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 benzene sulfonyl chloride with fluoro-alcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product; reacting the intermediate product with a polyether compound and a second alkaline substance in a second organic solvent to obtain fluoroether; wherein the general structural formula of the fluoroalcohol is RFOH, and RF comprises groups containing fluorine atoms; the polyether compound has a simple structural formula as shown in (I), and the fluoro-ether has a simple structural formula as shown in (II), wherein n is an integer greater than or equal to 0; r comprises at least one of alkyl, alkenyl and alkynyl. The preparation method has the advantages of cheap and easily available raw materials, simple preparation process, high yield and simple operation.

Description

Technical Field

[0001] The present application relates to the field of battery technology, and in particular to a preparation method of fluoroether, an electrolyte, a battery and an electrical device. Background Art

[0002] Currently, the synthesis of fluoroethers primarily involves reacting alcohols or phenols with fluoroolefins in the presence of a catalyst, either in the presence or absence of a solvent, to produce a fluoroether reaction solution. However, the difficulty in obtaining fluoroolefins, their high cost, and the associated risks hinder the synthesis of fluoroethers. Summary of the Invention

[0003] The present application is made in view of the above-mentioned problems, and its purpose is to provide a method for preparing fluoroethers, which has cheap and readily available raw materials, a mild preparation process, a high yield, and simple operation.

[0004] In order to achieve the above-mentioned objectives, the embodiments of the present application provide a method for preparing a fluoroether, an electrolyte, a battery, and an electrical device.

[0005] In a first aspect, the present invention provides a method for preparing a fluoroether, comprising the following steps:

[0006] reacting benzenesulfonyl chloride with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product;

[0007] reacting the intermediate product with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether;

[0008] Wherein, the general structural formula of the fluoroalcohol is R F OH, R F including groups containing fluorine atoms;

[0009] The polyether compound has a structural formula as shown in (I), and the fluoroether has a structural formula as shown in (II):

[0010]

[0011] n is an integer greater than or equal to 0;

[0012] R includes at least one of an alkyl group, an alkenyl group, and an alkynyl group.

[0013] Thus, in the technical scheme of the embodiment of the present application, benzenesulfonyl chloride is reacted with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product; the intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether. The raw materials of the present application are cheap and easy to obtain, the preparation process is simple, the yield is high, and the operation is simple. The reaction to generate the intermediate product is a reversible reaction, and hydrochloric acid is generated during the reaction. After the hydrochloric acid is neutralized with the first alkaline substance, the generation of the intermediate product can be promoted, and the yield of the intermediate product can be increased. The organic solvent can increase the contact probability of the reaction raw materials, increase the reaction speed, and increase the yield of the fluoroether.

[0014] It should be noted that the benzenesulfonyl chloride can be p-benzenesulfonyl chloride, bromobenzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride and methanesulfonyl chloride, among which p-toluenesulfonyl chloride is the cheapest and most readily available, less toxic and safer.

[0015] In any embodiment, R F Fluorinated alkyl groups with 1 to 5 carbon atoms; fluoroalkyl groups with less than 5 carbon atoms are selected. Fluorinated alcohols have good stability, low toxicity, readily available raw materials, low price, and more stable CC bonds, which are not easily oxidized or broken, thus increasing the yield of fluoroethers. And / or,

[0016] n being a positive integer of 1 to 5 can improve the solvation ability and antioxidant capacity of the fluoroether. And / or,

[0017] R includes any one of alkyl groups with 1 to 5 carbon atoms, which can improve the solvating ability of the fluoroether and reduce the viscosity of the fluoroether.

[0018] In any embodiment, R F Containing 1 to 3 fluorine atoms can improve the stability of fluoroethers and reduce their toxicity; and / or,

[0019] R includes any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopropane, cyclopentane and cyclohexane, which can further improve the stability of the fluoroether, reduce the occurrence of side reactions, and reduce the toxicity of the fluoroether.

[0020] In any embodiment, benzenesulfonyl chloride is reacted with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product:

[0021] The first alkaline substance includes at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine and pyridine. The first alkaline substance is cheap and easy to obtain, has low toxicity, stable properties and is safe to use; and / or,

[0022] The first organic solvent includes at least one of tetrahydrofuran, dichloromethane, N,N-dimethylformamide and dimethyl sulfoxide. The above solvents are all polar aprotic solvents, which are cheap and easy to obtain, have low toxicity, stable properties, safe to use, and have low boiling points and are easy to remove through subsequent purification.

[0023] In any embodiment, benzenesulfonyl chloride is reacted with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product:

[0024] The molar ratio of the fluoroalcohol to benzenesulfonyl chloride and the first alkaline substance is 1:(1-4):(1-16). At this mass ratio, on the one hand, the occurrence of side reactions can be reduced and the yield of intermediate products can be increased; on the other hand, the cost of raw materials can be reduced while ensuring sufficient reaction. Optionally, the molar ratio of the fluoroalcohol to benzenesulfonyl chloride and the first alkaline substance is 1:(1-2):(1-4).

[0025] In any embodiment, benzenesulfonyl chloride is reacted with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product:

[0026] The reaction temperature is -20 to 100°C. The reaction to generate the intermediate product is an exothermic reaction. Within this temperature range, a suitable reaction rate can be maintained, the risk of thermal runaway can be reduced, and the yield of the intermediate product can be increased. Optionally, the reaction temperature is 0 to 30°C. And / or,

[0027] The reaction time is 4 to 30 hours, during which the reaction can be more complete and the yield of the intermediate product can be higher; optionally, the reaction time is 10 to 20 hours, which can further make the reaction more complete and the yield of the intermediate product higher.

[0028] In any embodiment, the intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain the fluoroether:

[0029] The second alkaline substance includes at least one of sodium hydride, lithium hydride, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium acetate, sodium methoxide and sodium ethoxide. The second alkaline substance directly participates in the reaction as a reactant. Selecting the above second alkaline substance can reduce the toxicity of the reaction system, reduce the cost of raw materials, and improve the safety of the reaction; and / or,

[0030] The second organic solvent includes at least one of tetrahydrofuran, dichloromethane, N,N-dimethylformamide, and dimethyl sulfoxide. These solvents are polar aprotic solvents that are inexpensive, readily available, low in toxicity, stable, safe to use, and have low boiling points, making them easily removable through subsequent purification. Bromobenzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride, and methanesulfonyl chloride can also be used. Among these, p-toluenesulfonyl chloride is the most inexpensive, readily available, low in toxicity, and safer.

[0031] In any embodiment, the intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain the fluoroether:

[0032] The mass ratio of the intermediate product to the polyether compound and the second alkaline substance is 1:(1-4):(1-4). At this mass ratio, the yield of the fluoroether can be increased and the raw material cost can be reduced. Alternatively, the mass ratio of the intermediate product to the polyether compound and the second alkaline substance is 1:(1-2):(1-2), which can further increase the yield of the fluoroether and reduce the raw material cost.

[0033] In any embodiment, reacting the intermediate product with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether comprises:

[0034] The intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent under the catalytic action of a catalyst to obtain a fluoroether. The catalyst can reduce the probability of side reactions, increase the reaction rate, and improve the yield of the fluoroether.

[0035] In any embodiment, the catalyst comprises at least one of silver iodide, sodium iodide, potassium iodide, silver bromide, sodium bromide, potassium bromide, zinc bromide, cupric chloride, zinc chloride, ferrous chloride, and ferric chloride. The above-mentioned catalyst is a nucleophilic substitution catalyst. The above-mentioned catalyst can reduce the probability of side reactions, improve reaction rate, and improve the yield of fluoroether. At the same time, it is cheap and easy to obtain, has low toxicity, stable properties, and is safe to use and environmentally friendly. It should be noted that the nucleophilic substitution catalyst refers to a catalyst that promotes nucleophilic substitution reaction, which can improve reaction rate and selectivity. Nucleophilic substitution reaction refers to the reaction in which a nucleophile with negative or weak negative electricity attacks (or impacts) and replaces a positively charged or partially positively charged carbon nucleus on the target molecule. During the reaction, the substituent group provides a pair of electrons to form a new bond, and the substituted group leaves with a pair of electrons from the old bond.

[0036] In any embodiment, the intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain the fluoroether:

[0037] The reaction temperature is -20 to 150° C. At this reaction temperature, a suitable reaction rate can be maintained, the risk of thermal runaway can be reduced, and the yield of the fluoroether can be increased; optionally, the reaction temperature is 0 to 70° C., which can further maintain a suitable reaction rate, reduce the risk of thermal runaway, and increase the yield of the fluoroether; and / or,

[0038] The reaction time is 10 to 40 hours, during which the reaction can be more complete and the yield of the fluoroether can be increased; optionally, the reaction time is 12 to 24 hours, which can further make the reaction more complete and increase the yield of the fluoroether.

[0039] In a second aspect, an embodiment of the present application provides an electrolyte, comprising the fluoroether prepared by the preparation method of the fluoroether according to the first aspect of the present application.

[0040] In a third aspect, an embodiment of the present application provides a battery, comprising the electrolyte of the second aspect of the present application.

[0041] In a fourth aspect, an embodiment of the present application provides an electrical device comprising the battery according to the third aspect of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 Schematic diagram of a secondary battery according to one embodiment of the present application.

[0043] Figure 2 yes Figure 1 FIG. 1 is an exploded view of a secondary battery according to an embodiment of the present application.

[0044] Figure 3 Schematic diagram of a battery module according to one embodiment of the present application.

[0045] Figure 4 Schematic diagram of a battery pack according to one embodiment of the present application.

[0046] Figure 5 yes Figure 4 An exploded view of a battery pack according to an embodiment of the present application is shown.

[0047] Figure 6 FIG. 1 is a schematic diagram of an electrical device using a secondary battery according to an embodiment of the present application as a power source.

[0048] Description of reference numerals:

[0049] 1 battery pack; 2 upper case; 3 lower case; 4 battery module; 5 secondary battery; 51 housing; 52 electrode assembly; 53 top cover assembly. DETAILED DESCRIPTION

[0050] The following specifically discloses embodiments of the fluoroether preparation method, electrolyte, battery, and electrical device of the present application. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of substantially identical structures may be omitted. This is to avoid unnecessary length in the following description and to facilitate understanding by those skilled in the art. Furthermore, the drawings and the following description are provided to facilitate a thorough understanding of the present application by those skilled in the art and are not intended to limit the subject matter recited in the claims.

[0051] " range " disclosed in the present application is limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of special range. The scope limited in this way can be to include end value or not include end value, and can be arbitrarily combined, that is, any lower limit can form a range with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for specific parameters, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range value 1 and 2 are listed, and if the maximum range value 3,4 and 5 are listed, then the following range can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise specified, the numerical range " ab " represents the abbreviation of any real number combination between a and b, wherein a and b are all real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is simply an abbreviation for these numerical combinations. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0052] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0053] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0054] Unless otherwise specified, all steps of the present 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 may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), indicating that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0055] Currently, the synthesis of fluoroethers primarily involves reacting alcohols or phenols with fluoroolefins in the presence of a catalyst, either in the presence or absence of a solvent, to produce a fluoroether reaction solution. However, the difficulty in obtaining fluoroolefins, their high cost, and the associated risks hinder the synthesis of fluoroethers.

[0056] Consequently, research on the synthesis of fluoroethers has been ongoing. For example, one method for producing fluoroethers involves reacting a raw material, such as an alcohol or phenol, with a fluoroolefin in the presence of a catalyst, with or without a solvent, to produce a fluoroether reaction solution. The raw material is an alcohol or phenolic substance. The fluoroether reaction solution is then concentrated to obtain a concentrated solution and a clear solution. The clear solution is then purified and separated to produce the fluoroether product. However, these fluoroolefins are difficult to obtain, costly, and toxic. Furthermore, the reaction involves high temperatures and pressures, which can be hazardous.

[0057] Surprisingly, benzenesulfonyl chloride is reacted with a fluoroalcohol and a first alkaline substance in an organic solvent to obtain an intermediate product; and the intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether.

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

[0059] In a first aspect, the present invention provides a method for preparing a fluoroether, comprising the following steps:

[0060] reacting benzenesulfonyl chloride with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product;

[0061] reacting the intermediate product with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether;

[0062] Wherein, the general structural formula of the fluoroalcohol is R F OH, R F including groups containing fluorine atoms;

[0063] The polyether compound has a structural formula as shown in (I), and the fluoroether has a structural formula as shown in (II):

[0064]

[0065] n is an integer greater than or equal to 0;

[0066] R includes at least one of an alkyl group, an alkenyl group, and an alkynyl group.

[0067] Thus, in the technical scheme of the embodiment of the present application, benzenesulfonyl chloride is reacted with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product; the intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether. The raw materials of the present application are cheap and easy to obtain, the preparation process is simple, the yield is high, and the operation is simple. The reaction to generate the intermediate product is a reversible reaction, and hydrochloric acid is generated during the reaction. After the hydrochloric acid is neutralized with the first alkaline substance, the generation of the intermediate product can be promoted, and the yield of the intermediate product can be increased. The organic solvent can increase the contact probability of the reaction raw materials, increase the reaction speed, and increase the yield of the fluoroether.

[0068] It should be noted that the benzenesulfonyl chloride can be p-benzenesulfonyl chloride, bromobenzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride and methanesulfonyl chloride, among which p-toluenesulfonyl chloride is the cheapest and most readily available, less toxic and safer.

[0069] In any embodiment, R F Fluorinated alkyl groups with 1 to 5 carbon atoms are included; fluoroalkyl groups with fewer than 5 carbon atoms are selected. Fluorinated alcohols have better stability, lower toxicity, readily available raw materials, and are inexpensive. Furthermore, their C-C bonds are more stable and less susceptible to oxidation and cleavage, which can increase the yield of fluoroethers. For example, the fluoroalcohol can be any one of fluoromethanol, 2,2-difluoroethanol, 4,4,5,5,5-pentafluoropentanol, 2-fluoroethanol, 2,2-difluoropropanol, or 2,2,2-trifluoroethanol.

[0070] In any embodiment, n is a positive integer of 1 to 5, which can improve the solvation ability and antioxidant capacity of the fluoroether. The value of N can be any one of 1, 2, 3, 4 or 5.

[0071] In any embodiment, R includes any one of alkyl groups having 1 to 5 carbon atoms, which can improve the solvating ability of the fluoroether and reduce the viscosity of the fluoroether. The number of carbon atoms can be 1, 2, 3, 4 or 5.

[0072] In any embodiment, R F The inclusion of 1 to 3 fluorine atoms can improve the stability of the fluorinated ether and reduce the toxicity of the fluorinated ether. The number of fluorine atoms can be 1, 2 or 3.

[0073] In any embodiment, R includes any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopropane, cyclopentane and cyclohexane, which can further improve the stability of the fluoroether, reduce the occurrence of side reactions, and reduce the toxicity of the fluoroether.

[0074] In any embodiment, the intermediate product obtained by reacting benzenesulfonyl chloride with a fluoroalcohol and a first alkaline substance in a first organic solvent is: the first alkaline substance includes at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine and pyridine. The first alkaline substance is cheap and easy to obtain, has low toxicity, stable properties, and is safe to use.

[0075] In any embodiment, the intermediate product obtained by reacting benzenesulfonyl chloride with a fluoroalcohol and a first alkaline substance in a first organic solvent comprises: the first organic solvent comprises at least one of tetrahydrofuran, dichloromethane, N,N-dimethylformamide, and dimethyl sulfoxide, all of which are polar aprotic solvents that are inexpensive, readily available, low in toxicity, stable, safe to use, and have low boiling points and are easily removed through subsequent purification. It should be noted that polar aprotic solvents are solvents that do not contain easily substitutable hydrogen atoms and whose solvation occurs primarily through interactions with dipole moments or van der Waals forces.

[0076] In any embodiment, the benzenesulfonyl chloride is reacted with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product: the molar ratio of the fluoroalcohol to the benzenesulfonyl chloride and the first alkaline substance is 1:(1-4):(1-16). At this mass ratio, on the one hand, the occurrence of side reactions can be reduced and the yield of the intermediate product can be increased. On the other hand, the cost of raw materials can be reduced while ensuring sufficient reaction. The molar ratio of the fluoroalcohol to the benzenesulfonyl chloride and the first alkaline substance can be 1:1:1, 1:1:16, 1:4:1, 1:4:16, 1:1:4, 1:2:1, 1:2:4 or 1:1.2:2.5; optionally, the molar ratio of the fluoroalcohol to the benzenesulfonyl chloride and the first alkaline substance is 1:(1-2):(1-4), which can further reduce the occurrence of side reactions, increase the yield of the intermediate product, and reduce the cost of raw materials.

[0077] In any embodiment, the benzenesulfonyl chloride is reacted with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product: the reaction temperature is -20 to 100°C, and the reaction to form the intermediate product is an exothermic reaction. Within this temperature range, a suitable reaction rate can be maintained, the risk of thermal runaway can be reduced, and the yield of the intermediate product can be improved. 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 or 100°C; optionally, the reaction temperature is 0 to 30°C, which can further maintain a suitable reaction rate, reduce the risk of thermal runaway, and improve the yield of the intermediate product.

[0078] In any embodiment, the benzenesulfonyl chloride is reacted with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product: the reaction time is 4 to 30 hours. Within this reaction time, the reaction can be more complete and the yield of the intermediate product is higher. The reaction time can be 4 hours, 7 hours, 10 hours, 13 hours, 15 hours, 18 hours, 20 hours, 22 hours, 25 hours, 27 hours or 30 hours; optionally, the reaction time is 10 to 20 hours, which can further make the reaction more complete and the yield of the intermediate product higher.

[0079] In any embodiment, the intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether: the second alkaline substance includes at least one of sodium hydride, lithium hydride, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium acetate, sodium methoxide and sodium ethoxide. The second alkaline substance directly participates in the reaction as a reactant. Selecting the above second alkaline substance can reduce the toxicity of the reaction system, reduce the cost of raw materials, and improve the safety of the reaction.

[0080] In any embodiment, the intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether: the second organic solvent includes at least one of tetrahydrofuran, dichloromethane, N,N-dimethylformamide and dimethyl sulfoxide. The above solvents are all polar aprotic solvents, which are cheap and easy to obtain, have low toxicity, stable properties, safe to use, and have low boiling points and are easy to remove through subsequent purification.

[0081] In any embodiment, the intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether: the molar ratio of the intermediate product to the polyether compound and the second alkaline substance is 1:(1-4):(1-4). At this mass ratio, the yield of the fluoroether can be increased and the cost of raw materials can be reduced. The molar ratio of the intermediate product to the polyether compound and the second alkaline substance can be 1:1:1, 1:1:4, 1:4:1, 1:4:4, 1:2:1, 1:1:2, 1:2:2 or 1:1.5:1.5; optionally, the molar ratio of the intermediate product to the polyether compound and the second alkaline substance is 1:(1-2):(1-2), which can further increase the yield of the fluoroether and reduce the cost of raw materials.

[0082] In any embodiment, reacting the intermediate product with a polyether compound and a second alkaline substance in a second organic solvent to obtain the fluoroether comprises reacting the intermediate product with the polyether compound and the second alkaline substance in the second organic solvent under the catalytic action of a catalyst to obtain the fluoroether. The presence of a catalyst can reduce the probability of side reactions, increase the reaction rate, and improve the yield of the fluoroether.

[0083] In any embodiment, the catalyst comprises at least one of silver iodide, sodium iodide, potassium iodide, silver bromide, sodium bromide, potassium bromide, zinc bromide, cupric chloride, zinc chloride, ferrous chloride, and ferric chloride. The above-mentioned catalyst is a nucleophilic substitution catalyst. The above-mentioned catalyst can reduce the probability of side reactions, improve reaction rate, and improve the yield of fluoroether. At the same time, it is cheap and easy to obtain, has low toxicity, stable properties, and is safe to use and environmentally friendly. It should be noted that the nucleophilic substitution catalyst refers to a catalyst that promotes nucleophilic substitution reaction, which can improve reaction rate and selectivity. Nucleophilic substitution reaction refers to the reaction in which a nucleophile with negative or weak negative electricity attacks (or impacts) and replaces a positively charged or partially positively charged carbon nucleus on the target molecule. During the reaction, the substituent group provides a pair of electrons to form a new bond, and the substituted group leaves with a pair of electrons from the old bond.

[0084] In any embodiment, the intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether: the reaction temperature is -20 to 150°C. At this reaction temperature, a suitable reaction rate can be maintained, the risk of thermal runaway can be reduced, and the yield of the fluoroether can be increased. 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, 120°C, 130°C, 140°C or 150°C; optionally, the reaction temperature is 0 to 70°C, which can further maintain a suitable reaction rate, reduce the risk of thermal runaway, and increase the yield of the fluoroether.

[0085] In any embodiment, the intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether: the reaction time is 10 to 40 hours. During this reaction time, the reaction can be more complete and the yield of the fluoroether can be improved. The reaction time can be 10, 12, 14, 16, 18, 20, 24, 26, 30, 35 or 40 hours; optionally, the reaction time is 12 to 24 hours, which can further make the reaction more complete and improve the yield of the fluoroether.

[0086] In a second aspect, an embodiment of the present application provides an electrolyte, comprising the fluoroether prepared by the preparation method of the fluoroether according to the first aspect of the present application.

[0087] In a third aspect, an embodiment of the present application provides a battery comprising the electrolyte of the second aspect of the present application.

[0088] In any embodiment, the battery comprises a primary battery or a secondary battery.

[0089] In one embodiment of the present application, a secondary battery is provided. Typically, a secondary battery includes a positive electrode, a negative electrode, an electrolyte, and a separator. During the battery's charge and discharge processes, active ions are intercalated and released between the positive and negative electrodes. The electrolyte conducts ions between the positive and negative electrodes. The separator is positioned between the positive and negative electrodes, primarily preventing a short circuit between the positive and negative electrodes while allowing ions to pass through.

[0090] The positive electrode sheet includes a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector.

[0091] As an example, the positive electrode current collector has two surfaces opposite to each other in its thickness direction, and the positive electrode film layer is disposed on either or both of the two opposite surfaces of the positive electrode current collector.

[0092] In some embodiments, the positive electrode 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 material base and a metal layer formed on at least one surface of the polymer material base. 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 material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).

[0093] In some embodiments, the positive electrode active material may be a positive electrode active material for lithium ion batteries that is well known in the art. As an example, the positive electrode active material may include at least one of the following materials: lithium phosphates containing olivine structure, lithium transition metal oxides and their respective modified compounds. However, the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials for batteries 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 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 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O2 (also referred to as NCM 523 ), LiNi 0.5 Co 0.25 Mn0.25 O2 (also referred to as NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O2 (also referred to as NCM 622 ), LiNi 0.8 Co 0.1 Mn 0.1 O2 (also referred to as NCM 811 ), lithium nickel cobalt aluminum oxide (such as LiNi 0.85 Co 0.15 Al 0.05 O2) and its modified compounds. Examples of olivine-structured lithium-containing phosphates may include, but are not limited to, at least one of lithium iron phosphate (such as LiFePO4 (also referred to 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 iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.

[0094] 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), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluorine-containing acrylate resin.

[0095] In some embodiments, the positive electrode film layer further includes a conductive agent, which may include, for example, at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

[0096] In some embodiments, the positive electrode sheet can be prepared by the following method: the components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components, are dispersed in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode sheet structure, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.

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

[0098] As an example, the negative electrode sheet structure includes a negative electrode current collector having two opposite surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector structure.

[0099] 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 base layer and a metal layer formed on at least one surface of the polymer base material. 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 base material (such as a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).

[0100] In some embodiments, the negative electrode active material may be a negative electrode active material for a battery that is 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, lithium titanate, etc. The silicon-based material may be selected from at least one of elemental silicon, silicon oxides, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin oxides, and tin alloys. However, the present application is not limited to these materials, and other traditional 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.

[0101] 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).

[0102] In some embodiments, the negative electrode film layer further includes a conductive agent, which can be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

[0103] In some embodiments, the negative electrode film layer further includes other additives, such as a thickener (eg, sodium carboxymethyl cellulose (CMC-Na)).

[0104] In some embodiments, the negative electrode sheet can be prepared by the following method: the components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the binder and any other components, are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode sheet structure, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.

[0105] The electrolyte conducts ions between the positive and negative electrodes. This application does not specify the type of electrolyte, and the electrolyte can be selected based on the needs. For example, the electrolyte can be liquid, gel, or solid.

[0106] In some embodiments, the electrolyte is an electrolyte solution comprising an electrolyte salt and a solvent.

[0107] 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 difluorooxalatoborate, lithium dioxalatoborate, lithium difluorodioxalatophosphate, and lithium tetrafluorooxalatophosphate.

[0108] 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, methylpropyl carbonate, ethylpropyl 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, cyclopentane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.

[0109] In some embodiments, the electrolyte may further include additives. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, and additives that improve battery high or low temperature performance.

[0110] The electrolyte also includes the fluoroether prepared in the first aspect of the present application.

[0111] In some embodiments, the secondary battery further includes a separator. The present application has no particular limitation on the type of separator, and any known porous separator with good chemical and mechanical stability can be selected.

[0112] 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.

[0113] In some embodiments, the positive electrode sheet, the negative electrode sheet, and the separator may be formed into an electrode assembly by a winding process or a lamination process.

[0114] In some embodiments, the secondary battery may include an outer packaging that can be used to encapsulate the electrode assembly and the electrolyte.

[0115] 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. Alternatively, the outer packaging of the secondary battery can be a soft shell, such as a pouch-type soft shell. The soft shell can be made of plastic, such as polypropylene, polybutylene terephthalate, and polybutylene succinate.

[0116] The present application has no particular restrictions on the shape of the secondary battery, which can be cylindrical, square or any other shape. For example, Figure 1 The secondary battery 5 is a square structure as an example.

[0117] In some embodiments, reference Figure 2 The outer packaging may include a shell 51 and a cover plate 53. The shell 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity. The shell 51 has an opening connected to 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 isolation membrane can form an electrode assembly 52 through a winding process or a lamination 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 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.

[0118] In some embodiments, secondary batteries can be assembled into a battery module. The number of secondary batteries contained in the battery module can be one or more. The specific number can be selected by those skilled in the art according to the application and capacity of the battery module.

[0119] Figure 3 4 is an example of a battery module. Figure 3 In the battery module 4, the plurality of secondary batteries 5 may be arranged in sequence along the length of the battery module 4. Of course, they may also be arranged in any other manner. The plurality of secondary batteries 5 may further be fixed by fasteners.

[0120] Optionally, the battery module 4 may further include a housing having a receiving space, and the plurality of secondary batteries 5 are received in the receiving space.

[0121] In some embodiments, the battery modules described above may also be assembled into a battery pack. The battery pack may contain one or more battery modules, and the specific number may be selected by those skilled in the art based on the application and capacity of the battery pack.

[0122] Figure 4 and Figure 5 The battery pack 1 is used as an example. Figure 4 and Figure 5The battery pack 1 may include a battery box and multiple 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 an enclosed space for accommodating the battery modules 4. The multiple battery modules 4 can be arranged in any manner in the battery box.

[0123] In a fourth aspect, an embodiment of the present application provides an electrical device comprising the battery according to the third aspect of the present application.

[0124] In addition, the present application also provides an electric device, which includes at least one of the secondary battery, battery module, or battery pack provided in the present application. The secondary battery, battery module, or battery pack can be used as a power source for the electric device, and can also be used as an energy storage unit for the electric device. The electric 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 and satellites, energy storage systems, etc., but is not limited thereto.

[0125] As the electrical device, a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.

[0126] Figure 6 This is an example of an electric device. This device is 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, a battery pack or battery module can be used.

[0127] Another example device may be a mobile phone, a tablet computer, a notebook computer, etc. Such a device is generally required to be lightweight and thin, and may use a secondary battery as a power source.

[0128] The technical solutions of the present invention are 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.

[0129] In the step of generating the intermediate product of the present application, p-toluenesulfonyl chloride can be mixed with the fluoroalcohol, the first alkaline substance, and the catalyst by dropwise addition. After the dropwise addition is completed, the reaction is continued, and the reaction progress can be monitored by gas chromatography. After the reaction is complete, the organic phase can be washed twice, washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, the anhydrous sodium sulfate is filtered out, and the solvent is removed to obtain the intermediate product. The reaction temperature is room temperature and the reaction time is 12 hours.

[0130] In the step of generating a fluoroether in the present application, the polyether compound is mixed with a second alkaline substance and an organic solvent by dropwise addition, and the intermediate product is then added dropwise to the mixed solution. After the addition is complete, the reaction is continued, and the reaction progress can be monitored by gas chromatography. After the reaction is complete, the mixture is allowed to cool, quenched with water, the organic solvent is removed in vacuo, extracted with dichloromethane, the organic phases are combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, anhydrous sodium sulfate is filtered out, the solvent is removed, and vacuum distillation is performed to obtain a fluoroether. The reaction temperature is 66°C and the reaction time is 16h.

[0131] Among them, the other parameters of the preparation method of fluoroether of Examples 1 to 20 and Comparative Examples 1 to 3 are as follows:

[0132] Table 1 Parameters.

[0133]

[0134]

[0135] Performance Testing

[0136] The product purities and yields of the fluoroethers prepared by the methods for preparing the fluoroethers of Examples 1 to 20 and Comparative Examples 1 to 2 were statistically analyzed. Product purity was measured using gas chromatography using an Agilent 8860 gas chromatograph, FID detector, and HP-5 column. The test method included the following heating procedure: initial temperature: 40°C, hold for 1 minute, rate of 10°C / min, increase to 100°C, hold for 10 minutes, then increase to 170°C at a rate of 50°C / min, hold for 0 minutes; detector temperature: 200°C, injection port temperature: 150°C, column flow rate: 1 ml / min. Product yield = actual yield of target product / theoretical yield of target product × 100%. The results are shown in Table 1.

[0137] As can be seen from Table 1, by reacting benzenesulfonyl chloride with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product; the intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether. The raw materials of this application are cheap and easy to obtain, the preparation process is simple, the yield is high, and the operation is simple. The reaction to generate the intermediate product is a reversible reaction, and hydrochloric acid is generated during the reaction. After the hydrochloric acid is neutralized with the first alkaline substance, the generation of the intermediate product can be promoted, and the yield of the intermediate product can be increased. The organic solvent can increase the contact probability of the reaction raw materials, increase the reaction rate, and increase the yield of the fluoroether.

[0138] Selecting a fluorinated alkyl group with less than 5 carbon atoms can improve the yield of fluoroethers by increasing the stability of the fluoroalcohol, reducing toxicity, and making the raw materials readily available and inexpensive.

[0139] When n is a positive integer of 1 to 5, the solvating ability and antioxidant ability of the fluoroether can be improved.

[0140] R includes any one of alkyl groups with 1 to 5 carbon atoms, which can improve the solvating ability of the fluoroether and reduce the viscosity of the fluoroether.

[0141] The molar ratio of the fluoroalcohol to benzenesulfonyl chloride and the first alkaline substance is 1:(1-4):(1-16). At this mass ratio, on the one hand, the occurrence of side reactions can be reduced and the yield of the intermediate product can be increased; on the other hand, the cost of raw materials can be reduced while ensuring sufficient reaction.

[0142] The mass ratio of the intermediate product to the polyether compound and the second alkaline substance is 1:(1-4):(1-4). Under this mass ratio, the yield of the fluoroether can be increased and the raw material cost can be reduced.

[0143] The use of nucleophilic substitution catalysts can reduce the probability of side reactions, increase reaction rates, and improve the yield of fluoroethers. Furthermore, they are inexpensive, readily available, low in toxicity, stable in properties, safe to use, and environmentally friendly.

[0144] In Comparative Example 1, the yield of fluoroether was low because the first alkaline substance was not added. In Comparative Example 2, fluoroether was not formed because the second alkaline substance was not added.

[0145] The above are only preferred embodiments of the present application and are not intended to limit the scope of the present application. Those skilled in the art will readily appreciate that various modifications and variations are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present application shall be included within the scope of the present application.

Claims

1. A method for preparing a fluoroether, characterized in that: The following steps are involved: reacting benzenesulfonyl chloride with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product; reacting the intermediate product with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether; Wherein, the general structural formula of the fluoroalcohol is R F OH, R F including groups containing fluorine atoms; The polyether compound has a structural formula as shown in (I), and the fluoroether has a structural formula as shown in (II): n is an integer greater than or equal to 0; R includes at least one of an alkyl group, an alkenyl group, and an alkynyl group.

2. The method for preparing a fluoroether according to claim 1, wherein R F A fluorinated alkyl group comprising 1 to 5 carbon atoms; and / or n is a positive integer from 1 to 5; and / or, R includes any one of alkyl groups having 1 to 5 carbon atoms.

3. The method for preparing a fluoroether according to claim 1 or 2, wherein: R F Contains 1 to 3 fluorine atoms; and / or, R includes any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopropane, cyclopentane and cyclohexane.

4. The method for preparing a fluoroether according to any one of claims 1 to 3, wherein: The benzenesulfonyl chloride is reacted with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product: The first alkaline substance includes at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine and pyridine; and / or, The first organic solvent includes at least one of tetrahydrofuran, dichloromethane, N,N-dimethylformamide and dimethyl sulfoxide.

5. The method for preparing a fluoroether according to any one of claims 1 to 4, wherein: The benzenesulfonyl chloride is reacted with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product: The molar ratio of the fluoroalcohol, benzenesulfonyl chloride and the first alkaline substance is 1:(1-4):(1-16).

6. The method for preparing a fluoroether according to any one of claims 1 to 5, wherein: The benzenesulfonyl chloride is reacted with a fluoroalcohol and a first alkaline substance in a first organic solvent to obtain an intermediate product: The reaction temperature is -20 to 100°C; and / or, The reaction time is 4 to 30 hours.

7. The method for preparing a fluoroether according to any one of claims 1 to 6, wherein: The intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether: The second alkaline substance includes at least one of sodium hydride, lithium hydride, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium acetate, sodium methoxide and sodium ethoxide; and / or, The second organic solvent includes at least one of tetrahydrofuran, dichloromethane, N,N-dimethylformamide and dimethyl sulfoxide.

8. The method for preparing a fluoroether according to any one of claims 1 to 7, wherein: The intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether: The molar ratio of the intermediate product to the polyether compound and the second alkaline substance is 1:(1-4):(1-4).

9. The method for preparing a fluoroether according to any one of claims 1 to 8, wherein: The step of reacting the intermediate product with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether comprises: The intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent under the catalytic action of a catalyst to obtain a fluoroether.

10. The method for preparing a fluoroether according to claim 9, wherein The catalyst includes at least one of silver iodide, sodium iodide, potassium iodide, silver bromide, sodium bromide, potassium bromide, zinc bromide, cupric chloride, zinc chloride, ferrous chloride, and ferric chloride.

11. The method for preparing a fluoroether according to any one of claims 1 to 10, wherein: The intermediate product is reacted with a polyether compound and a second alkaline substance in a second organic solvent to obtain a fluoroether: The reaction temperature is -20 to 150°C; and / or, The reaction time is 10 to 40 hours.

12. An electrolyte, characterized in that: The invention relates to a fluoroether prepared by the method for preparing a fluoroether according to any one of claims 1 to 11.

13. A battery, characterized in that: Comprising the electrolyte as claimed in claim 12.

14. An electrical device, characterized in that: Comprising the battery of claim 13.

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