CN116987059A - Method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte - Google Patents
Method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte Download PDFInfo
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- CN116987059A CN116987059A CN202311004910.2A CN202311004910A CN116987059A CN 116987059 A CN116987059 A CN 116987059A CN 202311004910 A CN202311004910 A CN 202311004910A CN 116987059 A CN116987059 A CN 116987059A
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- sulfolane
- container
- fluorine
- fluorinated
- electrolyte
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 title claims abstract description 46
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 38
- 239000011737 fluorine Substances 0.000 title claims abstract description 38
- 239000003792 electrolyte Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 fluoro compound Chemical class 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 150000003457 sulfones Chemical class 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
- C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen 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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- 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)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
The invention discloses a method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte. The sulfolane additive is fluorinated by fluorine gas to form fluoro compound with high potential, the fluoro compound is fluorinated with high purity fluorine in special equipment to form fluorinated sulfolane, and the product is washed with alcohol and pure water to eliminate reaction anions and free radicals and is dried in a vacuum furnace to dewater. The method is suitable for organic/inorganic synthesis, is simple and easy to operate, has the byproduct of water being environment-friendly, and can be widely popularized and used in industry. The pre-lithiated binder prepared by the invention can be used for preparing the field of high-capacity batteries.
Description
Technical Field
The invention belongs to the field of organic electrodeless composite materials, and particularly relates to a method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte.
Background
Lithium ion batteries are effective energy storage devices, and the development of high-voltage lithium ion batteries is limited by oxidative decomposition of common lithium ion battery electrolytes at high voltages. Through developing the novel high-pressure resistant electrolyte, the electrolyte can show the advantages of strong cycling stability, high conductivity, good compatibility of the electrode surface and the like under the high-pressure condition. The performance and stability of the high-voltage electrolyte of the lithium battery have important influence on the performance and life of the lithium battery,
the sulfone electrolyte has low cost and electrochemical window over 5V, and is potential lithium cell high-voltage electrolyte, and has the disadvantages of high melting point, solid state at room temperature and poor compatibility with positive electrode. To solve these problems, the present invention uses sulfones and carbonates as co-solvents, which are stable at high voltages.
Disclosure of Invention
The invention discloses a method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte. The sulfolane additive is fluorinated by fluorine gas to form fluoro compound with high potential, the fluoro compound is fluorinated with high purity fluorine in special equipment to form fluorinated sulfolane, and the product is washed with alcohol and pure water to eliminate reaction anions and free radicals and is dried in a vacuum furnace to dewater.
A method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte comprises the steps of preparing solvent molecule fluorinated sulfolane in synthetic fluorinated electrolyte, and is characterized in that:
(1) Weighing a proper amount of sulfolane, pouring into a polytetrafluoroethylene container, placing the container in a high-pressure reaction container, and introducing fluorine reaction gas into the container for 0.5-2 hours
(2) Washing the reaction product with hot pure water and alcohol to remove anions and part of water;
(3) Stopping heating and standing, removing precipitate, and vacuum dehydrating to remove free fluorine;
(4) Half cell preparation: adding 80% of powder, uniformly stirring to form slurry lithium nickel manganese oxide serving as a raw material, adding 10% of binder, stirring to form transparent liquid, and adding 10% of conductive agent acetylene black;
(5) Coating the mixture on the surface of a copper electrode, drying, then installing buttons, and adding a mixture of common electrode liquid and fluorinated sulfolane.
The method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte is characterized by comprising the following steps of: the ratio of epoxy sulfone to fluorine gas in the step (2) is 1:0.1-0.6.
The method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte is characterized by comprising the following steps of: conventional electrode solutions described in step (4): fluorinated epoxy sulfone = 1:0.02-0.05.
Detailed Description
Example 1
A method for improving electrical performance by adding fluorine functionalized sulfolane into lithium battery electrolyte comprises the following steps:
(1) Weighing 2g of sulfolane, pouring into a polytetrafluoroethylene container, placing the container into a high-pressure reaction container, introducing 0.2g of fluorine reaction gas into the container, and reacting for 0.5 hours;
(2) Washing the reaction product with hot pure water and alcohol to remove anions and part of water;
(3) Stopping heating and standing, removing precipitate, and vacuum dehydrating to remove free fluorine to obtain fluorinated sulfolane;
(4) Half cell preparation: adding 80% of powder, uniformly stirring to form slurry lithium nickel manganese oxide serving as a raw material, adding 10% of binder, stirring to form transparent liquid, and adding 10% of conductive agent acetylene black;
(5) Coating the copper electrode surface, drying, then installing buttons, and adding a mixture of 0.02g of common electrolyte and 0.004g of fluorinated sulfolane; a high specific energy battery was obtained, and the resulting battery voltage was 4.7V.
The addition of the fluorinated sulfolane in the common electrolyte improves the voltage performance of the battery, and the battery is coated on the surface of a copper electrode, and the multiplying power is still more than 85% at 3 ℃. .
Example 2
A method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte comprises the following steps:
(1) Weighing 2g of sulfolane, pouring into a polytetrafluoroethylene container, placing the container into a high-pressure reaction container, introducing 1.2g of fluorine reaction gas into the container, and reacting for 2 hours;
(2) Washing the reaction product with hot pure water and alcohol to remove anions and part of water;
(3) Stopping heating and standing, removing precipitate, and vacuum dehydrating to remove free fluorine to obtain fluorinated sulfolane;
(4) Half cell preparation: adding 80% of powder, uniformly stirring to form slurry lithium nickel manganese oxide serving as a raw material, adding 10% of binder, stirring to form transparent liquid, and adding 10% of conductive agent acetylene black;
(5) Coating the mixture on the surface of a copper electrode, drying, then installing a button, adding a mixture of 0.02g of common electrode liquid and 0.01g of fluorinated sulfolane, drying, then installing the button to obtain a high specific energy battery, wherein the obtained battery voltage is 4.72V.
Example 3
A method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte comprises the following steps:
(1) Weighing 2g of sulfolane, pouring into a polytetrafluoroethylene container, placing the container into a high-pressure reaction container, and introducing 1.2g of fluorine reaction gas into the container for 1 hour;
(2) Washing the reaction product with hot pure water and alcohol to remove anions and part of water;
(3) Stopping heating and standing, removing precipitate, and vacuum dehydrating to remove free fluorine to obtain fluorinated sulfolane;
half cell preparation: adding 80% of lithium nickel manganese oxide as a raw material, uniformly stirring to form slurry, adding 10% of binder, stirring to form transparent liquid, and adding 10% of conductive agent acetylene black to obtain the conductive material; is coated on the surface of a copper electrode, dried and then is provided with buttons, and a mixture of 0.02g of common electrolyte and 0.005g of fluorinated sulfolane is added. After drying, buttons are arranged to obtain a high specific energy battery, and the obtained battery voltage is 4.68V.
Claims (5)
1. A method for improving voltage performance by adding fluorine functionalized sulfolane to lithium battery electrolyte, comprising the steps of: synthesizing solvent molecules in the fluorinated electrolyte to fluorinate sulfolane,
(1) Weighing sulfolane, pouring into a polytetrafluoroethylene container, placing the container into a high-pressure reaction container, and introducing fluorine reaction gas into the container, wherein the mass ratio of epoxy sulfone to fluorine gas is 1:0.1-0.6, reacting for 0.5-2 hours;
(2) Washing the reaction product with hot pure water and alcohol to remove anions and part of water;
(3) Stopping heating and standing, removing precipitate, and vacuum dehydrating to remove free fluorine to obtain fluorinated sulfolane;
(4) Half cell preparation: adding 80% of powder, uniformly stirring to form slurry lithium nickel manganese oxide serving as a raw material, adding 10% of binder, stirring to form transparent liquid, and adding 10% of conductive agent acetylene black;
(5) Coating the mixture on the surface of a copper electrode, drying, then installing buttons, and adding a mixture of common electrode liquid and fluorinated sulfolane.
2. A method of adding fluorine functionalized sulfolane to a lithium battery electrolyte to improve voltage performance according to claim 1, wherein: in the step (5), the mass ratio of the conventional electrode liquid to the fluorinated epoxy sulfone=1: 0.02-0.05.
3. A method for improving voltage performance by adding fluorine functionalized sulfolane to a lithium battery electrolyte according to claims 1 and 2, wherein: the method comprises the following steps:
(1) Weighing 2g of sulfolane, pouring into a polytetrafluoroethylene container, placing the container into a high-pressure reaction container, introducing 0.2g of fluorine reaction gas into the container, and reacting for 0.5 hours;
(2) Washing the reaction product with hot pure water and alcohol to remove anions and part of water;
(3) Stopping heating and standing, removing precipitate, and vacuum dehydrating to remove free fluorine to obtain fluorinated sulfolane;
(4) Half cell preparation: adding 80% of powder, uniformly stirring to form slurry lithium nickel manganese oxide serving as a raw material, adding 10% of binder, stirring to form transparent liquid, and adding 10% of conductive agent acetylene black;
(5) Coating the copper electrode surface, drying, then installing buttons, and adding a mixture of 0.02g of common electrolyte and 0.004g of fluorinated sulfolane; a high specific energy battery was obtained, and the resulting battery voltage was 4.7V.
4. A method for improving voltage performance by adding fluorine functionalized sulfolane to a lithium battery electrolyte according to claims 1 and 2, wherein: the method comprises the following steps:
(1) Weighing 2g of sulfolane, pouring into a polytetrafluoroethylene container, placing the container into a high-pressure reaction container, introducing 1.2g of fluorine reaction gas into the container, and reacting for 2 hours;
(2) Washing the reaction product with hot pure water and alcohol to remove anions and part of water;
(3) Stopping heating and standing, removing precipitate, and vacuum dehydrating to remove free fluorine to obtain fluorinated sulfolane;
(4) Half cell preparation: adding 80% of powder, uniformly stirring to form slurry lithium nickel manganese oxide serving as a raw material, adding 10% of binder, stirring to form transparent liquid, and adding 10% of conductive agent acetylene black;
(5) Coating the mixture on the surface of a copper electrode, drying, then installing a button, adding a mixture of 0.02g of common electrode liquid and 0.01g of fluorinated sulfolane, drying, then installing the button to obtain a high specific energy battery, wherein the obtained battery voltage is 4.72V.
5. A method for improving voltage performance by adding fluorine functionalized sulfolane to a lithium battery electrolyte according to claims 1 and 2, wherein: the method comprises the following steps:
(1) Weighing 2g of sulfolane, pouring into a polytetrafluoroethylene container, placing the container into a high-pressure reaction container, and introducing 1.2g of fluorine reaction gas into the container for 1 hour;
(2) Washing the reaction product with hot pure water and alcohol to remove anions and part of water;
(3) Stopping heating and standing, removing precipitate, and vacuum dehydrating to remove free fluorine to obtain fluorinated sulfolane;
half cell preparation: adding 80% of lithium nickel manganese oxide as a raw material, uniformly stirring to form slurry, adding 10% of binder, stirring to form transparent liquid, and adding 10% of conductive agent acetylene black to obtain the conductive material; coating the electrolyte on the surface of a copper electrode, drying, then installing a button, adding a mixture of 0.02g of common electrolyte and 0.005g of fluorinated sulfolane, drying, then installing the button to obtain a high specific energy battery, and obtaining a battery voltage of 4.68V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311004910.2A CN116987059A (en) | 2023-08-10 | 2023-08-10 | Method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311004910.2A CN116987059A (en) | 2023-08-10 | 2023-08-10 | Method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116987059A true CN116987059A (en) | 2023-11-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311004910.2A Pending CN116987059A (en) | 2023-08-10 | 2023-08-10 | Method for improving voltage performance by adding fluorine functionalized sulfolane into lithium battery electrolyte |
Country Status (1)
| Country | Link |
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| CN (1) | CN116987059A (en) |
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2023
- 2023-08-10 CN CN202311004910.2A patent/CN116987059A/en active Pending
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