CN112886059A - Lithium ion battery electrolyte containing imidazole compound - Google Patents
Lithium ion battery electrolyte containing imidazole compound Download PDFInfo
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- CN112886059A CN112886059A CN201911205142.0A CN201911205142A CN112886059A CN 112886059 A CN112886059 A CN 112886059A CN 201911205142 A CN201911205142 A CN 201911205142A CN 112886059 A CN112886059 A CN 112886059A
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- electrolyte
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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
- H01M10/0567—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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or 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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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The electrolyte comprises, by mass, 80-90% of 2-propyne-1-yl 1H-imidazole-1-carboxylate and 10-20% of 4-cyano-2-fluoropyridine, wherein the additive accounts for less than 3% of the mass of the battery electrolyte, and the addition amount of the additive is not 0. The electrolyte can inhibit defects caused in the battery, remove generated acid, inhibit lithium salt decomposition, and improve the high-low temperature cycle performance and the service life of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium battery electrolytes, and relates to a lithium ion battery electrolyte containing an imidazole compound. The electrolyte solution of the present invention can suppress defects caused inside the battery, remove generated acid, and suppress decomposition of lithium salt.
Background
The lithium battery has the characteristics of high performance, low self-discharge rate, factory storage life, environmental friendliness and the like, and is widely applied to the fields of instruments and meters, memory power supplies, military, oil drilling and the like. However, the capacity and the load voltage are greatly deviated from the normal discharge during high and low temperature discharge, which affects the use of the lithium battery.
The electrolyte is an important component of the battery, plays a role in transmitting ions between a positive electrode and a negative electrode through the inside of the battery, and has important influence on the capacity, the working temperature range, the cycle performance, the safety performance and the like of the battery. The electrolyte is generally divided into a liquid electrolyte and a solid electrolyte, the liquid organic electrolyte is the most commonly used electrolyte, but with the continuous widening of the application range of the battery, the requirements of people on various aspects of the battery are continuously increased, the original electrolyte system can not meet the use requirements, the performance of the battery is improved by researching the electrolyte additive, and the method is the most direct and better mode at present.
Disclosure of Invention
The invention aims to provide an imidazole compound-containing lithium ion battery electrolyte, which can inhibit defects caused in a battery, remove generated acid, and inhibit lithium salt decomposition, thereby improving the high-low temperature cycle performance and the service life of the battery.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the electrolyte of the lithium ion battery containing the imidazole compound comprises, by mass, 80-90% of 2-propyne-1-yl 1H-imidazole-1-carboxylate and 10-20% of 4-cyano-2-fluoropyridine, and the additive accounts for less than 3% of the mass of the battery electrolyte and is not 0.
The organic solvent comprises cyclic carbonate, chain carbonate or a combination of the cyclic carbonate and the chain carbonate.
The lithium salt is inorganic anionic electrolyte lithium salt, or organic anionic electrolyte lithium salt, or the combination of inorganic anionic electrolyte lithium salt and organic anionic electrolyte lithium salt.
The concentration of the lithium salt in the organic solvent is 1.0-1.1 mol/L.
The invention has the beneficial effects that:
the electrolyte can inhibit defects caused in the battery, remove generated acid, inhibit lithium salt decomposition, and improve the high-low temperature cycle performance and the service life of the battery.
Detailed Description
The present invention will be further described with reference to the following examples.
Detailed description of the preferred embodiments
The organic solvent can be selected from one or any combination of the following: ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, fluoroethylene carbonate, methylethyl carbonate, bis (trifluoromethanol) carbonate.
The lithium salt can be selected from one or any combination of the following: LiPF6、LiBF4、LiSO3CF3、LiClO4、LiN(CF3SO2)2、LiC(CF3SO2)3、Li(CF3SO2)N2。
Example 1
An imidazole compound-containing lithium ion battery electrolyte comprises an organic solvent composed of propylene carbonate, dimethyl carbonate and fluoroethylene carbonate in a volume ratio of 5:2: 3; LiPF with organic solvent concentration of 1mol/L6A lithium salt; the additive accounts for 1% of the mass of the battery electrolyte and consists of 80% of 2-propyne-1-yl 1H-imidazole-1-carboxylic ester and 20% of 4-cyano-2-fluoropyridine.
Example 2
An imidazole compound-containing lithium ion battery electrolyte comprises an organic solvent composed of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate in a volume ratio of 4:2: 4; LiPF accounting for 1.1mol/L of organic solvent6A lithium salt; the additive accounts for 2 percent of the mass of the battery electrolyte, and consists of 85 percent of 2-propyleneAlkyne-1-yl 1H-imidazole-1-carboxylate and 15% by mass of 4-cyano-2-fluoropyridine.
Example 3
An imidazole compound-containing lithium ion battery electrolyte comprises an organic solvent composed of diethyl carbonate and propylene carbonate in a volume ratio of 6: 4; LiPF accounting for 1.1mol/L of organic solvent6A lithium salt; the additive accounts for 2.5 percent of the mass of the battery electrolyte and consists of 90 percent of 2-propyne-1-yl 1H-imidazole-1-carboxylic ester and 10 percent of 4-cyano-2-fluoropyridine.
Example 4
An imidazole compound-containing lithium ion battery electrolyte comprises an organic solvent composed of methyl ethyl carbonate, propylene carbonate and diethyl carbonate in a volume ratio of 3:2: 5; LiPF with organic solvent concentration of 1mol/L6A lithium salt; the additive accounts for 0.5 percent of the mass of the battery electrolyte and consists of 83 percent of 2-propyne-1-yl 1H-imidazole-1-carboxylic ester and 17 percent of 4-cyano-2-fluoropyridine.
Example 5
An imidazole compound-containing lithium ion battery electrolyte comprises an organic solvent composed of methyl ethyl carbonate, bis (trifluoromethanol) carbonate and ethylene carbonate in a volume ratio of 3:1: 6; LiPF with organic solvent concentration of 1mol/L6A lithium salt; the additive accounts for 0.25 percent of the mass of the battery electrolyte and consists of 88 percent of 2-propyne-1-yl 1H-imidazole-1-carboxylic ester and 12 percent of 4-cyano-2-fluoropyridine.
Comparative example 1
An imidazole compound-containing lithium ion battery electrolyte comprises an organic solvent composed of propylene carbonate, dimethyl carbonate and fluoroethylene carbonate in a volume ratio of 5:2: 3; LiPF with organic solvent concentration of 1mol/L6A lithium salt; the additive accounts for 1% of the mass of the battery electrolyte, and is 2-propyne-1-yl 1H-imidazole-1-carboxylic ester.
Second, Performance test
1. Preparing a lithium ion battery:
preparing electrolyte: the organic solvent, lithium salt and additive of each example are mixed and stirred, and the whole process is completed in a glove box.
Preparing a positive electrode: LiCoO as positive electrode material2After fully grinding, weighing the positive active material, the acetylene black and the PVDF according to the mass ratio of 8:1: 1. Firstly, dropwise adding a proper amount of NMP to dissolve PVDF powder, and magnetically stirring until the PVDF powder is in a transparent adhesive package; then LiCoO is taken as a positive electrode material2And adding acetylene black, dropwise adding a proper amount of NMP, and continuing to magnetically stir for 10 hours to prepare slurry. And uniformly coating the prepared slurry on an aluminum foil by a film coater to obtain a product with the thickness of about 200 mu m, then carrying out vacuum drying at 120 ℃ for 12h, taking out after the product is cooled to room temperature, and carrying out rolling and cutting to obtain the positive pole piece.
Preparing a negative electrode: mixing styrene butadiene rubber, acetylene black and artificial graphite in a mass ratio of 3:2:95, adding deionized water, stirring and mixing uniformly to obtain a negative electrode material, uniformly coating the negative electrode material on two sides of a copper foil with the thickness of 18 mu m, drying in vacuum at 125 ℃ for 1h, rolling and cutting into pieces to obtain a negative electrode piece.
And welding the obtained positive pole piece and negative pole piece with lugs in a glove box, overlapping and winding the positive pole piece, the diaphragm, the negative pole piece and the diaphragm in the self-damaged sequence to manufacture a square lithium ion battery cell, putting the cell into a square aluminum shell battery, and respectively injecting the electrolyte of the embodiment to prepare the lithium ion battery with the capacity of 600 mAh.
2. Battery cycle performance test
In the experiment, a secondary lithium ion battery performance cabinet BS-9400 is adopted to test the cycle performance parameters of the battery at 45 ℃, and the specific experimental procedures are as follows:
(1) standing for 5 min;
(2) constant current charging at 0.5C, constant voltage charging at 4.3V, and final current of 25 mA;
(3) discharging at 0.5C constant current to 3.0V;
(4) the above steps are circulated 500 times and finished.
The cycle test results are shown in table 1.
TABLE 1
Note: the blank of the present invention refers to the base electrolyte without any additives (referring to example 1, no additives are added).
As can be seen from table 1, the imidazole compound 2-propyn-1-yl 1H-imidazole-1-carboxylate as an additive for battery electrolyte can improve the cycle performance of the battery at high temperature and high pressure, but there is still an improvement. By further matching with 4-cyano-2-fluoropyridine, 80-90% of 2-propyne-1-yl 1H-imidazole-1-carboxylate and 10-20% of 4-cyano-2-fluoropyridine in the additive are controlled, so that the high-temperature and high-pressure cycle performance of the battery can be further improved, and the improvement effect is remarkable.
3. Cyclic voltammetry test
An electrochemical workstation is utilized, graphite is used as a working electrode, a metal lithium sheet is used as an auxiliary electrode and a reference electrode, a three-electrode system is formed, the scanning voltage range is 2.6-4.3V, and the scanning speed is 0.1 mV/S. The difference in the potentials of the oxidation peak and the reduction peak of the electrode is shown in Table 2.
TABLE 2
| Item | Anode peak (V) | Cathode peak (V) | Potential difference value/V |
| Example 1 | 4.05 | 3.64 | 0.41 |
| Example 2 | 4.07 | 3.63 | 0.44 |
| Example 3 | 4.06 | 3.64 | 0.42 |
| Example 4 | 4.07 | 3.66 | 0.41 |
| Example 5 | 4.05 | 3.63 | 0.42 |
| Comparative example | 4.08 | 3.60 | 0.48 |
| Blank space | 4.10 | 3.58 | 0.52 |
As shown in Table 2, the addition of 2-propyn-1-yl 1H-imidazole-1-carboxylate and 4-cyano-2-fluoropyridine can reduce the potential difference between an oxidation peak and a reduction peak, reduce the occurrence of electrode polarization phenomenon and improve the reversibility of the battery, thereby indicating that the battery electrolyte provided by the invention can enable the battery to have good charge and discharge performance.
Claims (4)
1. The electrolyte of the lithium ion battery containing the imidazole compounds comprises lithium salt, an organic solvent and an additive, and is characterized in that the additive comprises 80-90% of 2-propyne-1-yl 1H-imidazole-1-carboxylate and 10-20% of 4-cyano-2-fluoropyridine by mass percent, the additive accounts for less than 3% of the mass of the battery electrolyte, and the addition amount of the additive is not 0.
2. The imidazole compound-containing lithium ion battery electrolyte solution according to claim 1, wherein the organic solvent comprises a cyclic carbonate, a chain carbonate, or a combination of a cyclic carbonate and a chain carbonate.
3. The lithium ion battery electrolyte containing imidazole compounds according to claim 1, wherein the lithium salt is an inorganic anionic electrolyte lithium salt, an organic anionic electrolyte lithium salt, or a combination of an inorganic anionic electrolyte lithium salt and an organic anionic electrolyte lithium salt.
4. The electrolyte of the lithium ion battery containing the imidazole compound according to claim 1, wherein the concentration of the lithium salt in the organic solvent is 1.0 to 1.1 mol/L.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911205142.0A CN112886059A (en) | 2019-11-29 | 2019-11-29 | Lithium ion battery electrolyte containing imidazole compound |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094186A (en) * | 2021-11-22 | 2022-02-25 | 珠海冠宇电池股份有限公司 | Non-aqueous electrolyte and battery comprising same |
| CN115704810A (en) * | 2021-08-16 | 2023-02-17 | 张家港市国泰华荣化工新材料有限公司 | Method for determining content of 2-propyn-1-yl 1H-imidazole-1-carboxylate by high performance liquid chromatography |
-
2019
- 2019-11-29 CN CN201911205142.0A patent/CN112886059A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115704810A (en) * | 2021-08-16 | 2023-02-17 | 张家港市国泰华荣化工新材料有限公司 | Method for determining content of 2-propyn-1-yl 1H-imidazole-1-carboxylate by high performance liquid chromatography |
| CN115704810B (en) * | 2021-08-16 | 2024-01-02 | 张家港市国泰华荣化工新材料有限公司 | Method for measuring content of 2-propyne-1-yl 1H-imidazole-1-carboxylate by high performance liquid chromatography |
| CN114094186A (en) * | 2021-11-22 | 2022-02-25 | 珠海冠宇电池股份有限公司 | Non-aqueous electrolyte and battery comprising same |
| CN114094186B (en) * | 2021-11-22 | 2022-09-09 | 珠海冠宇电池股份有限公司 | Non-aqueous electrolyte and battery comprising same |
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