CN111349058A - Synthesis method of 1, 4-bis (methylsulfonyl) piperazine - Google Patents
Synthesis method of 1, 4-bis (methylsulfonyl) piperazine Download PDFInfo
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- CN111349058A CN111349058A CN201811573411.4A CN201811573411A CN111349058A CN 111349058 A CN111349058 A CN 111349058A CN 201811573411 A CN201811573411 A CN 201811573411A CN 111349058 A CN111349058 A CN 111349058A
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- methylsulfonyl
- piperazine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
- C07D295/26—Sulfur atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Secondary Cells (AREA)
Abstract
A synthesis method of 1, 4-bis (methylsulfonyl) piperazine belongs to the technical field of battery electrolyte additives, piperazine is used as a raw material, a solvent and an organic base are added, the temperature is reduced to 0 ℃, methylsulfonyl chloride is dropwise added, the dropwise addition is completed within 1-1.2 hours, the temperature is increased to 5-10 ℃, the heat preservation reaction is performed for 4-5 hours, and after the reaction is completed, the 1, 4-bis (methylsulfonyl) piperazine is obtained through water washing, drying and concentration. The synthesis method is simple, the reaction process is mild and stable, and the yield is high.
Description
Technical Field
The invention belongs to the technical field of battery electrolyte additives, and relates to a method for synthesizing 1, 4-bis (methylsulfonyl) piperazine serving as a battery electrolyte additive.
Background
The commonly used lithium ion battery negative electrode mainly comprises various carbon materials (such as graphite, porous carbon and the like), silicon-based materials including silicon-carbon composite materials and SiOx materials, tin-based materials and the like. During the charging and formation of the battery, the electrolyte is decomposed and an electronically insulating Solid Electrolyte Interface (SEI) film is formed on the surface of the negative electrode. During the subsequent use of the battery, the SEI film of this layer may continue to grow due to various possible factors, resulting in deterioration of the conductivity of the negative electrode. Other causes may also cause the internal resistance of the battery to become large. As a result of the increase in polarization and internal resistance of the battery, the actual discharge potential of the battery becomes higher than the voltage obtained by measurement (apparent) thereof, and the negative electrode cannot store lithium sufficiently. Accordingly, the actual potential of the positive electrode of the battery is higher than the measured potential of the battery (overcharging). This not only lowers the actual specific capacity and design value of the battery, but also causes structural damage to the positive electrode material due to overcharge, and lowers the cycle performance of the battery. At the same time, overcharge of the battery (positive electrode) also accelerates elution of the transition metal in the positive electrode.
The prior art solves the problem by adding an additive into the electrolyte of the battery, wherein the additive is added to improve the electrochemical performance of the electrolyte and improve the deposition quality of a cathode. The electrolyte additive does not participate in electrode reaction in the electrolytic process, but can change the electrochemical performance of an electrolyte system, influence the discharge condition of ions and enable the electrolytic process to be in a better state, and is an indispensable part of the electrolyte system. Therefore, the research on the battery electrolyte additive has important significance on the development of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a synthesis method of 1, 4-bis (methylsulfonyl) piperazine, which is simple, mild and stable in reaction process and high in yield.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the synthesis method of 1, 4-bis (methylsulfonyl) piperazine comprises the steps of taking piperazine as a raw material, adding a solvent and an organic base, cooling to 0 ℃, dropwise adding methylsulfonyl chloride, heating to 5-10 ℃ after dropwise adding is completed within 1-1.2 hours, preserving heat for reaction for 4-5 hours, washing with water, drying and concentrating after the reaction is completed, and obtaining the 1, 4-bis (methylsulfonyl) piperazine.
The obtained 1, 4-bis (methylsulfonyl) piperazine was recrystallized to obtain a purified 1, 4-bis (methylsulfonyl) piperazine.
The molar ratio of piperazine to methylsulfonyl chloride is 1: (2-2.5).
The solvent is selected from dichloromethane, dichloroethane, chloroform or carbon tetrachloride.
The organic base is selected from triethylamine, trimethylamine or pyridine.
In the recrystallization, DMC, DEC or EMC is used as the solvent.
The invention has the beneficial effects that:
the invention has the advantages of simple synthetic route, high yield of 85 percent, mild and stable reaction process and high purity of the prepared product.
Detailed Description
The structural formula of the 1, 4-bis (methylsulfonyl) piperazine is as follows:
Detailed description of the preferred embodiments
Example 1
43g (0.5mol) of piperazine and 300ml of dichloromethane are added into a four-neck flask, 202g (2mol) of triethylamine is added, the temperature is reduced to 0 ℃, 127g (1.1mol) of methylsulfonyl chloride is added dropwise, after 1h of dropwise addition is finished, the temperature is raised to 8 ℃, the reaction is kept for 4h, after the reaction is finished, the mixture is washed, dried and concentrated to obtain a crude product, and the crude product is recrystallized by DMC to obtain 108.6g of a product with the yield of 89.75%.
The purity of the obtained product was checked to be 96.9%, and the density was 48.86g/cm3The boiling point was 420.6 deg.C (760 mmHg).
Example 2
43g (0.5mol) of piperazine and 300ml of dichloroethane are added into a four-neck flask, 212g (2.1mol) of triethylamine is added, the temperature is reduced to 0 ℃, 114.5g (1mol) of methylsulfonyl chloride is added dropwise, after 1.2h of dropwise addition, the temperature is raised to 5 ℃, the temperature is kept for 5h of reaction, after the reaction is finished, the reaction product is washed by water, dried and concentrated to obtain a crude product, and the crude product is recrystallized by DMC to obtain 102.9g of a product, wherein the yield is 85%.
The purity of the obtained product was checked to be 95.3%, and the density was checked to be 48.33g/cm3Boiling point 428.7 deg.C (760 mmHg).
Example 3
43g (0.5mol) of piperazine and 300ml of chloroform are added into a four-neck flask, 253g (2.5mol) of triethylamine is added, the temperature is reduced to 0 ℃, 143g (1.25mol) of methylsulfonyl chloride is added dropwise, after 1.1h of dropwise addition, the temperature is raised to 10 ℃, the temperature is kept for reaction for 4.5h, after the reaction is finished, water washing, drying and concentration are carried out to obtain a crude product, and the crude product is recrystallized by DMC to obtain 105.7g of a product, wherein the yield is 87.35%.
The purity of the obtained product was determined to be 96.2% and the density was determined to be 48.51g/cm3The boiling point was 423.4 deg.C (760 mmHg).
Second, Performance test
The battery is assembled and then subjected to cycle performance test, lithium cobaltate is used as a positive electrode material, a negative electrode adopts mesocarbon microbeads, positive and negative current collectors are distributed into aluminum foils and copper foils, a 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 performed after the soft package battery is kept stand for 8 hours. The electrolyte is prepared by dissolving LiPF in a mixed solvent of ethylene carbonate and methyl trifluoroacetate at a volume ratio of 4:66To obtain a 1.0M solution, and the solution was used as a base electrolyte.
The lithium battery with 1% of 1, 4-bis (methylsulfonyl) piperazine added by the weight of the electrolyte is taken as an experimental group, and the blank group of the lithium battery without the electrolyte is used for carrying out battery performance comparison, and the results are as follows:
1. the capacity retention was determined after 50 ℃ cycling, respectively, and the results are given in table 1 below:
as can be seen from the above Table 1, the 1, 4-bis (methylsulfonyl) piperazine of the present invention can improve the high temperature cycle performance and the service life of the battery.
2. The storage performance tests at 70 ℃/7D are respectively carried out, the following table 2 shows that the battery is stored for 7 days at 70 ℃ after standard charging and discharging, and then the capacity retention rate and the capacity recovery rate of the battery are measured.
TABLE 2
As can be seen from table 2 above, the 1, 4-bis (methylsulfonyl) piperazine of the present invention can improve the high temperature stability of the battery.
Claims (6)
- The synthesis method of 1, 4-bis (methylsulfonyl) piperazine is characterized in that piperazine is used as a raw material, a solvent and an organic base are added, the temperature is reduced to 0 ℃, methylsulfonyl chloride is dropwise added, the temperature is increased to 5-10 ℃ after dropwise addition of 1-1.2 hours, the reaction is kept at the temperature for 4-5 hours, and after the reaction is finished, the 1, 4-bis (methylsulfonyl) piperazine is obtained by washing, drying and concentrating.
- 2. The method for synthesizing 1, 4-bis (methylsulfonyl) piperazine according to claim 1, wherein the obtained 1, 4-bis (methylsulfonyl) piperazine is recrystallized to obtain purified 1, 4-bis (methylsulfonyl) piperazine.
- 3. The method for synthesizing 1, 4-bis (methylsulfonyl) piperazine according to claim 1, wherein the molar ratio of piperazine to methylsulfonyl chloride is 1: (2-2.5).
- 4. The method of synthesizing 1, 4-bis (methylsulfonyl) piperazine according to claim 1, wherein the solvent is selected from the group consisting of dichloromethane, dichloroethane, chloroform, and carbon tetrachloride.
- 5. The method for synthesizing 1, 4-bis (methylsulfonyl) piperazine according to claim 1, wherein the organic base is selected from triethylamine, trimethylamine, and pyridine.
- 6. The method for synthesizing 1, 4-bis (methylsulfonyl) piperazine according to claim 2, wherein the solvent used in the recrystallization is DMC, DEC or EMC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811573411.4A CN111349058A (en) | 2018-12-21 | 2018-12-21 | Synthesis method of 1, 4-bis (methylsulfonyl) piperazine |
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| CN201811573411.4A CN111349058A (en) | 2018-12-21 | 2018-12-21 | Synthesis method of 1, 4-bis (methylsulfonyl) piperazine |
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| CN201811573411.4A Pending CN111349058A (en) | 2018-12-21 | 2018-12-21 | Synthesis method of 1, 4-bis (methylsulfonyl) piperazine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112349961A (en) * | 2020-11-12 | 2021-02-09 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device and electronic apparatus including the same |
| CN114552016A (en) * | 2022-02-25 | 2022-05-27 | 珠海市赛纬电子材料股份有限公司 | Electrolyte additive, lithium ion battery electrolyte and lithium ion battery |
Citations (5)
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|---|---|---|---|---|
| GB1082062A (en) * | 1965-02-05 | 1967-09-06 | Ici Ltd | Difluoraminated piperazine derivatives |
| CN101747278A (en) * | 2009-12-22 | 2010-06-23 | 山东鑫泉医药中间体有限公司 | Method for synthesizing 1-chloroformyl-3-methyl sulfonyl-2-imidazo flavanone |
| CN102060811A (en) * | 2011-01-19 | 2011-05-18 | 山西大学 | Synthetic method of monosulfonyl piperazine |
| CN102408374A (en) * | 2011-12-27 | 2012-04-11 | 山东鑫泉医药有限公司 | Synthesis method of 1-(methylsulphonyl)imidazolidin-2-one |
| CN107400072A (en) * | 2017-06-30 | 2017-11-28 | 上海科技大学 | A kind of double ethenesulfonamide connexons and its preparation and application |
-
2018
- 2018-12-21 CN CN201811573411.4A patent/CN111349058A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1082062A (en) * | 1965-02-05 | 1967-09-06 | Ici Ltd | Difluoraminated piperazine derivatives |
| CN101747278A (en) * | 2009-12-22 | 2010-06-23 | 山东鑫泉医药中间体有限公司 | Method for synthesizing 1-chloroformyl-3-methyl sulfonyl-2-imidazo flavanone |
| CN102060811A (en) * | 2011-01-19 | 2011-05-18 | 山西大学 | Synthetic method of monosulfonyl piperazine |
| CN102408374A (en) * | 2011-12-27 | 2012-04-11 | 山东鑫泉医药有限公司 | Synthesis method of 1-(methylsulphonyl)imidazolidin-2-one |
| CN107400072A (en) * | 2017-06-30 | 2017-11-28 | 上海科技大学 | A kind of double ethenesulfonamide connexons and its preparation and application |
Non-Patent Citations (1)
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| HAROLD W. HEINE，ET AL.: "The Isomerization and Dimerization of Aziridine Derivatives. IV", 《J.AM.CHEM.SOC.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112349961A (en) * | 2020-11-12 | 2021-02-09 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device and electronic apparatus including the same |
| CN112349961B (en) * | 2020-11-12 | 2021-09-24 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device and electronic apparatus including the same |
| CN114552016A (en) * | 2022-02-25 | 2022-05-27 | 珠海市赛纬电子材料股份有限公司 | Electrolyte additive, lithium ion battery electrolyte and lithium ion battery |
| WO2023159800A1 (en) * | 2022-02-25 | 2023-08-31 | 珠海市赛纬电子材料股份有限公司 | Electrolyte additive, lithium ion battery electrolyte, and lithium ion battery |
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