CN113416178A - Lithium battery additive amido vinyl sulfate, and preparation method and application thereof - Google Patents
Lithium battery additive amido vinyl sulfate, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of lithium ion batteries, and discloses a lithium battery additive amido vinyl sulfate, a preparation method and application thereof aiming at the problems of low coulombic efficiency and poor cycle stability in the existing batteries, wherein the chemical structural formula is as follows:
the molecular structure consists of three parts of amido, alkyl chain and vinyl sulfate; wherein m and n are the same or different, m can be 0,1,2,3 …, and n can be 1,2,3 …. The amido part of the amido vinyl sulfate additive provided by the invention can stabilize metal in the electrolyteThe ion improves the cycling stability of the battery, and the vinyl sulfate part can be decomposed on the surface of the negative electrode to form a stable SEI film, which is beneficial to the uniform deposition of lithium ions, thereby improving the cycling performance of the battery; the stability of the lithium ion battery anode material under high voltage can be improved, the decomposition of electrolyte on the surface of the anode is inhibited, and the storage performance and the cycle performance of the high voltage lithium ion battery are improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium battery additive amido vinyl sulfate, and a preparation method and application thereof.
Background
Lithium ion batteries are made up of a carbon anode (graphite, coke, glassy carbon, etc.) and a lithiated transition metalOxide cathode (LiCoO)2，LiNiO2，LiMn2O4Etc.), lithium ion batteries can provide higher voltages and longer lifetimes, and have higher energy densities, as compared to other secondary batteries, such as nickel metal hydride (Ni-MH) and nickel cadmium (Ni-Cd) batteries. Lithium ion battery packs are smaller and lighter than other batteries, can maintain good capacity by repeated charging, and have been widely used in mobile electronic devices (e.g., digital cameras, camcorders, portable computers, cell phones, etc.). These electronic devices are now available in small lithium ion batteries with capacities of 2000-2400mAh (18,650 size). Due to the above-mentioned inherent wonderful characteristics, lithium ion batteries have attracted considerable interest in recent years as power sources for electric vehicles and/or for power load leveling. Although the electrochemical performance (such as capacity and high-rate discharge characteristic) is successfully improved, the inherent defects of the lithium ion battery, namely the endurance mileage and the safety problem are still not solved, and the problems seriously hinder the wide application of the lithium ion battery in Electric Vehicles (EV) and Hybrid Electric Vehicles (HEV). The appropriate electrolyte additive can stabilize an SEI film of the lithium ion battery, improve the conductivity of the electrolyte and improve the cycle performance and safety performance of the lithium ion battery.
Patent No. CN201780046312.8, entitled "additive for electrolyte of lithium battery, electrolyte of lithium battery including the additive, and lithium battery using the electrolyte", the present invention provides an additive for electrolyte of lithium battery, electrolyte of lithium battery including the additive, and lithium battery using the electrolyte. The additive for an electrolyte of a lithium battery includes a compound represented by the following formula 1: formula 1[ P4O10]x·[B(OSiR1R2R3)3]yWherein R1, R2, R3 and the molar ratio of x to y (x/y) are as defined in the specification. By adding the compound to the electrolyte,the life characteristics of the lithium battery at high temperatures can be improved.
It has a disadvantage in that its ability to protect the SEI layer from being stable and not deteriorating at high temperatures is yet to be improved.
Disclosure of Invention
The invention provides a lithium battery additive amido vinyl sulfate, a preparation method and application thereof, aiming at overcoming the problems of low coulombic efficiency and poor cycle stability in the existing battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium battery additive amido vinyl sulfate has a chemical structural formula as follows:
the molecular structure consists of three parts of amido, alkyl chain and vinyl sulfate; wherein m and n are the same or different, m can be 0,1,2,3 …, and n can be 1,2,3 ….
According to the amino vinyl sulfate additive provided by the invention, the amino part can improve the battery cycle stability by stabilizing metal ions in the electrolyte, and the vinyl sulfate part can be decomposed on the surface of a negative electrode to form a stable SEI film, so that lithium ions can be uniformly deposited, and the battery cycle performance is improved.
The preparation method of the lithium battery additive amido vinyl sulfate is characterized by comprising the following preparation steps:
(1) sequentially adding 3-dimethylamino-1, 2-propanediol, an acid-binding agent and carbon tetrachloride into a reaction device, bubbling nitrogen for 15-30min, continuously dropwise adding thionyl chloride into the reaction device to obtain a reaction mixed solution after dropwise adding, stirring at room temperature for 11.5-12h, after the reaction is finished, removing white solids by suction filtration, and spin-drying the obtained solution to obtain a light yellow oily substance;
(2) dissolving the light yellow oily substance in an organic solvent, adding a catalyst, stirring in an ice bath for 30-35min, continuously dropwise adding an oxidant, reacting for 2-2.2h, adding ethyl acetate to dissolve after the reaction is finished to obtain an organic phase, washing the organic phase with water, saturated sodium bicarbonate and saturated salt solution in turn, and performing column chromatography to obtain the target product 3-dimethylamino-ethylene sulfate.
The invention synthesizes a specific adding component of lithium battery additive amido vinyl sulfate and a reaction mechanism are as follows: adding 3-dimethyl-1, 2-propylene glycol, anhydrous carbon tetrachloride and pyridine in sequence, introducing nitrogen to remove oxygen in the solvent, slowly dropwise adding 14 g of thionyl chloride inwards, and separating out white solids;
after the reaction is finished, solid impurities are removed by suction filtration, and the obtained organic phase is dried in a spinning mode to obtain colorless oily matter which is directly reacted in the next step without further treatment; dissolving the obtained product in acetonitrile, adding ruthenium trichloride as a catalyst, dropwise adding a sodium periodate aqueous solution into a reaction bottle, and controlling the reaction temperature to be below 10 ℃ in the dropwise adding process (under an ice bath condition);
after the reaction is finished, adding ethyl acetate, washing the organic phase with water, saturated sodium bicarbonate and saturated saline solution for twice, removing water-soluble substances and promoting complete precipitation of the catalyst only by washing according to the steps, removing metal salts from the organic phase by column chromatography, and spin-drying the organic phase to obtain the 3-dimethylamino-1, 2-vinyl sulfate with high purity.
Preferably, the mol ratio of the thionyl chloride, the 3-dimethylamino-1, 2-propanediol, the acid-binding agent, the carbon tetrachloride, the catalyst and the oxidant is 110-: 500-1000: 100: 120-160: 1-5: 100-250.
Preferably, the acid scavenger is one or more selected from pyridine, trimethylamine and triethylamine.
Preferably, the catalyst is selected from transition metal oxides or chlorides.
Preferably, the oxidizing agent is selected from one or more of ammonium persulfate, sodium hypochlorite and sodium periodate.
Preferably, the organic solvent is selected from one or more of acetonitrile, chloroform and dichloromethane.
The lithium battery additive amido vinyl sulfate is applied to a lithium battery, the lithium battery comprises a positive electrode material, a negative electrode material, a diaphragm and electrolyte, the negative electrode material is a lithium sheet, and the electrolyte comprises electrolyte salt, a solvent and additive amido vinyl sulfate.
Preferably, the positive electrode material is selected from one of lithium iron phosphate and lithium cobaltate; the electrolyte salt is selected from one or more of lithium hexafluorophosphate, lithium perchlorate, lithium bis (trifluoromethylsulfonyl) amide, lithium tetrafluoroborate and lithium bis (oxalato) borate; the solvent is one or more selected from ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether and ethylene sulfite; the membrane is selected from Celgard2500 membrane or PP membrane.
Preferably, the concentration of the electrolyte is 1-1.2mol/L, and the addition amount of the amino vinyl sulfate accounts for 1-3% of the mass of the electrolyte, and more preferably 1-2%.
Therefore, the invention has the following beneficial effects:
(1) according to the amino vinyl sulfate additive provided by the invention, the amino part can improve the cycling stability of the battery by stabilizing metal ions in the electrolyte, the vinyl sulfate part can be decomposed to form a stable SEI film on the surface of a negative electrode, and the synergistic effect of the amino vinyl sulfate part and the vinyl sulfate part is more beneficial to uniform deposition of lithium ions, so that the cycling performance of the battery is improved;
(2) the amino vinyl sulfate additive provided by the invention can improve the stability of a lithium ion battery anode material under high voltage, inhibit the decomposition of electrolyte on the surface of an anode, and improve the storage performance and the cycle performance of a high-voltage lithium ion battery;
(3) the lithium ion battery applying the amino vinyl sulfate additive can work for a long time under high voltage, and keeps excellent cycle performance and rate capability;
(4) the technical scheme adopted by the invention has the advantages of simple and reliable synthesis method, high product yield and purity, and capability of obviously improving the cycle stability of the lithium ion battery by adding the amino vinyl sulfate additive with the mass fraction of 1-2%.
Drawings
Fig. 1 is a graph comparing the cycling stability of batteries with and without the addition of vinyl 3-dimethylamino-1, 2-sulfonate prepared using the present invention as a battery additive (where the triangle is example 1, the star is example 2, and the square is comparative example 1).
FIG. 2 is a plot of coulombic efficiency of batteries with and without addition of the vinyl 3-dimethylamino-1, 2-sulfonate prepared using the present invention as a battery additive (where the triangle is example 1, the star is example 2, and the square is comparative example 1).
Detailed Description
The invention is further described with reference to specific embodiments.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
General examples
A lithium battery additive amido vinyl sulfate has a chemical structural formula as follows:
the molecular structure consists of three parts of amido, alkyl chain and vinyl sulfate; wherein m and n are the same or different, m can be 0,1,2,3 …, and n can be 1,2,3 ….
The preparation method of the lithium battery additive amido vinyl sulfate comprises the following preparation steps:
(1) sequentially adding 3-dimethylamino-1, 2-propanediol, an acid-binding agent and carbon tetrachloride into a reaction device, bubbling nitrogen for 15-30min, continuously dropwise adding thionyl chloride into the reaction device to obtain a reaction mixed solution after dropwise adding, stirring at room temperature for 11.5-12h, after the reaction is finished, removing white solids by suction filtration, and spin-drying the obtained solution to obtain a light yellow oily substance;
(2) dissolving the light yellow oily substance in an organic solvent, adding a catalyst, stirring in an ice bath for 30-35min, continuously dropwise adding an oxidant, reacting for 2-2.2h, adding ethyl acetate to dissolve after the reaction is finished to obtain an organic phase, washing the organic phase with water, saturated sodium bicarbonate and saturated salt solution in turn, and performing column chromatography to obtain the target product 3-dimethylamino-ethylene sulfate. The mol ratio of thionyl chloride, 3-dimethylamino-1, 2-propanediol, acid-binding agent, carbon tetrachloride, catalyst and oxidant is 110-: 500-1000: 100: 120-160: 1-5: 100-250.
The acid-binding agent is selected from one or more of pyridine, trimethylamine and triethylamine; the catalyst is selected from transition metal oxides or chlorides; the oxidant is selected from one or more of ammonium persulfate, sodium hypochlorite and sodium periodate; the organic solvent is selected from one or more of acetonitrile, trichloromethane and dichloromethane.
The lithium battery additive amido vinyl sulfate is applied to a lithium battery, the lithium battery comprises a positive electrode material, a negative electrode material, a diaphragm and electrolyte, the negative electrode material is a lithium sheet, and the electrolyte comprises electrolyte salt, a solvent and additive amido vinyl sulfate. The positive electrode material is selected from one of lithium iron phosphate and lithium cobaltate; the electrolyte salt is selected from one or more of lithium hexafluorophosphate, lithium perchlorate, lithium bis (trifluoromethylsulfonyl) amide, lithium tetrafluoroborate and lithium bis (oxalato) borate; the solvent is one or more selected from ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether and ethylene sulfite; the membrane is selected from Celgard2500 membrane or PP membrane. The concentration of the electrolyte is 1-1.2mol/L, and the addition amount of the amido vinyl sulfate accounts for 1-3% of the mass of the electrolyte, and is more preferably 1-2%.
Example 1
A lithium battery additive amido vinyl sulfate has a chemical structural formula as follows:
the molecular structure consists of three parts of amido, alkyl chain and vinyl sulfate; wherein m and n are the same or different, m can be 0,1,2,3 …, and n can be 1,2,3 ….
The preparation method of the lithium battery additive amido vinyl sulfate comprises the following preparation steps:
(1) sequentially adding 3-dimethylamino-1, 2-propanediol, trimethylamine and carbon tetrachloride into a reaction device, blowing nitrogen for 22min, continuously dropwise adding thionyl chloride into the reaction device to obtain a reaction mixed solution after dropwise adding, stirring at room temperature for 11.8h, after the reaction is finished, performing suction filtration to remove white solids, and spin-drying the obtained solution to obtain a light yellow oily substance;
(2) dissolving the light yellow oily substance in acetonitrile, adding ruthenium trichloride, stirring in ice bath for 32min, continuously dropwise adding ammonium sulfate, reacting for 2.1h, adding ethyl acetate to dissolve after the reaction is finished to obtain an organic phase, washing the organic phase with water, saturated sodium bicarbonate and saturated salt solution in turn, and performing column chromatography to obtain the target product 3-dimethylamino-vinyl sulfate. The mol ratio of thionyl chloride, 3-dimethylamino-1, 2-propanediol, trimethylamine, carbon tetrachloride, ruthenium trichloride and ammonium sulfate is 120: 7500: 100: 140: 3: 180.
the lithium battery comprises a positive electrode material lithium iron phosphate, a negative electrode material lithium sheet, a Celgard2500 diaphragm and electrolyte, wherein the electrolyte comprises electrolyte salt lithium hexafluorophosphate, solvent ethylene carbonate and additive ethylene amidosulfate. The concentration of the electrolyte is 1.1mol/L, and the addition amount of the amido vinyl sulfate is 2%.
The battery assembled according to the components is tested for the change of the battery cycling performance and the coulombic efficiency along with the electrochemical cycling in a blue-electricity system by using the multiplying power of 1C.
Example 2
A lithium battery additive amido vinyl sulfate has a chemical structural formula as follows:
the molecular structure consists of three parts of amido, alkyl chain and vinyl sulfate; wherein m and n are the same or different, m can be 0,1,2,3 …, and n can be 1,2,3 ….
The preparation method of the lithium battery additive amido vinyl sulfate comprises the following preparation steps:
(1) sequentially adding 3-dimethylamino-1, 2-propanediol, pyridine and carbon tetrachloride into a reaction device, blowing nitrogen for 15min, continuously dropwise adding thionyl chloride into the reaction device to obtain a reaction mixed solution after dropwise adding, stirring at room temperature for 12h, after the reaction is finished, performing suction filtration to remove white solids, and spin-drying the obtained solution to obtain a light yellow oily substance;
(2) dissolving the yellowish oily substance in chloroform, and adding RuO2Stirring in ice bath for 30min, continuously dropwise adding sodium hypochlorite, reacting for 2.2h, adding ethyl acetate to dissolve after the reaction is finished to obtain an organic phase, washing the organic phase with water, saturated sodium bicarbonate and saturated salt solution in turn, and performing column chromatography to obtain the target product 3-dimethylamino-ethylene sulfate. Thionyl chloride, 3-dimethylamino-1, 2-propanediol, pyridine, carbon tetrachloride, RuO2The molar ratio of sodium hypochlorite is 110: 1000: 100: 120: 5: 100.
the lithium battery additive amido ethylene sulfate is applied to a lithium battery, the lithium battery comprises a positive electrode material lithium iron phosphate, a negative electrode material lithium sheet, a PP diaphragm and electrolyte, and the electrolyte comprises electrolyte salt lithium hexafluorophosphate, solvent ethylene carbonate and additive amido ethylene sulfate. The concentration of the electrolyte is 1mol/L, and the addition amount of the amino vinyl sulfate is 1%.
The battery assembled according to the components is tested for the change of the battery cycling performance and the coulombic efficiency along with the electrochemical cycling in a blue-electricity system by using the multiplying power of 1C.
Example 3
A lithium battery additive amido vinyl sulfate has a chemical structural formula as follows:
the molecular structure consists of three parts of amido, alkyl chain and vinyl sulfate; wherein m and n are the same or different, m can be 0,1,2,3 …, and n can be 1,2,3 ….
The preparation method of the lithium battery additive amido vinyl sulfate comprises the following preparation steps:
(1) sequentially adding 3-dimethylamino-1, 2-propanediol, triethylamine and carbon tetrachloride into a reaction device, blowing nitrogen for 30min, continuously dropwise adding thionyl chloride into the reaction device to obtain a reaction mixed solution after dropwise adding, stirring at room temperature for 11.5h, after the reaction is finished, performing suction filtration to remove white solids, and spin-drying the obtained solution to obtain a light yellow oily substance;
(2) dissolving the light yellow oily substance in dichloromethane, adding ruthenium trichloride, stirring in ice bath for 35min, continuously dropwise adding sodium hypochlorite, reacting for 2h, adding ethyl acetate after the reaction is finished, dissolving to obtain an organic phase, washing the organic phase with water, saturated sodium bicarbonate and saturated salt solution in turn, and performing column chromatography to obtain the target product 3-dimethylamino-vinyl sulfate. The mol ratio of thionyl chloride, 3-dimethylamino-1, 2-propanediol, triethylamine, carbon tetrachloride, ruthenium trichloride and sodium hypochlorite is 130: 500: 100: 160: 1: 250.
the lithium battery comprises a positive electrode material lithium iron phosphate, a negative electrode material lithium sheet, a Celgard2500 diaphragm and electrolyte, wherein the electrolyte comprises electrolyte salt lithium hexafluorophosphate, solvent ethylene carbonate and additive ethylene amidosulfate. The concentration of the electrolyte is 1.2mol/L, and the addition amount of the amino vinyl sulfate is 3%.
The battery assembled according to the components is tested for the change of the battery cycling performance and the coulombic efficiency along with the electrochemical cycling in a blue-electricity system by using the multiplying power of 1C.
Comparative example 1 (which is different from example 1 in that the lithium battery additive, vinyl amidosulfate, is not added to the electrolyte) a lithium battery additive, vinyl amidosulfate, has the following chemical structural formula:
the molecular structure consists of three parts of amido, alkyl chain and vinyl sulfate; wherein m and n are the same or different, m can be 0,1,2,3 …, and n can be 1,2,3 ….
The preparation method of the lithium battery additive amido vinyl sulfate comprises the following preparation steps:
(1) sequentially adding 3-dimethylamino-1, 2-propanediol, trimethylamine and carbon tetrachloride into a reaction device, blowing nitrogen for 22min, continuously dropwise adding thionyl chloride into the reaction device to obtain a reaction mixed solution after dropwise adding, stirring at room temperature for 11.8h, after the reaction is finished, performing suction filtration to remove white solids, and spin-drying the obtained solution to obtain a light yellow oily substance;
(2) dissolving the light yellow oily substance in acetonitrile, adding ruthenium trichloride, stirring in ice bath for 32min, continuously dropwise adding ammonium sulfate, reacting for 2.1h, adding ethyl acetate to dissolve after the reaction is finished to obtain an organic phase, washing the organic phase with water, saturated sodium bicarbonate and saturated salt solution in turn, and performing column chromatography to obtain the target product 3-dimethylamino-vinyl sulfate. The mol ratio of thionyl chloride, 3-dimethylamino-1, 2-propanediol, trimethylamine, carbon tetrachloride, ruthenium trichloride and ammonium sulfate is 120: 7500: 100: 140: 3: 180.
the lithium battery comprises a positive electrode material lithium iron phosphate, a negative electrode material lithium sheet, a Celgard2500 diaphragm and electrolyte, wherein the electrolyte comprises electrolyte salt lithium hexafluorophosphate, solvent ethylene carbonate and additive ethylene amidosulfate. The concentration of the electrolyte is 1.1mol/L, and the addition amount of the amido vinyl sulfate is 0.
The battery assembled according to the components is tested for the change of the battery cycling performance and the coulombic efficiency along with the electrochemical cycling in a blue-electricity system by using the multiplying power of 1C.
Comparative example 2 (different from example 1 in that an excessive amount of amino vinyl sulfate was added to the electrolyte, and the amount of the amino vinyl sulfate added was 5%)
A lithium battery additive amido vinyl sulfate has a chemical structural formula as follows:
the molecular structure consists of three parts of amido, alkyl chain and vinyl sulfate; wherein m and n are the same or different, m can be 0,1,2,3 …, and n can be 1,2,3 ….
The preparation method of the lithium battery additive amido vinyl sulfate comprises the following preparation steps:
(1) sequentially adding 3-dimethylamino-1, 2-propanediol, trimethylamine and carbon tetrachloride into a reaction device, blowing nitrogen for 22min, continuously dropwise adding thionyl chloride into the reaction device to obtain a reaction mixed solution after dropwise adding, stirring at room temperature for 11.8h, after the reaction is finished, performing suction filtration to remove white solids, and spin-drying the obtained solution to obtain a light yellow oily substance;
(2) dissolving the light yellow oily substance in acetonitrile, adding ruthenium trichloride, stirring in ice bath for 32min, continuously dropwise adding ammonium sulfate, reacting for 2.1h, adding ethyl acetate to dissolve after the reaction is finished to obtain an organic phase, washing the organic phase with water, saturated sodium bicarbonate and saturated salt solution in turn, and performing column chromatography to obtain the target product 3-dimethylamino-vinyl sulfate. The mol ratio of thionyl chloride, 3-dimethylamino-1, 2-propanediol, trimethylamine, carbon tetrachloride, ruthenium trichloride and ammonium sulfate is 120: 7500: 100: 140: 3: 180.
the lithium battery comprises a positive electrode material lithium iron phosphate, a negative electrode material lithium sheet, a Celgard2500 diaphragm and electrolyte, wherein the electrolyte comprises electrolyte salt lithium hexafluorophosphate, solvent ethylene carbonate and additive ethylene amidosulfate. The concentration of the electrolyte is 1.1mol/L, and the addition amount of the amido vinyl sulfate is 0.
The battery assembled according to the components is tested for the change of the battery cycling performance and the coulombic efficiency along with the electrochemical cycling in a blue-electricity system by using the multiplying power of 1C.
The attenuation speed is much higher than that of the comparison document 1, and the cycle performance and the coulombic efficiency are reduced.
And (4) conclusion: examples 1-3 show that lithium batteries prepared by the preparation process and preparation process range of the present invention have good cycle performance and rate capability, especially thermal cycle stability at high temperature.
FIG. 1 is a graph comparing the cycling stability of batteries with and without addition of 3-dimethylamino-1, 2-vinyl sulfonate prepared by the technical scheme of the present invention as a battery additive, wherein squares are a comparative group without addition (comparative example 1), stars are an experimental group with an addition mass fraction of 1% (example 2), and triangles are an experimental group with an addition mass fraction of 2% (example 2); when the mass fraction of the additive is 2%, the cycling stability of the battery is the best, and the additive scheme is the preferred scheme of the invention.
FIG. 2 is a coulombic efficiency chart of a lithium ion battery with 3-dimethylamino-1, 2-vinyl sulfonate prepared by the technical scheme of the invention as a battery additive and without addition, wherein squares are comparison groups without addition, stars are experimental groups with 1% of addition mass fraction, and triangles are experimental groups with 2% of addition mass fraction; the embodiments described above are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the claims below.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The lithium battery additive amido vinyl sulfate is characterized in that the chemical structural formula is as follows:
the molecular structure consists of three parts of amido, alkyl chain and vinyl sulfate; wherein m and n are the same or different, m can be 0,1,2,3 …, and n can be 1,2,3 ….
2. The method for preparing the lithium battery additive of the ethylene amido sulfate according to claim 1, which is characterized by comprising the following preparation steps:
(1) sequentially adding 3-dimethylamino-1, 2-propanediol, an acid-binding agent and carbon tetrachloride into a reaction device, bubbling nitrogen for 15-30min, continuously dropwise adding thionyl chloride into the reaction device to obtain a reaction mixed solution after dropwise adding, stirring at room temperature for 11.5-12h, after the reaction is finished, removing white solids by suction filtration, and spin-drying the obtained solution to obtain a light yellow oily substance;
(2) dissolving the light yellow oily substance in an organic solvent, adding a catalyst, stirring in an ice bath for 30-35min, continuously dropwise adding an oxidant, reacting for 2-2.2h, adding ethyl acetate to dissolve after the reaction is finished to obtain an organic phase, washing the organic phase with water, saturated sodium bicarbonate and saturated salt solution in turn, and performing column chromatography to obtain the target product 3-dimethylamino-ethylene sulfate.
3. The method for preparing the amino vinyl sulfate as the lithium battery additive of claim 1, wherein the molar ratio of thionyl chloride, 3-dimethylamino-1, 2-propanediol, the acid-binding agent, carbon tetrachloride, the catalyst and the oxidant is 110-: 500-1000: 100: 120-160: 1-5: 100-250.
4. The method for preparing the lithium battery additive of the vinyl amidosulfate as claimed in claim 3, wherein the acid-binding agent is one or more selected from pyridine, trimethylamine and triethylamine.
5. The method for preparing the lithium battery additive of the ethylene amidosulfate as claimed in claim 3, wherein the catalyst is selected from transition metal oxides or chlorides.
6. The method for preparing the lithium battery additive of the ethylene amidosulfate as claimed in claim 3, wherein the oxidant is one or more selected from ammonium persulfate, sodium hypochlorite and sodium periodate.
7. The method for preparing the lithium battery additive of the ethylene amidosulfate as claimed in claim 3, wherein the organic solvent is selected from one or more of acetonitrile, chloroform and dichloromethane.
8. The lithium battery as claimed in claim 1, wherein the lithium battery comprises a positive electrode material, a negative electrode material, a separator and an electrolyte, the negative electrode material is a lithium sheet, and the electrolyte comprises an electrolyte salt, a solvent and an additive of ethylene amine sulfate.
9. The use according to claim 8, wherein the positive electrode material is selected from one of lithium iron phosphate and lithium cobaltate; the electrolyte salt is selected from one or more of lithium hexafluorophosphate, lithium perchlorate, lithium bis (trifluoromethylsulfonyl) amide, lithium tetrafluoroborate and lithium bis (oxalato) borate; the solvent is one or more selected from ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether and ethylene sulfite; the membrane is selected from Celgard2500 membrane or PP membrane.
10. The use of claim 8 or 9, wherein the electrolyte has a concentration of 1-1.2mol/L, and the addition amount of the amidoethylene sulfate is 1-3% of the electrolyte mass.
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| CN113416178B (en) | 2022-05-17 |
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