CN111261924B - Lithium battery electrolyte and lithium battery - Google Patents
Lithium battery electrolyte and lithium battery Download PDFInfo
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- CN111261924B CN111261924B CN201811465572.1A CN201811465572A CN111261924B CN 111261924 B CN111261924 B CN 111261924B CN 201811465572 A CN201811465572 A CN 201811465572A CN 111261924 B CN111261924 B CN 111261924B
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- carbonate
- lithium battery
- additive
- electrolyte
- battery 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
- H01M10/056—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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- 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
Abstract
The invention relates to a lithium battery electrolyte, which comprises a lithium salt, an organic solvent and a functional additive, wherein the functional additive comprises a first additive accounting for 0.1-10% of the total mass of the lithium battery electrolyte, a second additive accounting for 0.1-2% of the total mass of the lithium battery electrolyte and a third additive accounting for 0.1-3% of the total mass of the lithium battery electrolyte, the first additive is fluorinated cyclic carbonate and/or fluorinated ether, the second additive is a silane compound, and the third additive is a nitrile compound. In the lithium ion battery with the high-nickel anode material matched with the silicon cathode, the coordination of the fluorinated cyclic carbonate, the fluoroether, the silane and the nitrile in the non-aqueous electrolyte improves the initial capacity, inhibits the increase of internal resistance, and improves the normal-temperature cycle performance and the high-temperature gas expansion.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a lithium battery electrolyte and a lithium battery.
Background
At present, lithium ion batteries are widely used in the fields of digital products, electric automobiles and the like, and people put higher requirements on the energy density of the lithium ion batteries. A power battery system with high nickel ternary matched with a silicon cathode is an important direction for the development of the lithium ion battery at present. The method is generally adopted at present by selecting a high-nickel ternary positive electrode material and a silicon negative electrode material to improve the energy density of the power battery and prolong the endurance mileage.
However, as the content of nickel increases, the Ni of the positive electrode material increases and the battery performance decreases: the oxidation reduction peak polarization is increased, the volume shrinkage, the capacity attenuation and the cycle performance deterioration are caused by the structural transformation; the discharge voltage is reduced along with the circulation, the Ni content is increased, and the internal resistance is also increased; the thermal decomposition temperature is reduced, the heat release is increased, and the thermal stability of the material is deteriorated; ni4+High content of Ni4+Has strong reduction tendency and is easy to generate Ni4+—Ni3+Thereby oxidizing the electrolyte, so that thermal stability is deteriorated; in a large proportion of Ni2+Resulting in oxidation of the material and thus electricityThe electrode material can slowly decompose liquid electrolyte, and safety problems such as battery gas expansion, overcharge and the like are more prominent. Meanwhile, the silicon cathode has huge volume deformation, poor electronic conductivity and ionic conductivity in the charging and discharging processes and is easy to pulverize in the charging and discharging processes; this affects the use of high nickel matched silicon power cells.
Disclosure of Invention
The invention aims to provide a lithium battery electrolyte and a lithium battery, which can improve the initial capacity of the battery, inhibit the increase of internal resistance and improve the normal-temperature cycle performance and high-temperature ballooning.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention aims to provide a lithium battery electrolyte, which comprises a lithium salt, an organic solvent and a functional additive, wherein the functional additive comprises a first additive accounting for 0.1-10% of the total mass of the lithium battery electrolyte, a second additive accounting for 0.1-2% of the total mass of the lithium battery electrolyte and a third additive accounting for 0.1-3% of the total mass of the lithium battery electrolyte, the first additive is fluorinated cyclic carbonate and/or fluorinated ether, the second additive is a silane compound, and the third additive is a nitrile compound.
Preferably, the fluorinated cyclic carbonate is fluoroethylene carbonate and/or difluoroethylene carbonate.
Preferably, the fluoroether is one or more of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, hexafluoropropyl methyl ether, hexafluoropropyl ethyl ether and hexafluoroisopropyl methyl ether.
Preferably, the silane compound is one or more of tris (trimethylsilane) phosphate, tris (trimethylsilane) borate, tris (trimethylsilane) phosphite, diphenyldifluorosilane and diphenyldimethoxysilane.
Preferably, the nitrile compound is one or more of succinonitrile, adiponitrile, 1, 4-dicyano-2-butene and hexanetrinitrile.
Preferably, the first additive is the fluorinated cyclic carbonate and the fluorinated ether in a mass ratio of 0.5-0.7: 1.
Preferably, the feeding mass of the first additive accounts for 3-8% of the total mass of the lithium battery electrolyte.
Preferably, the feeding mass of the second additive accounts for 0.5-1.5% of the total mass of the lithium battery electrolyte.
Preferably, the feeding mass of the third additive accounts for 1.5-2.5% of the total mass of the lithium battery electrolyte.
Preferably, the lithium salt is LiClO4、LiPF6、LiAsF6、LiSO3F、LiCF3SO3The molar concentration of the lithium salt in the lithium battery electrolyte is 0.001-2 mol/L.
Preferably, the organic solvent is a carbonate organic solvent and/or an ether organic solvent.
Further preferably, the carbonate organic solvent is one or a combination of several of cyclic carbonate compounds and/or one or a combination of several of chain carbonate compounds;
the cyclic carbonate compound is one or a combination of more of ethylene carbonate, propylene carbonate, gamma-butyrolactone and butylene carbonate;
the chain carbonate compound is one or a combination of more of dimethyl carbonate, diethyl carbonate, dipropyl carbonate and methyl ethyl carbonate;
the ether organic solvent is one or a combination of more of tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane and diglyme.
According to a preferred embodiment, the organic solvent is a mixed solvent of diethyl carbonate, ethylene carbonate and ethyl methyl carbonate in a mass ratio of 1: 1.2-1.4: 0.9-1.1.
The invention also aims to provide a lithium battery, which comprises a positive electrode, a negative electrode and the electrolyte, wherein the electrolyte is the electrolyte of the lithium battery.
Preferably, the positive electrode is a high nickel material LiNi1-x-yCoxMyO2Wherein x is more than or equal to 0 and less than or equal to 0.4, y is more than or equal to 0 and less than or equal to 0.4, x + y is more than or equal to 0.6 and less than or equal to 1, and M is transition metal.
Preferably, the negative electrode material is a mixture of one or more selected from silicon, silicon monoxide and silicon carbon composite materials.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
in the lithium ion battery with the high-nickel anode material matched with the silicon cathode, the coordination of the fluorinated cyclic carbonate, the fluoroether, the silane and the nitrile in the non-aqueous electrolyte improves the initial capacity, inhibits the increase of internal resistance, and improves the normal-temperature cycle performance and the high-temperature gas expansion.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples. In this specification, "%" represents mass% unless otherwise specified.
Examples 1 to 8
Electrolyte solution: the lithium salt is lithium hexafluorophosphate, the molar concentration of the lithium salt is 1 mol/L, the solvent is diethyl carbonate, ethylene carbonate and methyl ethyl carbonate, and the mass ratio of the diethyl carbonate to the ethylene carbonate to the methyl ethyl carbonate is 30: 40: 30, of a nitrogen-containing gas; other components and amounts of the electrolyte are shown in table 1.
Negative electrode: Si-O-C negative electrode, positive electrode: the NCM811 material is characterized in that an electrolyte, a positive electrode and a negative electrode are assembled into a lithium battery according to a conventional process, and the capacity percentage and the internal resistance of the lithium battery prepared in each embodiment are tested after 1C charge-discharge cycle for 300 times at normal temperature; the lithium batteries prepared in the examples were also tested for swelling after being left at a high temperature of 85 ℃ for 4 hours, and the results are shown in table 1.
TABLE 1
Note: FEC is fluoroethylene carbonate; HFE is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether; TMSP is tris (trimethylsilane) phosphate; AN is adiponitrile.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (6)
1. The lithium battery electrolyte consists of lithium salt, organic solvent and functional additive, and is characterized in that: the functional additive comprises a first additive accounting for 0.1-10% of the total mass of the lithium battery electrolyte, a second additive accounting for 0.1-2% of the total mass of the lithium battery electrolyte and a third additive accounting for 0.1-3% of the total mass of the lithium battery electrolyte, wherein the first additive is fluorinated cyclic carbonate and fluorinated ether, the second additive is a silane compound, and the third additive is a nitrile compound;
the fluorinated cyclic carbonate is fluoroethylene carbonate and/or difluoroethylene carbonate;
the fluoroether is one or more of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, hexafluoropropyl methyl ether, hexafluoropropyl ethyl ether and hexafluoroisopropyl methyl ether;
the silane compound is one or more of tris (trimethylsilane) phosphate, tris (trimethylsilane) borate, tris (trimethylsilane) phosphite, diphenyldifluorosilane and diphenyldimethoxysilane;
the nitrile compound is one or more of succinonitrile, adiponitrile, 1, 4-dicyano-2-butene and hexanetrinitrile;
the lithium salt is LiClO4、LiPF6、LiAsF6、LiSO3F、LiCF3SO3One or a combination of several of them;
the organic solvent is a carbonate organic solvent and/or an ether organic solvent; the carbonate organic solvent is one or a combination of more of cyclic carbonate compounds and/or one or a combination of more of chain carbonate compounds;
the cyclic carbonate compound is one or a combination of more of ethylene carbonate, propylene carbonate, gamma-butyrolactone and butylene carbonate;
the chain carbonate compound is one or a combination of more of dimethyl carbonate, diethyl carbonate, dipropyl carbonate and methyl ethyl carbonate;
the ether organic solvent is one or a combination of more of tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane and diglyme.
2. A lithium battery electrolyte as claimed in claim 1, characterized in that: the first additive is the fluorinated cyclic carbonate and the fluorinated ether in a mass ratio of 0.5-0.7: 1.
3. A lithium battery electrolyte as claimed in claim 1, characterized in that: the molar concentration of the lithium salt in the lithium battery electrolyte is 0.001-2 mol/L.
4. A lithium battery comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that: the electrolyte is the lithium battery electrolyte as claimed in any one of claims 1 to 3.
5. A lithium battery as claimed in claim 4, characterized in that: the positive electrode is made of high nickel material LiNi1-x-yCoxMyO2Wherein x is more than or equal to 0 and less than or equal to 0.4, y is more than or equal to 0 and less than or equal to 0.4, x + y is more than or equal to 0.6 and less than or equal to 1, and M is transition metal.
6. A lithium battery as claimed in claim 4, characterized in that: the negative electrode material is a mixture consisting of one or more of silicon, silicon monoxide and silicon-carbon composite materials.
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| CN201811465572.1A CN111261924B (en) | 2018-12-03 | 2018-12-03 | Lithium battery electrolyte and lithium battery |
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| CN201811465572.1A CN111261924B (en) | 2018-12-03 | 2018-12-03 | Lithium battery electrolyte and lithium battery |
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| CN111261924A CN111261924A (en) | 2020-06-09 |
| CN111261924B true CN111261924B (en) | 2021-09-14 |
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| CN103354297A (en) * | 2013-06-21 | 2013-10-16 | 珠海市赛纬电子材料有限公司 | Non-water electrolyte of high voltage lithium ion battery and preparation method thereof |
| CN103401020B (en) * | 2013-08-08 | 2015-11-04 | 东莞市杉杉电池材料有限公司 | A kind of high-voltage lithium-ion battery electrolyte |
| CN105098237A (en) * | 2014-05-20 | 2015-11-25 | 浙江省化工研究院有限公司 | High-voltage electrolyte additive and application thereof |
| CN104900916A (en) * | 2015-06-26 | 2015-09-09 | 广州天赐高新材料股份有限公司 | Electrolyte solution for high-capacity lithium-ion battery, preparation method and lithium-ion battery |
| CN105355970B (en) * | 2015-12-16 | 2018-01-12 | 东莞市杉杉电池材料有限公司 | A kind of tertiary cathode material lithium-ion battery electrolytes and tertiary cathode material lithium ion battery |
| CN105428701B (en) * | 2015-12-21 | 2018-02-09 | 东莞新能源科技有限公司 | A kind of electrolyte and the lithium ion battery including the electrolyte |
| CN105703007A (en) * | 2016-03-30 | 2016-06-22 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte for high-voltage rapid-charging type lithium ion battery |
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