CN105047996A - Lithium ion battery low temperature electrolyte and lithium ion battery - Google Patents
Lithium ion battery low temperature electrolyte and lithium ion battery Download PDFInfo
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- CN105047996A CN105047996A CN201510281787.8A CN201510281787A CN105047996A CN 105047996 A CN105047996 A CN 105047996A CN 201510281787 A CN201510281787 A CN 201510281787A CN 105047996 A CN105047996 A CN 105047996A
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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
- H01M10/0569—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
-
- 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
-
- 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 present invention relates to a lithium ion battery low temperature electrolyte and a lithium ion battery, and belongs to the technical field of lithium ion batteries. The lithium ion battery low temperature electrolyte comprises, by weight, 5-20% of lithium hexafluorophosphate, 0.1-3% of lithium fluoride, 0.2-5% of lithium tetrafluoroborate, 48-94.7% of an electrolyte solvent, 2-5% of vinylene carbonate, 2-10% of ethyl propionate, and 1-5% of ethyl acetate. With the lithium ion battery low temperature electrolyte of the present invention, the charge-discharge performance and the cycle performance of the electrolyte at the low temperature can be improved.
Description
Technical field
The present invention relates to a kind of low temperature electrolytes for Li-ion batteries and lithium ion battery, belong to technical field of lithium ion.
Background technology
Lithium rechargeable battery is since commercialization, and battery performance obtains continuous raising, as energy density, power density, cycle performance, large multiplying power discharging property etc. all achieve significant lifting.Along with the continuous investigation and application of field of lithium ion battery new material and new technology, the fail safe of lithium ion battery have also been obtained great raising.The continuous lifting of performance of lithium ion battery, facilitates lithium ion battery and is widely used in increasing field.But more and more extensive along with lithium ion battery applications scope, it becomes increasingly conspicuous to the problem that the adaptive capacity of applied environment is poor.As poor in lithium ion battery charge-discharge performance at low ambient temperatures, particularly in cold district, winter, temperature was in the environment of subzero more than 30 degree, lithium ion battery almost cannot normally use, cause it to be greatly affected in the use that temperature is lower ground square, its range of application also receives the restriction of region.In order to solve the problem of lithium ion battery low temperature charge-discharge performance difference, when practical application, the method for employing has heating of battery, build constant temperature subenvironment, avoid cold tempera-tures outdoors service time etc.In these methods, the use cost of lithium ion battery all can be made to increase heating of battery or construction isoperibol, avoid low temperature to use the normal use that then can affect battery.
In order to improve the cryogenic property of lithium ion battery, avoid again increasing cost and causing restriction to the use of battery, the battery material that research and development can improve lithium ion battery cryogenic property becomes ideal solution.Wherein, to have raising lithium ion cryogenic property with low temperature electrolytes for Li-ion batteries and the most significantly act on.Publication number is the electrolyte that the Chinese invention patent of CN101017918A discloses a kind of lithium ion battery of energy ultra-low temperature discharge, its electrolyte adopts lithium hexafluoro phosphate, LiBF4 and solvent to form, and solvent comprises ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, dimethoxy-ethane.This electrolyte improves the cryogenic property of lithium ion battery to a certain extent, but its discharge performance under-40 DEG C of low temperature environments is still poor.
Summary of the invention
The object of the present invention is to provide low temperature electrolytes for Li-ion batteries and lithium ion battery that a kind of-40 DEG C of low temperature performances are good.
In order to realize above object, the technical scheme of low temperature electrolytes for Li-ion batteries of the present invention is as follows:
A kind of low temperature electrolytes for Li-ion batteries, be made up of the component of following percentage by weight: the lithium hexafluoro phosphate of 5-20%, the lithium fluoride of 0.1-3%, the LiBF4 of 0.2-5%, the electrolyte solvent of 48-94.7%, the vinylene carbonate of 2-5%, the ethyl propionate of 2-10%, the ethyl acetate of 1-5%.
In the present invention, electrolyte solvent is the electrolyte solvent that this area is commonly used, in order to realize better cryogenic property, electrolyte solvent of the present invention is preferably made up of the component of following percentage by weight: the dimethyl carbonate of 5-30%, the ethylene carbonate of 20-30%, the methyl ethyl carbonate of 15-30%, the dibutyl carbonate of 8-30%.
In order to improve the cryogenic property of electrolyte further, low temperature electrolytes for Li-ion batteries of the present invention can preferably be made up of the component of following percentage by weight: the lithium hexafluoro phosphate of 5-20%, the lithium fluoride of 0.3-1%, the LiBF4 of 0.2-3%, the dimethyl carbonate of 5-30%, the ethylene carbonate of 20-30%, the methyl ethyl carbonate of 15-25%, the dibutyl carbonate of 8-30%, the vinylene carbonate of 2-5%, the ethyl propionate of 2-5%, the ethyl acetate of 1-3.7%.
In order to improve the cryogenic property of electrolyte further, low temperature electrolytes for Li-ion batteries of the present invention can preferably be made up of the component of following percentage by weight: the lithium hexafluoro phosphate of 5-20%, the lithium fluoride of 0.5-1%, the LiBF4 of 0.2-2%, the dimethyl carbonate of 5-30%, the ethylene carbonate of 20-26.5%, the methyl ethyl carbonate of 15-25%, the dibutyl carbonate of 8-30%, the vinylene carbonate of 2-5%, the ethyl propionate of 2%, the ethyl acetate of 1-2%.
In order to improve the cryogenic property of electrolyte further, low temperature electrolytes for Li-ion batteries of the present invention can preferably be made up of the component of following percentage by weight: the lithium hexafluoro phosphate of 12.5-20%, the lithium fluoride of 0.5-1%, the LiBF4 of 1-2%, the dimethyl carbonate of 5-20%, the ethylene carbonate of 20-25%, the methyl ethyl carbonate of 15-18%, the dibutyl carbonate of 15-30%, the vinylene carbonate of 3-5%, the ethyl propionate of 2%, the ethyl acetate of 1-2%.
In order to improve the cryogenic property of electrolyte further, low temperature electrolytes for Li-ion batteries of the present invention can preferably be made up of the component of following percentage by weight: the lithium hexafluoro phosphate of 20%, the lithium fluoride of 1%, the LiBF4 of 1%, the dimethyl carbonate of 5%, the ethylene carbonate of 20%, the methyl ethyl carbonate of 15%, the dibutyl carbonate of 30%, the vinylene carbonate of 5%, the ethyl propionate of 2%, the ethyl acetate of 1%.
The technical scheme of lithium ion battery of the present invention is as follows:
A kind of lithium ion battery, uses above-mentioned low temperature electrolytes for Li-ion batteries.
Low temperature electrolytes for Li-ion batteries of the present invention uses lithium hexafluoro phosphate as electrolytic salt, and with the addition of lithium fluoride, LiBF4, vinylene carbonate, ethyl propionate and ethyl acetate in a solvent, this several material synergy, has increased substantially the cryogenic property of electrolyte.The capability retention of the lithium ion battery that low temperature electrolytes for Li-ion batteries of the present invention obtains at-40 DEG C after 500 circulations, more than 60%, is up to 98%.
Embodiment
Technical scheme of the present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
The low temperature electrolytes for Li-ion batteries of the present embodiment, be made up of the component of following percentage by weight: lithium hexafluoro phosphate 5%, lithium fluoride 0.3%, LiBF4 0.2%, dimethyl carbonate 30%, ethylene carbonate 26.5%, methyl ethyl carbonate 25%, dibutyl carbonate 8%, vinylene carbonate 2%, ethyl propionate 2%, ethyl acetate 1%.
In the glove box being full of argon gas, control moisture <0.1ppm, oxygen content <0.1ppm, by above-mentioned each component proportionally Homogeneous phase mixing namely obtain low temperature electrolytes for Li-ion batteries.
The lithium ion battery of the present embodiment take ternary material as positive pole, Delanium is negative pole, and above-mentioned low temperature electrolytes for Li-ion batteries is injected battery system, adopts prior art to prepare the lithium ion battery that battery capacity is 10Ah, to obtain final product.
Embodiment 2
The low temperature electrolytes for Li-ion batteries of the present embodiment, be made up of the component of following percentage by weight: lithium hexafluoro phosphate 12%, lithium fluoride 0.3%, LiBF4 1%, dimethyl carbonate 30%, ethylene carbonate 20%, methyl ethyl carbonate 15%, dibutyl carbonate 10%, vinylene carbonate 3%, ethyl propionate 5%, ethyl acetate 3.7%.
In the glove box being full of argon gas, control moisture <0.1ppm, oxygen content <0.1ppm, by above-mentioned each component proportionally Homogeneous phase mixing namely obtain low temperature electrolytes for Li-ion batteries.
The lithium ion battery of the present embodiment take ternary material as positive pole, Delanium is negative pole, and above-mentioned low temperature electrolytes for Li-ion batteries is injected battery system, adopts the method identical with embodiment 1 to prepare the lithium ion battery that battery capacity is 10Ah, to obtain final product.
Embodiment 3
The low temperature electrolytes for Li-ion batteries of the present embodiment, be made up of the component of following percentage by weight: lithium hexafluoro phosphate 12.5%, lithium fluoride 0.5%, LiBF4 2%, dimethyl carbonate 20%, ethylene carbonate 25%, methyl ethyl carbonate 18%, dibutyl carbonate 15%, vinylene carbonate 3%, ethyl propionate 2%, ethyl acetate 2%.
In the glove box being full of argon gas, control moisture <0.1ppm, oxygen content <0.1ppm, by above-mentioned each component proportionally Homogeneous phase mixing namely obtain low temperature electrolytes for Li-ion batteries.
The lithium ion battery of the present embodiment take ternary material as positive pole, Delanium is negative pole, and above-mentioned low temperature electrolytes for Li-ion batteries is injected battery system, adopts the method identical with embodiment 1 to prepare the lithium ion battery that battery capacity is 10Ah, to obtain final product.
Embodiment 4
The low temperature electrolytes for Li-ion batteries of the present embodiment, be made up of the component of following percentage by weight: lithium hexafluoro phosphate 5%, lithium fluoride 0.5%, LiBF4 0.2%, dimethyl carbonate 30%, ethylene carbonate 26.5%, methyl ethyl carbonate 25%, dibutyl carbonate 8%, vinylene carbonate 2%, ethyl propionate 2%, ethyl acetate 1%.
In the glove box being full of argon gas, control moisture <0.1ppm, oxygen content <0.1ppm, by above-mentioned each component proportionally Homogeneous phase mixing namely obtain low temperature electrolytes for Li-ion batteries.
The lithium ion battery of the present embodiment take ternary material as positive pole, Delanium is negative pole, and above-mentioned low temperature electrolytes for Li-ion batteries is injected battery system, adopts the method identical with embodiment 1 to prepare the lithium ion battery that battery capacity is 10Ah, to obtain final product.
Embodiment 5
The low temperature electrolytes for Li-ion batteries of the present embodiment, be made up of the component of following percentage by weight: lithium hexafluoro phosphate 15%, lithium fluoride 1%, LiBF4 3%, dimethyl carbonate 10%, ethylene carbonate 30%, methyl ethyl carbonate 15%, dibutyl carbonate 20%, vinylene carbonate 2%, ethyl propionate 2%, ethyl acetate 2%.
In the glove box being full of argon gas, control moisture <0.1ppm, oxygen content <0.1ppm, by above-mentioned each component proportionally Homogeneous phase mixing namely obtain low temperature electrolytes for Li-ion batteries.
The lithium ion battery of the present embodiment take ternary material as positive pole, Delanium is negative pole, and above-mentioned low temperature electrolytes for Li-ion batteries is injected battery system, adopts the method identical with embodiment 1 to prepare the lithium ion battery that battery capacity is 10Ah, to obtain final product.
Embodiment 6
The low temperature electrolytes for Li-ion batteries of the present embodiment, be made up of the component of following percentage by weight: lithium hexafluoro phosphate 20%, lithium fluoride 1%, LiBF4 1%, dimethyl carbonate 5%, ethylene carbonate 20%, methyl ethyl carbonate 15%, dibutyl carbonate 30%, vinylene carbonate 5%, ethyl propionate 2%, ethyl acetate 1%.
In the glove box being full of argon gas, control moisture <0.1ppm, oxygen content <0.1ppm, by above-mentioned each component proportionally Homogeneous phase mixing namely obtain low temperature electrolytes for Li-ion batteries.
The lithium ion battery of the present embodiment take ternary material as positive pole, Delanium is negative pole, and above-mentioned low temperature electrolytes for Li-ion batteries is injected battery system, adopts the method identical with embodiment 1 to prepare the lithium ion battery that battery capacity is 10Ah, to obtain final product.
Embodiment 7
The low temperature electrolytes for Li-ion batteries of the present embodiment, be made up of the component of following percentage by weight: lithium hexafluoro phosphate 20%, lithium fluoride 1%, LiBF4 1%, dimethyl carbonate 5%, ethylene carbonate 20%, methyl ethyl carbonate 15%, propene carbonate 30%, vinylene carbonate 5%, ethyl propionate 2%, ethyl acetate 1%.
In the glove box being full of argon gas, control moisture <0.1ppm, oxygen content <0.1ppm, by above-mentioned each component proportionally Homogeneous phase mixing namely obtain low temperature electrolytes for Li-ion batteries.
The lithium ion battery of the present embodiment take ternary material as positive pole, Delanium is negative pole, and above-mentioned low temperature electrolytes for Li-ion batteries is injected battery system, adopts the method identical with embodiment 1 to prepare the lithium ion battery that battery capacity is 10Ah, to obtain final product.
Embodiment 8
The low temperature electrolytes for Li-ion batteries of the present embodiment, be made up of the component of following percentage by weight: lithium hexafluoro phosphate 10%, lithium fluoride 3%, LiBF4 5%, dimethyl carbonate 5%, ethylene carbonate 20%, methyl ethyl carbonate 30%, dibutyl carbonate 10%, vinylene carbonate 2%, ethyl propionate 10%, ethyl acetate 5%.
In the glove box being full of argon gas, control moisture <0.1ppm, oxygen content <0.1ppm, by above-mentioned each component proportionally Homogeneous phase mixing namely obtain low temperature electrolytes for Li-ion batteries.
The lithium ion battery of the present embodiment take ternary material as positive pole, Delanium is negative pole, and above-mentioned low temperature electrolytes for Li-ion batteries is injected battery system, adopts the method identical with embodiment 1 to prepare the lithium ion battery that battery capacity is 10Ah, to obtain final product.
Embodiment 9
The low temperature electrolytes for Li-ion batteries of the present embodiment, be made up of the component of following percentage by weight: lithium hexafluoro phosphate 14.5%, lithium fluoride 0.7%, LiBF4 1.3%, dimethyl carbonate 14%, ethylene carbonate 22.7%, methyl ethyl carbonate 16%, dibutyl carbonate 23%, vinylene carbonate 4.2%, ethyl propionate 2%, ethyl acetate 1.6%.
In the glove box being full of argon gas, control moisture <0.1ppm, oxygen content <0.1ppm, by above-mentioned each component proportionally Homogeneous phase mixing namely obtain low temperature electrolytes for Li-ion batteries.
The lithium ion battery of the present embodiment take ternary material as positive pole, Delanium is negative pole, and above-mentioned low temperature electrolytes for Li-ion batteries is injected battery system, adopts the method identical with embodiment 1 to prepare the lithium ion battery that battery capacity is 10Ah, to obtain final product.
Each component in embodiment 1-9 and proportioning can see tables 1.
Table 1
Experimental example
The lithium ion battery obtained in embodiment 1-9 is tested according to following testing scheme:
1. probe temperature :-40 DEG C.
2. discharge and recharge system be:
1) 5min is shelved;
2) 333mA constant-current discharge, cut-ff voltage 3.0V;
3) 5min is shelved;
4) 4.5V constant voltage charge 1min;
5) 333mA, 4.2V constant-current constant-voltage charging, cut-off current 200mA;
6) 5min is shelved.
3. cycle-index: 500 times.
Test result is as shown in table 2:
Capability retention at lithium ion battery in table 2 embodiment 1-9-40 DEG C after 500 circulations
As seen from Table 2, the cycle performance of the lithium ion battery using low temperature electrolytes for Li-ion batteries of the present invention to obtain obtains and significantly improves, and the capability retention at-40 DEG C after 500 circulations, more than 60%, is up to 98%.
Claims (7)
1. a low temperature electrolytes for Li-ion batteries, it is characterized in that, be made up of the component of following percentage by weight: the lithium hexafluoro phosphate of 5-20%, the lithium fluoride of 0.1-3%, the LiBF4 of 0.2-5%, the electrolyte solvent of 48-94.7%, the vinylene carbonate of 2-5%, the ethyl propionate of 2-10%, the ethyl acetate of 1-5%.
2. low temperature electrolytes for Li-ion batteries as claimed in claim 1, it is characterized in that, described electrolyte solvent is made up of the component of following percentage by weight: the dimethyl carbonate of 5-30%, the ethylene carbonate of 20-30%, the methyl ethyl carbonate of 15-30%, the dibutyl carbonate of 8-30%.
3. low temperature electrolytes for Li-ion batteries as claimed in claim 2, it is characterized in that, be made up of the component of following percentage by weight: the lithium hexafluoro phosphate of 5-20%, the lithium fluoride of 0.3-1%, the LiBF4 of 0.2-3%, the dimethyl carbonate of 5-30%, the ethylene carbonate of 20-30%, the methyl ethyl carbonate of 15-25%, the dibutyl carbonate of 8-30%, the vinylene carbonate of 2-5%, the ethyl propionate of 2-5%, the ethyl acetate of 1-3.7%.
4. low temperature electrolytes for Li-ion batteries as claimed in claim 3, it is characterized in that, be made up of the component of following percentage by weight: the lithium hexafluoro phosphate of 5-20%, the lithium fluoride of 0.5-1%, the LiBF4 of 0.2-2%, the dimethyl carbonate of 5-30%, the ethylene carbonate of 20-26.5%, the methyl ethyl carbonate of 15-25%, the dibutyl carbonate of 8-30%, the vinylene carbonate of 2-5%, the ethyl propionate of 2%, the ethyl acetate of 1-2%.
5. low temperature electrolytes for Li-ion batteries as claimed in claim 4, it is characterized in that, be made up of the component of following percentage by weight: the lithium hexafluoro phosphate of 12.5-20%, the lithium fluoride of 0.5-1%, the LiBF4 of 1-2%, the dimethyl carbonate of 5-20%, the ethylene carbonate of 20-25%, the methyl ethyl carbonate of 15-18%, the dibutyl carbonate of 15-30%, the vinylene carbonate of 3-5%, the ethyl propionate of 2%, the ethyl acetate of 1-2%.
6. low temperature electrolytes for Li-ion batteries as claimed in claim 5, it is characterized in that, be made up of the component of following percentage by weight: the lithium hexafluoro phosphate of 20%, the lithium fluoride of 1%, the LiBF4 of 1%, the dimethyl carbonate of 5%, the ethylene carbonate of 20%, the methyl ethyl carbonate of 15%, the dibutyl carbonate of 30%, the vinylene carbonate of 5%, the ethyl propionate of 2%, the ethyl acetate of 1%.
7. a lithium ion battery, is characterized in that, uses the low temperature electrolytes for Li-ion batteries in claim 1-6 any one.
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| CN106099193A (en) * | 2016-07-29 | 2016-11-09 | 华蓥友达精密模具制造有限公司 | A kind of low temperature electrolyte for lithium ion battery |
| CN109560324A (en) * | 2018-12-05 | 2019-04-02 | 江西赛特新能源科技有限公司 | A kind of resistance to super-low-temperature lithium-ion cell electrolyte |
| CN109860711A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of low temperature electrolyte for lithium ion battery and application |
| WO2021108995A1 (en) * | 2019-12-03 | 2021-06-10 | 宁德时代新能源科技股份有限公司 | Secondary battery, electrolyte, and device containing secondary battery |
| EP4030524A1 (en) * | 2017-08-10 | 2022-07-20 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte secondary battery |
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| WO2021108995A1 (en) * | 2019-12-03 | 2021-06-10 | 宁德时代新能源科技股份有限公司 | Secondary battery, electrolyte, and device containing secondary battery |
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| JP2022545896A (en) * | 2019-12-03 | 2022-11-01 | 寧徳時代新能源科技股▲分▼有限公司 | Secondary battery, electrolyte and device with secondary battery |
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| CN105047996B (en) | 2017-08-04 |
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