CN111063933A - Lithium ion battery electrolyte suitable for high-voltage system - Google Patents
Lithium ion battery electrolyte suitable for high-voltage system Download PDFInfo
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- CN111063933A CN111063933A CN201911268280.3A CN201911268280A CN111063933A CN 111063933 A CN111063933 A CN 111063933A CN 201911268280 A CN201911268280 A CN 201911268280A CN 111063933 A CN111063933 A CN 111063933A
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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
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M10/05—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
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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
Abstract
The utility model provides a lithium ion battery electrolyte that is suitable for high voltage system, belongs to lithium ion battery technical field, solves the electrolyte of high voltage system battery and is oxidized decomposition under higher voltage, and positive pole metal ion dissolves out under the high temperature condition and leads to the battery capacity decay too fast, the technical problem of cycle life variation. The solution is as follows: the electrolyte consists of an organic solvent, electrolyte lithium salt and a functional additive; the weight of the organic solvent accounts for 60-90% of the total weight of the electrolyte, the weight of the electrolyte lithium salt accounts for 10-20% of the total weight of the electrolyte, the weight of the functional additive accounts for 5-20% of the total weight of the electrolyte, and the sum of the weight percentages of the organic solvent, the electrolyte lithium salt and the functional additive is 100%; the functional additives are SEI film forming additives and positive electrode protection additives. The electrolyte disclosed by the invention meets the long cycle performance of a high-voltage system battery and also gives consideration to high and low temperature performances through the optimized combination of the solvent, the lithium salt and the additive.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte applicable to a high-voltage system.
Background
At present, lithium ion batteries are widely applied to the field of electric automobiles due to the points of long cycle life, high energy density and the like. With the development of electric vehicles, the current demands for power ion batteries are: high specific energy, long circulation and excellent high and low temperature performance. The purpose of improving the energy density of the battery can be achieved by improving the working voltage of the battery, so that the high-voltage system lithium ion battery becomes a development trend.
In recent years, LiNi0.5Mn1.5O4、Li1.2Ni0.2Mn0.6O2High-voltage materials such as lithium-rich materials and the like are widely researched and hopefully applied to lithium ion batteries in batches, and the anode materials have a high-voltage platform of more than 4.5V. The electrolyte used commercially at present is mainly carbonate solvent, and the oxidation decomposition of the electrolyte begins at a voltage of about 4.5V, so that the capacity of the battery is decayed too fast, and the cycle performance is deteriorated. In addition, the high-voltage material generally has the phenomenon that positive metal ions are dissolved out, and particularly, the positive metal ions are more seriously dissolved out under the high-temperature condition of the battery, so that the capacity attenuation of the battery is aggravated, and the cycle performance and the high-temperature performance are poor.
Disclosure of Invention
The invention of the invention is: in order to overcome the defects of the prior art and solve the technical problems that the capacity of the high-voltage system lithium ion battery is too fast attenuated and the cycle life is poor due to the fact that the electrolyte of the high-voltage system lithium ion battery is oxidized and decomposed under high voltage and positive metal ions are dissolved out under the high-temperature condition, the invention provides the electrolyte which meets the requirement of the long service life of the high-voltage system lithium ion battery and also considers the high-temperature and low-temperature performances.
The design concept of the invention is as follows: the key point of inhibiting the decomposition of the electrolyte is to select a proper solvent to improve the oxidative decomposition potential of the electrolyte. The key to solve the problem of dissolving out the metal ions of the anode is to form a stable protective film on the surface of the anode by using an anode protective additive to separate the anode from the electrolyte. The mixed use of multiple lithium salts makes up the functional defect of single lithium salt and improves the comprehensive performance of the battery. The high and low temperature performance of the battery is mainly optimized by diversification and different proportions of solvents.
The invention is realized by the following technical scheme.
The lithium ion battery electrolyte applicable to the high-voltage system is characterized in that: the electrolyte consists of an organic solvent, electrolyte lithium salt and a functional additive; the weight of the organic solvent accounts for 60-90% of the total weight of the electrolyte, the weight of the electrolyte lithium salt accounts for 10-20% of the total weight of the electrolyte, the weight of the functional additive accounts for 5-20% of the total weight of the electrolyte, and the sum of the weight percentages of the organic solvent, the electrolyte lithium salt and the functional additive is 100%.
Further, the organic solvent is a carbonate organic solvent, a carboxylic acid organic solvent or a fluoro organic solvent.
Further, the carbonate organic solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
Further, the carboxylic acid organic solvent is one or more of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, gamma-butyrolactone, gamma-valerolactone, delta-valerolactone and epsilon-caprolactone.
Further, the fluorinated organic solvent is one or more of fluoromethyl-substituted ethylene carbonate, perfluorobutyl-substituted ethylene carbonate, perfluorohexyl-substituted ethylene carbonate and perfluorooctyl-substituted ethylene carbonate.
Further, the electrolyte lithium salt is one or more of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium difluorophosphate and lithium difluorooxalato borate.
Further, the functional additive comprises an SEI film forming additive and an anode protecting additive, wherein the weight of the SEI film forming additive accounts for 3% -10% of the total weight of the electrolyte, and the weight of the anode protecting additive accounts for 5% -10% of the total weight of the electrolyte.
Further, the SEI film forming additive is one or more of vinylene carbonate, vinyl sulfate, methylene methanedisulfonate, vinyl ethylene carbonate and 1, 3-propane sultone.
Further, the positive electrode protection additive is one or more of tris (trimethylsilyl) borate, tris (trimethylsilyl) phosphate, succinonitrile, adiponitrile and hexanetrinitrile. The tri (trimethylsilyl) borate and the tri (trimethylsilyl) phosphate can form a stable protective film on the surface of the high-voltage positive electrode material, so that the electrolyte is isolated from the positive electrode material, and the oxidative decomposition of the positive electrode on the electrolyte is inhibited; succinonitrile, adiponitrile and hexanetrinitrile can carry out complex reaction with a high-voltage positive electrode material, and the precipitation of metal ions of the positive electrode is inhibited, so that the performance of the battery is improved.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through the optimized combination of the solvent, the lithium salt and the additive, the mixed use of multiple lithium salts is adopted, so that the functional defects of a single lithium salt are made up, and the comprehensive performance of the battery is improved; the fluorinated solvent is adopted, so that the oxidative decomposition potential of the electrolyte is improved; the carboxylate solvent is adopted to improve the conductivity of the electrolyte and improve the low-temperature performance; the SEI film forming additive is adopted, so that the protection of the negative electrode is enhanced, and the cycle performance is improved; the anode protection additive is adopted, a protective film is formed on the surface of the high-voltage anode, the electrolyte is separated from the anode, and the oxidative decomposition of the electrolyte is inhibited.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Mixing an organic solvent: ethylene carbonate, fluoroethylene carbonate, fluoromethyl-substituted ethylene carbonate, propyl propionate, lithium salt: lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, SEI film forming additive: vinylene carbonate, positive electrode protection additive: the tri (trimethylsilyl) borate and the succinonitrile are uniformly mixed according to the proportion to obtain the electrolyte suitable for the high-voltage system battery. Wherein the mass ratio of the ethylene carbonate to the fluoroethylene carbonate to the fluoromethyl-substituted ethylene carbonate to the propyl propionate is 2:2:3: 3; the molar concentration of lithium hexafluorophosphate is 0.8mol/L, and the molar concentration of lithium bis (fluorosulfonyl) imide is 0.2 mol/L; the SEI film forming additive vinylene carbonate accounts for 3% of the total mass of the electrolyte; positive electrode protective additive: the tris (trimethylsilyl) borate accounts for 3% of the total weight of the electrolyte, and the succinonitrile accounts for 3% of the total weight of the electrolyte.
Example 2
Mixing an organic solvent: propylene carbonate, fluoroethylene carbonate, perfluorobutyl-substituted ethylene carbonate, ethyl propionate, lithium salt: lithium hexafluorophosphate, lithium tetrafluoroborate, SEI film forming additive: vinyl ethylene carbonate, 1, 3-Propane Sultone (PS), positive electrode protective additive: the tris (trimethylsilyl) phosphate and the adiponitrile are uniformly mixed according to the proportion to obtain the electrolyte suitable for the high-voltage system battery. Wherein the mass ratio of the propylene carbonate to the fluoroethylene carbonate to the perfluorobutyl-substituted ethylene carbonate to the ethyl propionate is 3:1:4: 2; the molar concentration of lithium hexafluorophosphate is 1.0mol/L, and the molar concentration of lithium tetrafluoroborate is 0.2 mol/L; the SEI film forming additive is vinyl vinylene carbonate accounting for 2% of the total mass of the electrolyte, and the 1, 3-propane sultone accounting for 2% of the total mass of the electrolyte; positive electrode protective additive: the tris (trimethylsilyl) phosphate accounts for 3% of the total weight of the electrolyte, and the succinonitrile accounts for 2% of the total weight of the electrolyte.
Example 3
Mixing an organic solvent: propylene carbonate, perfluorohexyl-substituted ethylene carbonate, perfluorooctyl-substituted ethylene carbonate, γ -butyrolactone, lithium salt: lithium hexafluorophosphate, lithium difluorooxalato borate, SEI film forming additive: ethylene carbonate, methylene methanedisulfonate, positive electrode protective additive: the tri (trimethylsilyl) borate and hexanetricarbonitrile are uniformly mixed according to the proportion to obtain the electrolyte suitable for the high-voltage system battery. Wherein the mass ratio of the propylene carbonate, the perfluorohexyl-substituted ethylene carbonate, the perfluorooctyl-substituted ethylene carbonate and the gamma-butyrolactone is 3:2:2: 3; the molar concentration of lithium hexafluorophosphate is 1.1mol/L, and the molar concentration of lithium difluorooxalato borate is 0.3 mol/L; the SEI film-forming additive vinylene carbonate accounts for 2% of the total mass of the electrolyte, and the methylene methanedisulfonate accounts for 3% of the total mass of the electrolyte; positive electrode protective additive: the tris (trimethylsilyl) borate accounts for 4% of the total mass of the electrolyte, and the hexanetricarbonitrile accounts for 3% of the total mass of the electrolyte.
The electrolyte prepared according to the above embodiment is used in a 4.7V high-voltage system battery, and the test results of 300-cycle performance, battery capacity retention rate after 7 days of high-temperature storage at 60 ℃ and-20 ℃ discharge retention rate are shown in table 1 as follows:
as can be seen from table 1, the electrolyte of the present invention can effectively maintain the battery capacity in the high voltage system battery, and can also achieve the high and low temperature performance of the battery.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. The lithium ion battery electrolyte applicable to the high-voltage system is characterized in that: the electrolyte consists of an organic solvent, electrolyte lithium salt and a functional additive; the weight of the organic solvent accounts for 60-90% of the total weight of the electrolyte, the weight of the electrolyte lithium salt accounts for 10-20% of the total weight of the electrolyte, the weight of the functional additive accounts for 5-20% of the total weight of the electrolyte, and the sum of the weight percentages of the organic solvent, the electrolyte lithium salt and the functional additive is 100%.
2. The lithium ion battery electrolyte applicable to a high voltage system according to claim 1, wherein: the organic solvent is a carbonate organic solvent, a carboxylic acid organic solvent or a fluoro organic solvent.
3. The lithium ion battery electrolyte applicable to a high voltage system according to claim 2, wherein: the carbonate organic solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
4. The lithium ion battery electrolyte applicable to a high voltage system according to claim 2, wherein: and one or more of carboxylic acid organic solvents such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, gamma-butyrolactone, gamma-valerolactone, delta-valerolactone and epsilon-caprolactone.
5. The lithium ion battery electrolyte applicable to a high voltage system according to claim 2, wherein: the fluorinated organic solvent is one or more of fluoromethyl-substituted ethylene carbonate, perfluorobutyl-substituted ethylene carbonate, perfluorohexyl-substituted ethylene carbonate and perfluorooctyl-substituted ethylene carbonate.
6. The lithium ion battery electrolyte applicable to a high voltage system according to claim 1, wherein: the electrolyte lithium salt is one or more of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium difluorophosphate and lithium difluorooxalato borate.
7. The lithium ion battery electrolyte applicable to a high voltage system according to claim 1, wherein: the functional additive comprises an SEI film forming additive and an anode protecting additive, wherein the weight of the SEI film forming additive accounts for 3-10% of the total weight of the electrolyte, and the weight of the anode protecting additive accounts for 5-10% of the total weight of the electrolyte.
8. The lithium ion battery electrolyte applicable to a high voltage system according to claim 7, wherein: the SEI film forming additive is one or more of vinylene carbonate, vinyl sulfate, methylene methanedisulfonate, vinyl ethylene carbonate and 1, 3-propane sultone.
9. The lithium ion battery electrolyte applicable to a high voltage system according to claim 7, wherein: the positive electrode protection additive is one or more of tri (trimethylsilyl) borate, tri (trimethylsilyl) phosphate, succinonitrile, adiponitrile and hexanetrinitrile.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117832626A (en) * | 2024-03-06 | 2024-04-05 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device, and electronic apparatus |
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