阅读说明：本技术 一种1,3,2,4-二氧杂噻唑-2,2-二氧化物类化合物的合成方法 (Synthesis method of 1,3,2, 4-dioxathiazole-2, 2-dioxide compound ) 是由 张茜 闫朋飞 杨世雄 张民 闫彩桥 于 2020-06-02 设计创作，主要内容包括：本发明属于电池电解液添加剂技术领域,提出了一种1,3,2,4-二氧杂噻唑-2,2-二氧化物类化合物的合成方法,以脂肪酸酯或芳香酸酯为原料,与盐酸羟胺反应生成羟肟酸,羟肟酸与氯化亚砜反应生成1,3,2,4-二氧杂噻唑-2-氧化物类化合物,再以1,3,2,4-二氧杂噻唑-2-氧化物类化合物为原料,以三氯化钌和次氯酸钠为催化剂,经氧化反应得到1,3,2,4-二氧杂噻唑-2,2-二氧化物类化合物。通过上述技术方案,解决了现有技术中锂离子电池在高温下的可重复充电次数及循环性能不好的问题。(The invention belongs to the technical field of battery electrolyte additives, and provides a synthesis method of a 1,3,2, 4-dioxathiazole-2, 2-dioxide compound, which comprises the steps of taking fatty acid ester or aromatic acid ester as a raw material, reacting with hydroxylamine hydrochloride to generate hydroximic acid, reacting the hydroximic acid with thionyl chloride to generate the 1,3,2, 4-dioxathiazole-2-oxide compound, taking the 1,3,2, 4-dioxathiazole-2-oxide compound as a raw material, taking ruthenium trichloride and sodium hypochlorite as catalysts, and carrying out oxidation reaction to obtain the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound. Through the technical scheme, the problems that the lithium ion battery in the prior art is poor in repeated charging times and cycle performance at high temperature are solved.)

1. A synthesis method of 1,3,2, 4-dioxathiazole-2, 2-dioxide compounds is characterized in that fatty acid esters or aromatic acid esters are used as raw materials to react with hydroxylamine hydrochloride to generate hydroximic acid, the hydroximic acid reacts with thionyl chloride to generate 1,3,2, 4-dioxathiazole-2-oxide compounds, then the 1,3,2, 4-dioxathiazole-2-oxide compounds are used as raw materials, ruthenium trichloride and sodium hypochlorite are used as catalysts, and the 1,3,2, 4-dioxathiazole-2, 2-dioxide compounds are obtained through oxidation reaction,

the synthetic route is as follows:

wherein R is a C1-C6 linear alkyl group or a phenyl group.

2. The method for synthesizing the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound according to claim 1, which comprises the following steps:

A. dissolving hydroxylamine hydrochloride in methanol, adding a potassium hydroxide solution, adding a fatty acid ester or an aromatic acid ester, heating to 50-60 ℃, and reacting for 2-3 hours to obtain hydroximic acid;

B. dissolving the hydroximic acid obtained in the step A in dichloromethane, adding thionyl chloride, and reacting for 2-3 hours to obtain a 1,3,2, 4-dioxathiazole-2-oxide compound;

C. and D, dissolving the 1,3,2, 4-dioxathiazole-2-oxide compound obtained in the step B in acetonitrile, adding ruthenium trichloride and sodium hypochlorite at the temperature of 0-5 ℃, and reacting for 15-30 min to obtain the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound.

3. The method for synthesizing the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound according to claim 2, wherein the molar ratio of hydroxylamine hydrochloride to potassium hydroxide in the step A is 1: (1.1-1.3), the mass volume ratio of the hydroxylamine hydrochloride to the methanol is 1 g: 6mL, wherein the mass ratio of the hydroxylamine hydrochloride to the fatty acid ester or the aromatic acid ester is 10: 9.

4. the method for synthesizing the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound according to claim 2, wherein the molar volume ratio of the potassium hydroxide in the potassium hydroxide solution to the distilled water in the step A is 1 mol: 250 mL.

5. The method for synthesizing the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound according to claim 2, wherein the molar ratio of the hydroximic acid to the thionyl chloride in the step B is 1: (1.2-1.5), the mass-to-volume ratio of the hydroximic acid to the dichloromethane is 1 g: (6-8 mL).

6. The method for synthesizing the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound according to claim 2, wherein the molar ratio of the 1,3,2, 4-dioxathiazole-2-oxide compound to the sodium hypochlorite in the step C is 1: (1.1-1.4), the mass ratio of the 1,3,2, 4-dioxathiazole-2-oxide compound to the ruthenium trichloride is 1: (0.001-0.005), the mass-to-volume ratio of the 1,3,2, 4-dioxathiazole-2-oxide compound to the acetonitrile is 1 g: (2.5-4) mL.

7. The method for synthesizing the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound according to claim 2, wherein the potassium hydroxide solution is added dropwise in the step A, and the addition is completed within 0.5-1 hour.

8. The method for synthesizing the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound according to claim 2, wherein sodium bicarbonate is added to adjust the pH value to 6.5-7.5 before the ruthenium trichloride and the sodium hypochlorite are added in the step C.

9. The method for synthesizing the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound according to claim 2, wherein the ruthenium trichloride and the sodium hypochlorite are mixed before the ruthenium trichloride and the sodium hypochlorite are added in the step C to obtain a mixed solution, and then the mixed solution is added dropwise in a manner of finishing the dropwise addition within 2-2.5 hours.

Technical Field

The invention belongs to the technical field of battery electrolyte additives, and relates to a synthesis method of a 1,3,2, 4-dioxathiazole-2, 2-dioxide compound.

Background

A lithium ion battery is a secondary battery (rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. During charging and discharging, Li + is inserted and extracted back and forth between two electrodes: during charging, Li + is extracted from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge. The lithium ion battery has the advantages of high energy density, high output power, long cycle life, small environmental pollution and the like, and is widely applied to electric automobiles and consumer electronic products.

When the existing lithium battery is applied, the charging and discharging are required to be carried out at the high temperature of more than 50 ℃, so that the performance of the battery is reduced, and the rechargeable frequency and the cycle characteristic are not good, therefore, it is necessary to develop a lithium battery electrolyte additive which is applied to the battery electrolyte to improve the battery performance of the lithium battery and increase the rechargeable frequency and the cycle characteristic of the lithium battery at the high temperature.

Disclosure of Invention

The invention provides a synthesis method of a 1,3,2, 4-dioxathiazole-2, 2-dioxide compound, which solves the problems of poor rechargeable frequency and poor cycle performance of a lithium ion battery at high temperature in the prior art.

The technical scheme of the invention is realized as follows:

a synthetic method of 1,3,2, 4-dioxathiazole-2, 2-dioxide compounds uses fatty acid ester or aromatic acid ester as raw materials, reacts with hydroxylamine hydrochloride to generate hydroximic acid, the hydroximic acid reacts with thionyl chloride to generate 1,3,2, 4-dioxathiazole-2-oxide compounds, then uses 1,3,2, 4-dioxathiazole-2-oxide compounds as raw materials, uses ruthenium trichloride and sodium hypochlorite as catalysts, and obtains the 1,3,2, 4-dioxathiazole-2, 2-dioxide compounds through oxidation reaction,

the synthetic route is as follows:

wherein R is a C1-C6 linear alkyl group or a phenyl group.

As a further technical scheme, the method comprises the following steps:

A. dissolving hydroxylamine hydrochloride in methanol, adding a potassium hydroxide solution, adding a fatty acid ester or an aromatic acid ester, heating to 50-60 ℃, and reacting for 2-3 hours to obtain hydroximic acid;

B. dissolving the hydroximic acid obtained in the step A in dichloromethane, adding thionyl chloride, and reacting for 2-3 hours to obtain a 1,3,2, 4-dioxathiazole-2-oxide compound;

C. and D, dissolving the 1,3,2, 4-dioxathiazole-2-oxide compound obtained in the step B in acetonitrile, adding ruthenium trichloride and sodium hypochlorite at the temperature of 0-5 ℃, and reacting for 15-30 min to obtain the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound.

As a further technical scheme, the molar ratio of the hydroxylamine hydrochloride to the potassium hydroxide in the step A is 1: (1.1-1.3), the mass volume ratio of the hydroxylamine hydrochloride to the methanol is 1 g: 6mL, wherein the mass ratio of the hydroxylamine hydrochloride to the fatty acid ester or the aromatic acid ester is 10: 9.

as a further technical scheme, the molar volume ratio of the potassium hydroxide in the potassium hydroxide solution in the step A to the distilled water is 1 mol: 250 mL.

As a further technical scheme, the molar ratio of the hydroximic acid to the thionyl chloride in the step B is 1: (1.2-1.5), the mass-to-volume ratio of the hydroximic acid to the dichloromethane is 1 g: (6-8 mL).

As a further technical scheme, the mol ratio of the 1,3,2, 4-dioxathiazole-2-oxide compound to the sodium hypochlorite in the step C is 1: (1.1-1.4), the mass ratio of the 1,3,2, 4-dioxathiazole-2-oxide compound to the ruthenium trichloride is 1: (0.001-0.005), the mass-to-volume ratio of the 1,3,2, 4-dioxathiazole-2-oxide compound to the acetonitrile is 1 g: (2.5-4) mL.

As a further technical scheme, the potassium hydroxide solution is added dropwise in the step A, and the addition is completed within 0.5-1 hour.

And as a further technical scheme, before adding the ruthenium trichloride and the sodium hypochlorite in the step C, adding sodium bicarbonate to adjust the pH value to 6.5-7.5.

And C, mixing ruthenium trichloride and sodium hypochlorite before adding ruthenium trichloride and sodium hypochlorite in the step C to obtain a mixed solution, and then adding the mixed solution dropwise in a manner of finishing dripping for 2-2.5 hours.

The working principle and the beneficial effects of the invention are as follows:

1. in the invention, the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound is prepared by taking fatty acid ester or aromatic acid ester as a starting material through three steps of reactions, the source of the raw material is wide, the reaction condition is mild, the product yield is high, and the method is suitable for popularization and use.

2. In the invention, the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound obtained by the invention is added into the battery electrolyte, so that the performance of the lithium battery at high temperature is obviously improved, the rechargeable frequency and the cycle performance of the lithium battery at high temperature are improved, and the practicability is high.

Drawings

The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

FIG. 1 shows the preparation of 1,3,2, 4-dioxathiazole-2, 2-dioxides of the invention having the formula I¹H NMR spectrum;

FIG. 2 shows the preparation of 1,3,2, 4-dioxathiazole-2, 2-dioxides of the invention having the formula I¹³A C NMR spectrum;

FIG. 3 shows the preparation of 1,3,2, 4-dioxathiazole-2, 2-dioxides of the invention having the formula II¹H NMR spectrum;

FIG. 4 shows the preparation of 1,3,2, 4-dioxathiazole-2, 2-dioxides of the invention having the formula II¹³A C NMR spectrum;

FIG. 5 shows the preparation of 1,3,2, 4-dioxathiazole-2, 2-dioxides of the invention having the formula III¹H NMR spectrum;

FIG. 6 shows 1,3,2, 4-dioxathiazole-2, 2-dioxide of the formula III according to the inventionOf the class of compounds¹³C NMR spectrum.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A method for synthesizing 1,3,2, 4-dioxathiazole-2, 2-dioxide compounds comprises the following steps:

A. adding 69.5g of hydroxylamine hydrochloride and 417mL of methanol into a reaction container, stirring until the hydroxylamine hydrochloride is completely dissolved, dripping potassium hydroxide solution at room temperature, dripping for 0.7 hour, adding 66.6g of methyl acetate at room temperature, heating to 60 ℃, reacting for 2 hours, performing suction filtration and concentration to obtain a crude product, adding the crude product into the hydrochloric acid solution, acidifying to a pH value of 4, performing suction filtration, recrystallization and drying to obtain 62.64g of hydroxamic acid, wherein the yield of the hydroxamic acid is 92.8%; wherein the potassium hydroxide solution is obtained by dissolving 61.6g of potassium hydroxide in 275mL of distilled water,

B. weighing 37.5g of the hydroxamic acid obtained in the step A and 260mL of dichloromethane, adding the mixture into a reaction container, stirring until the hydroxamic acid is completely dissolved, adding 71.4g of thionyl chloride at room temperature, reacting for 2 hours, separating liquid, concentrating an organic layer at 60 ℃ under-0.09 MPa, performing suction filtration and drying to obtain 50.76g of 1,3,2, 4-dioxathiazole-2-oxide compounds, wherein the yield of the 1,3,2, 4-dioxathiazole-2-oxide compounds is 83.9%;

C. weighing 36.3g of the 1,3,2, 4-dioxathiazole-2-oxide compound obtained in the step B, dissolving in 100mL of acetonitrile, adding 50mg of ruthenium trichloride and 30g of sodium hypochlorite at 0-5 ℃, and reacting for 20min to obtain 37.44g of the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound with the structural formula I, wherein the yield is 91.1%, and the structural formula I is as follows:

example 2

A method for synthesizing 1,3,2, 4-dioxathiazole-2, 2-dioxide compounds comprises the following steps:

A. adding 69.5g of hydroxylamine hydrochloride and 417mL of methanol into a reaction container, stirring until the hydroxylamine hydrochloride is completely dissolved, dripping potassium hydroxide solution at room temperature, dripping for 0.7 hour, adding 66.6g of methyl acetate at room temperature, heating to 60 ℃, reacting for 2 hours, performing suction filtration and concentration to obtain a crude product, adding the crude product into the hydrochloric acid solution, acidifying to a pH value of 4, performing suction filtration, recrystallization and drying to obtain 62.64g of hydroxamic acid, wherein the yield of the hydroxamic acid is 92.8%; wherein the potassium hydroxide solution is obtained by dissolving 61.6g of potassium hydroxide in 275mL of distilled water,

B. weighing 37.5g of the hydroxamic acid obtained in the step A and 280mL of dichloromethane, adding the mixture into a reaction container, stirring until the hydroxamic acid is completely dissolved, adding 83.3g of thionyl chloride at room temperature, reacting for 2.5 hours, separating liquid, concentrating an organic layer at-0.09 MPa and 60 ℃, performing suction filtration and drying to obtain 51.12g of 1,3,2, 4-dioxathiazole-2-oxide compounds, wherein the yield of the 1,3,2, 4-dioxathiazole-2-oxide compounds is 84.5%;

C. weighing 36.3g of the 1,3,2, 4-dioxathiazole-2-oxide compound obtained in the step B, dissolving in 110mL of acetonitrile, adding 40mg of ruthenium trichloride and 28g of sodium hypochlorite at 0-5 ℃, and reacting for 15min to obtain 37.24g of the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound with the structural formula I, wherein the yield is 90.6%, and the structural formula I is as follows:

example 3

A method for synthesizing 1,3,2, 4-dioxathiazole-2, 2-dioxide compounds comprises the following steps:

A. adding 69.5g of hydroxylamine hydrochloride and 417mL of methanol into a reaction container, stirring until the hydroxylamine hydrochloride is completely dissolved, dripping potassium hydroxide solution at room temperature, dripping for 0.7 hour, adding 66.6g of methyl acetate at room temperature, heating to 60 ℃, reacting for 2 hours, performing suction filtration and concentration to obtain a crude product, adding the crude product into the hydrochloric acid solution, acidifying to a pH value of 4, performing suction filtration, recrystallization and drying to obtain 62.64g of hydroxamic acid, wherein the yield of the hydroxamic acid is 92.8%; wherein the potassium hydroxide solution is obtained by dissolving 61.6g of potassium hydroxide in 275mL of distilled water,

B. weighing 37.5g of the hydroxamic acid obtained in the step A and 300mL of dichloromethane, adding the mixture into a reaction container, stirring until the hydroxamic acid is completely dissolved, adding 89.25g of thionyl chloride at room temperature, reacting for 3 hours, separating liquid, concentrating an organic layer at-0.09 MPa and 60 ℃, performing suction filtration and drying to obtain 51.55g of 1,3,2, 4-dioxathiazole-2-oxide compounds, wherein the yield of the 1,3,2, 4-dioxathiazole-2-oxide compounds is 85.2%;

C. weighing 36.3g of the 1,3,2, 4-dioxathiazole-2-oxide compound obtained in the step B, dissolving in 120mL of acetonitrile, adding 50mg of ruthenium trichloride and 25g of sodium hypochlorite at 0-5 ℃, and reacting for 30min to obtain 37.77g of the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound with the structural formula I, wherein the yield is 91.9%, and the structural formula I is as follows:

example 4

A method for synthesizing 1,3,2, 4-dioxathiazole-2, 2-dioxide compounds comprises the following steps:

A. adding 69.5g of hydroxylamine hydrochloride and 417mL of methanol into a reaction container, stirring until the hydroxylamine hydrochloride is completely dissolved, dripping potassium hydroxide solution at room temperature, dripping for 0.6 hour, adding 66.6g of methyl acetate at room temperature, heating to 55 ℃, reacting for 2.5 hours, carrying out suction filtration and concentration to obtain a crude product, adding the crude product into the hydrochloric acid solution, acidifying to a pH value of 4, carrying out suction filtration, recrystallization and drying to obtain 63.18g of hydroxamic acid, wherein the yield of the hydroxamic acid is 93.6%; wherein the potassium hydroxide solution is obtained by dissolving 67.2g of potassium hydroxide in 300mL of distilled water,

B. weighing 37.5g of the hydroxamic acid obtained in the step A and 225mL of dichloromethane, adding the mixture into a reaction container, stirring until the hydroxamic acid is completely dissolved, adding 71.4g of thionyl chloride at room temperature, reacting for 2 hours, separating liquid, concentrating an organic layer at 60 ℃ under-0.09 MPa, performing suction filtration and drying to obtain 50.64g of 1,3,2, 4-dioxathiazole-2-oxide compounds, wherein the yield of the 1,3,2, 4-dioxathiazole-2-oxide compounds is 83.7%;

C. weighing 36.3g of the 1,3,2, 4-dioxathiazole-2-oxide compound obtained in the step B, dissolving in 130mL of acetonitrile, adding 150mg of ruthenium trichloride and 26g of sodium hypochlorite at 0-5 ℃, and reacting for 25min to obtain 37.03g of the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound with the structural formula I, wherein the yield is 90.1%, and the structural formula I is as follows:

example 5

A method for synthesizing 1,3,2, 4-dioxathiazole-2, 2-dioxide compounds comprises the following steps:

A. adding 69.5g of hydroxylamine hydrochloride and 417mL of methanol into a reaction container, stirring until the hydroxylamine hydrochloride is completely dissolved, dripping potassium hydroxide solution at room temperature, dripping for 0.5 hour, adding 66.6g of methyl acetate at room temperature, heating to 50 ℃, reacting for 3 hours, performing suction filtration and concentration to obtain a crude product, adding the crude product into the hydrochloric acid solution, acidifying to a pH value of 4, performing suction filtration, recrystallization and drying to obtain 62.37g of hydroxamic acid, wherein the yield of the hydroxamic acid is 92.4%; wherein, the potassium hydroxide solution is obtained by dissolving 72.8g of potassium hydroxide in 325mL of distilled water,

B. weighing 37.5g of the hydroxamic acid obtained in the step A and 250mL of dichloromethane, adding the mixture into a reaction container, stirring until the hydroxamic acid is completely dissolved, adding 71.4g of thionyl chloride at room temperature, reacting for 3 hours, separating liquid, concentrating an organic layer at-0.09 MPa and 60 ℃, performing suction filtration and drying to obtain 51.18g of 1,3,2, 4-dioxathiazole-2-oxide compounds, wherein the yield of the 1,3,2, 4-dioxathiazole-2-oxide compounds is 84.6%;

C. weighing 36.3g of the 1,3,2, 4-dioxathiazole-2-oxide compound obtained in the step B, dissolving in 140mL of acetonitrile, adding 180mg of ruthenium trichloride and 25g of sodium hypochlorite at 0-5 ℃, and reacting for 20min to obtain 37.07g of the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound with the structural formula I, wherein the yield is 90.2%, and the structural formula I is as follows:

example 6

A method for synthesizing 1,3,2, 4-dioxathiazole-2, 2-dioxide compounds comprises the following steps:

A. adding 69.5g of hydroxylamine hydrochloride and 417mL of methanol into a reaction container, stirring until the hydroxylamine hydrochloride is completely dissolved, dripping potassium hydroxide solution at room temperature, dripping for 1 hour, adding 79.2g of methyl propionate at room temperature, heating to 55 ℃, reacting for 2.5 hours, performing suction filtration and concentration to obtain a crude product, adding the crude product into the hydrochloric acid solution, acidifying to a pH value of 4, performing suction filtration, recrystallization and drying to obtain 73.29g of propylhydroxamic acid, wherein the yield of the propylhydroxamic acid is 91.5%; wherein the potassium hydroxide solution is obtained by dissolving 61.6g of potassium hydroxide in 275mL of distilled water,

B. weighing 44.5g of the propylhydroxamic acid obtained in the step A and 350mL of dichloromethane, adding the mixture into a reaction container, stirring the mixture until the propylhydroxamic acid is completely dissolved, adding 71.4g of thionyl chloride at room temperature, reacting for 2.5 hours, separating liquid, concentrating an organic layer at 60 ℃ under-0.09 MPa, performing suction filtration and drying to obtain 56.36g of 1,3,2, 4-dioxathiazole-2-oxide compounds, wherein the yield of the 1,3,2, 4-dioxathiazole-2-oxide compounds is 83.5%;

C. weighing 40.5g of the 1,3,2, 4-dioxathiazole-2-oxide compound obtained in the step B, dissolving in 120mL of acetonitrile, adding 160mg of ruthenium trichloride and 28g of sodium hypochlorite at 0-5 ℃, and reacting for 20min to obtain 41.09g of the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound with the structural formula II, wherein the yield is 90.7%, and the structural formula II is as follows:

example 7

A method for synthesizing 1,3,2, 4-dioxathiazole-2, 2-dioxide compounds comprises the following steps:

A. adding 69.5g of hydroxylamine hydrochloride and 417mL of methanol into a reaction container, stirring until the hydroxylamine hydrochloride is completely dissolved, dripping potassium hydroxide solution at room temperature, dripping for 0.8 hour, adding 122.4g of methyl benzoate at room temperature, heating to 50-60 ℃, reacting for 3 hours, carrying out suction filtration and concentration to obtain a crude product, adding the crude product into the hydrochloric acid solution, acidifying until the pH value is 4, carrying out suction filtration, recrystallization and drying to obtain 113.56g of benzohydroxamic acid, wherein the yield of the benzohydroxamic acid is 92.1%; wherein the potassium hydroxide solution is obtained by dissolving 61.6g of potassium hydroxide in 275mL of distilled water,

B. weighing 68.5g of the benzohydroxamic acid obtained in the step A and 540mL of dichloromethane, adding the weighed materials into a reaction container, stirring the materials until the benzohydroxamic acid is completely dissolved, adding 71.4g of thionyl chloride at room temperature, reacting for 3 hours, separating liquid, concentrating an organic layer at 60 ℃ under-0.09 MPa, performing suction filtration and drying to obtain 78.01g of 1,3,2, 4-dioxathiazole-2-oxide compounds, wherein the yield of the 1,3,2, 4-dioxathiazole-2-oxide compounds is 86.2%;

C. weighing 54.9g of the 1,3,2, 4-dioxathiazole-2-oxide compound obtained in the step B, dissolving in 180mL of acetonitrile, adding 230mg of ruthenium trichloride and 30g of sodium hypochlorite at 0-5 ℃, and reacting for 20min to obtain 54.63g of the 1,3,2, 4-dioxathiazole-2, 2-dioxide compound with the structural formula III, wherein the yield is 91.5%, and the structural formula III is as follows:

application test:

test one, taking 1% by weight of the electrolyte solution of 1,3,2, 4-dioxathiazole-2, 2-dioxide compounds obtained in examples 1 and 67 of the present invention as an additive, adding the additive into the electrolyte solution of a basic battery, and performing performance detection of the battery, wherein the electrolyte solution is marked as electrolyte solution 1, electrolyte solution 2 and electrolyte solution 3, the electrolyte solution of the basic battery is a blank control group, and the electrolyte solution of the basic battery is: DC/EMC 1/3, LiPF 6: 1.1M FEC, PST, positive and negative current collectors are distributed as aluminum foils and copper foils, the diaphragm adopts a ceramic diaphragm to form a soft package battery, after electrolyte is injected, the soft package battery is assembled in a glove box, and the test is carried out after the soft package battery is kept stand for 8 hours. The battery is activated by charging and discharging at room temperature of 25 ℃ and at a constant temperature of 1/10C 3.0V to 4.5V or more, and then the battery is charged and discharged at 1C in cycles at 50 ℃. The cycle test results are shown in table 1.

TABLE 1 results of the cycling tests

And test II, evaluation of high-temperature storage performance of the battery: the storage performance of 60 ℃/30D and 85 ℃/7D are tested, and the following table 2 shows that the battery is stored for 30 days at 60 ℃ and 7 days at 85 ℃ after standard charging and discharging, and then the capacity retention rate of the battery is measured.

TABLE 2 test results of high-temperature storage properties of batteries

Group of	Capacity retention at 60 ℃ for 30 days%	Capacity retention at 85 ℃ for 7 days%
			Electrolyte solution 1	93.7	94.9
Electrolyte 2	92.6	95.3
			Electrolyte 3	93.5	95.2
Blank control group	72.5	58.3

The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.