CN109980287B - Electrolyte for lithium battery and preparation method thereof - Google Patents
Electrolyte for lithium battery and preparation method thereof Download PDFInfo
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- CN109980287B CN109980287B CN201910268891.1A CN201910268891A CN109980287B CN 109980287 B CN109980287 B CN 109980287B CN 201910268891 A CN201910268891 A CN 201910268891A CN 109980287 B CN109980287 B CN 109980287B
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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
- 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
- H01M10/0569—Liquid materials characterised by the solvents
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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
- H01M2300/0028—Organic electrolyte characterised by the solvent
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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 belongs to the technical field of lithium batteries, and particularly relates to an electrolyte for a lithium battery and a preparation method thereof. The obtained electrolyte has low melting point, is not easy to volatilize, is chemically stable and has a larger electrochemical window.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to an electrolyte for a lithium battery and a preparation method thereof.
Background
With the increasing demand to create new clean and sustainable energy sources to replace traditional fossil fuels, lithium ion batteries have attracted much attention as one of the most promising energy storage devices. Lithium batteries generally consist of a positive electrode, a negative electrode and an electrolyte. Wherein, the positive electrode comprises lithium cobaltate and a plurality of additive components, and the additive components are coated on the aluminum foil to generate charge-discharge chemical reaction; the negative electrode is a nano-scale carbon powder such as graphite, and these materials are used by being coated on a copper foil. The electrolyte in the electrolyte usually comprises lithium perchlorate, lithium hexafluorophosphate and the like, but the battery prepared by taking the lithium perchlorate as the raw material has poor low-temperature effect and has explosion danger; the battery made of the lithium salt containing fluorine has good performance, no explosion danger and strong applicability, and particularly the battery made of the lithium hexafluorophosphate has the advantages that the treatment work of the discarded battery in the future is relatively simple and is eco-friendly, so the electrolyte has very wide market prospect.
Organic carbonate mixtures are currently the most commonly used liquid electrolyte solvent systems for commercial lithium ion batteries. Ethylene carbonate/dimethyl carbonate (EC/DMC) and lithium hexafluorophosphate (LiPF)6) Can be used as a standard solution of a lithium ion battery system. However, the conventional lithium ion battery electrolyte systemHigh flammability and poor low temperature performance of the system are major challenges for large scale applications (e.g., electric vehicles).
Disclosure of Invention
Aiming at the technical problems of the lithium ion battery electrolyte in the prior art, the invention provides the electrolyte for the lithium battery and the preparation method thereof.
The invention provides a lithium battery electrolyte, which consists of a lithium salt and a symmetrical star-shaped organic solvent synthesized by the invention based on a borate amino ether ligand, wherein the mass ratio of the lithium salt to the organic solvent is 1: 2.5-3.5;
the structural formula of the symmetrical star organic solvent based on the borate amino ether ligand is as follows:
the specific preparation method of the electrolyte for the lithium battery is as follows:
(1) preparation of symmetrical star organic solvents based on borate aminoether ligands
Dissolving boric acid and 2-dimethylaminoethanol in an organic solvent according to a molar ratio in a dean-Stark device, placing the solution in a 250ml round-bottom flask, and heating the solution under reflux for one day; removing all volatile matters in the obtained liquid in a rotary evaporator and high vacuum distillation, and obtaining pure transparent organic liquid after passing through an alumina column;
the specific procedure for preparing symmetrical star organic solvents based on borate aminoether ligands is shown in the following equation.
(2) Preparation of the electrolyte
And (2) dissolving lithium bistrifluoromethanesulfonylimide (LiTFSI) in the product solvent in the step (1) to obtain the electrolyte for the lithium battery.
Wherein the molar ratio of the boric acid and the 2-dimethylaminoethanol in the step (1) is 1: 3.2-4.0; the organic solvent is toluene, xylene or cyclohexane, and the dosage of the organic solvent is 100-170 ml.
A polypropylene separator (Celgard corporation model 2400) was immersed in the electrolyte of the present invention, and the immersed separator was used as a liquid electrolyte.
Has the advantages that:
aiming at the problems that the existing electrolyte is easy to be flammable and easy to relapse, has poor low-temperature performance and the like, the symmetric star-shaped solvent based on the borate amino ether ligand is used for replacing the existing lithium battery ethylene carbonate/dimethyl carbonate (EC/DMC) mixed solvent to obtain the electrolyte with the concentration of 1 mol of lithium bistrifluoromethanesulfonylimide (LiTFSI), and the electrolyte obtained by the method has the following characteristics: low melting point, difficult volatilization, chemical stability and large electrochemical window. The ionic conductivity can reach 1.18mS/cm at 25 ℃, and is relative to Li+Electrochemical stability of up to 3.9V/Li. In addition, the electrolyte exhibits an excellent low freezing point (-80 ℃), which means that it can provide excellent low temperature performance.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
(1) Boric acid and 2-dimethylaminoethanol were dissolved in a molar ratio of 1:3.2 in 150ml toluene under a dean-Stark apparatus and placed in a 250ml round bottom flask and heated under reflux for one day. All volatiles were removed from the resulting liquid in a rotary evaporator and high vacuum distillation. A clear transparent organic liquid was obtained after passing through the alumina column based on a symmetric star organic solvent of borate aminoether ligand. The yield was 97%.
(2) 1 g of lithium bistrifluoromethanesulfonylimide (LiTFSI) was dissolved in 2.5 g of the above-mentioned product (boron compound) solvent to prepare a liquid electrolyte solution.
The polypropylene separator is immersed in an electrolyte solution, and the immersed separator may be used as a liquid electrolyte.
The solidifying point of the pure boron compound solvent is-80.9 ℃, and the solidifying point of the electrolyte is-84.0 ℃.
The ionic conductivity can reach 0.43mS/cm at 25 ℃.
With respect to Li+Electrochemical stability of up to 3.9V/Li.
Example 2
(1) Boric acid and 2-dimethylaminoethanol were dissolved in a molar ratio of 1:3.2 in 100ml xylene under a dean-Stark apparatus and placed in a 250ml round bottom flask and heated under reflux for one day. All volatiles were removed from the resulting liquid in a rotary evaporator and high vacuum distillation. A clear transparent organic liquid was obtained after passing through the alumina column based on a symmetric star organic solvent of borate aminoether ligand. The yield was 97%.
(2) 1 g of lithium bistrifluoromethanesulfonylimide (LiTFSI) was dissolved in 2.9 g of the above-mentioned product (boron compound) solvent to prepare a liquid electrolyte solution.
The polypropylene separator is immersed in an electrolyte solution, and the immersed separator may be used as a liquid electrolyte.
The solidifying point of the pure boron compound solvent is-80.9 ℃, and the solidifying point of the electrolyte is-84.0 ℃.
The ionic conductivity can reach 0.72mS/cm at 25 ℃.
With respect to Li+Electrochemical stability of up to 3.9V/Li.
Example 3
(1) Boric acid and 2-dimethylaminoethanol were dissolved in a molar ratio of 1:3.2 in 170ml toluene under a dean-Stark apparatus and placed in a 250ml round bottom flask and heated under reflux for one day. All volatiles were removed from the resulting liquid in a rotary evaporator and high vacuum distillation. A clear transparent organic liquid was obtained after passing through the alumina column based on a symmetric star organic solvent of borate aminoether ligand. The yield was 97%.
(2) 1 g of lithium bistrifluoromethanesulfonylimide (LiTFSI) was dissolved in 3.5 g of the above-mentioned product (boron compound) solvent to prepare a liquid electrolyte solution.
The polypropylene separator is immersed in an electrolyte solution, and the immersed separator may be used as a liquid electrolyte.
The solidifying point of the pure boron compound solvent is-80.9 ℃, and the solidifying point of the electrolyte is-83.2 ℃.
The ionic conductivity can reach 1.18mS/cm at 25 ℃.
With respect to Li+Electrochemical stability of up to 3.9V/Li.
Example 4
(1) Boric acid and 2-dimethylaminoethanol were dissolved in a molar ratio of 1:3.6 in 150ml cyclohexane under a dean-Stark apparatus and placed in a 250ml round bottom flask and heated under reflux for one day. All volatiles were removed from the resulting liquid in a rotary evaporator and high vacuum distillation. A pure, transparent organic liquid was obtained after passing through the alumina column, based on a symmetrical star organic solvent of borate aminoether ligand, in a yield of 97%.
(2) 1 g of lithium bistrifluoromethanesulfonylimide (LiTFSI) was dissolved in 3.5 g of the above-mentioned product (boron compound) solvent to prepare a liquid electrolyte solution.
The polypropylene separator is immersed in an electrolyte solution, and the immersed separator may be used as a liquid electrolyte.
The separator is immersed in an electrolyte solution, and the immersed separator may be used as a liquid electrolyte.
The solidifying point of the pure boron compound solvent is-80.9 ℃, and the solidifying point of the electrolyte is-83.2 ℃.
The ionic conductivity can reach 1.18mS/cm at 25 ℃.
With respect to Li+Electrochemical stability of up to 3.9V/Li.
Example 5
(1) Boric acid and 2-dimethylaminoethanol were dissolved in a molar ratio of 1:4.0 in 150ml toluene under a dean-Stark apparatus and placed in a 250ml round bottom flask and heated under reflux for one day. All volatiles were removed from the resulting liquid in a rotary evaporator and high vacuum distillation. A clear transparent organic liquid was obtained after passing through the alumina column based on a symmetric star organic solvent of borate aminoether ligand. The yield was 97%.
(2) 1 g of lithium bistrifluoromethanesulfonylimide (LiTFSI) was dissolved in 3.5 g of the above-mentioned product (boron compound) solvent to prepare a liquid electrolyte solution.
The separator is immersed in an electrolyte solution, and the immersed separator may be used as a liquid electrolyte.
The solidifying point of the pure boron compound solvent is-80.9 ℃, and the solidifying point of the electrolyte is-83.2 ℃.
The ionic conductivity can reach 1.18mS/cm at 25 ℃.
With respect to Li+Electrochemical stability of up to 3.9V/Li.
Claims (5)
1. An electrolyte for a lithium battery, characterized in that: the electrolyte consists of a lithium salt and a symmetrical star-shaped organic solvent based on a borate amino ether ligand, wherein the mass ratio of the lithium salt to the organic solvent is 1: 2.5-3.5; the structural formula of the symmetrical star organic solvent based on the borate amino ether ligand is as follows:
2. a method of preparing the electrolyte for a lithium battery as claimed in claim 1, wherein: the preparation method comprises the following specific steps:
(1) preparation of symmetrical star organic solvents based on borate aminoether ligands
Dissolving boric acid and 2-dimethylaminoethanol in an organic solvent according to a molar ratio in a dean-Stark device, placing the solution in a 250ml round-bottom flask, and heating the solution under reflux for one day; removing all volatile matters in the obtained liquid in a rotary evaporator and high vacuum distillation, and obtaining pure transparent organic liquid after passing through an alumina column;
(2) preparation of the electrolyte
And (2) dissolving lithium bistrifluoromethanesulfonylimide (LiTFSI) in the product solvent in the step (1) to obtain the electrolyte for the lithium battery.
3. The method of preparing an electrolyte for a lithium battery as claimed in claim 2, wherein: the molar ratio of the boric acid to the 2-dimethylaminoethanol in the step (1) is 1: 3.2-4.0.
4. The method of preparing an electrolyte for a lithium battery as claimed in claim 2, wherein: the organic solvent in the step (1) is toluene, xylene or cyclohexane, and the dosage of the organic solvent is 100-170 ml.
5. Use of an electrolyte for a lithium battery according to claim 1, characterized in that: a polypropylene separator was immersed in the electrolyte, and the immersed separator was used as a liquid electrolyte.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4187959B2 (en) * | 2001-10-24 | 2008-11-26 | 三井化学株式会社 | Non-aqueous electrolyte and secondary battery using the same |
| CN102074736A (en) * | 2010-06-07 | 2011-05-25 | 中国科学院广州能源研究所 | Organic silicon amine electrolyte material containing polyether chain and application thereof in lithium battery electrolyte |
| CN103346351A (en) * | 2013-06-28 | 2013-10-09 | 国家电网公司 | Novel borate solvent for lithium-ion secondary battery |
| JP2017168375A (en) * | 2016-03-17 | 2017-09-21 | 株式会社Ｇｓユアサ | Nonaqueous electrolyte solution for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and method for manufacturing nonaqueous electrolyte secondary battery |
| CN107666007A (en) * | 2016-07-29 | 2018-02-06 | 比亚迪股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8334268D0 (en) * | 1983-12-22 | 1984-02-01 | Turner New Technology Ltd John | Surface coating compositions |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4187959B2 (en) * | 2001-10-24 | 2008-11-26 | 三井化学株式会社 | Non-aqueous electrolyte and secondary battery using the same |
| CN102074736A (en) * | 2010-06-07 | 2011-05-25 | 中国科学院广州能源研究所 | Organic silicon amine electrolyte material containing polyether chain and application thereof in lithium battery electrolyte |
| CN103346351A (en) * | 2013-06-28 | 2013-10-09 | 国家电网公司 | Novel borate solvent for lithium-ion secondary battery |
| JP2017168375A (en) * | 2016-03-17 | 2017-09-21 | 株式会社Ｇｓユアサ | Nonaqueous electrolyte solution for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and method for manufacturing nonaqueous electrolyte secondary battery |
| CN107666007A (en) * | 2016-07-29 | 2018-02-06 | 比亚迪股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery |
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