Amphiphilic imidazole sulfonate ionic liquid, synthetic method thereof and solid-state battery

Abstract

The invention discloses an amphiphilic imidazole sulfonate ionic liquid, a synthetic method thereof and a solid-state battery, and belongs to the technical field of ionic liquid synthesis. The amphiphilic imidazole sulfonate ionic liquid comprises an acceptable combined salt which is formed by imidazole cations and sulfonic acid anions in pharmacy, and the amphiphilic imidazole sulfonate ionic liquid has an ionic conduction characteristic in a solution or solid state; the amphiphilic imidazole sulfonate ionic liquid can be obtained through simple synthesis, and the amphiphilic imidazole sulfonate ionic liquid has good ionic conduction characteristics in a solution or solid state, and is suitable for preparing an electrolyte of a solid-state battery.

Description

Technical Field

[0001] The present application relates to the technical field of ionic liquid materials, specifically to amphiphilic imidazole sulfonate ionic liquids, synthesis methods thereof, and solid-state batteries. Background Art

[0002] Ionic liquids are a new class of solvents that are attracting considerable attention. They are salts with melting points near room temperature. They are typically composed of large, poorly symmetrical cations and relatively small, well-symmetrical anions. Their high electrical conductivity, low vapor pressure, and strong dissolving power make them considered green chemical reaction media that can replace traditional volatile solvents. As their understanding deepens, their applications have expanded far beyond their initial green chemistry roots, showing enormous promise in electrolysis, solar cells, fuel cells, catalysis, and even medicine.

[0003] Imidazolium ionic liquids are the most widely studied and mature core system in the field of ionic liquids. Their structural tunability and excellent physicochemical properties make them the cornerstone of ionic liquid theoretical research and industrial applications. However, traditional imidazolium ionic liquids often use halogen ions, tetrafluoroborate ions, and other coordinating anions, which have many drawbacks. Halogen ions can easily cause equipment corrosion and reduce device life; tetrafluoroborate ions are unstable at high temperatures and easily decompose to produce corrosive gases. Their limited ion conduction efficiency makes it difficult to meet the stringent ion conduction performance requirements of high-energy-density energy storage devices. Summary of the Invention

[0004] In response to the problems existing in the prior art, the present application provides an amphiphilic imidazole sulfonate ionic liquid, a synthesis method thereof, and a solid-state battery. The amphiphilic imidazole sulfonate ionic liquid is simple to synthesize and has a high yield. It can serve as an ion conduction carrier to achieve high ion charge transfer and has the ability to be widely used in electrochemical devices, electrolyte membranes, and solid-state electrolytes.

[0005] To achieve the above application objectives, the technical solutions adopted in this application are as follows: In a first aspect, the present application provides an amphiphilic imidazole sulfonate ionic liquid, wherein the amphiphilic imidazole sulfonate ionic liquid comprises: a pharmaceutically acceptable combined salt formed by an imidazole cation and a sulfonic acid anion, and having ion-conducting properties in a solution or solid state; The imidazolium cation is selected from 1-vinylimidazolium cation derivatives, and the general structural formula of the 1-vinylimidazolium cation is (I) or (II); the sulfonic acid anion is selected from sulfonic acid anion derivatives, and the general structural formula of the sulfonic acid anion is (III);

[0006] Wherein, A is a C1~C16 alkyl group; B is a C1-C5 alkyl group, a vinyl group, a C3-C6 cycloalkyl group, an aryl group, an alkylaryl group, a halogenated aryl group, a halogenated methyl group, a benzyl group or a halogenated benzyl group; C represents a C1~C16 alkyl group or a polyethylene glycol segment; The cycloalkyl group contains 3 to 6 C atoms; the alkylaryl group is an ortho-para methyl substituted aryl group or a meta-para methyl substituted aryl group; the halogenated aryl group is an ortho-, meta-, or para-halogenated aryl group; the halogenated phenylmethyl group is an ortho-, meta-, or para-halogenated phenylmethyl group.

[0007] As an embodiment of the present application, the imidazolium cation is selected from any one of the following:

[0008] The sulfonic acid anion is selected from any one of the following:

[0009] in, a is 1 to 15, b is 1 to 23, c is 1 to 16, d is 0 to 4, X is a carbon element or a halogen; and Y is a halogen, an aryl group, or a halogenated aryl group.

[0010] As an embodiment of the present application, the amphiphilic imidazole sulfonate ionic liquid is specifically selected from the following compounds: Compound 1

[0011] Compound 2

[0012] Compound 3

[0013] Compound 4

[0014] Compound 5

[0015] Compound 6

[0016] Compound 7

[0017] Compound 8

[0018] Compound 9

[0019] Compound 10

[0020] Compound 11

[0021] Compound 12

[0022] Compound 13

[0023] Compound 14

[0024] Compound 15

[0025] Compound 16

[0026] Compound 17

[0027] Compound 18

[0028] Compound 19

[0029] Compound 20

[0030] Compound 21

[0031] Compound 22 .

[0032] In a second aspect, the present application provides a method for synthesizing an amphiphilic imidazole sulfonate ionic liquid, comprising: According to the structural formula of the sulfonic acid anion, the corresponding sulfonyl chloride compound and alcohol compound are dissolved in a first solvent, the reaction is placed at 0 degrees Celsius, an equivalent amount of base required for the reaction is added, and stirred until the reaction is complete, and then quenched and purified with an aqueous solution to obtain an intermediate product; The intermediate product and 1-vinylimidazole are added to a second solvent, fully reacted in a protective atmosphere, and the second solvent is removed and purified to obtain an amphiphilic imidazole sulfonate ionic liquid.

[0033] As an embodiment of the present application, the alcohol compound is selected from one of methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, and 1-hexadecanol.

[0034] As an embodiment of the present application, the alcohol compound is selected from one of 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, and polyethylene glycol.

[0035] As an embodiment of the present application, the conditions for sufficient reaction in a protective atmosphere are: reaction at 60-70° C. for 20-30 hours; As an embodiment of the present application, the first solvent is dichloromethane or chloroform; As an embodiment of the present application, the second solvent is ethanol or acetonitrile.

[0036] As an example of the present application, the addition of an equivalent amount of base required for the reaction is stirred until the reaction is complete. Add 4 to 5 equivalents of base to the reaction, and the final amphiphilic imidazole sulfonate ionic liquid structure is as follows:

[0037] Add 10-11 equivalents of base to the reaction, and the final amphiphilic imidazole sulfonate ionic liquid structure is as follows: .

[0038] In a third aspect, the present application provides an application of the amphiphilic imidazole sulfonate ionic liquid, wherein the amphiphilic imidazole sulfonate ionic liquid is used to prepare electrolytes in electronic products; the electronic products include batteries, sensors or supercapacitors.

[0039] In a fourth aspect, the present application provides a solid-state battery comprising an electrolyte; The electrolyte adopts the amphiphilic imidazole sulfonate ionic liquid.

[0040] Compared with the existing technology, this application has the following advantages: The present application provides an amphiphilic imidazole sulfonate ionic liquid, including a pharmaceutically acceptable combined salt formed by an imidazole cation and a sulfonic acid anion. The amphiphilic imidazole sulfonate ionic liquid is obtained by a simple synthesis. On the one hand, the 1-vinyl imidazole cation provides a polymerizable ion transport site as a positively charged group, and on the other hand, the sulfonic acid anion has an anion coordination property with controllable molecular volume and easy removal. The amphiphilic imidazole sulfonate ionic liquid has good ion conduction properties in both solution and solid state and is suitable for use in preparing electrolytes. The method for preparing the compound of the present application is simple and is a method suitable for development into industrial production.

[0041] This application describes a simple synthesis method to produce amphiphilic imidazole sulfonate ionic liquids, which can be used as new ionic liquids with unique structural and performance characteristics. Their molecular structure contains an unsaturated vinyl double bond and an imidazole ring structure. The introduction of a sulfonic acid group also imparts both good polarity and ionization capabilities, which endows them with the property of being liquid at a certain temperature and having a wide liquid temperature range. Furthermore, these amphiphilic imidazole sulfonate ionic liquids exhibit excellent thermal and chemical stability, are nonvolatile and nonflammable, and can maintain a stable state in a variety of harsh environments, laying a solid foundation for their practical application.

[0042] The ability of this amphiphilic imidazole sulfonate ionic liquid to form an ionic liquid stems from the unique design of its molecular structure. The nitrogen atom on the imidazole ring has a strong electronegativity. Under certain conditions, it can undergo proton transfer with the sulfonic acid group or chemical reaction to form an ion pair, thereby breaking the covalent bonds between the molecules and generating freely mobile ions. When vinyl imidazole is combined with a sulfonic acid compound through appropriate synthetic methods (such as neutralization or quaternization), the resulting ionic compound, due to its moderate interionic forces, cannot form crystals at a certain temperature and instead exists in a liquid state, thus forming an ionic liquid.

[0043] In terms of ion transport, ions in amphiphilic imidazolium sulfonate-based ionic liquids can migrate within the liquid system using molecular thermal motion, external electric fields, concentration gradients, and other driving forces. When an external electric field is applied, cations (imidazolium cations) and anions (sulfonate ions, etc.) migrate toward different electrodes, enabling charge conduction. In the absence of an electric field, concentration differences also promote ion diffusion and transport.

[0044] Furthermore, the amphiphilic imidazole sulfonate ionic liquids prepared in this application not only possess the low vapor pressure and high ionic conductivity characteristics of traditional ionic liquids, but also possess polymerizability due to the presence of vinyl groups, enabling the formation of ionic liquid polymers through free radical polymerization and other reactions, thus expanding the material's application. Furthermore, the introduction of sulfonic acid groups gives them unique advantages in areas such as acid catalysis and proton conduction, and their physical and chemical properties can be precisely controlled by adjusting their molecular structure.

[0045] In terms of application prospects, this amphiphilic imidazole sulfonate ionic liquid can be used as a high-performance electrolyte in the field of electrochemistry for lithium-ion batteries, supercapacitors and other devices, thereby improving the energy density and stability of the equipment; in the field of catalysis, it can be used as an acidic catalyst in organic synthesis reactions, with the advantages of high catalytic efficiency and reusability; in the field of functional materials, ionic liquid polymers prepared by polymerization reactions can be used to prepare proton exchange membranes, sensor materials, etc.; in addition, it also has potential application value in separation and purification, biomedicine and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 Photos and optical microscope images of the amphiphilic imidazole sulfonate ionic liquids provided in this application; Figure 2 Schematic diagram of the application principle of the amphiphilic imidazole sulfonate ionic liquid provided in this application as a solid-state battery electrolyte; Figure 3 This is an AC impedance test curve of the amphiphilic imidazole sulfonate ionic liquid provided in this application; Figure 4 This is the LSV (Linear Sweep Voltammetry) test diagram of the amphiphilic imidazole sulfonate ionic liquid provided in this application. DETAILED DESCRIPTION

[0047] In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0048] In this application, the term "and / or" describes the relationship between associated objects, indicating that three possible relationships exist. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0049] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c" or "at least one of a, b and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can each be single or plural.

[0050] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0051] The terms used in the embodiments of the present application are for the purpose of describing specific embodiments only and are not intended to limit the present application. The singular forms "a," "an," and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

[0052] The weights of the relevant components mentioned in the examples of this application may not only refer to the specific content of each component, but also represent the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally increased or decreased according to the examples of this application, it is within the scope disclosed in the examples of this application. Specifically, the mass in the examples of this application may be a mass unit known in the chemical industry, such as μg, mg, g, kg, etc.

[0053] The terms "first" and "second" are used solely for descriptive purposes, to distinguish objects, such as substances, from one another. They should not be construed as indicating or implying relative importance or implicitly specifying the quantity of the technical features being referred to. For example, a first XX could also be referred to as a second XX, and similarly, a second XX could also be referred to as a first XX, without departing from the scope of the embodiments of this application. Thus, features defined as "first" or "second" may explicitly or implicitly include one or more of such features.

[0054] Sulfonic acid anions possess unique chemical structures and performance advantages, effectively addressing existing challenges. The sulfonic acid groups within their structures enhance the thermal and chemical stability of ionic liquids, reducing high-temperature decomposition and the generation of corrosive gases. Furthermore, sulfonic acid anions dissociate and migrate more efficiently within the system, significantly improving ion conduction efficiency and offering new avenues for the development of high-performance ion-conducting materials. Currently, there are no commercial products utilizing imidazolium cations and sulfonic acid anions for ion transport in ionic liquids or solid-state batteries.

[0055] To address the challenges of the prior art, the present application provides an amphiphilic imidazole sulfonate ionic liquid. This imidazole sulfonate derivative boasts simple synthesis and high yields. It can function as an ion-conducting carrier, achieving high ion charge transfer. In particular, the amphiphilic imidazole sulfonate ionic liquid exhibits excellent ion-conducting properties in both solution and solid state, making it suitable for use in the preparation of electrolytes. It has broad application potential in electrochemical devices, electrolyte membranes, and solid-state battery electrolytes. This material can be used in ion-conducting components (such as electrochemical devices, electrolyte membranes, and solid-state batteries).

[0056] The present application provides an amphiphilic imidazole sulfonate ionic liquid, comprising: a pharmaceutically acceptable combined salt formed by an imidazole cation and a sulfonic acid anion, specifically an imidazole sulfonate derivative, which has ion conductivity properties in solution or solid state.

[0057] The imidazolium cation is selected from 1-vinylimidazolium cation derivatives, and the general structural formula of the 1-vinylimidazolium cation is (I) or (II); the sulfonic acid anion is selected from sulfonic acid anion derivatives, and the general structural formula of the sulfonic acid anion is (III);

[0058] Wherein, A is a C1~C16 alkyl group; B is a C1-C5 alkyl group, a vinyl group, a C3-C6 cycloalkyl group, an aryl group, an alkylaryl group, a halogenated aryl group, a halogenated methyl group, a benzyl group or a halogenated benzyl group; C represents a C1~C16 alkyl group or a polyethylene glycol segment (relative molecular mass Mw=100-1000).

[0059] The cycloalkyl group contains 3 to 6 C atoms; the alkylaryl group is an ortho-para methyl substituted aryl group or a meta-para methyl substituted aryl group; the halogenated aryl group is an ortho-, meta-, or para-halogenated aryl group; the halogenated phenylmethyl group is an ortho-, meta-, or para-halogenated phenylmethyl group.

[0060] The amphiphilic imidazole sulfonate ionic liquid of the present application includes a pharmaceutically acceptable combined salt formed by an imidazole cation and a sulfonic acid anion. The imidazole cation can specifically be a 1-vinyl imidazolium cation derivative. The pharmaceutically acceptable salt combination of the amphiphilic imidazole sulfonate ionic liquid is (I) + (III) or (II) + (III).

[0061] Preferably, the imidazolium cation is a 1-vinylimidazolium cation derivative, and the structural formula may be (I) or (II), and the sulfonic acid anion, i.e. (III), is specifically selected from one of the ions listed in Table 1 below: Table 1

[0062] In the compound structure, a is 1 to 15, b is 1 to 23, c is 1 to 16, d is 0 to 4, X is a carbon element or a halogen, and Y is a halogen or an aryl group or an ortho / meta / para halogenated aryl group.

[0063] Preferably, the amphiphilic imidazole sulfonate ionic liquid of the present application is preferably a combined salt having the structure shown in Table 2 below.

[0064] Table 2

[0065] (Continued Table 2)

[0066] (Continued Table 2)

[0067] (Continued Table 2)

[0068] (Continued Table 2)

[0069] (Continued Table 2)

[0070] (Continued Table 2)

[0071] The first synthesis method of the present application, the synthesis route of the amphiphilic imidazole sulfonate ionic liquid of the general structural formula (I) and (III) is as follows:

[0072] Specifically include: (1) Preparation of compound a-1 Based on the structural formula of the sulfonic acid anion, specifically the group represented by B, the corresponding sulfonyl chloride compound and alcohol compound are dissolved in dichloromethane or chloroform (as the first solvent) at a ratio of 1:1. The reaction is placed at 0°C and slowly added with 4-5 equivalents of potassium hydroxide (as a base) with stirring until the reaction is complete. The reaction is then quenched with an aqueous solution and purified to obtain the intermediate product a-1. B is a C1-C5 alkyl group, a vinyl group, a C3-C6 cycloalkyl group, an aryl group, an alkyl / haloaryl group, a halomethyl group, a benzyl group, or a halobenzyl group.

[0073] Potassium hydroxide is used as a strong base, and other bases may be used instead, without specific limitation here.

[0074] (2) Preparation of compound a-2 Compound b-1 and 1-vinylimidazole are added to dry ethanol or acetonitrile solvent (as the second solvent) in a ratio of 1:3. The internal atmosphere is replaced with nitrogen. The reaction is carried out at 60-70°C for 20-30 hours. The second solvent is removed and purified to obtain the corresponding product b-2.

[0075] In the above synthesis route, the alcohol compound is selected from one of methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, and 1-hexadecanol.

[0076] Among them, the reaction at 60-70°C for 20-30h can also be the reaction at 60-65°C for 20-25h; the reaction at 65-70°C for 24-30h; the reaction at 60°C for 30h; the reaction at 70°C for 20h; the reaction at 63°C for 27h; the reaction at 68°C for 24h; the reaction at 65°C for 24h, etc., which are not specifically limited here.

[0077] In the above scheme, nitrogen can also be other protective atmospheres, such as inert gases such as argon.

[0078] The second synthesis method of this application, the synthesis route of the amphiphilic imidazole sulfonate ionic liquids of structural formula (II) and (III) is as follows:

[0079] The specific synthesis process includes: (1) Preparation of compound b-1 Based on the structural formula of the sulfonic acid anion, specifically the group represented by B, the corresponding sulfonyl chloride compound and alcohol compound are dissolved in dichloromethane or chloroform (as the first solvent) at a ratio of 2:1. The reaction mixture is placed at 0°C and slowly added with 10-11 equivalents of potassium hydroxide, followed by stirring until the reaction is complete. The reaction is then quenched with an aqueous solution and purified to obtain the intermediate product b-1. B is a C1-C5 alkyl group, a vinyl group, a C3-C6 cycloalkyl group, an aryl group, an alkyl / haloaryl group, a halomethyl group, a benzyl group, or a halobenzyl group.

[0080] (2) Preparation of compound b-2 Compound a-1 and 1-vinylimidazole are added to dry ethanol or acetonitrile solvent (as a second solvent) in a ratio of 1:6, and the internal atmosphere is replaced with nitrogen. The reaction is carried out at 60-70°C for 20-30 hours. The second solvent is removed and purified to obtain the corresponding product b-2, which is an amphiphilic imidazole sulfonate ionic liquid.

[0081] In the above synthesis route, the alcohol compound is selected from one of 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, and polyethylene glycol (molecular weight Mw = 100~1000).

[0082] Among them, the reaction at 60-70°C for 20-30h can also be the reaction at 60-65°C for 20-25h; the reaction at 65-70°C for 24-30h; the reaction at 60°C for 30h; the reaction at 70°C for 20h; the reaction at 63°C for 27h; the reaction at 68°C for 24h; the reaction at 65°C for 24h, etc., which are not specifically limited here.

[0083] In the above scheme, nitrogen can also be other protective atmospheres, such as argon and other protective gases.

[0084] The following describes the details in conjunction with specific embodiments.

[0085] Example 1 1) The synthesis route is as follows:

[0086] The specific method is as follows: Reactants 1 and 2, namely 1-n-hexanol (30 g, 0.29 mol) and methanesulfonyl chloride (33.6 g, 0.29 mmol), are added to 200 mL of dichloromethane. The reaction flask is then placed at 0°C and slowly added with potassium hydroxide powder (65.1 g, 1.16 mol). Stir for 5 hours and then quench with an aqueous solution. After three extractions with dichloromethane, the extract is washed with brine, dried over anhydrous magnesium sulfate, and the dichloromethane is rotary evaporated to obtain 37 g of hexyl methanesulfonate, with a yield of 70%.

[0087] 2) The synthesis route is as follows:

[0088] The specific method is as follows: methanesulfonic acid hexyl ester (30g, 0.12mol) is added to 100mL of dry acetonitrile, followed by reactant 3: vinyl imidazole (35g, 0.37mol). The atmosphere in the flask is replaced with nitrogen. The reaction is carried out at 65°C for 24 hours. The solution will separate into layers, indicating the reaction is progressing. After the reaction is complete, the solvent is evaporated to dryness, and the mixture is washed three times with ethyl acetate to obtain 36g of the corresponding 1-vinyl-3-n-hexyl imidazole 1-methanesulfonate (1:1 ratio), with a yield of 80%.

[0089] The nuclear magnetic resonance hydrogen spectrum (1H NMR) of the prepared product is: 1H NMR (600MHz, CDCl3) δ (ppm): 8.92 (s, 1H), 7.92 (s, 1H) , 7.75 (s, 1H), 5.45 (s, 1H), 5.2 (s, 2H), 5.01 (s, 2H), 2.84 (s, 3H), 2.01 (s, 2H), 1.29 (s, 6H), 0.88 (s, 3H).

[0090] Among them, NMR refers to nuclear magnetic resonance, and its full English name is Nuclear Magnetic Resonance.

[0091] Example 2 1) The synthesis route is as follows:

[0092] The specific method is as follows: 1-n-hexanol (30 g, 0.29 mol) and benzenesulfonyl chloride (51 g, 0.29 mmol) are added to 200 mL of dichloromethane. The reaction flask is then placed at 0°C and slowly added with potassium hydroxide powder (65.1 g, 1.16 mol). Stir for 5 hours and then quench with an aqueous solution. After three extractions with dichloromethane, the extract is washed with brine, dried over anhydrous magnesium sulfate, and the dichloromethane is rotary evaporated to yield 52 g of hexyl benzenesulfonate (73% yield).

[0093] 2) The synthesis route is as follows:

[0094] The specific method is as follows: Hexyl methanesulfonate (30 g, 0.17 mol) is added to 100 mL of dry acetonitrile, followed by vinyl imidazole (47.0 g, 0.4992 mol) to replace the atmosphere in the flask with nitrogen. The reaction is carried out at 65°C for 24 hours. The solution will separate into layers, indicating the reaction is progressing. After the reaction is complete, the solvent is evaporated to dryness, and the mixture is washed three times with ethyl acetate to obtain 44 g of the corresponding 1-vinyl-3-n-hexyl imidazole 1-phenylsulfonate (1:1 ratio), with a yield of 85%.

[0095] The nuclear magnetic resonance hydrogen spectrum (1H NMR) of the prepared product is: 1H NMR (600MHz, CDCl3) δ (ppm): 8.92 (s, 1H), 7.92 (s, 1H) , 7.80 (s, 2H), 7.75 (s, 2H), 7.68 (s, 2H), 5.45 (s, 1H), 5.2 (s, 2H), 5.01 (s, 2H), 2.84 (s, 3H), 2.01 (s, 2H), 1.29 (s, 6H), 0.88 (s, 3H).

[0096] Example 3 1) The synthesis route is as follows:

[0097] The specific method is as follows: 1-n-hexanol (30 g, 0.29 mol) and p-toluenesulfonyl chloride (55.9 g, 0.29 mmol) are added to 200 mL of dichloromethane. The reaction flask is then placed at 0°C and slowly added with potassium hydroxide powder (65.1 g, 1.16 mol). Stir for 5 hours and then quench with an aqueous solution. After three extractions with dichloromethane, the extract is washed with brine, dried over anhydrous magnesium sulfate, and the dichloromethane is rotary evaporated to yield 53.4 g of hexyl benzenesulfonate (75% yield).

[0098] 2) The synthesis route is as follows:

[0099] The specific method is as follows: methanesulfonic acid hexyl ester (30g, 0.12mol) is added to 100mL of dry acetonitrile, followed by vinyl imidazole (33.0g, 0.35mol) to replace the atmosphere in the flask with nitrogen. The reaction is carried out at 65°C for 24 hours. The solution will separate into layers, indicating the reaction is progressing. After the reaction is complete, the solvent is evaporated to dryness, and the mixture is washed three times with ethyl acetate to obtain 39g of the corresponding 1-vinyl-3-n-hexyl imidazole 4-methylbenzenesulfonate (1:1 ratio), with a yield of 75%.

[0100] The nuclear magnetic resonance hydrogen spectrum (1H NMR) of the prepared product is: 1H NMR (600MHz, CDCl3) δ (ppm): 8.92 (s, 1H), 7.92 (s, 1H) , 7.44 (s, 2H), 7.75 (s, 3H), 5.45 (s, 1H), 5.2 (s, 2H), 5.01 (s, 2H), 2.84 (s, 3H), 2.43 (s, 3H), 2.01 (s, 2H), 1.29 (s, 6H), 0.88 (s, 3H).

[0101] Example 4 1) The synthesis route is as follows:

[0102] The specific method is as follows: 1,11-undecanediol (30 g, 0.16 mol) and p-toluenesulfonyl chloride (56.3 g, 0.32 mmol) are added to 200 mL of dichloromethane. The reaction flask is then placed at 0°C and slowly added with potassium hydroxide powder (89.4 g, 1.59 mol). Stir for 5 hours before quenching with an aqueous solution. After three extractions with dichloromethane, the extract is washed with brine, dried over anhydrous magnesium sulfate, and the dichloromethane is rotary evaporated to yield 43.3 g of 11-[(dioxyphenyl-λ6-thio)oxy]undecylbenzenesulfonate (58% yield).

[0103] 2) The synthesis route is as follows:

[0104] The specific method is as follows: 11-[(dioxyphenylene-λ6-thio)oxy]undecylbenzenesulfonate (30g, 0.06mol) was added to 100mL of dry acetonitrile, followed by vinylimidazole (36.1g, 0.38mol). The atmosphere in the flask was replaced with nitrogen. The reaction was incubated at 65°C for 24 hours. The solution separated into separate layers, indicating the reaction was progressing. After the reaction was complete, the solvent was evaporated to dryness, and the mixture was washed three times with ethyl acetate to obtain 42g of the corresponding 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(1-phenylsulfonate) (1:1) in a yield of 74%.

[0105] The nuclear magnetic resonance hydrogen spectrum (1H NMR) of the prepared product is: 1H NMR (600MHz, CDCl3) δ(ppm): 8.92(s,2H), 7.92(s,1H), 7.80(s,4H), 7.75(s,4H), 7.68(s,4H), 5.45(s,2H), 5.2(s ,4H), 5.01(s,4H), 2.01~1.26(s,18H).

[0106] Example 5 1) The synthesis route is as follows:

[0107] The specific method is as follows: 1,11-undecanediol (30 g, 0.16 mol) and p-toluenesulfonyl chloride (61.0 g, 0.32 mmol) are added to 200 mL of dichloromethane. The reaction flask is then placed at 0°C and slowly added with potassium hydroxide powder (89.4 g, 1.59 mol). Stir for 5 hours before quenching with an aqueous solution. After three extractions with dichloromethane, the extracts are washed with brine, dried over anhydrous magnesium sulfate, and the dichloromethane is rotary evaporated to yield 47.1 g of 4-methylbenzenesulfonic acid 11-{[(4-methylphenyl)dioxy-λ6-thio]oxy}undecyl ester (63% yield).

[0108] 2) The synthesis route is as follows:

[0109] The specific method is as follows: 11-[(dioxyphenylene-λ6-thio)oxy]undecylbenzenesulfonate (30g, 0.06mol) was added to 100mL of dry acetonitrile, followed by the addition of vinylimidazole (32.3g, 0.34mol). The atmosphere in the flask was replaced with nitrogen. The reaction was incubated at 65°C for 24 hours. The solution separated into separate layers, indicating the reaction was progressing. After the reaction was complete, the solvent was evaporated to dryness, and the mixture was washed three times with ethyl acetate to obtain 33.6g of the corresponding 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(4-methylbenzenesulfonate) (1:1 ratio), with a yield of 70%.

[0110] The nuclear magnetic resonance hydrogen spectrum (1H NMR) of the prepared product is: 1H NMR (600MHz, CDCl3) δ(ppm): 8.92(s,2H), 7.92(s,2H), 7.75(s,6H), 7.44(s,4H), 5.45(s,2H), 5.2(s,4H), 5.01(s,4H), 2.43(s ,6H), 2.01~1.26(s,18H).

[0111] Example 6 1) The synthesis route is as follows:

[0112] The specific method is as follows: Polyethylene glycol (Mn = 400, 30 g, 0.07 mol) and p-toluenesulfonyl chloride (28.6 g, 0.15 mmol) are added to 200 mL of dichloromethane. The reaction flask is then placed at 0°C. Potassium hydroxide powder (42.1 g, 0.75 mol) is slowly added, stirred for 5 hours, and then quenched with an aqueous solution. After three extractions with dichloromethane, the extract is washed with brine, dried over anhydrous magnesium sulfate, and the dichloromethane is rotary evaporated to obtain 27.7 g of bis(p-toluenesulfonic acid) polyethylene glycol ester, with a yield of 52%.

[0113] 2) The synthesis route is as follows:

[0114] The specific method is as follows: 11-[(dioxyphenylene-λ6-thio)oxy]undecylbenzenesulfonate (30 g, 0.04 mol) was added to 100 mL of dry acetonitrile, followed by vinylimidazole (23.8 g, 0.25 mol). The atmosphere in the flask was replaced with nitrogen. The reaction was incubated at 65°C for 24 hours. The solution separated into separate layers, indicating the reaction was progressing. After the reaction was complete, the solvent was evaporated to dryness, and the mixture was washed three times with ethyl acetate to obtain 39.6 g of the corresponding 3-vinyl-1-({26-[(3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxahexacosa-1-yl}oxy)imidazole bis(4-methylbenzenesulfonate) (1:1 ratio), with a yield of 69%.

[0115] Example 7 1) The synthesis route is as follows:

[0116] The specific method is as follows: polyethylene glycol (Mn = 400, 30 g, 0.07 mol) and p-toluenesulfonyl chloride (26.5 g, 0.15 mmol) are added to 200 mL of dichloromethane. The reaction flask is then placed at 0°C and slowly added with potassium hydroxide powder (42.1 g, 0.75 mol). Stir for 5 hours and then quench with an aqueous solution. After three extractions with dichloromethane, the extract is washed with brine, dried over anhydrous magnesium sulfate, and the dichloromethane is rotary evaporated to obtain 25.7 g of polyethylene glycol bis(benzenesulfonate) in a 50% yield.

[0117] 2) The synthesis route is as follows:

[0118] The specific method is as follows: 11-[(dioxyphenylene-λ6-thio)oxy]undecylbenzenesulfonate (30 g, 0.04 mol) is added to 100 mL of dry acetonitrile, followed by the addition of vinylimidazole (24.8 g, 0.25 mol). The atmosphere in the flask is replaced with nitrogen. The reaction is carried out at 65°C for 24 hours. The solution undergoes stratification, indicating that the reaction is progressing. After the reaction is complete, the solvent is evaporated to dryness, and the mixture is washed three times with ethyl acetate to obtain 39.0 g of the corresponding 3-vinyl-1-({26-[(3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxahexacosamidazole-1-yl}oxy)imidazole bis(1-phenylsulfonate) (1:1) in a yield of 67%.

[0119] Example 8 According to the synthesis method of Examples 1-7, the synthesis conditions and products of similar reactants are shown in Table 3: Table 3

[0120] (Continued Table 3)

[0121] (Continued Table 3)

[0122] In the above examples, amphiphilic imidazole sulfonate ionic liquids were used for ion conduction, including the following experiments: (1) Electrochemical window detection: a certain amount of amphiphilic imidazole sulfonate ionic liquid is used as electrolyte, glassy carbon / platinum / gold electrode is used as working electrode, Ag / Ag is used as + Or use a non-aqueous reference electrode and a platinum wire as the auxiliary electrode. After pretreating the electrodes, build a three-electrode system. Perform cyclic voltammetry scanning at an appropriate scan rate (such as 50 mV / s) on the electrochemical workstation, and gradually scan from low potential to high potential until a clear redox peak appears. The potential range corresponding to the initial peak is its electrochemical window.

[0123] (2) Ion conduction test: A two-electrode or four-electrode system is used, with platinum or stainless steel sheets as electrodes. The electrodes are fixed in a conductivity cell with a constant temperature bath, the temperature is controlled (e.g. 25°C) and kept stable, and an AC voltage (usually 10 -2 ~10 6 Hz), impedance data at different frequencies were collected and fitted to obtain the solution resistance. Then, based on the cell constant, the ionic conductivity was calculated using the formula σ = L / (R • A), where σ is the conductivity, L is the electrode distance, R is the resistance, and A is the electrode area.

[0124] After testing Figures 1 to 4The test results are analyzed as follows: See also Figure 1 , wherein 1A, 1B, and 1C are state diagrams of the product of Example 1 under a microscope, a crossed polarizing microscope, and a state at room temperature, respectively; 2A, 2B, and 2C are state diagrams of the product of Example 5 under a microscope, a crossed polarizing microscope, and a state at room temperature, respectively; 3A, 3B, and 3C are state diagrams of the product of Example 6 under a microscope, a crossed polarizing microscope, and a state at room temperature, respectively; Figure 1 It can be concluded that amphiphilic imidazole sulfonate ionic liquids have three states at room temperature: solid, gel, and liquid. Under an orthogonal polarizing microscope, the amphiphilic imidazole sulfonate ionic liquid can have crystalline, semi-crystalline, and non-crystalline properties. In different physical states, the amphiphilic imidazole sulfonate ionic liquid can be used as an ionic liquid for ion transport.

[0125] Therefore, the amphiphilic imidazole sulfonate ionic liquid provided in the present application is used to prepare electrolytes in electronic products; the electronic products include batteries, sensors or supercapacitors.

[0126] like Figure 2 As shown, when the amphiphilic imidazole sulfonate ionic liquid works as an ionic liquid battery, it realizes energy conversion and storage by ion transfer between the positive and negative electrodes. When charging, current is input from an external power source, the positive electrode material is oxidized, the negative electrode material is reduced, and ions are transferred in the electrolyte to store electrical energy. When discharging, current is output from the battery, the positive electrode material is reduced, the negative electrode material is oxidized, and ions are transferred in the electrolyte again to release the stored electrical energy. Ionic liquid batteries can use different positive and negative electrode materials and ionic liquids to meet different application requirements. Figure 2 It can be concluded that amphiphilic imidazole sulfonate ionic liquids are capable of normal charging and discharging, and are suitable as ion transport media between the positive and negative electrodes of a battery. They can efficiently transport anions and cations, providing power supply for electrical equipment (such as automobiles), and can specifically be used as solid-state batteries for automobiles.

[0127] Therefore, the present application also provides a solid-state battery, comprising an electrolyte; the electrolyte adopts the amphiphilic imidazole sulfonate ionic liquid.

[0128] Figure 3 The AC impedance test curves of the amphiphilic imidazole sulfonate ionic liquids prepared in Examples 1 to 7 of the present application are as follows; Figure 3It can be concluded that the ionic conductivity of amphiphilic imidazole sulfonate ionic liquids was tested by AC impedance spectroscopy. The figure shows the AC impedance spectra of different amphiphilic imidazole sulfonate ionic liquids. According to the spectra and the ionic conductivity calculation formula, all amphiphilic imidazole sulfonate ionic liquids have high ionic conductivity and are capable of being used in solid-state batteries. Where Z' is the real part of the impedance, in ohms; -Z is the negative value of the imaginary part, in ohms.

[0129] Figure 4 The LSV test curves of the amphiphilic imidazole sulfonate ionic liquids prepared in Examples 1 to 7 of the present application are shown in FIG. Figure 4 It can be concluded that the electrochemical window of amphiphilic imidazole sulfonate ionic liquids was tested by linear sweep voltammetry. Figure 4 The figure shows linear sweep voltammograms of different amphiphilic imidazole sulfonate ionic liquids. The initial redox potentials calculated from these plots indicate that all amphiphilic imidazole sulfonate ionic liquids have good initial redox potentials, suggesting potential for application in solid-state batteries. "Potential" is the potential in V. "Current" is the current in A.

[0130] Table 4

[0131] Table 4 shows the ionic conductivity and electrochemical window of amphiphilic imidazole sulfonate ionic liquids. As can be seen from Table 4, the products prepared in the examples of this application, according to the ionic conductivity and electrochemical window test values ​​of azole sulfonate derivatives, have an initial redox potential of more than 3 V as electrolytes, and an ionic conductivity of 10 -3 ~10 -4 S / cm, which can be used to prepare electrolytes for solid-state batteries.

[0132] Combining the synthetic characteristics and structural design of the amphiphilic imidazole sulfonate ionic liquids described in this application, their application advantages in the preparation of electrolytes for electronic products such as batteries, sensors, and supercapacitors can be more accurately analyzed. This type of ionic liquid can be prepared through simple synthesis processes (such as neutralization reaction and quaternization reaction). The 1-vinylimidazole cation serves as the core positively charged group, which not only provides a polymerizable ion transport site, but also contains vinyl unsaturated double bonds that reserve reaction sites for functional modification of the electrolyte. Ionic liquid polymers can be formed through reactions such as free radical polymerization, which can maintain high ionic conductivity while improving the mechanical strength of the electrolyte, adapting to the morphological requirements of different electronic products.

[0133] The controllable molecular size and easily removable coordination properties of sulfonic acid anions are key to optimizing electrolyte performance. On the one hand, by adjusting the molecular structure of sulfonic acid anions (such as carbon chain length and substituent type), the viscosity and ion mobility of the ionic liquid can be precisely controlled. For example, smaller sulfonic acid anions can reduce ion transport resistance, further improving conductivity. On the other hand, their easily removable coordination properties can reduce strong adsorption of electrode active materials and minimize interfacial side reactions. This is particularly important for sensors, as it can avoid distortion of detection signals due to strong ion coordination and improve response accuracy.

[0134] The excellent ion-conducting properties of this ionic liquid, whether in solution or solid state, stem from the synergistic effects of its molecular structure: the conjugated structure of the imidazole ring enhances charge delocalization, the strong polarity of the sulfonic acid group promotes ion dissociation, and the amphiphilic structure ensures the continuity of the ion transport channel in different states. In the solution state, ions can diffuse freely due to molecular thermal motion and concentration gradients. In the solid state (such as after polymerization), the network skeleton formed by vinyl polymerization provides "rigid support" for ion migration, while the flexible movement of the sulfonic acid anions can still maintain the ion conduction path. This makes it suitable for use as a liquid electrolyte in traditional batteries and as a solid electrolyte precursor in flexible electronic devices. The simplicity of industrial production significantly reduces its application cost.

[0135] The unique synthetic background and structural design of the amphiphilic imidazole sulfonate ionic liquids described in this application further enhance their performance advantages when used as solid-state battery electrolytes. The simplicity of the synthesis method means that the electrolytes can be easily scaled up for production, lowering the raw material cost threshold for the industrialization of solid-state batteries. Furthermore, the structural characteristics of 1-vinylimidazole and sulfonic acid derivatives fundamentally address the core pain points of traditional solid-state electrolytes.

[0136] In terms of ion conduction, in addition to the inherent dynamic network structure, the polymerizability of the 1-vinylimidazolium cation imparts dynamically tunable conductivity to the electrolyte. By controlling the degree of polymerization, a balance can be achieved between backbone rigidity and ion mobility. Moderate polymerization forms a cross-linked network that inhibits excessive flow of the ionic liquid, preventing the risk of liquid leakage. Meanwhile, incompletely polymerized vinyl sites maintain a certain degree of molecular flexibility, which, combined with the volume controllability of the sulfonic acid anion, stabilizes ionic conductivity at low temperatures. Furthermore, the strong electronegativity of the imidazole ring nitrogen atom and the proton transfer properties of the sulfonic acid group combine to create an efficient proton / ion conduction pathway, making it particularly suitable for systems requiring rapid ion transport, such as lithium metal batteries.

[0137] Its excellent thermal and chemical stability stems from the inherent design of its molecular structure: the strong chemical bond between the imidazole ring and the sulfonic acid group significantly increases the decomposition temperature (above 200°C), while its non-volatility and non-flammability eliminate safety hazards at the source. More importantly, the easily removable coordination of the sulfonic acid anion reduces corrosion and dendrite induction on lithium metal. While the strong coordination between anions and lithium in traditional electrolytes can easily lead to interfacial instability, the weak coordination properties of this ionic liquid form a more stable solid electrolyte interface, significantly extending the battery cycle life.

[0138] Furthermore, the ionic liquid's adaptability to high-voltage cathode materials is directly related to the oxidation resistance of the sulfonic acid anion. Its wide liquidus temperature range (due to moderate interionic forces that hinder crystallization) ensures stable operation of solid-state batteries in extreme temperature environments. Combined with its polymerizable morphological plasticity, it can be tightly combined with electrodes of varying structures (such as laminated and flexible electrodes), providing a practical material foundation for achieving energy densities exceeding 500Wh / kg for solid-state batteries.

[0139] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. An amphiphilic imidazole sulfonate ionic liquid, characterized in that The amphiphilic imidazole sulfonate ionic liquid comprises: a pharmaceutically acceptable combined salt formed by an imidazole cation and a sulfonic acid anion, and has ion-conducting properties in a solution or solid state; The imidazolium cation is selected from 1-vinylimidazolium cation derivatives, and the general structural formula of the 1-vinylimidazolium cation is (I) or (II); the sulfonic acid anion is selected from sulfonic acid anion derivatives, and the general structural formula of the sulfonic acid anion is (III); Wherein, A is a C1~C16 alkyl group; B is a C1-C5 alkyl group, a vinyl group, a C3-C6 cycloalkyl group, an aryl group, an alkylaryl group, a halogenated aryl group, a halogenated methyl group, a benzyl group or a halogenated benzyl group; C represents a C1~C16 alkyl group or a polyethylene glycol segment; The cycloalkyl group contains 3 to 6 C atoms; the alkylaryl group is an ortho-para methyl substituted aryl group or a meta-para methyl substituted aryl group; the halogenated aryl group is an ortho-, meta-, or para-halogenated aryl group; the halogenated phenylmethyl group is an ortho-, meta-, or para-halogenated phenylmethyl group.

2. An amphiphilic imidazole sulfonate ionic liquid according to claim 1, characterized in that The imidazolium cation is selected from any one of the following: The sulfonic acid anion is selected from any one of the following: in, a is 1 to 15, b is 1 to 23, c is 1 to 16, d is 0 to 4, X is a carbon element or a halogen; and Y is a halogen, an aryl group, or a halogenated aryl group.

3. An amphiphilic imidazole sulfonate ionic liquid according to claim 1, characterized in that The amphiphilic imidazole sulfonate ionic liquid specifically selects the following compounds: Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Compound 6 Compound 7 Compound 8 Compound 9 Compound 10 Compound 11 Compound 12 Compound 13 Compound 14 Compound 15 Compound 16 Compound 17 Compound 18 Compound 19 Compound 20 Compound 21 Compound 22 .

4. A method for synthesizing the amphiphilic imidazole sulfonate ionic liquid according to any one of claims 1 to 3, characterized in that: include: According to the structural formula of the sulfonic acid anion, the corresponding sulfonyl chloride compound and alcohol compound are dissolved in a first solvent, the reaction is placed at 0 degrees Celsius, an equivalent amount of base required for the reaction is added, and stirred until the reaction is complete, and then quenched and purified with an aqueous solution to obtain an intermediate product; The intermediate product and 1-vinylimidazole are added to a second solvent, fully reacted in a protective atmosphere, and the second solvent is removed and purified to obtain an amphiphilic imidazole sulfonate ionic liquid.

5. The method for synthesizing the amphiphilic imidazole sulfonate ionic liquid according to claim 4, wherein: The alcohol compound is selected from one of methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, and 1-hexadecanol.

6. The method for synthesizing the amphiphilic imidazole sulfonate ionic liquid according to claim 4, wherein: The alcohol compound is selected from one of 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol and polyethylene glycol.

7. The method for synthesizing the amphiphilic imidazole sulfonate ionic liquid according to claim 4, wherein: The conditions for sufficient reaction in a protective atmosphere are: reaction at 60-70°C for 20-30h; The first solvent is dichloromethane or chloroform; The second solvent is ethanol or acetonitrile.

8. The method for synthesizing the amphiphilic imidazole sulfonate ionic liquid according to claim 4, wherein: The base required for the reaction is added and stirred until the reaction is complete; Add 4 to 5 equivalents of base to the reaction, and the final amphiphilic imidazole sulfonate ionic liquid structure is as follows: Add 10-11 equivalents of base to the reaction, and the final amphiphilic imidazole sulfonate ionic liquid structure is as follows: 。 9. Use of the amphiphilic imidazole sulfonate ionic liquid according to any one of claims 1 to 3, characterized in that: The amphiphilic imidazole sulfonate ionic liquid is used to prepare electrolytes in electronic products; the electronic products include batteries, sensors or supercapacitors.

10. A solid-state battery, characterized in that: including electrolytes; The electrolyte adopts the amphiphilic imidazole sulfonate ionic liquid according to any one of claims 1 to 3.

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