Preparation method of fluoroether, battery and electric device

Abstract

The invention discloses a preparation method of fluoro-ether, a battery and a power utilization device, and relates to the technical field of batteries, the battery comprises a positive pole piece, a negative pole piece and an electrolyte, the electrolyte comprises fluoro-ether, the fluoro-ether has a structural formula represented by a formula (I), R1 and R3 are independently selected from alkyl groups, R2 is 1-3 fluorine atoms, and R3 is 1-3 fluorine atoms. And R4 represents 1 to 3 fluorine atoms and is different from R2. Asymmetric fluoro-ether with different numbers of fluorine atoms introduced to carbon atoms at two ends is added into the electrolyte of the battery, the fluoro-ether has high oxidation resistance and oxidation stability, the oxidation resistance of the electrolyte can be improved, meanwhile, the asymmetric structure of the fluoro-ether can also improve the solvation ability of the electrolyte, and the service life of the battery is prolonged. The formation of an SEI film of the battery is promoted, so that the capacity retention ratio and the cycling stability of the battery can be improved.

Description

Technical Field

[0001] This application relates to the field of battery technology, specifically to methods for preparing fluorinated ethers, batteries, and electrical devices. Background Technology

[0002] Introducing fluorine atoms into ethers can give them excellent salt-dissolving capabilities, and the introduction of fluorine atoms can also effectively reduce the electron cloud density of the ether oxygen, improving the oxidation stability of the ether molecule and achieving excellent cycle stability in high-voltage batteries. However, the position and number of fluorine atoms introduced into the fluorinated ether also affect the antioxidant properties of the fluorinated ether and the electrolyte, thus affecting the cycle performance of the battery. Summary of the Invention

[0003] This application is made in view of the above-mentioned problems, and its purpose is to provide an asymmetric fluorinated ether with different numbers of fluorine atoms introduced on the carbon atoms at both ends, which can make the fluorinated ether have higher antioxidant properties and oxidation stability, improve the antioxidant performance of the electrolyte, and at the same time, the asymmetric structure of the fluorinated ether can also improve the solubility of the electrolyte, promote the formation of the SEI film in the battery, and thus improve the capacity retention and cycle stability of the battery.

[0004] To achieve the above objectives, embodiments of this application provide a method for preparing fluoroethers, a battery, and an electrical device.

[0005] In a first aspect, embodiments of this application propose a battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein the electrolyte comprises a fluorinated ether having a structural formula as represented by formula (I):

[0006]

[0007] R1 and R3 are each independently selected from alkyl groups;

[0008] R2 consists of 1 to 3 fluorine atoms;

[0009] R4 has 1 to 3 fluorine atoms and is different from R2.

[0010] Therefore, in the technical solution of this application embodiment, an asymmetric fluorinated ether is added to the electrolyte of the battery, which has different numbers of fluorine atoms substituted on the carbon atoms at both ends. The fluorinated ether has a lower HOMO (highest occupied molecular orbital) energy level, higher antioxidant properties and oxidation stability, which can improve the antioxidant performance of the electrolyte. At the same time, the asymmetric structure of the fluorinated ether can also improve the solubility of the electrolyte, promote the formation of the battery SEI film (solid electrolyte interface), and thus improve the battery's capacity retention rate and cycle stability.

[0011] In any embodiment, the number of carbon atoms in the R1 alkyl group ranges from 1 to 4. Within this range, a fluoroether with suitable molecular weight, melting point, boiling point, and viscosity can be obtained, which is beneficial for improving the battery's capacity retention and cycle stability; and / or,

[0012] The number of carbon atoms in the R3 alkyl group ranges from 1 to 4. Within this range, fluorinated ethers with suitable molecular weight, melting point, boiling point, and viscosity can be obtained, which is beneficial for improving the battery's capacity retention and cycle stability.

[0013] In any embodiment, the electrolyte comprises a solvent and an electrolyte salt, wherein the solvent comprises the fluoroether. Adding the fluoroether as part of the solvent to the electrolyte is beneficial for improving the battery's capacity retention and cycle stability; and / or,

[0014] The electrolyte salt is a lithium salt. Adding fluorinated ethers to the lithium salt electrolyte helps improve the battery's capacity retention and cycle stability.

[0015] Secondly, embodiments of this application provide a method for preparing fluoroethers, comprising the following steps:

[0016] The first fluoro alcohol, p-toluenesulfonyl chloride, and the first basic substance are added to the first solvent and reacted to obtain p-toluenesulfonate intermediates;

[0017] The second fluorinated alcohol, the p-toluenesulfonate intermediate, and the second basic substance are added to the second solvent and reacted to obtain a fluorinated ether.

[0018] Wherein, the fluoroether has a structural formula as represented by formula (I), the first fluorool has a structural formula as represented by formula (II), and the second fluorool has a structural formula as represented by formula (III):

[0019]

[0020] R1 and R3 are each independently selected from alkyl groups;

[0021] R2 consists of 1 to 3 fluorine atoms;

[0022] R4 has 1 to 3 fluorine atoms and is different from R2.

[0023] First, the first fluoro alcohol is reacted with p-toluenesulfonyl chloride to obtain a p-toluenesulfonate intermediate. Then, the second fluoro alcohol is reacted with the p-toluenesulfonate intermediate to obtain a fluoroether. By using two different fluoro alcohols as raw materials, asymmetric fluoroethers can be synthesized. The process is simple and can also improve the yield and purity of fluoroethers.

[0024] In any embodiment, the number of carbon atoms in the R1 alkyl group ranges from 1 to 4. Within this range, a fluoroether with suitable molecular weight, melting point, boiling point, and viscosity can be obtained, which is beneficial for improving the battery's capacity retention and cycle stability; and / or,

[0025] The number of carbon atoms in the R3 alkyl group ranges from 1 to 4. Within this range, fluorinated ethers with suitable molecular weight, melting point, boiling point, and viscosity can be obtained, which is beneficial for improving the battery's capacity retention and cycle stability.

[0026] In any embodiment, the step of adding the first fluorool, p-toluenesulfonyl chloride, and the first basic substance to the first solvent to react and obtain the p-toluenesulfonate intermediate:

[0027] The molar ratio of the first fluorool to the p-toluenesulfonyl chloride is 1:1 to 2. Within this range, the molar ratio of the first fluorool to the p-toluenesulfonyl chloride can improve the yield of p-toluenesulfonate intermediates; and / or,

[0028] The molar ratio of the first fluorinated alcohol to the first basic substance is 1:1 to 3. Within this range, the molar ratio of the first fluorinated alcohol to the first basic substance can promote the synthesis of p-toluenesulfonate intermediates; and / or,

[0029] The first alkaline substance includes at least one of sodium hydroxide and potassium hydroxide. Using at least one of the above-mentioned first alkaline substances can promote the synthesis of p-toluenesulfonate intermediates; and / or,

[0030] The first alkaline substance is added in the form of a solution containing the first alkaline substance, wherein the mass percentage of the first alkaline substance in the solution is 5% to 50%. Within this range, the mass percentage of the first alkaline substance in the solution can promote the synthesis of p-toluenesulfonate intermediates; optionally, a mass percentage of the first alkaline substance in the solution of the first alkaline substance of 20% to 30% is beneficial for further promoting the synthesis of p-toluenesulfonate intermediates; and / or,

[0031] The volume ratio of the first solvent to the first fluorinated alcohol is 1 to 5:1. Within this range, the volume ratio of the first solvent to the first fluorinated alcohol can promote the synthesis of p-toluenesulfonate intermediates; and / or,

[0032] The first solvent includes at least one selected from toluene, dichloromethane, benzene, carbon tetrachloride, ethyl acetate, cyclohexane, n-hexane, N-methylpyrrolidone, and 1,2-dichloroethane. Using at least one of the above first solvents can promote the synthesis of p-toluenesulfonate intermediates; and / or,

[0033] The reaction temperature is -10℃ to 40℃. A reaction temperature within this range is beneficial for ensuring the synthesis of p-toluenesulfonate intermediates; alternatively, a reaction temperature of 0℃ to 20℃ is beneficial for promoting the synthesis of p-toluenesulfonate intermediates and can also reduce production costs.

[0034] In any embodiment, the step of reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in a first solvent to obtain a p-toluenesulfonate intermediate includes: adding the first fluorool, p-toluenesulfonyl chloride, the first basic substance, and a first phase transfer catalyst to the first solvent to react and obtain the p-toluenesulfonate intermediate. Adding a first phase transfer catalyst to the reaction system can increase the reaction rate and further promote the synthesis of the p-toluenesulfonate intermediate.

[0035] In any embodiment, the step of adding the first fluorool, p-toluenesulfonyl chloride, the first basic substance, and the first phase transfer catalyst to the first solvent to react and obtain the p-toluenesulfonate intermediate:

[0036] The mass ratio of the first phase transfer catalyst to the first fluorinated alcohol is 0.005 to 0.05:1. Within this range, the mass ratio of the first phase transfer catalyst to the first fluorinated alcohol can promote the synthesis of p-toluenesulfonate intermediates; and / or,

[0037] The first phase transfer catalyst includes at least one selected from tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylammonium chloride, and 18-crown ether-6. Using at least one of the above-mentioned first phase transfer catalysts can promote the synthesis of p-toluenesulfonate intermediates.

[0038] In any embodiment, the step of adding the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance to the second solvent to react and obtain the fluoroether:

[0039] The molar ratio of the second fluorool to the p-toluenesulfonate intermediate is 1:1 to 2. Within this range, the molar ratio of the second fluorool to the p-toluenesulfonate intermediate can improve the yield of the fluoroether; and / or,

[0040] The molar ratio of the second fluorool to the second basic substance is 1:1 to 3. Maintaining this molar ratio can improve the yield of the fluoroether; and / or,

[0041] The second alkaline substance includes at least one of sodium hydroxide and potassium hydroxide. Using at least one of the above-mentioned second alkaline substances can increase the yield of fluoroethers; and / or,

[0042] The second alkaline substance is added in the form of a solution containing the second alkaline substance, wherein the mass percentage of the second alkaline substance in the solution is 20% to 60%. Within this range, the yield of the fluoroether can be increased; alternatively, a mass percentage of the second alkaline substance in the solution of the second alkaline substance of 40% to 50% is beneficial for further increasing the yield of the fluoroether; and / or,

[0043] The volume ratio of the second solvent to the second fluoroalcohol is 1 to 5:1. Within this range, the volume ratio of the second solvent to the second fluoroalcohol can promote the synthesis of fluoroethers and increase their yield; and / or,

[0044] The second solvent includes at least one selected from toluene, dichloromethane, benzene, carbon tetrachloride, ethyl acetate, cyclohexane, n-hexane, N-methylpyrrolidone, and 1,2-dichloroethane. Using at least one of the above-mentioned second solvents can improve the yield of fluoroethers.

[0045] In any embodiment, the step of reacting the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance in a second solvent to obtain the fluoroether includes: first adding the p-toluenesulfonate intermediate and the second basic substance to the second solvent, cooling the solution, then adding the second fluorool, and heating the solution to obtain the fluoroether. By first adding the second basic substance and cooling the solution before adding the second fluorool, the yield of the fluoroether can be increased.

[0046] In any embodiment, the step of first adding the p-toluenesulfonate intermediate and the second basic substance to the second solvent, cooling, then adding the second fluorinated alcohol, and heating to react to obtain the fluorinated ether:

[0047] The cooled temperature is between -10℃ and 10℃. Cooling to this temperature range can increase the yield of fluoroethers; and / or,

[0048] The reaction temperature is between 30℃ and 80℃. Heating the reaction within this range can increase the yield of fluoroethers.

[0049] In any embodiment, the step of first adding the p-toluenesulfonate intermediate and the second basic substance to a second solvent, cooling, and then adding the second fluorinated alcohol and heating to react to obtain the fluorinated ether includes: first adding the p-toluenesulfonate intermediate, the second basic substance, and the second phase transfer catalyst to a second solvent, cooling, and then adding the second fluorinated alcohol and heating to react to obtain the fluorinated ether. By adding a second phase transfer catalyst to the reaction system, the reaction rate can be increased, further improving the yield of the fluorinated ether.

[0050] In any embodiment, the step of first adding the p-toluenesulfonate intermediate, the second basic substance, and the second phase transfer catalyst to the second solvent, cooling, then adding the second fluorinated alcohol, and heating to react to obtain the fluorinated ether:

[0051] The mass ratio of the second phase transfer catalyst to the second fluorool is 0.005–0.05:1. Maintaining this mass ratio can improve the yield of the fluoroether; and / or,

[0052] The second phase transfer catalyst includes at least one of tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylammonium chloride, and 18-crown ether-6. Using at least one of the above-mentioned second phase transfer catalysts can improve the yield of fluorinated ethers.

[0053] In any embodiment, the step of reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in a first solvent to obtain a p-toluenesulfonate intermediate includes: reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in a first solvent, separating the liquids to obtain an organic phase; wherein, the organic phase includes the p-toluenesulfonate intermediate and the first solvent.

[0054] The step of reacting the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance in a second solvent to obtain a fluoroether includes: reacting the second fluorool and the second basic substance in the organic phase to obtain a fluoroether; wherein the second solvent includes the first solvent in the organic phase.

[0055] By separating the reaction products in the first step of the reaction to obtain an organic phase including p-toluenesulfonate intermediates and the first solvent, and then directly using the organic phase in the second step of the reaction, the processes of extraction and purification of p-toluenesulfonate intermediates, recovery of the first solvent, and addition of the second solvent can be eliminated. This makes the operation simpler, improves production efficiency, and reduces production costs.

[0056] Thirdly, embodiments of this application provide an electrical device including the battery of the first aspect of this application. Attached Figure Description

[0057] Figure 1 This is a schematic diagram of a secondary battery according to one embodiment of this application.

[0058] Figure 2 yes Figure 1 An exploded view of a secondary battery according to an embodiment of this application is shown.

[0059] Figure 3 This is a schematic diagram of a battery module according to one embodiment of this application.

[0060] Figure 4 This is a schematic diagram of a battery pack according to one embodiment of this application.

[0061] Figure 5 yes Figure 4 An exploded view of a battery pack according to one embodiment of this application is shown.

[0062] Figure 6 This is a schematic diagram of an electrical device that uses a secondary battery as a power source according to one embodiment of this application.

[0063] Figure 7 This is the gas chromatography-mass spectrum of the fluoroether prepared in Example 19 of this application.

[0064] Figure 8 This is the carbon spectrum of the fluoroether prepared in Example 19 of this application.

[0065] Figure 9 This is the hydrogen spectrum of the fluoroether prepared in Example 19 of this application.

[0066] Figure 10 This is the fluorine spectrum of the fluorinated ether obtained in Example 19 of this application.

[0067] Figure 11 This is the gas chromatography-mass spectrum of the fluoroether prepared in Example 16 of this application.

[0068] Figure 12 This is the carbon spectrum of the fluoroether obtained in Example 16 of this application.

[0069] Figure 13 This is the hydrogen spectrum of the fluoroether prepared in Example 16 of this application.

[0070] Figure 14 This is the fluorine spectrum of the fluorinated ether obtained in Example 16 of this application.

[0071] Figure 15 This is the gas chromatography-mass spectrum of the fluoroether prepared in Example 17 of this application.

[0072] Figure 16 This is the carbon spectrum of the fluoroether prepared in Example 17 of this application.

[0073] Figure 17 This is the hydrogen spectrum of the fluoroether prepared in Example 17 of this application.

[0074] Figure 18 This is the fluorine spectrum of the fluorinated ether obtained in Example 17 of this application.

[0075] Explanation of reference numerals in the attached figures:

[0076] 1 Battery pack; 2 Upper housing; 3 Lower housing; 4 Battery module; 5 Secondary battery; 51 Housing; 52 Electrode assembly; 53 Top cover assembly. Detailed Implementation

[0077] The following details the preparation method of the fluoroether, and embodiments of the battery and electrical device of this application. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of actually identical structures may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0078] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; 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, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0079] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0080] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0081] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0082] Introducing fluorine atoms into ethers can give them excellent salt-dissolving capabilities, and the introduction of fluorine atoms can also effectively reduce the electron cloud density of the ether oxygen, improving the oxidation stability of the ether molecule and achieving excellent cycle stability in high-voltage batteries. However, the position and number of fluorine atoms introduced into the fluorinated ether also affect the antioxidant properties of the fluorinated ether and the electrolyte, thus affecting the cycle performance of the battery.

[0083] Based on this, this application provides a method for preparing fluoroethers, a battery, and an electrical device.

[0084] In a first aspect, embodiments of this application propose a battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein the electrolyte comprises a fluorinated ether having a structural formula as represented by formula (I):

[0085]

[0086] R1 and R3 are each independently selected from alkyl groups;

[0087] R2 consists of 1 to 3 fluorine atoms;

[0088] R4 has 1 to 3 fluorine atoms and is different from R2.

[0089] Therefore, in the technical solution of this application embodiment, an asymmetric fluorinated ether is added to the electrolyte of the battery, in which different numbers of fluorine atoms are substituted on the carbon atoms at both ends. This gives the fluorinated ether a lower HOMO (highest occupied molecular orbital) energy level, higher antioxidant properties and oxidation stability, which can improve the antioxidant performance of the electrolyte. At the same time, the asymmetric structure of the fluorinated ether can also improve the solubility of the electrolyte, promote the formation of the battery SEI film (solid electrolyte interface), and thus improve the battery's capacity retention and cycle stability.

[0090] It should be noted that the alkyl structures of R1 and R3 can be the same or different; the number of fluorine atoms of R2 and R4 are different. When R2 has 1 fluorine atom on the carbon atom of R1, R4 can have 2 or 3 fluorine atoms on the carbon atom of R3; when R2 has 2 fluorine atoms on the carbon atom of R1, R4 can have 1 or 3 fluorine atoms on the carbon atom of R3; when R2 has 3 fluorine atoms on the carbon atom of R1, R4 can have 1 or 2 fluorine atoms on the carbon atom of R3.

[0091] In any embodiment, the number of carbon atoms in the R1 alkyl group ranges from 1 to 4. Within this range, fluoroethers with suitable molecular weight, melting point, boiling point, and viscosity can be obtained, which is beneficial for improving the battery's capacity retention and cycle stability; the number of carbon atoms in the R1 alkyl group can be 1, 2, 3, or 4.

[0092] In any embodiment, the number of carbon atoms in the R3 alkyl group ranges from 1 to 4. Within this range, fluorinated ethers with suitable molecular weight, melting point, boiling point, and viscosity can be obtained, which is beneficial for improving the battery's capacity retention and cycle stability; the number of carbon atoms in the R3 alkyl group can be 1, 2, 3, or 4.

[0093] In any embodiment, the electrolyte comprises a solvent and an electrolyte salt, wherein the solvent comprises the fluoroether. Adding a fluoroether as part of the solvent to the electrolyte is beneficial for improving the battery's capacity retention and cycle stability. It is understood that fluoroethers can be mixed with commonly used solvents as a solvent for the electrolyte.

[0094] In any embodiment, the electrolyte comprises a solvent and an electrolyte salt, wherein the electrolyte salt is a lithium salt. Adding fluoroethers to the lithium salt electrolyte is beneficial for improving the battery's capacity retention and cycle stability.

[0095] In one embodiment of this application, a secondary battery is provided. Typically, a secondary battery includes a positive electrode, a negative electrode, an electrolyte, and a separator. During charging and discharging, active ions repeatedly insert and extract between the positive and negative electrodes. The electrolyte acts as a conductor of ions between the positive and negative electrodes. The separator, disposed between the positive and negative electrodes, primarily prevents short circuits between the positive and negative electrodes while allowing ions to pass through.

[0096] [Positive electrode plate]

[0097] The positive electrode includes a positive current collector and a positive electrode film layer disposed on at least one surface of the positive current collector.

[0098] As an example, the positive current collector has two surfaces opposite each other in its own thickness direction, and the positive electrode film layer is disposed on either or both of the two opposite surfaces of the positive current collector.

[0099] In some embodiments, the positive current collector may be a metal foil or a composite current collector. For example, aluminum foil may be used as the metal foil. The composite current collector may include a polymer substrate and a metal layer formed on at least one surface of the polymer substrate. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).

[0100] In some embodiments, the positive electrode active material may be a known positive electrode active material for lithium-ion batteries. As an example, the positive electrode active material may include at least one of the following materials: lithium phosphates with an olivine structure, lithium transition metal oxides, and their respective modified compounds. However, this application is not limited to these materials, and other conventional materials that can be used as battery positive electrode active materials may also be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of lithium transition metal oxides include, but are not limited to, lithium cobalt oxides (such as LiCoO2), lithium nickel oxides (such as LiNiO2), lithium manganese oxides (such as LiMnO2, LiMn2O4), lithium nickel cobalt oxides, lithium manganese cobalt oxides, lithium nickel manganese oxides, and lithium nickel cobalt manganese oxides (such as LiNi). 1 / 3 Co 1 / 3 Mn 1 / 3 O2 (also known as NCM) 333 LiNi 0.5 Co 0.2 Mn 0.3 O2 (also known as NCM) 523 LiNi 0.5 Co 0.25 Mn 0.25 O2 (also known as NCM) 211 LiNi 0.6 Co 0.2 Mn 0.2 O2 (also known as NCM) 622 LiNi 0.8 Co 0.1 Mn 0.1 O2 (also known as NCM) 811 ), lithium nickel cobalt aluminum oxide (such as LiNi) 0.85 Co 0.15 Al0.05 At least one of O2 and its modified compounds. Examples of lithium phosphates with an olivine structure include, but are not limited to, lithium iron phosphate (such as LiFePO4 (also referred to as LFP)), lithium iron phosphate and carbon composites, lithium manganese phosphate (such as LiMnPO4), lithium manganese phosphate and carbon composites, lithium manganese iron phosphate, and lithium manganese iron phosphate and carbon composites.

[0101] 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), PVDF-tetrafluoroethylene-propylene terpolymer, PVDF-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorinated acrylate resin.

[0102] In some embodiments, the positive electrode film layer further includes a conductive agent. As an example, the conductive agent may include at least one selected from superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

[0103] In some embodiments, the positive electrode sheet can be prepared by dispersing the above-mentioned components for preparing the positive electrode sheet, such as positive active material, conductive agent, binder and any other components, in a solvent (e.g., N-methylpyrrolidone) to form a positive electrode slurry; coating the positive electrode slurry onto the positive electrode sheet structure, and obtaining the positive electrode sheet after drying, cold pressing and other processes.

[0104] [Negative electrode plate]

[0105] The negative electrode sheet includes a negative current collector and a negative electrode film layer disposed on at least one surface of the negative current collector, the negative electrode film layer including a negative electrode active material.

[0106] As an example, the negative electrode structure includes a negative current collector having two surfaces opposite each other in its own thickness direction, and a negative electrode film layer disposed on either or both of the two opposite surfaces of the negative current collector structure.

[0107] In some embodiments, the negative electrode current collector may be a metal foil or a composite current collector. For example, copper foil may be used as the metal foil. The composite current collector may include a polymer substrate and a metal layer formed on at least one surface of the polymer substrate. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).

[0108] In some embodiments, the negative electrode active material may be a negative electrode active material known in the art for use in batteries. 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, this application is not limited to these materials, and other conventional materials that can be used as negative electrode active materials for batteries may also be used. These negative electrode active materials may be used alone or in combination of two or more.

[0109] In some embodiments, the negative electrode film layer further includes an adhesive. The adhesive 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).

[0110] 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.

[0111] In some embodiments, the negative electrode film layer also includes other additives, such as thickeners (e.g., sodium carboxymethyl cellulose (CMC-Na)).

[0112] In some embodiments, the negative electrode sheet can be prepared by dispersing the components used to prepare the negative electrode sheet, such as negative electrode active material, conductive agent, binder and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry; coating the negative electrode slurry onto the negative electrode sheet structure, and obtaining the negative electrode sheet after drying, cold pressing and other processes.

[0113] Electrolyte

[0114] In some embodiments, the electrolyte salt may 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 difluorooxalate borate, lithium dioxalate borate, lithium difluorodioxalate phosphate, and lithium tetrafluorooxalate phosphate.

[0115] In some embodiments, the solvent may 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, butyl 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; the solvent may also include fluoroethers.

[0116] In some embodiments, the electrolyte may optionally include additives. For example, additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain battery performance, such as additives that improve battery overcharge performance, additives that improve battery high-temperature or low-temperature performance, etc.

[0117] [Isolation membrane]

[0118] In some embodiments, the secondary battery also includes a separator. This application does not impose any particular limitation on the type of separator; any known porous separator with good chemical and mechanical stability can be selected.

[0119] In some embodiments, the material of the separator can be selected from at least one of glass fiber, nonwoven 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.

[0120] In some implementations, the positive electrode, negative electrode, and separator can be fabricated into an electrode assembly using a winding or stacking process.

[0121] In some embodiments, the secondary battery may include an outer packaging. This outer packaging may be used to encapsulate the electrode assembly and electrolyte described above.

[0122] In some embodiments, the outer packaging of the secondary battery can be a hard shell, such as a hard plastic shell, an aluminum shell, or a steel shell. The outer packaging of the secondary battery can also be a soft pack, such as a pouch. The material of the soft pack can be plastic; examples of plastics include polypropylene, polybutylene terephthalate, and polybutylene succinate.

[0123] This application does not impose any particular limitation on the shape of the secondary battery; it can be cylindrical, square, or any other arbitrary shape. For example, Figure 1 This is an example of a square-structured secondary battery 5.

[0124] In some implementations, refer to Figure 2The outer packaging may include a housing 51 and a cover 53. The housing 51 may include a base plate and side plates connected to the base plate, the base plate and side plates forming a receiving cavity. The housing 51 has an opening communicating with the receiving cavity, and the cover 53 can be placed over the opening to close the receiving cavity. A positive electrode, a negative electrode, and a separator can be formed into an electrode assembly 52 using a winding or stacking process. The electrode assembly 52 is encapsulated within the receiving cavity. Electrolyte is immersed in the electrode assembly 52. ​​The secondary battery 5 may contain one or more electrode assemblies 52, which can be selected by those skilled in the art according to specific practical needs.

[0125] In some implementations, the secondary batteries can be assembled into a battery module, and the number of secondary batteries contained in the battery module can be one or more, the specific number of which can be selected by those skilled in the art according to the application and capacity of the battery module.

[0126] Figure 3 This is battery module 4, used as an example. (See reference...) Figure 3 In battery module 4, multiple secondary batteries 5 can be arranged sequentially along the length of battery module 4. Of course, they can also be arranged in any other manner. Furthermore, these multiple secondary batteries 5 can be fixed in place using fasteners.

[0127] Optionally, the battery module 4 may also include a housing with a receiving space in which a plurality of secondary batteries 5 are received.

[0128] In some embodiments, the battery modules described above can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be one or more, the specific number of which can be selected by those skilled in the art according to the application and capacity of the battery pack.

[0129] Figure 4 and Figure 5 This is battery pack 1 as an example. (See reference...) Figure 4 and Figure 5 The battery pack 1 may include a battery box and multiple battery modules 4 disposed within the battery box. The battery box includes an upper body 2 and a lower body 3, with the upper body 2 covering the lower body 3 to form a closed space for accommodating the battery modules 4. The multiple battery modules 4 can be arranged in any manner within the battery box.

[0130] Secondly, embodiments of this application provide a method for preparing fluoroethers, comprising the following steps:

[0131] The first fluoro alcohol, p-toluenesulfonyl chloride, and the first basic substance are added to the first solvent and reacted to obtain p-toluenesulfonate intermediates;

[0132] The second fluorinated alcohol, the p-toluenesulfonate intermediate, and the second basic substance are added to the second solvent and reacted to obtain a fluorinated ether.

[0133] Wherein, the fluoroether has a structural formula as represented by formula (I), the first fluorool has a structural formula as represented by formula (II), and the second fluorool has a structural formula as represented by formula (III):

[0134]

[0135] R1 and R3 are each independently selected from alkyl groups;

[0136] R2 consists of 1 to 3 fluorine atoms;

[0137] R4 has 1 to 3 fluorine atoms and is different from R2.

[0138] First, the first fluoro alcohol is reacted with p-toluenesulfonyl chloride to obtain a p-toluenesulfonate intermediate. Then, the second fluoro alcohol is reacted with the p-toluenesulfonate intermediate to obtain a fluoroether. By using two different fluoro alcohols as raw materials, asymmetric fluoroethers can be synthesized. The process is simple and can also improve the yield and purity of fluoroethers.

[0139] Understandably, the first alkaline substance can be added to the reaction system either in the form of particles or in the form of a solution; the second alkaline substance can be added to the reaction system either in the form of particles or in the form of a solution.

[0140] It should be noted that the preparation methods of fluoroethers include the following general reaction formulas:

[0141]

[0142] In any embodiment, the number of carbon atoms in the R1 alkyl group ranges from 1 to 4. Within this range, fluoroethers with suitable molecular weight, melting point, boiling point, and viscosity can be obtained, which is beneficial for improving the battery's capacity retention and cycle stability; the number of carbon atoms in the R1 alkyl group can be 1, 2, 3, or 4.

[0143] In any embodiment, the number of carbon atoms in the R3 alkyl group ranges from 1 to 4. Within this range, fluorinated ethers with suitable molecular weight, melting point, boiling point, and viscosity can be obtained, which is beneficial for improving the battery's capacity retention and cycle stability; the number of carbon atoms in the R3 alkyl group can be 1, 2, 3, or 4.

[0144] In any embodiment, in the step of reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in the first solvent to obtain the p-toluenesulfonate intermediate, the molar ratio of the first fluorool to the p-toluenesulfonyl chloride is 1:1 to 2. Maintaining this molar ratio within this range can improve the yield of the p-toluenesulfonate intermediate; the molar ratio of the first fluorool to the p-toluenesulfonyl chloride can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, or 1:2.

[0145] In any embodiment, in the step of reacting the first fluorinated alcohol, p-toluenesulfonyl chloride, and the first basic substance in the first solvent to obtain the p-toluenesulfonate intermediate: the molar ratio of the first fluorinated alcohol to the first basic substance is 1:1 to 3. Maintaining this molar ratio promotes the synthesis of the p-toluenesulfonate intermediate; the molar ratio of the first fluorinated alcohol to the first basic substance can be 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, or 1:3.

[0146] In any embodiment, in the step of reacting the first fluoroalcohol, p-toluenesulfonyl chloride, and the first basic substance in the first solvent to obtain the p-toluenesulfonate intermediate: the first basic substance includes at least one of sodium hydroxide and potassium hydroxide. Using at least one of the above-mentioned first basic substances can promote the synthesis of the p-toluenesulfonate intermediate; the first basic substance can be sodium hydroxide, potassium hydroxide, or a mixture of sodium hydroxide and potassium hydroxide.

[0147] In any embodiment, in the step of reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in a first solvent to obtain a p-toluenesulfonate intermediate: the first basic substance is added in the form of a solution containing the first basic substance, wherein the mass percentage of the first basic substance in the solution is 5% to 50%. The mass percentage of the first basic substance in the solution within this range can promote the synthesis of the p-toluenesulfonate intermediate; the mass percentage of the first basic substance in the solution can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%; optionally, the mass percentage of the first basic substance in the solution is 20% to 30%, which is beneficial for further promoting the synthesis of the p-toluenesulfonate intermediate.

[0148] In any embodiment, in the step of reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in the first solvent to obtain the p-toluenesulfonate intermediate, the volume ratio of the first solvent to the first fluorool is 1 to 5:1. Within this volume ratio range, the synthesis of the p-toluenesulfonate intermediate can be promoted; if the volume ratio is too low, the reaction solution becomes too viscous, the reaction rate is slow, and the reaction time is prolonged; if the volume ratio is too high, the first solvent will be wasted, and the recovery of the second solvent after the reaction will be difficult, resulting in significant product loss and affecting the yield of the fluoroether. The volume ratio of the first solvent to the first fluorool can be 1:1, 2:1, 3:1, 4:1, or 5:1.

[0149] In any embodiment, the step of reacting the first fluoroalcohol, p-toluenesulfonyl chloride, and the first basic substance in a first solvent to obtain a p-toluenesulfonate intermediate includes at least one of toluene, dichloromethane, benzene, carbon tetrachloride, ethyl acetate, cyclohexane, n-hexane, N-methylpyrrolidone, and 1,2-dichloroethane. Using at least one of the above-mentioned first solvents can promote the synthesis of the p-toluenesulfonate intermediate; the first solvent can be any one or any combination of multiple of toluene, dichloromethane, benzene, carbon tetrachloride, ethyl acetate, cyclohexane, n-hexane, N-methylpyrrolidone, and 1,2-dichloroethane.

[0150] In any embodiment, in the step of reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in the first solvent to obtain the p-toluenesulfonate intermediate, the reaction temperature is -10°C to 40°C. A reaction temperature within this range is beneficial for ensuring the synthesis of the p-toluenesulfonate intermediate; the reaction temperature can be -10°C, 5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, or 40°C; optionally, a reaction temperature of 0°C to 20°C is beneficial for promoting the synthesis of the p-toluenesulfonate intermediate and can also reduce production costs.

[0151] In any embodiment, the step of reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in a first solvent to obtain a p-toluenesulfonate intermediate includes: adding the first fluorool, p-toluenesulfonyl chloride, the first basic substance, and a first phase transfer catalyst to the first solvent to react and obtain the p-toluenesulfonate intermediate. Adding a first phase transfer catalyst to the reaction system can increase the reaction rate and further promote the synthesis of the p-toluenesulfonate intermediate.

[0152] In any embodiment, in the step of adding the first fluorinated alcohol, p-toluenesulfonyl chloride, the first basic substance, and the first phase transfer catalyst to the first solvent to react and obtain the p-toluenesulfonate intermediate: the mass ratio of the first phase transfer catalyst to the first fluorinated alcohol is 0.005 to 0.05:1. This mass ratio promotes the synthesis of the p-toluenesulfonate intermediate; the mass ratio of the first phase transfer catalyst to the first fluorinated alcohol can be 0.005:1, 0.01:1, 0.015:1, 0.02:1, 0.025:1, 0.03:1, 0.035:1, 0.04:1, 0.045:1, or 0.05:1.

[0153] In any embodiment, in the step of adding the first fluorinated alcohol, p-toluenesulfonyl chloride, the first basic substance, and the first phase transfer catalyst to the first solvent to react and obtain the p-toluenesulfonate intermediate: the first phase transfer catalyst includes at least one selected from tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylammonium chloride, and 18-crown ether-6. Using at least one of the above-mentioned first phase transfer catalysts can promote the synthesis of the p-toluenesulfonate intermediate; the first phase transfer catalyst can be any one or any combination of tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylammonium chloride, and 18-crown ether-6.

[0154] In any embodiment, in the step of reacting the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance in the second solvent to obtain the fluoroether, the molar ratio of the second fluorool to the p-toluenesulfonate intermediate is 1:1 to 2. Maintaining this molar ratio within this range can improve the yield of the fluoroether; the molar ratio of the second fluorool to the p-toluenesulfonate intermediate can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, or 1:2.

[0155] In any embodiment, in the step of reacting the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance in the second solvent to obtain the fluoroether, the molar ratio of the second fluorool to the second basic substance is 1:1 to 3. Maintaining this molar ratio within this range can improve the yield of the fluoroether; the molar ratio of the second fluorool to the second basic substance can be 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, or 1:3.

[0156] In any embodiment, in the step of reacting the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance in a second solvent to obtain the fluoroether: the second basic substance includes at least one of sodium hydroxide and potassium hydroxide. Using at least one of the above-mentioned second basic substances can improve the yield of fluoroether; the second basic substance can be sodium hydroxide, potassium hydroxide, or a mixture of sodium hydroxide and potassium hydroxide.

[0157] In any embodiment, in the step of reacting the second fluorinated alcohol, the p-toluenesulfonate intermediate, and the second basic substance in a second solvent to obtain the fluorinated ether: the second basic substance is added in the form of a solution containing the second basic substance, wherein the mass percentage of the second basic substance in the solution is 20% to 60%. Maintaining the mass percentage of the second basic substance in the solution within this range can improve the yield of the fluorinated ether; the mass percentage of the second basic substance in the solution can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60%; optionally, a mass percentage of the second basic substance in the solution of the second basic substance of 40% to 50% is beneficial for further improving the yield of the fluorinated ether.

[0158] In any embodiment, in the step of adding the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance to the second solvent to react and obtain the fluoroether, the volume ratio of the second solvent to the second fluorool is 1 to 5:1. Within this range, the volume ratio of the second solvent to the second fluorool can promote the synthesis of the fluoroether and increase its yield. If the volume ratio is too low, the reaction solution will be too viscous, the reaction rate will be slow, and the reaction time will be prolonged. If the volume ratio is too high, it will waste the second solvent, and the recovery of the second solvent after the reaction will be difficult, resulting in significant product loss and affecting the yield of the fluoroether. The volume ratio of the second solvent to the second fluorool can be 1:1, 2:1, 3:1, 4:1, or 5:1.

[0159] In any embodiment, in the step of reacting the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance in a second solvent to obtain the fluoroether, the second solvent includes at least one selected from toluene, dichloromethane, benzene, carbon tetrachloride, ethyl acetate, cyclohexane, n-hexane, N-methylpyrrolidone, and 1,2-dichloroethane. Using at least one of the above-mentioned second solvents can improve the yield of the fluoroether; the second solvent can be any one or any combination of toluene, dichloromethane, benzene, carbon tetrachloride, ethyl acetate, cyclohexane, n-hexane, N-methylpyrrolidone, and 1,2-dichloroethane.

[0160] In any embodiment, the step of reacting the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance in a second solvent to obtain the fluoroether includes: first adding the p-toluenesulfonate intermediate and the second basic substance to the second solvent, cooling the solution, then adding the second fluorool, and heating the solution to obtain the fluoroether. By adding the second basic substance first and then cooling the solution before adding the second fluorool, the yield of the fluoroether can be increased. The mixing of the second fluorool and the second basic substance releases a large amount of heat. If the second fluorool is cooled first and then the second basic substance is added, it is easy for the second fluorool to generate byproducts, affecting the yield of the fluoroether. However, cooling the second basic substance first and then adding the second fluoroether allows for a rapid reaction, which is beneficial for increasing the yield of the fluoroether.

[0161] In any embodiment, in the step of first adding the p-toluenesulfonate intermediate and the second basic substance to the second solvent, cooling, then adding the second fluoroalcohol, and heating to react to obtain the fluoroether, the temperature after cooling is -10℃ to 10℃. Maintaining a temperature within this range after cooling can improve the yield of the fluoroether; the temperature after cooling can be -10℃, -5℃, 0℃, 5℃, or 10℃.

[0162] In any embodiment, in the step of first adding the p-toluenesulfonate intermediate and the second basic substance to the second solvent, cooling, then adding the second fluorinated alcohol, and heating to react to obtain the fluorinated ether, the heating temperature is 30°C to 80°C. Heating within this range can increase the yield of the fluorinated ether; the heating temperature can be 30°C, 40°C, 50°C, 60°C, 70°C, or 80°C.

[0163] In any embodiment, the step of first adding the p-toluenesulfonate intermediate and the second basic substance to a second solvent, cooling, and then adding the second fluorinated alcohol and heating to react to obtain the fluorinated ether includes: first adding the p-toluenesulfonate intermediate, the second basic substance, and the second phase transfer catalyst to a second solvent, cooling, and then adding the second fluorinated alcohol and heating to react to obtain the fluorinated ether. By adding a second phase transfer catalyst to the reaction system, the reaction rate can be increased, further improving the yield of the fluorinated ether.

[0164] In any embodiment, in the step of first adding the p-toluenesulfonate intermediate, the second basic substance, and the second phase transfer catalyst to the second solvent, cooling, and then adding the second fluorinated alcohol and heating to react to obtain the fluorinated ether: the mass ratio of the second phase transfer catalyst to the second fluorinated alcohol is 0.005 to 0.05:1. Maintaining this mass ratio can improve the yield of the fluorinated ether; the mass ratio of the second phase transfer catalyst to the second fluorinated alcohol can be 0.005:1, 0.01:1, 0.015:1, 0.02:1, 0.025:1, 0.03:1, 0.035:1, 0.04:1, 0.045:1, or 0.05:1.

[0165] In any embodiment, in the step of first adding the p-toluenesulfonate intermediate, the second basic substance, and the second phase transfer catalyst to the second solvent, cooling, and then adding the second fluorinated alcohol and heating to react and obtain the fluorinated ether: the second phase transfer catalyst includes at least one of tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylammonium chloride, and 18-crown ether-6. Using at least one of the above-mentioned second phase transfer catalysts can improve the yield of the fluorinated ether; the second phase transfer catalyst can be any one or any combination of tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylammonium chloride, and 18-crown ether-6.

[0166] In any embodiment, the step of reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in a first solvent to obtain a p-toluenesulfonate intermediate includes: reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in a first solvent, separating the liquids to obtain an organic phase; wherein, the organic phase includes the p-toluenesulfonate intermediate and the first solvent.

[0167] The step of reacting the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance in a second solvent to obtain a fluoroether includes: reacting the second fluorool and the second basic substance in the organic phase to obtain a fluoroether; wherein the second solvent includes the first solvent in the organic phase.

[0168] By separating the reaction products in the first step of the reaction to obtain an organic phase including p-toluenesulfonate intermediates and the first solvent, and then directly using the organic phase in the second step of the reaction, the processes of extraction and purification of p-toluenesulfonate intermediates, recovery of the first solvent, and addition of the second solvent can be eliminated. This makes the operation simpler, improves production efficiency, and reduces production costs.

[0169] Thirdly, embodiments of this application provide an electrical device including the battery of the first aspect of this application.

[0170] In addition, this application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided in this application. The secondary battery, battery module, or battery pack can be used as a power source for the electrical device, or as an energy storage unit for the electrical device. The electrical device may include, but is not limited to, mobile devices (e.g., mobile phones, laptops, etc.), electric vehicles (e.g., pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.

[0171] As the electrical device, a secondary battery, battery module, or battery pack can be selected according to its usage requirements.

[0172] Figure 6 This is an example of an electrical device. The device could be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle. To meet the high power and high energy density requirements of the secondary battery for this device, a battery pack or battery module can be used.

[0173] Another example device could be a mobile phone, tablet, or laptop. These devices typically require a slim and lightweight design and can use a rechargeable battery as their power source.

[0174] Example

[0175] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0176] The fluoroethers in Examples 1 to 7 of this application are as per the parameters in Table 1.

[0177] Table 1. Fluoroether parameters for Examples 1 to 7

[0178]

[0179] Examples 8 to 22 illustrate the preparation methods of fluoroethers.

[0180] Example 8

[0181] A method for preparing a fluoroether includes the following steps:

[0182] 1 mol of the first fluoro alcohol was dissolved in 300 mL of the first solvent and added to the reaction vessel. The mixture was stirred at room temperature, and 300 mL of sodium hydroxide solution (sodium hydroxide solution containing 20% ​​sodium hydroxide by mass) was added dropwise. Then, 1.1 mol of p-toluenesulfonyl chloride was dissolved in 250 mL of the first solvent and added dropwise to the reaction vessel. The mixture was stirred for 6 h, and the reaction was confirmed to be complete by GC. The reaction was stopped, and the mixture was allowed to stand and separate into layers to obtain the lower organic phase, which included p-toluenesulfonate intermediates and the first solvent. The first fluoro alcohol was 2,2,2-trifluoroethanol, and the molar ratio of the first fluoro alcohol, p-toluenesulfonyl chloride, and sodium hydroxide was 1:1.1:1.8. The first solvent was dichloromethane.

[0183] Add 200 mL of potassium hydroxide solution (potassium hydroxide in the solution accounts for 40% by mass) to the organic phase obtained in the previous step, cool to 0 °C, and add 0.9 mol of difluorool dropwise at 0 °C. After the addition is complete, raise the temperature to 50 °C and heat the reaction for 8 h. After the reaction is complete, dilute with water, separate the layers, remove the aqueous layer, wash the organic layer twice with deionized water, dry with anhydrous sodium sulfate, and distill under normal pressure to obtain fluoroether. The difluorool is 2,2-difluoroethanol, and the molar ratio of difluorool, p-toluenesulfonate intermediate to potassium hydroxide is 1:1.1:2.6.

[0184] The preparation methods of the fluoroethers in Examples 9 to 22 differ from those in Example 8 in the parameters set as shown in Table 2; wherein:

[0185] In Examples 9 to 17, in the first step, no first phase transfer catalyst was added, and the stirring reaction time was 6 hours; in the second step, no second phase transfer catalyst was added, and the heating reaction time was 8 hours.

[0186] In Examples 18 to 21, in the first step, a first phase transfer catalyst was added before the sodium hydroxide solution was added, and the reaction was stirred for 1 hour. In the second step, a second phase transfer catalyst was added to the organic phase before the temperature was lowered, and the reaction was heated for 1 hour.

[0187] In Example 22, in the second step, 0.9 mol of difluorool was first added to the organic phase obtained in the previous step, and the temperature was lowered to 0°C. Then, at 0°C, 200 mL of potassium hydroxide solution (the mass percentage of potassium hydroxide in the potassium hydroxide solution was 40%) was added dropwise. The order of addition of difluorool and potassium hydroxide solution in Example 22 is different from that in Example 8.

[0188] The fluoroethers prepared in Examples 8 to 15 and Examples 18 to 22 are 1,1,1-trifluoro-2-(2,2-difluoroethoxy)ethane, the fluoroether prepared in Example 16 is 1-fluoro-2-(2,2-difluoroethoxy)ethane, and the fluoroether prepared in Example 17 is 1-fluoro-2-(2,2,2-trifluoroethoxy)ethane.

[0189]

[0190]

[0191] Performance testing

[0192] (1) Purity test:

[0193] Device Model: 8860GC System; Brand: Agilent;

[0194] Injection volume: 0.8 μl, split ratio: 10:1;

[0195] Inlet temperature: 280℃, detector temperature: 280℃

[0196] Column flow rate: 1 mL / min;

[0197] Chromatographic column type: HP-5, dimensions: 30m × 320μm × 0.25μm;

[0198] Programmed temperature rise method: Hold at 50℃ for 5 minutes, then increase to 210℃ at a rate of 15℃ / min and hold for 1 minute.

[0199] (2) Yield test: Yield (%) = Actual product quality / Theoretical product quality × 100%.

[0200] The fluoroethers prepared by the methods described in Examples 8 to 22 were subjected to purity and yield tests, and the test results are shown in Table 2.

[0201] (3) The fluorinated ethers prepared in Example 19 were subjected to gas chromatography-mass spectrometry, carbon chromatography, hydrogen chromatography and fluorine chromatography.

[0202] Figure 7 The above are gas chromatograms of the fluoroethers prepared in Example 19, where (a) is a primary spectrum and (b) is a secondary spectrum. Figure 7 (b) It can be seen that the main ion fragment peaks of the synthesized product are: 165, 145, 113, 95, 83, 65, 51, 45, 33, 15.

[0203] Figure 8 The carbon spectrum of the fluoroether obtained in Example 19 is shown below. Figure 8It can be seen that the synthesized product contains four groups of carbons, located at 68.98 ppm, 71.08 ppm, 113.85 ppm and 123.56 ppm respectively. Among them, 68.98 ppm is the carbon near the carbon bonded to three fluorine atoms, 71.08 ppm is the carbon near the carbon bonded to two fluorine atoms, 113.85 ppm is the carbon bonded to two fluorine atoms, 123.56 ppm is the carbon bonded to three fluorine atoms, and 76.89 ppm is the carbon atom elution peak in the solvent CDCl3.

[0204] Figure 9 The 1H NMR spectrum of the fluoroether prepared in Example 19 is shown below. Figure 9 It can be seen that the synthesized product contains three groups of hydrogen, at 3.82 ppm, 3.98 ppm and 5.88 ppm respectively. Among them, 3.82 ppm is hydrogen on the carbon near the carbon bonded to two fluorine atoms, 3.98 ppm is hydrogen on the carbon near the carbon bonded to three fluorine atoms, and 5.88 ppm is hydrogen on the carbon bonded to two fluorine atoms.

[0205] Figure 10 The fluorine spectrum of the fluorinated ether obtained in Example 19 is shown below. Figure 10 It is known that the synthesized product contains two groups of fluorine, at -75.21ppm and -126.41ppm respectively. The -75.21ppm concentration represents three identical fluorine molecules simultaneously bonded to the terminal carbon, while the -126.41ppm concentration represents two identical fluorine molecules simultaneously bonded to the terminal carbon.

[0206] (4) The fluorinated ethers prepared in Example 16 were subjected to gas chromatography-mass spectrometry, carbon chromatography, hydrogen chromatography and fluorine chromatography.

[0207] Figure 11 The above are gas chromatograms of the fluoroethers prepared in Example 16, where (a) is a primary spectrum and (b) is a secondary spectrum. Figure 11 (b) It can be seen that the main ion fragment peaks of the synthesized product are: 129, 109, 95, 77, 65, 51, 47, 31, 15.

[0208] Figure 12 The carbon spectrum of the fluoroether prepared in Example 16 is shown below. Figure 12 It can be seen that the synthesized product contains four groups of carbons, located at 70.25 ppm, 71.08 ppm, 82.18 ppm and 114.45 ppm respectively. Among them, 70.25 ppm is the carbon near the carbon atom bonded to one fluorine atom, 71.08 ppm is the carbon near the carbon atom bonded to two fluorine atoms, 82.18 ppm is the carbon atom bonded to one fluorine atom, 114.45 ppm is the carbon atom bonded to two fluorine atoms, and 77.0 ppm is the carbon atom elution peak in the solvent CDCl3.

[0209] Figure 13The 1H NMR spectrum of the fluoroether prepared in Example 16 is shown below. Figure 13 It can be seen that the synthesized product contains four groups of hydrogen atoms, at 3.66 ppm, 3.73 ppm, 4.49 ppm and 5.83 ppm respectively. Among them, 3.66 ppm is the hydrogen on the carbon near the carbon atom bonded to one fluorine atom, 3.73 ppm is the hydrogen on the carbon near the carbon atom bonded to two fluorine atoms, 4.49 ppm is the hydrogen on the carbon atom bonded to one fluorine atom, 5.83 ppm is the hydrogen on the carbon atom bonded to two fluorine atoms, and 1.98 ppm is the hydrogen atom peak of water in the synthesized product.

[0210] Figure 14 The fluorine spectrum of the fluorinated ether obtained in Example 16 is shown below. Figure 14 It can be seen that the synthesized product contains two groups of fluorine, at -126.18 ppm and -224.08 ppm respectively. The -126.18 ppm indicates that two identical fluorine molecules are connected to the terminal carbon, while the -224.08 ppm indicates that only one fluorine molecule is connected to the terminal carbon.

[0211] (5) The fluorinated ethers prepared in Example 17 were subjected to gas chromatography-mass spectrometry, carbon chromatography, hydrogen chromatography and fluorine chromatography.

[0212] Figure 15 The above are the gas chromatography-mass spectra of the fluoroether obtained in Example 17, where (a) is the primary spectrum and (b) is the secondary spectrum. Figure 15 (b) It can be seen that the main ion fragment peaks of the synthesized product are: 147, 127, 113, 101, 83, 77, 69, 47, 33, 15.

[0213] Figure 16 The carbon spectrum of the fluoroether prepared in Example 17 is shown below. Figure 16 It can be seen that the synthesized product contains four groups of carbons, located at 68.44 ppm, 71.43 ppm, 82.76 ppm and 123.93 ppm respectively. Among them, 68.44 ppm is the carbon near the carbon bonded to three fluorine atoms, 71.43 ppm is the carbon near the carbon bonded to one fluorine atom, 82.76 ppm is the carbon bonded to one fluorine atom, 123.93 ppm is the carbon bonded to three fluorine atoms, and 76.92 ppm is the carbon atom elution peak in the solvent CDCl3.

[0214] Figure 17 The 1H NMR spectrum of the fluoroether prepared in Example 17 is shown below. Figure 17 It can be seen that the synthesized product contains three groups of hydrogen atoms, at 3.83 ppm, 3.92 ppm and 4.54 ppm respectively. Among them, 3.83 ppm is the hydrogen on the carbon near the carbon atom bonded to one fluorine atom, 3.92 ppm is the hydrogen on the carbon near the carbon atom bonded to three fluorine atoms, 4.54 ppm is the hydrogen on the carbon atom bonded to one fluorine atom, and 1.97 ppm is the hydrogen atom peak of water in the synthesized product.

[0215] Figure 18 The fluorine spectrum of the fluorinated ether obtained in Example 17 is shown below. Figure 18 It is known that the synthesized product contains two groups of fluorine, at -75.10 ppm and -224.35 ppm respectively. The -75.10 ppm concentration indicates that three identical fluorine molecules are simultaneously attached to the terminal carbon, while the -224.35 ppm concentration indicates that only one fluorine molecule is attached to the terminal carbon.

[0216] As shown in Table 2, by using two different fluoroalcohols as raw materials, first reacting the first fluoroalcohol with p-toluenesulfonyl chloride to obtain a p-toluenesulfonate intermediate, and then reacting the second fluoroalcohol with the p-toluenesulfonate intermediate, asymmetric fluoroethers with different numbers of fluorine atoms on the carbon atoms at both ends can be obtained. As shown in Examples 8 and 18 to 21, adding a phase transfer catalyst to the reaction system can improve the yield of fluoroethers. As shown in Examples 8 and 22, cooling the second alkaline substance first and then adding the second fluoroalcohol can improve the yield of fluoroethers.

[0217] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the patent protection scope of the present invention.

Claims

1. A battery, characterized in that, The electrolyte includes a positive electrode, a negative electrode, and an electrolyte solution, wherein the electrolyte solution includes a fluorinated ether having a structural formula as represented by formula (I): R1 and R3 are each independently selected from alkyl groups; R2 consists of 1 to 3 fluorine atoms; R4 has 1 to 3 fluorine atoms and is different from R2.

2. The battery as described in claim 1, characterized in that, The number of carbon atoms in the R1 alkyl group ranges from 1 to 4; and / or, The number of carbon atoms in R3 alkyl groups ranges from 1 to 4.

3. The battery as described in claim 1 or 2, characterized in that, The electrolyte comprises a solvent and an electrolyte salt, wherein: The solvent includes the fluoroether; and / or, The electrolyte salt is a lithium salt.

4. A method for preparing a fluoroether, characterized in that, Includes the following steps: The first fluoro alcohol, p-toluenesulfonyl chloride, and the first basic substance are added to the first solvent and reacted to obtain p-toluenesulfonate intermediates; The second fluorinated alcohol, the p-toluenesulfonate intermediate, and the second basic substance are added to the second solvent and reacted to obtain a fluorinated ether. Wherein, the fluoroether has a structural formula as represented by formula (I), the first fluorool has a structural formula as represented by formula (II), and the second fluorool has a structural formula as represented by formula (III): R1 and R3 are each independently selected from alkyl groups; R2 consists of 1 to 3 fluorine atoms; R4 has 1 to 3 fluorine atoms and is different from R2.

5. The method for preparing fluoroethers according to claim 4, characterized in that, The number of carbon atoms in the R1 alkyl group ranges from 1 to 4; and / or, The number of carbon atoms in R3 alkyl groups ranges from 1 to 4.

6. The method for preparing fluoroethers as described in claim 4 or 5, characterized in that, In the step of reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in the first solvent to obtain the p-toluenesulfonate intermediate: The molar ratio of the first fluorool to the p-toluenesulfonyl chloride is 1:1 to 2; and / or, The molar ratio of the first fluorinated alcohol to the first basic substance is 1:1 to 3; and / or, The first alkaline substance includes at least one of sodium hydroxide and potassium hydroxide; and / or, The first alkaline substance is added in the form of a solution containing the first alkaline substance, wherein the mass percentage of the first alkaline substance in the solution is 5% to 50%; and / or, The volume ratio of the first solvent to the first fluoroalcohol is 1 to 5:1; and / or, The first solvent comprises at least one selected from toluene, dichloromethane, benzene, carbon tetrachloride, ethyl acetate, cyclohexane, n-hexane, N-methylpyrrolidone, and 1,2-dichloroethane; and / or, The reaction temperature is -10℃ to 40℃.

7. The method for preparing fluoroethers according to any one of claims 4 to 6, characterized in that, The step of reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in the first solvent to obtain the p-toluenesulfonate intermediate includes: The first fluoro alcohol, p-toluenesulfonyl chloride, the first basic substance, and the first phase transfer catalyst are added to the first solvent to react and obtain p-toluenesulfonate intermediates.

8. The method for preparing fluoroethers according to claim 7, characterized in that, In the step of adding the first fluorool, p-toluenesulfonyl chloride, the first basic substance, and the first phase transfer catalyst to the first solvent to react and obtain the p-toluenesulfonate intermediate: The mass ratio of the first phase transfer catalyst to the first fluorinated alcohol is 0.005–0.05:1; and / or, The first phase transfer catalyst includes at least one of tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylammonium chloride, and 18-crown ether-6.

9. The method for preparing fluoroethers according to any one of claims 4 to 8, characterized in that, In the step of reacting the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance in the second solvent to obtain the fluoroether: The molar ratio of the second fluorool to the p-toluenesulfonate intermediate is 1:1 to 2; and / or, The molar ratio of the second fluorinated alcohol to the second basic substance is 1:1 to 3; and / or, The second alkaline substance includes at least one of sodium hydroxide and potassium hydroxide; and / or, The second alkaline substance is added in the form of a solution containing the second alkaline substance, wherein the mass percentage of the second alkaline substance in the solution is 20% to 60%; and / or, The volume ratio of the second solvent to the second fluoroalcohol is 1 to 5:1; and / or, The second solvent includes at least one of toluene, dichloromethane, benzene, carbon tetrachloride, ethyl acetate, cyclohexane, n-hexane, N-methylpyrrolidone, and 1,2-dichloroethane.

10. The method for preparing fluoroethers according to any one of claims 4 to 9, characterized in that, The step of reacting the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance in the second solvent to obtain the fluoroether includes the following steps: First, the p-toluenesulfonate intermediate and the second basic substance are added to the second solvent, cooled, and then the second fluorinated alcohol is added and heated to react, yielding a fluorinated ether.

11. The method for preparing fluoroethers according to claim 10, characterized in that, In the step of first adding the p-toluenesulfonate intermediate and the second basic substance to the second solvent, cooling, then adding the second fluorinated alcohol, and heating to react, a fluorinated ether is obtained: The temperature after cooling is -10℃ to 10℃; and / or, The temperature for the heating reaction is 30℃~80℃.

12. The method for preparing fluoroethers according to claim 10 or 11, characterized in that, The steps of first adding the p-toluenesulfonate intermediate and the second basic substance to the second solvent, cooling, then adding the second fluorinated alcohol, and heating to react to obtain the fluorinated ether include: First, the p-toluenesulfonate intermediate, the second basic substance, and the second phase transfer catalyst are added to the second solvent, cooled, and then the second fluorinated alcohol is added and heated to react, yielding a fluorinated ether.

13. The method for preparing fluoroethers according to claim 12, characterized in that, In the step of first adding the p-toluenesulfonate intermediate, the second basic substance, and the second phase transfer catalyst to the second solvent, cooling, then adding the second fluorinated alcohol, and heating to react, a fluorinated ether is obtained: The mass ratio of the second phase transfer catalyst to the second fluorinated alcohol is 0.005–0.05:1; and / or, The second phase transfer catalyst includes at least one of tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylammonium chloride, and 18-crown ether-6.

14. The method for preparing fluoroethers according to any one of claims 4 to 13, characterized in that, The step of reacting the first fluorool, p-toluenesulfonyl chloride, and the first basic substance in the first solvent to obtain the p-toluenesulfonate intermediate includes: A first fluoro alcohol, p-toluenesulfonyl chloride, and a first basic substance are added to a first solvent and reacted. The mixture is then separated to obtain an organic phase. The organic phase includes a p-toluenesulfonate intermediate and the first solvent. The step of reacting the second fluorool, the p-toluenesulfonate intermediate, and the second basic substance in the second solvent to obtain the fluoroether includes: A second fluorinated alcohol and a second basic substance are added to the organic phase and reacted to obtain a fluorinated ether; wherein the second solvent includes the first solvent in the organic phase.

15. An electrical appliance, characterized in that, Includes the battery as described in any one of claims 1 to 3.

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