CN111540952A - High-voltage electrolyte for improving high-temperature storage performance of lithium ion battery - Google Patents
High-voltage electrolyte for improving high-temperature storage performance of lithium ion battery Download PDFInfo
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- CN111540952A CN111540952A CN202010396698.9A CN202010396698A CN111540952A CN 111540952 A CN111540952 A CN 111540952A CN 202010396698 A CN202010396698 A CN 202010396698A CN 111540952 A CN111540952 A CN 111540952A
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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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- 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
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- 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
- H01M10/056—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
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
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- 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 discloses a high-voltage electrolyte for improving the high-temperature storage performance of a lithium ion battery, which comprises a composite lithium salt, a composite solvent and a composite additive. By adding the composite additive and the composite lithium salt, the composite additive preferentially forms a stable and compact solid electrolyte layer on the surface of the electrode in the working process, and the reaction on the surface of the electrode is inhibited, so that the working voltage and the thermal stability of the original electrolyte system are improved, and the working voltage is expanded to about 5.0V. The electrolyte can broaden the working voltage of the lithium ion battery, can improve the long-term stability of the operation, and meanwhile, the additive can improve the high-temperature stability, thereby having important application value for improving the capacity of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-voltage electrolyte capable of improving the high-temperature storage performance of a lithium ion battery and improving the working voltage of the lithium ion battery.
Background
Along with the development of electronic products and the application of new energy automobiles, the demand on high-capacity and long-cycle energy storage equipment is higher, and a lithium ion battery is an important secondary battery and is the main development direction of energy storage batteries. However, the capacity of the lithium ion battery at present is difficult to meet the actual demand, and the development of a high-capacity lithium ion battery is urgently needed.
Recent studies have shown that, for example, LiNi0.5Mn1.5O4The capacity of the anode materials can be increased by increasing the working voltage, however, the electrolyte is easily decomposed in the high-voltage working process of the current electrolytic liquid system, so that the long-term stability of the operation is reduced, and the capacity attenuation of the electrolyte under the high-temperature working condition is also a bottleneck limiting the application of the electrolyte.
The invention can improve the long-term stability and high-temperature storage performance of the lithium ion battery in the high-voltage working process by utilizing the composite solvent and the composite additive.
Disclosure of Invention
In order to improve the high-temperature storage performance and the cycling stability of the lithium ion battery under the high-voltage condition, the invention aims to provide the high-voltage electrolyte for improving the high-temperature storage performance of the lithium ion battery.
The purpose of the invention is realized by the following scheme:
a high-voltage electrolyte for improving the high-temperature storage performance of a lithium ion battery comprises a lithium salt, a basic solvent and an additive, wherein,
the base solvent is a composite solvent of propylene carbonate, ethyl methyl carbonate and diethyl carbonate, and the mass ratio of the propylene carbonate to the ethyl methyl carbonate to the diethyl carbonate is 25-35: 45-55: 18-25;
the additive is a composite additive and is a composition comprising fluoroethylene carbonate, ethoxy pentafluorocyclotriphosphazene, dimethyl fluoromethyl phosphate and triphenyl phosphate, wherein the mass ratio of the four is 1: 0.8-1.1: 0.8-1.2: 0.8-1.2, wherein the amount of the additive accounts for 15-25% of the total mass of the solvent;
the lithium salt is a composite lithium salt and is a binary or multi-element combination of lithium hexafluorophosphate and lithium bis (trifluoromethylsulfonyl) imide or lithium bis (fluorosulfonyl) imide, the concentration of the lithium hexafluorophosphate in the composite solvent is 1mol/L, and the mass of the lithium bis (trifluoromethylsulfonyl) imide or lithium bis (fluorosulfonyl) imide in the composite solvent accounts for 10-15 wt%.
On the basis of the scheme, the mixing process of the composite lithium salt, the composite solvent and the composite additive is carried out in the air atmosphere and comprises any one of high-purity nitrogen or high-purity argon inert gas, the water content is less than 10ppm, and the oxygen content is less than 10 ppm.
Based on the scheme, the electrolyte is suitable for the positive electrode active material LiNi0.5Mn1.5O4。
According to the invention, by adding the composite additive and the composite lithium salt, in the working process, the composite additive preferentially forms a stable and compact solid electrolyte layer on the surface of the electrode to inhibit the reaction on the surface of the electrode, so that the working voltage and the thermal stability of the original electrolyte system are improved, and the working voltage is expanded to about 5.0V; the electrolyte can broaden the working voltage of the lithium ion battery, can improve the long-term stability of the work, and meanwhile, the additive can improve the high-temperature stability, thereby having important application value for improving the capacity of the lithium ion battery.
Drawings
FIG. 1 shows the normal temperature cycle performance of the electrolyte of example 1 of the present invention.
Detailed Description
Example 1:
a high-voltage electrolyte for improving the high-temperature storage performance of a lithium ion battery comprises a lithium salt, a basic solvent and an additive, wherein,
the base solvent is a composite solvent of propylene carbonate, ethyl methyl carbonate and diethyl carbonate, and the mass ratio of the base solvent to the composite solvent is 30: 50: 20;
the additive is a composite additive and is a composition comprising fluoroethylene carbonate, ethoxy pentafluorocyclotriphosphazene, dimethyl fluoromethyl phosphate and triphenyl phosphate, wherein the mass ratio of the four is 1: 1: 1: 1, the addition amount accounts for 20 percent of the total mass of the solvent;
the lithium salt is a binary combination of lithium hexafluorophosphate and lithium bis (trifluoromethylsulfonyl) imide, the concentration of the lithium hexafluorophosphate in the composite solvent is 1mol/L, and the mass of the lithium bis (trifluoromethylsulfonyl) imide accounts for 10wt% of the composite solvent.
The mixing process of the lithium salt, the composite solvent and the additive is carried out in the air atmosphere, the inert gas is any one of high-purity nitrogen and high-purity argon, the water content is less than 10ppm, and the oxygen content is less than 10 ppm.
The electrolyte is suitable for the positive active material LiNi0.5Mn1.5O4。
The capacity retention rate of the electrolyte prepared in the embodiment after being stored for 7 days at 45 ℃ is 85%.
Fig. 1 shows the normal temperature cycle performance of the electrolyte in this embodiment 1, and the voltage range of the power-on test is 2.7-5.0V, and it can be seen from the figure that after 100 cycles at normal temperature, the capacity retention rate is above 97%, which illustrates that the electrolyte solution of the present invention can effectively improve the stability of the anode material in the high-voltage working state.
Example 2
A high-voltage electrolyte for improving the high-temperature storage performance of a lithium ion battery is similar to that of the embodiment 1,
the base solvent is a composite solvent of propylene carbonate, ethyl methyl carbonate and diethyl carbonate, and the mass ratio of the base solvent to the composite solvent is 25: 48: 20;
the additive is a composite additive and is a composition comprising fluoroethylene carbonate, ethoxy pentafluorocyclotriphosphazene, dimethyl fluoromethyl phosphate and triphenyl phosphate, wherein the mass ratio of the four is 1: 0.8: 0.8: 0.8, the amount of the additive accounts for 25 percent of the total mass of the solvent;
the lithium salt is binary or multi-element combination of lithium hexafluorophosphate and lithium bis (trifluoromethylsulfonyl) imide or lithium bis (fluorosulfonyl) imide, the concentration of the lithium hexafluorophosphate in the composite solvent is 1mol/L, and the mass of the lithium bis (trifluoromethylsulfonyl) imide or lithium bis (fluorosulfonyl) imide in the composite solvent accounts for 10 wt%.
The mixing process of the lithium salt, the composite solvent and the additive is carried out in the air atmosphere, the inert gas is any one of high-purity nitrogen and high-purity argon, the water content is less than 10ppm, and the oxygen content is less than 10 ppm;
the electrolyte is suitable for the positive active material LiNi0.5Mn1.5O4。
The capacity retention rate of the electrolyte prepared in the embodiment after being stored for 7 days at 45 ℃ is 83%.
Example 3:
a high-voltage electrolyte for improving the high-temperature storage performance of a lithium ion battery is similar to that of the embodiment 1,
the basic solvent is a composite solvent of propylene carbonate, ethyl methyl carbonate and diethyl carbonate, and the mass ratio of the propylene carbonate to the ethyl methyl carbonate to the diethyl carbonate is 35: 55: 25;
the additive is a composition of fluoroethylene carbonate, ethoxy pentafluorocyclotriphosphazene, dimethyl fluoromethylphosphonate and triphenyl phosphate, and the mass ratio of the four is 1: 1.1: 1.1: 1.1, the total mass of the additive accounts for 20 percent of the total mass of the solvent;
the lithium salt is binary or multi-element combination of lithium hexafluorophosphate and lithium bis (trifluoromethylsulfonyl) imide or lithium bis (fluorosulfonyl) imide, the concentration of the lithium hexafluorophosphate in the composite solvent is 1mol/L, and the mass of the lithium bis (trifluoromethylsulfonyl) imide or lithium bis (fluorosulfonyl) imide in the composite solvent accounts for 13 wt%.
The mixing process of the lithium salt, the composite solvent and the additive is carried out in the air atmosphere, the inert gas is any one of high-purity nitrogen and high-purity subspecies, the water content is less than 10ppm, and the oxygen content is less than 10 ppm;
the electrolyte is suitable for the positive active material LiNi0.5Mn1.5O4。
The capacity retention rate of the electrolyte prepared in the embodiment after being stored for 7 days at 45 ℃ is 86.5%.
The embodiments described above are described to facilitate an understanding and appreciation of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications to the present invention based on the disclosure of the present invention within the protection scope of the present invention.
Claims (3)
1. A high-voltage electrolyte for improving the high-temperature storage performance of a lithium ion battery comprises a lithium salt, a basic solvent and an additive,
the base solvent is a composite solvent of propylene carbonate, ethyl methyl carbonate and diethyl carbonate, and the mass ratio of the propylene carbonate to the ethyl methyl carbonate to the diethyl carbonate is 25-35: 45-55: 18-25;
the additive is a composite additive and is a composition comprising fluoroethylene carbonate, ethoxy pentafluorocyclotriphosphazene, dimethyl fluoromethyl phosphate and triphenyl phosphate, wherein the mass ratio of the four is 1: 0.8-1.1: 0.8-1.2: 0.8-1.2, wherein the amount of the additive accounts for 15-25% of the total mass of the solvent;
the lithium salt is a composite lithium salt and is a binary or multi-element combination of lithium hexafluorophosphate and lithium bis (trifluoromethylsulfonyl) imide or lithium bis (fluorosulfonyl) imide, the concentration of the lithium hexafluorophosphate in the composite solvent is 1mol/L, and the mass of the lithium bis (trifluoromethylsulfonyl) imide or lithium bis (fluorosulfonyl) imide in the composite solvent accounts for 10-15 wt%.
2. The high-voltage electrolyte for improving the high-temperature storage performance of the lithium ion battery according to claim 1, wherein: the mixing process of the composite lithium salt, the composite solvent and the composite additive is carried out in the air atmosphere and comprises any one of high-purity nitrogen or high-purity argon inert gas, the water content is less than 10ppm, and the oxygen content is less than 10 ppm.
3. The high-voltage electrolyte for improving the high-temperature storage performance of the lithium ion battery according to claim 1, wherein: the electrolyte is suitable for the positive active material LiNi0.5Mn1.5O4。
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| US20130122379A1 (en) * | 2011-11-16 | 2013-05-16 | National Taiwan University Of Science And Technology | Lithium-ion battery and method for fabricating the same |
| WO2014114068A1 (en) * | 2013-01-28 | 2014-07-31 | 华为技术有限公司 | Non-aqueous organic electrolyte, preparation method therefor and lithium ion secondary battery |
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| CN109546219A (en) * | 2018-12-19 | 2019-03-29 | 珠海光宇电池有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery using the electrolyte |
| CN109671982A (en) * | 2018-12-25 | 2019-04-23 | 河南电池研究院有限公司 | A kind of high-temperature lithium ion battery high safety electrolyte matching silicon-carbon cathode material |
| WO2019139041A1 (en) * | 2018-01-10 | 2019-07-18 | マツダ株式会社 | Electrolyte solution for lithium ion secondary battery, and lithium ion secondary battery |
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2020
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Patent Citations (9)
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| CN105576282A (en) * | 2011-02-10 | 2016-05-11 | 三菱化学株式会社 | Non-aqueous electrolyte solution and non-aqueous electrolyte secondary battery employing the same |
| US20130122379A1 (en) * | 2011-11-16 | 2013-05-16 | National Taiwan University Of Science And Technology | Lithium-ion battery and method for fabricating the same |
| WO2014114068A1 (en) * | 2013-01-28 | 2014-07-31 | 华为技术有限公司 | Non-aqueous organic electrolyte, preparation method therefor and lithium ion secondary battery |
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Application publication date: 20200814 |