Preparation method of fluoroether, electrolyte, battery and electric device

Abstract

The invention discloses a preparation method of fluoroether, an electrolyte, a battery and a power utilization device. The invention relates to the technical field of batteries, in particular to a preparation method of fluoroether, an electrolyte, a battery and a power utilization device. The preparation method of the fluoro-ether comprises the following steps: reacting a metal fluoride solution with a carbonyl compound and an alkyl compound to obtain the fluoro-ether, wherein the fluoroether has a simple structural formula as shown in a formula (I), and R1 is straight-chain or branched-chain alkane; r2 is fluoroalkane, wherein the number of fluorine atoms is 4. The invention provides a novel fluoro-ether synthesis route which can be carried out in a normal pressure environment, the process is simple, the post-treatment is simple, the yield of fluoro-ether is improved, side reactions are reduced, and the product is easy to separate.

Description

Technical Field

[0001] This application relates to the technical field of batteries, and specifically relates to a preparation method of fluoroether, an electrolyte, a battery, and an electrical device. Background Art

[0002] Currently, the main method for synthesizing fluoroether is to use metal halides to promote the formation of perfluoroxide ions and react with hexafluoropropylene oxide to produce hexafluoropropylene oxide oligomers. The use of hexafluoropropylene oxide cannot control the degree of polymerization of the product, and the product will form dimers to hexamers, with many by-products. Summary of the Invention

[0003] This application is made in view of the above problems, and its purpose is to provide a preparation method of fluoroether with simple process, simple post-treatment, few side reactions, and easy separation of products.

[0004] To achieve the above purpose, the embodiments of this application provide a preparation method of fluoroether, an electrolyte, a battery, and an electrical device.

[0005] In a first aspect, the embodiments of this application propose a preparation method of fluoroether, including the following steps:

[0006] React a solution of metal fluoride with a carbonyl compound and an alkyl compound to obtain fluoroether;

[0007] Wherein the fluoroether has a structural formula shown in formula (Ⅰ):

[0008]

[0009] Wherein, R1 is a straight-chain or branched-chain alkane;

[0010] R2 is a fluoroalkane with 4 fluorine atoms.

[0011] Thus, in the technical solution of the embodiments of this application, by reacting a solution of metal fluoride with a carbonyl compound and an alkyl compound to obtain fluoroether, a metal-oxygen ion compound is formed at the carbonyl position, and fluorine atoms are positioned at the carbonyl position to achieve carbonyl-position fluorination. The atomic radius of fluorine element is small and its electronegativity is strong, making metal fluoride have specific catalytic properties. Therefore, metal fluoride can not only act as a catalyst to promote the formation of a metal-oxygen ion compound from a carbonyl compound, but also act as a fluorination reagent to provide fluorine atoms. R1 being a straight-chain or branched-chain alkane can improve the antioxidant performance and stability of fluoroether, thereby improving the antioxidant performance and stability of the electrolyte, increasing the yield of fluoroether, and reducing the occurrence of side reactions.

[0012] It should be noted that the reaction general formula for reacting a solution of metal fluoride with a carbonyl compound and an alkyl compound to obtain fluoroether is:

[0013]

[0014] In any embodiment, R1 is a straight-chain or branched-chain alkane having 1 to 12 carbon atoms. The straight-chain or branched-chain alkane having 1 to 12 carbon atoms can improve the antioxidant performance of the fluoroether while reducing the impact on the viscosity of the electrolyte.

[0015] In any embodiment, R2 is a fluoroalkane having 2 to 6 carbon atoms. The fluoroalkane having 2 to 6 carbon atoms can improve the antioxidant performance of the fluoroether while reducing the impact on the viscosity of the electrolyte. It should be noted that the number of fluorine atoms is 4. In any embodiment, the step of "reacting a solution of a metal fluoride with a carbonyl compound and an alkyl compound to obtain a fluoroether" includes:

[0016] Mixing a metal fluoride with an organic solvent to obtain a metal fluoride solution;

[0017] Adding a carbonyl compound to the metal fluoride solution to obtain a mixture;

[0018] Mixing an alkyl compound with the mixture and reacting to obtain a fluoroether.

[0019] By first mixing a metal fluoride with an organic solvent to obtain a metal fluoride solution, then adding a carbonyl compound to the metal fluoride solution to obtain a mixture, and finally mixing an alkyl compound with the mixture and reacting to obtain a fluoroether, it is possible to make the metal fluoride react with the carbonyl compound first to form an intermediate, and then the intermediate reacts with the alkyl compound to form a fluoroether.

[0020] In any embodiment, the organic solvent includes at least one of acetonitrile, dichloromethane, dimethyl sulfoxide, sulfolane, and dimethylformamide. Using at least one of the above organic solvents can improve the reaction rate; and / or,

[0021] The mass ratio of the organic solvent to the metal fluoride is 1:(1 - 10). Using the above mass ratio of the organic solvent to the metal fluoride can increase the concentration of the metal fluoride, improve the reaction rate, and increase the yield of the fluoroether; optionally, the mass ratio of the organic solvent to the metal fluoride is 1:(2 - 5), which can further increase the concentration of the metal fluoride and increase the yield of the fluoroether.

[0022] In any embodiment, the metal fluoride includes at least one of an alkali metal fluoride and an alkaline earth metal fluoride. Using at least one of an alkali metal fluoride and an alkaline earth metal fluoride can improve the catalytic performance and reaction activity of the metal fluoride and increase the yield of the fluoroether; and / or,

[0023] The carbonyl compound includes a carbonyl compound having 2 to 6 carbon atoms. By using the above-mentioned hydroxy compound, the antioxidant performance and stability of the fluoroether can be improved, thereby improving the antioxidant performance and stability of the electrolyte, increasing the yield of the fluoroether, and reducing the occurrence of side reactions; and / or,

[0024] The alkyl compound includes at least one of methane compounds, ethane compounds, propane compounds, and toluene compounds. By using at least one of methane compounds, ethane compounds, propane compounds, and toluene compounds, a suitable alkyl compound can be selected according to needs to obtain the desired fluoroether.

[0025] In any embodiment, the alkaline earth metal fluoride includes at least one of calcium fluoride, barium fluoride, and magnesium fluoride. By using at least one of the above-mentioned alkali metal fluorides, the catalytic performance and reaction activity of the metal fluoride can be further improved, and the yield of the fluoroether can be increased; and / or,

[0026] The alkali metal fluoride includes at least one of lithium fluoride, potassium fluoride, sodium fluoride, and cesium fluoride. By using at least one of the above-mentioned alkaline earth metal fluorides, the catalytic performance and reaction activity of the metal fluoride are improved, and the yield of the fluoroether is increased.

[0027] In any embodiment, the carbonyl compound includes at least one of glyoxal, oxalyl chloride, oxalyl bromide, malondialdehyde, malonyl chloride, succinaldehyde, and succinyl chloride. By using at least one of the above-mentioned carbonyl compounds, a suitable carbonyl compound can be selected according to needs to obtain the desired fluoroether; and / or,

[0028] The methane compound includes at least one of iodomethane, bromomethane, and methyl trifluoromethanesulfonate. By using at least one of iodomethane, bromomethane, and methyl trifluoromethanesulfonate included in the methane compound, a suitable methane compound can be selected according to needs to obtain the desired fluoroether; and / or,

[0029] The ethane compound includes at least one of iodoethane, bromoethane, and chloroethane. By using at least one of iodoethane, bromoethane, and chloroethane, a suitable ethane compound can be selected according to needs to obtain the desired fluoroether; and / or,

[0030] The propane compound includes at least one of iodopropane, bromopropane, and chloropropane. By using at least one of iodopropane, bromopropane, and chloropropane, a suitable propane compound can be selected according to needs to obtain the desired fluoroether; and / or,

[0031] The toluene compound includes at least one of ethyl p-toluenesulfonate and methyl p-toluenesulfonate. By using at least one of ethyl p-toluenesulfonate and methyl p-toluenesulfonate, a suitable toluene compound can be selected according to needs to obtain the desired fluoroether.

[0032] In any embodiment, the molar ratio of the carbonyl compound to the metal fluoride is 1:(1-15). The molar ratio of the carbonyl compound to the metal fluoride within this range can increase the yield of the fluoroether and reduce the occurrence of side reactions. Optionally, the molar ratio of the carbonyl compound to the metal fluoride is 1:(4-10), which can further increase the yield of the fluoroether and reduce the occurrence of side reactions; and / or,

[0033] The molar ratio of the carbonyl compound to the alkyl compound is 1:(1-10). The molar ratio of the carbonyl compound to the alkyl compound within this range can increase the yield of the fluoroether and reduce the occurrence of side reactions. Optionally, the molar ratio of the carbonyl compound to the alkyl compound is 1:(1-4), which can further increase the yield of the fluoroether and reduce the occurrence of side reactions.

[0034] In any embodiment, the reaction temperature is -20 to 120 °C. Within this reaction temperature range, the yield of the fluoroether can be increased and the occurrence of side reactions can be reduced. Optionally, the reaction temperature is -10 to 100 °C, which can further increase the yield of the fluoroether and reduce the occurrence of side reactions; and / or,

[0035] The reaction time is 1 to 72 h. Within this reaction time, the yield of the fluoroether can be increased and the occurrence of side reactions can be reduced. Optionally, the reaction time is 24 to 48 h, which can further increase the yield of the fluoroether and reduce the occurrence of side reactions.

[0036] In a second aspect, an electrolyte solution provided by an embodiment of the present application includes a fluoroether prepared by the method for preparing a fluoroether according to the first aspect of the present application.

[0037] In a third aspect, an embodiment of the present application provides a battery, including the electrolyte solution according to the second aspect of the present application.

[0038] In a fourth aspect, an embodiment of the present application provides an electrical device, including the battery according to the third aspect of the present application. Description of the Drawings

[0039] Figure 1 is a schematic diagram of a secondary battery according to an embodiment of the present application.

[0040] Figure 2 is Figure 1 a decomposition diagram of the secondary battery according to an embodiment of the present application shown in

[0041] Figure 3 is a schematic diagram of a battery module according to an embodiment of the present application.

[0042] Figure 4 It is a schematic diagram of a battery pack according to an embodiment of the present application.

[0043] Figure 5 is Figure 4 An exploded view of the battery pack according to an embodiment of the present application shown.

[0044] Figure 6 It is a schematic diagram of an electrical device using a secondary battery as a power source according to an embodiment of the present application.

[0045] Figure 7 It is a carbon spectrum diagram of the fluorinated ether prepared in Example 16 of the present application.

[0046] Figure 8 It is a hydrogen spectrum diagram of the fluorinated ether prepared in Example 16 of the present application.

[0047] Figure 9 It is a fluorine spectrum diagram of the fluorinated ether prepared in Example 16 of the present application.

[0048] Explanation of reference numerals:

[0049] 1 Battery pack; 2 Upper box body; 3 Lower box body; 4 Battery module; 5 Secondary battery; 51 Housing; 52 Electrode assembly; 53 Top cover assembly. Specific embodiments

[0050] Hereinafter, embodiments of a method for preparing a fluorinated ether, an electrolyte, a battery, and an electrical device of the present application are specifically disclosed. However, there may be cases where unnecessary details are omitted. For example, there are cases where detailed descriptions of well-known matters are omitted and repeated descriptions of actually identical structures are omitted. This is to avoid the following description from becoming unnecessarily long and to facilitate the understanding of those skilled in the art. In addition, the drawings and the following description are provided for those skilled in the art to fully understand the present application and are not intended to limit the subject matter recited in the claims.

[0051] The "ranges" disclosed in this application are defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of a particular range. The ranges defined in this way can include or exclude the end values and can be combined arbitrarily, that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60 - 120 and 80 - 110 are listed for a specific parameter, ranges of 60 - 110 and 80 - 120 are also contemplated. In addition, if the minimum range values of 1 and 2 are listed, and if the maximum range values of 3, 4, and 5 are listed, the following ranges are all contemplated: 1 - 3, 1 - 4, 1 - 5, 2 - 3, 2 - 4, and 2 - 5. In this application, unless otherwise stated, the numerical range "a - b" represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0 - 5" means that all real numbers between "0 - 5" are fully listed herein, and "0 - 5" is only an abbreviated representation of these numerical combinations. Additionally, when stating that a certain parameter is an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0052] If there is no special instruction, all embodiments and optional embodiments of this application can be combined with each other to form new technical solutions.

[0053] If there is no special instruction, all technical features and optional technical features of this application can be combined with each other to form new technical solutions.

[0054] If there is no special instruction, all steps of this application can be carried out in sequence or randomly, preferably in sequence. For example, the method includes steps (a) and (b), which means that the method can include steps (a) and (b) carried out in sequence, or can also include steps (b) and (a) carried out in sequence. For example, it is mentioned that the method may further include step (c), which means that step (c) can be added to the method in any order. For example, the method can include steps (a), (b), and (c), or can also include steps (a), (c), and (b), or can also include steps (c), (a), and (b), etc.

[0055] Currently, the main method for synthesizing fluoroethers is to use metal halides to promote the formation of perfluoroxide ions and react with hexafluoropropylene oxide to produce hexafluoropropylene oxide oligomers. Using hexafluoropropylene oxide cannot control the degree of polymerization of the product, and the product will form dimers to hexamers, with many by-products.

[0056] Therefore, research on the synthesis of fluoroethers has emerged in an endless stream. For example, a production method of a fluoroether: by using a metal halide to promote the formation of perfluoroxide ions and reacting with hexafluoropropylene oxide to generate hexafluoropropylene oxide oligomers. However, the above preparation method of fluoroethers cannot control the degree of polymerization of the product, and the product will form dimers to hexamers, with many by-products.

[0057] Surprisingly, by using a carbonyl compound, a metal fluoride and an alkylating agent to obtain a fluoroether, the yield of the fluoroether can be increased and side reactions can be reduced.

[0058] Based on this, the present application provides a preparation method of a fluoroether, an electrolyte, a battery and an electrical device.

[0059] React a solution of a metal fluoride with a carbonyl compound and an alkyl compound to obtain a fluoroether;

[0060] Wherein the fluoroether has a structural formula shown in formula (Ⅰ):

[0061]

[0062] Wherein, R1 is a straight-chain or branched-chain alkane;

[0063] R2 is a fluoroalkane, and the number of fluorine atoms is 4.

[0064] Thus, in the technical solution of the embodiment of the present application, by reacting a solution of a metal fluoride with a carbonyl compound and an alkyl compound to obtain a fluoroether, by forming a metal-oxygen ion compound at the carbonyl position, the fluorine atom is positioned at the carbonyl position to achieve carbonyl-position fluorination. The atomic radius of the fluorine element is small and the electronegativity is strong, so that the metal fluoride has specific catalytic properties, so that the metal fluoride can not only act as a catalyst to promote the formation of a metal-oxygen ion compound by the carbonyl compound, but also act as a fluorination reagent to provide fluorine atoms. R1 being a straight-chain or branched-chain alkane can improve the antioxidant performance and stability of the fluoroether, and further improve the antioxidant performance and stability of the electrolyte. Increase the yield of the fluoroether and reduce the occurrence of side reactions.

[0065] It should be noted that the reaction general formula for reacting a solution of a metal fluoride with a carbonyl compound and an alkyl compound to obtain a fluoroether is:

[0066]

[0067] In any embodiment, R1 is a straight-chain or branched-chain alkane with 1 to 12 carbon atoms. A straight-chain or branched-chain alkane with 1 to 12 carbon atoms can improve the antioxidant performance of the fluoroether and at the same time reduce the influence on the viscosity of the electrolyte.

[0068] In any embodiment, R2 is a fluoroalkane having 2 to 6 carbon atoms. The fluoroalkane having 2 to 6 carbon atoms can improve the antioxidant performance of the fluoroether while reducing the impact on the viscosity of the electrolyte. It should be noted that the number of fluorine atoms is 4. In any embodiment, the step of "reacting a solution of metal fluoride with a carbonyl compound and an alkyl compound to obtain a fluoroether" includes:

[0069] Mixing the metal fluoride with an organic solvent to obtain a metal fluoride solution;

[0070] Adding the carbonyl compound to the metal fluoride solution to obtain a mixture;

[0071] Mixing the alkyl compound with the mixture and reacting to obtain a fluoroether.

[0072] By first mixing the metal fluoride with an organic solvent to obtain a metal fluoride solution, then adding the carbonyl compound to the metal fluoride solution to obtain a mixture, and finally mixing the alkyl compound with the mixture and reacting to obtain a fluoroether, it is possible to make the metal fluoride react with the carbonyl compound to form an intermediate first, and then the intermediate reacts with the alkyl compound to form a fluoroether.

[0073] In any embodiment, the organic solvent includes at least one of acetonitrile, dichloromethane, dimethyl sulfoxide, sulfolane, and dimethylformamide. Using at least one of the above organic solvents can increase the reaction rate.

[0074] In any embodiment, the mass ratio of the organic solvent to the metal fluoride is 1:(1 to 10). Using the above mass ratio of the organic solvent to the metal fluoride can increase the concentration of the metal fluoride and the yield of the fluoroether. The mass ratio of the organic solvent to the metal fluoride can be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10; optionally, the mass ratio of the organic solvent to the metal fluoride is 1:(2 to 5), which can further increase the concentration of the metal fluoride and the yield of the fluoroether.

[0075] In any embodiment, the metal fluoride includes at least one of an alkali metal fluoride and an alkaline earth metal fluoride. Using at least one of the alkali metal fluoride and the alkaline earth metal fluoride can improve the catalytic performance and reaction activity of the metal fluoride and increase the yield of the fluoroether.

[0076] In any embodiment, the carbonyl compound includes a carbonyl compound having 2 to 6 carbon atoms. Using the above hydroxy compound can improve the antioxidant performance and stability of the fluoroether, thereby improving the antioxidant performance and stability of the electrolyte, increasing the yield of the fluoroether, and reducing the occurrence of side reactions.

[0077] In any embodiment, the alkyl compound includes at least one of methane compounds, ethane compounds, propane compounds, and toluene compounds. By using at least one of methane compounds, ethane compounds, propane compounds, and toluene compounds, a suitable alkyl compound can be selected according to needs to obtain the desired fluoroether.

[0078] In any embodiment, the alkaline earth metal fluoride includes at least one of calcium fluoride, barium fluoride, and magnesium fluoride. By using at least one of the above alkaline earth metal fluorides, the catalytic performance and reaction activity of the metal fluoride can be further improved, and the yield of the fluoroether can be increased.

[0079] In any embodiment, the alkali metal fluoride includes at least one of lithium fluoride, potassium fluoride, sodium fluoride, and cesium fluoride. By using at least one of the above alkaline earth metal fluorides, the catalytic performance and reaction activity of the metal fluoride can be improved, and the yield of the fluoroether can be increased.

[0080] In any embodiment, the carbonyl compound includes at least one of glyoxal, oxalyl chloride, oxalyl bromide, malondialdehyde, malonyl chloride, succinaldehyde, and succinyl chloride. By using at least one of the above carbonyl compounds, a suitable carbonyl compound can be selected according to needs to obtain the desired fluoroether.

[0081] In any embodiment, the methane compound includes at least one of methyl iodide, methyl bromide, and ethyl trifluoromethanesulfonate. By using at least one of methyl iodide, methyl bromide, and ethyl trifluoromethanesulfonate as the methane compound, a suitable methane compound can be selected according to needs to obtain the desired fluoroether.

[0082] In any embodiment, the ethane compound includes at least one of ethyl iodide, ethyl bromide, and ethyl chloride. By using at least one of ethyl iodide, ethyl bromide, and ethyl chloride, a suitable ethane compound can be selected according to needs to obtain the desired fluoroether.

[0083] In any embodiment, the propane compound includes at least one of propyl iodide, propyl bromide, and propyl chloride. By using at least one of propyl iodide, propyl bromide, and propyl chloride, a suitable propane compound can be selected according to needs to obtain the desired fluoroether.

[0084] In any embodiment, the toluene compound includes at least one of ethyl p-toluenesulfonate and methyl p-toluenesulfonate. By using at least one of ethyl p-toluenesulfonate and methyl p-toluenesulfonate, a suitable toluene compound can be selected according to needs to obtain the desired fluoroether.

[0085] In any embodiment, the molar ratio of the carbonyl compound to the metal fluoride is 1:(1-15). When the molar ratio of the carbonyl compound to the metal fluoride is within this range, the yield of the fluoroether can be increased and the occurrence of side reactions can be reduced. The molar ratio of the carbonyl compound to the metal fluoride can be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14 or 1:15; optionally, the molar ratio of the carbonyl compound to the metal fluoride is 1:(4-10), which can further increase the yield of the fluoroether and reduce the occurrence of side reactions.

[0086] In any embodiment, the molar ratio of the carbonyl compound to the alkyl compound is 1:(1-10). When the molar ratio of the carbonyl compound to the alkyl compound is within this range, the yield of the fluoroether can be increased and the occurrence of side reactions can be reduced. The molar ratio of the carbonyl compound to the alkyl compound can be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10; optionally, the molar ratio of the carbonyl compound to the alkyl compound is 1:(1-4), which can further increase the yield of the fluoroether and reduce the occurrence of side reactions.

[0087] In any embodiment, the reaction temperature is -20 to 120 °C. Within this reaction temperature range, the yield of the fluoroether can be increased and the occurrence of side reactions can be reduced. The reaction temperature can be -20 °C, -10 °C, 0 °C, 10 °C, 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C or 120 °C; optionally, the reaction temperature is -10 to 100 °C, which can further increase the yield of the fluoroether and reduce the occurrence of side reactions.

[0088] In any embodiment, the reaction time is 1 to 72 h. During this reaction time, the yield of the fluoroether can be increased and the occurrence of side reactions can be reduced. The reaction time can be 1 h, 12 h, 24 h, 36 h, 48 h, 60 h or 72 h; optionally, the reaction time is 24 to 48 h, which can further increase the yield of the fluoroether and reduce the occurrence of side reactions.

[0089] In a second aspect, an electrolyte solution provided by an embodiment of the present application includes a fluoroether prepared by the method for preparing a fluoroether according to the first aspect of the present application. In a third aspect, a battery provided by an embodiment of the present application includes the electrolyte solution according to the second aspect of the present application.

[0090] In any embodiment, the battery includes a primary battery or a secondary battery.

[0091] In one embodiment of the present application, a secondary battery is provided. Generally, a secondary battery includes a positive electrode sheet, a negative electrode sheet, an electrolyte, and a separator. During the charge and discharge process of the battery, active ions are embedded and extracted back and forth 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 disposed between the positive electrode sheet and the negative electrode sheet, mainly playing a role in preventing short circuit between the positive and negative electrodes, and at the same time allowing ions to pass through.

[0092] The positive electrode sheet includes a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector.

[0093] As an example, the positive electrode current collector has two surfaces opposite to each other in its own thickness direction, and the positive electrode film layer is provided on any one or both of the two opposite surfaces of the positive electrode current collector.

[0094] In some embodiments, the positive electrode current collector may be a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector may be formed by forming a metal material (such as aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).

[0095] In some embodiments, the positive electrode active material may be a positive electrode active material known in the art for lithium ion batteries. As an example, the positive electrode active material may include at least one of the following materials: lithium phosphate with an olivine structure, lithium transition metal oxides, and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as the positive electrode active material of the battery may also be used. These positive electrode active materials may be used alone or in combination of two or more. Among them, examples of lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide (such as LiCoO2), lithium nickel oxide (such as LiNiO2), lithium manganese oxide (such as LiMnO2, LiMn2O4), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 (which can also be abbreviated as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O2 (which can also be abbreviated as NCM 523 ), LiNi 0.5 Co 0.25Mn 0.25 O2 (which can also be abbreviated as NCM 211 )、LiNi 0.6 Co 0.2 Mn 0.2 O2 (which can also be abbreviated as NCM 622 )、LiNi 0.8 Co 0.1 Mn 0.1 O2 (which can also be abbreviated as NCM 811 )、lithium nickel cobalt aluminum oxide (such as LiNi 0.85 Co 0.15 Al 0.05 O2), and at least one of its modified compounds, etc. Examples of olivine-structured lithium-containing phosphates can include but are not limited to lithium iron phosphate (such as LiFePO4 (which can also be abbreviated as LFP)), a composite material of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO4), a composite material of lithium manganese phosphate and carbon, lithium manganese iron phosphate, and at least one of a composite material of lithium manganese iron phosphate and carbon.

[0096] In some embodiments, the positive electrode film layer further includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorinated acrylate resin.

[0097] In some embodiments, the positive electrode film layer further includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

[0098] In some embodiments, the positive electrode sheet can be prepared by the following method: dispersing the above components for preparing the positive electrode sheet, such as the positive electrode active material, conductive agent, binder, and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; coating the positive electrode slurry on the positive electrode sheet structure, and after processes such as drying and cold pressing, the positive electrode sheet can be obtained.

[0099] The negative electrode sheet includes a positive electrode current collector and a negative electrode film layer provided on at least one surface of the positive electrode current collector, and the negative electrode film layer includes a negative electrode active material.

[0100] As an example, the negative electrode sheet structure includes a negative electrode current collector having two surfaces opposite to each other in its own thickness direction, and the negative electrode film layer is provided on any one or both of the two opposite surfaces of the negative electrode current collector structure.

[0101] In some embodiments, the negative electrode current collector may be a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector may be formed by forming a metal material (such as copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).

[0102] In some embodiments, the negative electrode active material may be a negative electrode active material for batteries well-known in the art. As an example, the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, and lithium titanate, etc. The silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin oxide compounds, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as the negative electrode active material of the battery may also be used. These negative electrode active materials may be used alone or in combination of two or more.

[0103] In some embodiments, the negative electrode film layer further includes a binder. The binder may 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).

[0104] In some embodiments, the negative electrode film layer further includes a conductive agent. The conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

[0105] In some embodiments, the negative electrode film layer further includes other additives, such as thickeners (such as sodium carboxymethyl cellulose (CMC-Na)), etc.

[0106] In some embodiments, the negative electrode sheet may be prepared by the following method: dispersing the 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 (such as deionized water) to form a negative electrode slurry; coating the negative electrode slurry on the negative electrode sheet structure, and after processes such as drying and cold pressing, the negative electrode sheet can be obtained.

[0107] The electrolyte plays a role in conducting ions between the positive electrode and the negative electrode. There is no specific limitation on the type of electrolyte in this application, and it can be selected according to requirements. For example, the electrolyte can be liquid, gel-like, or all-solid-state.

[0108] In some embodiments, the electrolyte uses an electrolytic solution. The electrolytic solution includes an electrolyte salt and a solvent.

[0109] In some embodiments, the electrolyte salt can be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluoro(oxalato)borate, lithium bis(oxalato)borate, lithium difluoro bis(oxalato)phosphate, and lithium tetrafluoro(oxalato)phosphate.

[0110] In some embodiments, the solvent can be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl 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.

[0111] In some embodiments, the electrolytic solution may optionally further include additives. For example, the additives can include negative electrode film-forming additives, positive electrode film-forming additives, and can also include additives that can improve certain battery performance, such as additives for improving the overcharge performance of the battery, additives for improving the high-temperature or low-temperature performance of the battery, etc.

[0112] The electrolytic solution further includes the fluoroether prepared in the first aspect of this application.

[0113] In some embodiments, the secondary battery further includes a separator. There is no particular limitation on the type of separator in this application, and any well-known porous structure separator with good chemical stability and mechanical stability can be selected.

[0114] In some embodiments, the material of the separator can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene, and polyvinylidene fluoride. The separator can be a single-layer film or a multi-layer composite film, without particular limitation. When the separator is a multi-layer composite film, the materials of each layer can be the same or different, without particular limitation.

[0115] In some embodiments, the positive electrode, the negative electrode, and the separator can be made into an electrode assembly by a winding process or a stacking process.

[0116] In some embodiments, the secondary battery may include an outer package. The outer package can be used to encapsulate the above electrode assembly and electrolyte.

[0117] In some embodiments, the outer packaging of the secondary battery can be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc. The outer packaging of the secondary battery can also be a soft package, such as a pouch soft package. The material of the soft package can be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate, etc.

[0118] The present application places no particular limitation on the shape of the secondary battery, and it can be cylindrical, square, or any other arbitrary shape. For example, Figure 1 is a secondary battery 5 with a square structure as an example.

[0119] In some embodiments, with reference to Figure 2 , the outer packaging may include a housing 51 and a cover plate 53. Among them, the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose to form a receiving cavity. The housing 51 has an opening communicating with the receiving cavity, and the cover plate 53 can be covered on the opening to close the receiving cavity. The positive electrode sheet, the negative electrode sheet, and the separator can form an electrode assembly 52 through a winding process or a stacking process. The electrode assembly 52 is encapsulated in the receiving cavity. The electrolyte is infiltrated in the electrode assembly 52. The number of electrode assemblies 52 included in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual requirements.

[0120] In some embodiments, secondary batteries can be assembled into a battery module, and the number of secondary batteries included in the battery module can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery module.

[0121] Figure 3 is a battery module 4 as an example. With reference to Figure 3 , in the battery module 4, multiple secondary batteries 5 can be arranged in sequence along the length direction of the battery module 4. Of course, they can also be arranged in any other arbitrary manner. Further, the multiple secondary batteries 5 can be fixed by fasteners.

[0122] Optionally, the battery module 4 can further include a housing with a receiving space, and the multiple secondary batteries 5 are accommodated in the receiving space.

[0123] In some embodiments, the above battery module can be further assembled into a battery pack, and the number of battery modules included in the battery pack can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery pack.

[0124] Figure 4 and Figure 5 is a battery pack 1 as an example. With reference to Figure 4 and Figure 5, a battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box. The battery box includes an upper box body 2 and a lower box body 3. The upper box body 2 can cover 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.

[0125] In a fourth aspect, an embodiment of the present application provides an electrical device, including the battery of the third aspect of the present application.

[0126] In addition, the present application further provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application. The secondary battery, battery module, or battery pack can be used as the power source of the electrical device or as the energy storage unit of the electrical device. The electrical device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships, satellites, energy storage systems, etc., but is not limited thereto.

[0127] As the electrical device, a secondary battery, battery module, or battery pack can be selected according to its usage requirements.

[0128] Figure 6 is an electrical device as an example. The electrical device is a pure electric vehicle, hybrid electric vehicle, or plug-in hybrid electric vehicle, etc. In order to meet the high power and high energy density requirements of the electrical device for the secondary battery, a battery pack or battery module can be used.

[0129] As another example of the device, it can be a mobile phone, tablet computer, laptop computer, etc. This device usually requires being thin and light, and a secondary battery can be used as the power source.

[0130] The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0131] In the present application, the preparation method of fluoroether can be carried out by dispersing metal fluoride in an organic solvent and then sequentially dropping a carbonyl compound and an alkylating agent for reaction, and rectifying the reactants to obtain fluoroether. Among them, the reaction temperature is at room temperature, and the reaction time is taken as 18 h for illustration. Among them, the other parameters of the preparation methods of fluoroethers in Examples 1 to 18 and Comparative Example 1 are according to the parameters in Table 1.

[0132] Table 1 Parameters of the preparation methods of fluoroethers in Examples 1 to 18 and Comparative Example 1

[0133]

[0134] In Comparative Example 1, since metal fluoride was not used as a raw material, fluoroethers could not be produced.

[0135] Comparative Example 2

[0136] The preparation method of the fluoroether in Comparative Example 2 was as follows:

[0137] Potassium iodide (1.7 g, 0.01 mol) and diethylene glycol (50 g) were mixed and cooled to -20 °C. Trifluoroacetyl fluoride, CF3COF (10 g, 0.086 mol), was added in gaseous form with stirring for about 10 minutes, and the mixture was further stirred for 20 minutes. Hexafluoropropylene oxide (17.9 g, 80% purity, 0.086 mol) was added and the mixture was stirred until no liquid refluxed. The fluorine-containing compound layer was separated and reacted with methanol-BF3 at 0 - 5 °C for 10 minutes to convert the volatile acyl fluoride into the corresponding fluoroether. The fluoroether contained a compound of about 100% fluorine-containing aliphatic ether, C2F5O[CF(CF3)CF2O]xCF(CF3)CO2CH3, and its product distribution was x = 0 (49%), x = 1 (45%) and x = 2 (6%). Among them, hexafluoropropylene oxide oligomers were formed. There were a variety of by-products and the separation was relatively difficult.

[0138] Performance Test

[0139] The product purity and product yield of the fluoroethers prepared by the preparation methods of Examples 1 to 20 and Comparative Examples 1 to 2 were statistically analyzed. Among them, the product purity was measured by gas chromatography, and the product yield = actual production amount of the target product / theoretical production amount of the target product × 100%. The results are shown in Table 1. The fluoroether prepared in Example 16 was characterized, and its carbon spectrum was as Figure 7 shown, the hydrogen spectrum was as Figure 8 shown, and the fluorine spectrum was as Figure 9 shown.

[0140] As can be seen from Table 1, by reacting a solution of metal fluoride with a carbonyl compound and an alkyl compound, fluoroethers were obtained. By forming a metal-oxygen ion compound at the carbonyl position, fluorine atoms were positioned at the carbonyl position to achieve carbonyl-position fluorination. The atomic radius of the fluorine element is small and its electronegativity is relatively strong, making metal fluoride have specific catalytic properties. Thus, metal fluoride can not only act as a catalyst to promote the formation of a metal-oxygen ion compound from a carbonyl compound, but also act as a fluorination reagent to provide fluorine atoms. When R1 is a straight-chain or branched-chain alkane, it can improve the antioxidant performance and stability of the fluoroether, thereby improving the antioxidant performance and stability of the electrolyte, increasing the yield of the fluoroether, and reducing the occurrence of side reactions.

[0141] Figure 7 It can be known that the peak at 15 ppm is the carbon of the methyl group, the peak at 60 ppm is the carbon of the methylene group, and the peak at 117 is the quaternary carbon.

[0142] Figure 8 It can be seen that the triplet at 1.4 ppm is the hydrogen on the methyl group, and the quartet at 4.0 ppm is the hydrogen on the methylene group connected to oxygen.

[0143] Figure 9 It can be seen that the peak at -85 ppm is the peak of fluorine.

[0144] The above are only the preferred embodiments of the present invention, and do not limit the patent scope of the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the patent protection scope of the present invention.

Claims

1. A method for preparing a fluoroether, characterized in that, It includes the following steps: React a solution of metal fluoride with a carbonyl compound and an alkyl compound to obtain a fluoroether; Wherein the fluoroether has the structural formula shown in formula (Ⅰ): Wherein, R1 is a straight-chain or branched-chain alkane; R2 is a fluoroalkane, and the number of fluorine atoms is 4.

2. The method for preparing a fluoroether according to claim 1, wherein R1 is a straight-chain or branched-chain alkane with 1 to 12 carbon atoms.

3. The method for preparing a fluoroether according to claim 1 or 2, characterized in that, R2 is a fluoroalkane with 2 to 6 carbon atoms.

4. The method for preparing a fluoroether according to any one of claims 1 to 3, characterized in that, The step of "reacting a solution of metal fluoride with a carbonyl compound and an alkyl compound to obtain a fluoroether" includes: Mix metal fluoride with an organic solvent to obtain a metal fluoride solution; Add the carbonyl compound to the metal fluoride solution to obtain a mixture; Mix the alkyl compound with the mixture and react to obtain a fluoroether.

5. The method for preparing a fluoroether according to claim 4, wherein The organic solvent includes at least one of acetonitrile, dichloromethane, dimethyl sulfoxide, sulfolane, and dimethylformamide; and / or, The mass ratio of the organic solvent to the metal fluoride is 1:(1 - 10).

6. The method for preparing a fluoroether according to any one of claims 1 to 5, wherein The metal fluoride includes at least one of alkali metal fluorides and alkaline earth metal fluorides; and / or, The carbonyl compound includes a carbonyl compound with 2 to 6 carbon atoms; and / or, The alkyl compound includes at least one of methane compounds, ethane compounds, propane compounds, and toluene compounds.

7. The method for preparing a fluoroether according to claim 6, wherein The alkaline earth metal fluoride includes at least one of calcium fluoride, barium fluoride, and magnesium fluoride; and / or, The alkali metal fluoride includes at least one of lithium fluoride, potassium fluoride, sodium fluoride, and cesium fluoride.

8. The method for preparing a fluoroether according to claim 6 or 7, wherein The carbonyl compound includes at least one of glyoxal, oxalyl chloride, oxalyl bromide, malondialdehyde, malonyl chloride, succinaldehyde, and succinyl chloride; and / or, The methane compound includes at least one of methyl iodide, methyl bromide, and ethyl trifluoromethanesulfonate; and / or, The ethane compound includes at least one of ethyl iodide, ethyl bromide, and chloroethane; and / or, The propane compound includes at least one of propyl iodide, propyl bromide, and propyl chloride; and / or, The toluene compound includes at least one of ethyl p-toluenesulfonate and methyl p-toluenesulfonate.

9. The method for preparing a fluoroether according to any one of claims 1 to 8, wherein The molar ratio of the carbonyl compound to the metal fluoride is 1:(1 - 15); and / or, The molar ratio of the carbonyl compound to the alkyl compound is 1:(1 - 10).

10. The method for preparing a fluoroether according to any one of claims 1 to 9, wherein The temperature of the reaction is -20 to 120 °C; and / or, The time of the reaction is 1 to 72 h.

11. An electrolyte, characterized in that, It includes a fluoroether prepared by the method for preparing a fluoroether according to any one of claims 1 to 10.

12. A battery, characterized in that, It includes the electrolyte according to claim 11.

13. An electrical device, characterized in that, It includes the battery according to claim 12.

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