments are merely examples, and embodiments having substantially the same configuration as the technical idea and exerting the same effects within the scope of the technical solution of the present application are included in the technical scope of the present application. Furthermore, within the scope of the gist of the present application, other modes obtained by applying various modifications to the embodiments, or by combining part of the configuration elements of the embodiments, are also included in the scope of the present application.

Claims

1. A process for the preparation of a fluorosulfone characterized in that, The method comprises the following steps: mixing a sulfinate salt comprising a structure shown in Formula I with a haloalkane in a solvent to generate an alkylation reaction to prepare a fluoro-sulfone comprising a structure shown in Formula II; wherein the solvent is capable of dissolving the sulfinate salt and the haloalkane; wherein a structural formula of the haloalkane comprises R2-X, R1 comprises a C1-C6 alkyl group comprising at least one fluorine atom, R2 comprises any one of a C1-C6 alkyl group, a substituted or unsubstituted C6-C12 aryl group, M comprises an alkali metal element, and X comprises a halogen.

2. The production method according to claim 1, characterized by, R1 comprises a C1-C3 alkyl group comprising at least one fluorine atom; and / or R2 comprises a C1-C5 alkyl group.

3. The production method according to claim 1 or 2, characterized by, The sulfinate salt comprising a structure shown in Formula I comprises at least one of sodium trifluoromethylsulfinate, potassium trifluoromethylsulfinate, sodium trifluoroethylsulfinate, and sodium 3,3,3-trifluoropropyl-1-sulfinate.

4. The production method according to any one of claims 1 to 3, characterized by, R2 comprises any one of a methyl group, an ethyl group, an isopropyl group, and a n-butyl group, and X comprises chlorine, bromine, or iodine.

5. The method of any one of claims 1-4, wherein, The solvent comprises any one of polyethylene glycol, ethanol, a mixture of water and acetonitrile, and a mixture of polyethylene glycol and acetonitrile.

6. The production method according to claim 5, wherein The polyethylene glycol has a number average molecular weight of 200-400.

7. The preparation method according to claim 5, characterized in that, In the mixture of polyethylene glycol and acetonitrile, the volume ratio of polyethylene glycol to acetonitrile is (1-10):1; and / or In the mixture of water and acetonitrile, the volume ratio of water to acetonitrile is (1-10):

1.

8. The method of any one of claims 1-7, wherein, The molar ratio of the sulfinate salt comprising a structure shown in Formula I to the haloalkane is 1:(1-3).

9. The method of any one of claims 1-8, wherein, The mass ratio of the sulfinate salt comprising a structure shown in Formula I to the solvent is 1:(20-50).

10. The method of any one of claims 1-9, wherein, The reaction temperature of the alkylation reaction is 40-80°C.

11. The method of any one of claims 1-10, wherein, The reaction time of the alkylation reaction is 3-6 hours.

12. The method of any one of claims 1-11, wherein, The step of mixing the sulfinate salt comprising a structure shown in Formula I with the haloalkane in the solvent to generate the alkylation reaction to prepare the fluoro-sulfone comprising a structure shown in Formula II comprises: dissolving the sulfinate salt comprising a structure shown in Formula I into a solvent to obtain a mixture; dropping the haloalkane into the mixture to generate the alkylation reaction to prepare the fluoro-sulfone comprising a structure shown in Formula II.

13. The method of any one of claims 1-12, wherein, The preparation method further comprises subjecting a product of the alkylation reaction to a distillation treatment to prepare the fluoro-sulfone comprising a structure shown in Formula II.

14. An electrolyte, characterized by The fluoro-sulfone is prepared by the preparation method according to any one of claims 1-13.

15. A secondary battery characterized by comprising: The method comprises: a positive electrode sheet, a negative electrode sheet, a separator, and the electrolyte solution according to claim 14.

16. An electrical device, comprising: The electrical device comprises the secondary battery according to claim 15.

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