CN110911750B - High-voltage lithium ion battery electrolyte, additive and preparation method of additive - Google Patents
High-voltage lithium ion battery electrolyte, additive and preparation method of additive Download PDFInfo
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- CN110911750B CN110911750B CN201911217966.XA CN201911217966A CN110911750B CN 110911750 B CN110911750 B CN 110911750B CN 201911217966 A CN201911217966 A CN 201911217966A CN 110911750 B CN110911750 B CN 110911750B
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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
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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
- H01M10/052—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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- 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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Abstract
The invention discloses a high-voltage lithium ion battery electrolyte, an additive and a preparation method of the additive, wherein the additive is thiourea derivative salt, and the preparation method of the additive comprises the following steps: (1) firstly, placing a solvent, a catalyst and thiourea in a reaction container, gradually dropwise adding organic acid, and carrying out polycondensation reaction in an ice-water bath to obtain a thiourea lipid compound; (2) separating the by-product by a water separator and high-temperature reduced pressure distillation to obtain a crude product of the thiourea ester compound; (3) and extracting the product by using a solvent, recrystallizing, purifying and drying to obtain the thiourea lipid compound. The thiourea ester compound can be used as an additive of high-voltage lithium ion battery electrolyte, can capture oxygen free radicals generated by a positive electrode material under high voltage, and can also form an SEI film. The invention has the advantages of easily obtained raw materials, low cost, simple process, high production efficiency and high purity, and the product is expected to be used as an electrolyte additive.
Description
[ technical field ]
The invention relates to the technical field of lithium ion battery electrolyte additives, in particular to a high-voltage lithium ion battery electrolyte, an additive and a preparation method of the additive.
[ background art ]
Lithium ion batteries are one of the most successful technologies of modern electrochemistry and are commercially available, and are now widely used in the fields of portable electronic devices and electric automobiles. Currently, lithium ion batteries mainly use graphite as an anode material, lithium cobaltate or a ternary material as a cathode material, and a mixed solution of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and lithium hexafluorophosphate as an electrolyte solution.
There are several problems with lithium ion batteries during use: 1. during the charging and discharging processes of the high-voltage lithium battery, a carbonate solvent in the electrolyte can be decomposed on the surface of the anode to generate gases such as CH4, CO2, CO and the like, so that the performance of the lithium ion battery is seriously influenced; 2. the high voltage positive electrode material slowly releases lattice oxygen during charging, which oxidatively decomposes carbonate solvents and affects battery performance. Compared with the complexity of the modification process of the anode material, the modification research of the electrolyte is more economical and convenient. Therefore, the development of the electrolyte suitable for the high-voltage lithium ion battery is significant.
The stable CEI film is formed on the surface of the anode, so that the decomposition of the electrolyte can be effectively inhibited, and the chemical stability of the electrolyte is improved. The addition of different additives to the electrolyte is the most effective and economical way to solve this problem. During the charging process, the positive film forming additive (such as VC, PS, VES, PST and the like) can be better than a carbonate solvent to perform oxidation reaction on the interface of the positive material in advance to form an SEI film so as to isolate side reaction between the positive material and electrolyte and protect the positive material. When the additives are formed into a film under high voltage, gas is generated to cause battery ballooning and influence battery performance, and the additives cannot absorb lattice oxygen generated by a positive electrode material and cannot effectively improve the battery performance. Therefore, the finding of the additive which can participate in film formation at the interface of the cathode material and can effectively absorb oxygen free radicals has great theoretical and practical significance.
[ summary of the invention ]
In order to solve the problems, the invention provides an additive for lithium ion battery electrolyte, in particular to a thiourea ester compound, and also provides a synthetic method of the additive. The invention is realized by the following technical scheme:
the structural formula of the high-voltage lithium ion battery electrolyte additive-thiourea ester compound is shown as the formula I:
wherein R is independently selected from C1-C8Acetic acid, sulfonic acid and phosphoric acid containing unsaturated bond, carbonyl group, cyano group and ester group.
Preferably, the thiourea ester compound of the formula I is any one of the following structural formulas:
in another aspect, the present invention provides a method for preparing the above thiourea ester compounds, the method comprising the steps of: (1) placing a solvent, a catalyst and thiourea in a reaction container, gradually dropwise adding an organic acid, and carrying out a polycondensation reaction in an ice-water bath; (2) separating the by-product by a water separator and high-temperature reduced pressure distillation to obtain a crude product of the thiourea ester compound; (3) and extracting the product by using a solvent, recrystallizing, purifying and drying to obtain the thiourea lipid compound.
Preferably, in the above preparation method, the solvent is any one or more of acetonitrile, propionitrile, butyronitrile, 1, 2-dichloroethane, N-Dimethylformamide (DMF), dimethyl sulfoxide, dioxane, and tetrahydrofuran.
Preferably, in the above preparation method, the catalyst is one or more selected from N, N-Dicyclohexylcarbodiimide (DCC), N-Diisopropylcarbodiimide (DIC), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), 2- (7-benzotriazole oxide) -N, N-tetramethylurea Hexafluorophosphate (HATU), 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI), and 1-Hydroxybenzotriazole (HOBT).
Preferably, in the preparation method, the catalyst used in the step 1 is 1-10% of the substrate.
Preferably, in the above preparation method, the reaction temperature in the step 1 is 0 to 30 ℃.
Preferably, in the above production method, the organic acid in the step 1 is acrylic acid, 2-butenoic acid, 2-methyl-3-butenoic acid, 4-pentenoic acid, 3-methyl-2-pentenoic acid, 2, 3-dimethyl-2-pentenoic acid, (S) -2-hydroxy-2-pentenoic acid, strawberry acid, 2-methylpentenoic acid, 2-hydroxy-4-pentenoic acid, 2-cyano-3-ethyl-2-pentenoic acid, 2-difluoro-4-pentenoic acid, 1-butene-1-isopropylcarboxylic acid, 4-methyl-4-pentenoic acid, 4,5, 5-trifluoro-4-pentenoic acid, methacrylsulfonic acid, methacrylic acid, or methacrylic acid, or methacrylic acid, or a salt, methacrylic acid, or a salt, a salt thereof, or a salt thereof, Any one of propylene sulfonic acid, vinyl sulfonic acid, cis-propenyl sulfonic acid and vinyl phosphoric acid.
Preferably, in the above preparation method, the solvent used for recrystallization is any one or more of methanol, ethanol, acetonitrile, tetrahydrofuran, n-butane, n-pentane, n-hexane, n-heptane, n-octane, diethyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, petroleum ether, anisole, phenetole, benzene, toluene and xylene.
Preferably, in the above preparation method, the drying method in step 3 is vacuum drying, and the drying temperature is 40-70 ℃.
Meanwhile, the invention also provides a high-voltage lithium ion battery electrolyte, which comprises the thiourea ester compound additive or contains the thiourea ester compound additive prepared by the method.
Preferably, in the above production method, the solvent obtained by extraction and recrystallization is recovered, separated by rectification, and reused.
The thiourea ester compound can be used as an additive of high-voltage lithium ion battery electrolyte, can capture oxygen free radicals generated by a positive electrode material under high voltage, and can form an SEI film. The invention has the advantages of easily available raw materials, low cost, simple process, high production efficiency and high product purity, and lays a good foundation for the application of the lithium ion battery electrolyte.
[ detailed description of the invention ]
The present invention will be described in detail with reference to examples, which are provided only for the understanding of the present invention and are not intended to limit the scope of the present invention.
Example 1: writing the reaction equation, the following cases also require
300g of water is put into a 1000mL three-neck flask, then 100g of thiourea and 6g of DCC are put into the flask, a stirrer is put into the flask, nitrogen is introduced into the flask, the three-neck flask is immersed into a water bath kettle at the temperature of 20 ℃, a magnetic stirrer is started, the three-neck flask is fully stirred and reacts for 2 hours, then 198.9g of acrylic acid is dripped into the three-neck flask, and the three-neck flask is fully reacted for 8 hours.
And (2) distilling the reactant at 50 ℃ under reduced pressure to obtain a solid, adding 300g of n-hexane for washing, washing for three times to obtain a white solid, and carrying out vacuum drying at 40 ℃ for 12 hours to obtain 222.7g of thiourea ethyl acrylate, wherein the yield is 92.0%, and the product purity is 99.1%.
Example 2:
adding 300g of ethanol into a 1000mL three-neck flask, then adding 100g of thiourea and 12g of DIC into the three-neck flask, adding a stirrer, introducing nitrogen, immersing the three-neck flask into a water bath kettle at 20 ℃, starting a magnetic stirrer, fully stirring for reaction for 2 hours, then dropwise adding 425.5g of 4,5, 5-trifluoro-4-pentenoic acid, and reacting for 8 hours to fully react.
And (3) carrying out reduced pressure distillation on the reactant at 50 ℃ to obtain a solid, adding 300g of diethyl ether for washing, washing for three times to obtain a white solid, and carrying out vacuum drying at 40 ℃ for 12h to obtain 454.1g of thiourea ethyl trifluoropentenoate, wherein the yield is 95.1% and the product purity is 99.5%.
Example 3:
the method comprises the steps of putting 300g of DMF into a 1000mL three-neck flask, then putting 100g of thiourea and 18g of EDC into the DMF, putting a stirrer into the DMF, introducing nitrogen, immersing the three-neck flask into a water bath kettle at 20 ℃, starting a magnetic stirrer, fully stirring for reaction for 2 hours, then dropwise adding 337.1g of propylene sulfonic acid, and reacting for 8 hours to fully react.
And (2) distilling the reactant at 50 ℃ under reduced pressure to obtain a solid, adding 300g of toluene for washing, washing for three times to obtain a white solid, and performing vacuum drying at 40 ℃ for 12 hours to obtain 382.7g of thiourea propylene sulfonate, wherein the yield is 92.1%, and the product purity is 99.7%.
Example 4:
the method comprises the steps of putting 300g of dimethyl sulfoxide into a 1000mL three-neck flask, then putting 100g of thiourea and 18g of EDC into the three-neck flask, putting a stirrer into the three-neck flask, introducing nitrogen, immersing the three-neck flask into a water bath kettle at the temperature of 20 ℃, starting a magnetic stirrer, fully stirring for reaction for 2 hours, then dropwise adding 298.4g of vinylphosphoric acid, and reacting for 8 hours to fully react.
And (2) distilling the reactant at 50 ℃ under reduced pressure to obtain a solid, adding 300g of methyl ethyl ether for washing, washing for three times to obtain a white solid, and performing vacuum drying at 40 ℃ for 12 hours to obtain 332.0g of thiourea ethylene phosphate, wherein the yield is 94.6%, and the product purity is 99.3%.
The above embodiments are illustrative of the present invention in detail, but it is not intended that the present invention be limited to these examples. It is intended that the present invention shall be covered by the claims and the technology without departing from the technical principle of the present invention, and that the modifications and the changes shall fall within the protective scope of the present invention.
Claims (8)
2. the high-voltage lithium ion battery electrolyte of claim 1, wherein the preparation method of the thiourea ester compound comprises the following steps: placing a solvent, a catalyst and thiourea in a reaction container, gradually dropwise adding an organic acid, and carrying out a polycondensation reaction in an ice-water bath; separating the by-product by a water separator and high-temperature reduced pressure distillation to obtain a crude product of the thiourea ester compound; and (3) extracting the product by adopting a solvent, recrystallizing, purifying and drying to obtain the thiourea lipid compound.
3. The high voltage lithium ion battery electrolyte as claimed in claim 2, wherein the solvent in step (1) is one or more selected from acetonitrile, propionitrile, butyronitrile, 1, 2-dichloroethane, N-Dimethylformamide (DMF), dimethyl sulfoxide, dioxane and tetrahydrofuran.
4. The high voltage lithium ion battery electrolyte as claimed in claim 3, wherein the catalyst in step (1) is any one or more of N, N-Dicyclohexylcarbodiimide (DCC), N, N-Diisopropylcarbodiimide (DIC), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), 2- (7-benzotriazole oxide) -N, N, N, N-tetramethylurea Hexafluorophosphate (HATU), 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI), and 1-Hydroxybenzotriazole (HOBT).
5. The high voltage lithium ion battery electrolyte of claim 2, wherein the amount of the catalyst is 1-10% of the total weight of the substrate; the substrate refers to the total weight of the solvent and thiourea.
6. The high voltage lithium ion battery electrolyte of claim 2, wherein the reaction temperature of step 1 is 0-30 ℃; the drying mode of the step 3 is vacuum drying, and the drying temperature is 40-70 ℃.
7. The high voltage lithium ion battery electrolyte of claim 2, wherein the organic acid of step (1) is acrylic acid, 2-butenoic acid, 2-methyl-3-butenoic acid, 4-pentenoic acid, 3-methyl-2-pentenoic acid, 2, 3-dimethyl-2-pentenoic acid, (S) -2-hydroxy-2-pentenoic acid, strawberry acid, 2-methylpentenoic acid, 2-hydroxy-4-pentenoic acid, 2-difluoro-4-pentenoic acid, 1-butene-1-isopropylcarboxylic acid, 4-methyl-4-pentenoic acid, 4,5, 5-trifluoro-4-pentenoic acid, methacrylic sulfonic acid, acrylic acid, or acrylic acid, or acrylic acid, any one of vinylsulfonic acid, cis-propenyl sulfonic acid and vinylphosphoric acid.
8. The high-voltage lithium ion battery electrolyte as claimed in claim 2, wherein the recrystallization solvent in step 3 is any one or more of methanol, ethanol, acetonitrile, tetrahydrofuran, n-butane, n-pentane, n-hexane, n-heptane, n-octane, diethyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, petroleum ether, anisole, phenetole, benzene, toluene and xylene.
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JP2003208920A (en) * | 2002-01-16 | 2003-07-25 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution and lithium secondary battery using the same |
CN104733785A (en) * | 2013-12-20 | 2015-06-24 | 苏州宝时得电动工具有限公司 | Battery |
CN105153366A (en) * | 2015-09-30 | 2015-12-16 | 杭州方圆塑机股份有限公司 | Preparation method of flame-retardant modified polyvinyl acetate used for expanded polystyrene beads |
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JP2003208920A (en) * | 2002-01-16 | 2003-07-25 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution and lithium secondary battery using the same |
CN104733785A (en) * | 2013-12-20 | 2015-06-24 | 苏州宝时得电动工具有限公司 | Battery |
CN105153366A (en) * | 2015-09-30 | 2015-12-16 | 杭州方圆塑机股份有限公司 | Preparation method of flame-retardant modified polyvinyl acetate used for expanded polystyrene beads |
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基于锌负极的混合水溶液电池的构建及电化学性能研究;吕世强等;《矿冶工程》;20171015(第05期);全文 * |
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