CN109560324A - A kind of resistance to super-low-temperature lithium-ion cell electrolyte - Google Patents
A kind of resistance to super-low-temperature lithium-ion cell electrolyte Download PDFInfo
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- CN109560324A CN109560324A CN201811478992.3A CN201811478992A CN109560324A CN 109560324 A CN109560324 A CN 109560324A CN 201811478992 A CN201811478992 A CN 201811478992A CN 109560324 A CN109560324 A CN 109560324A
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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
- 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
- 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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- Condensed Matter Physics & Semiconductors (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a kind of resistance to super-low-temperature lithium-ion cell electrolyte, it is made of solute and solvent, the ratio of the solute and solvent is (10-16): 1, the solute is binary system, it is made of lithium hexafluoro phosphate and LiBF4, its mass ratio is (7 ~ 9): 1, the solvent is quaternary system, it is made of ethylene carbonate, ethyl propionate, ethyl acetate and vinylene carbonate, its volume ratio is (25 ~ 30): (30 ~ 35): (30 ~ 35): (1 ~ 3), and the overall density of the electrolyte is 0.9 ~ 1.3mol/L.This case reduces electrolyte fusing point as electrolyte solvent by using ethyl acetate, the fusing point of ethyl acetate is -84 DEG C, electrolyte low-temperature characteristics is greatlyd improve, a small amount of LiBF4 is added in lithium hexafluoro phosphate solute, improves the low-temperature characteristics and security feature of electrolyte.
Description
Technical field
The invention belongs to technical field of lithium-ion battery, and in particular to a kind of resistance to super-low-temperature lithium-ion cell electrolysis
Liquid.
Background technique
Lithium ion battery was widely recognized by people in recent years, and had also obtained preferable application, in particular with
The fast development of new-energy automobile, there has also been quick raising and progress for lithium ion battery technology.However, lithium ion battery is poor
Low-temperature characteristics, seriously constrain its development.For the northern area of China, the cryogenic property of lithium ion battery
Promotion is more particularly important.Influence many because being known as of lithium battery cryogenic property, type, electrolysis including positive and negative electrode material
The component of liquid, manufacturing process etc..Wherein electrolyte is the most important factor for influencing lithium battery cryogenic property, this is because low temperature
When electrolyte viscosity become larger, ion and electronic conductivity are lower, and the ion-transfer between positive and negative anodes receives limitation, the work of battery
Property reduce.
Summary of the invention
The invention proposes a kind of resistance to super-low-temperature lithium-ion cell electrolyte, by using ethyl acetate as electrolyte
Solvent reduces electrolyte fusing point, and the fusing point of ethyl acetate is -84 DEG C, electrolyte low-temperature characteristics is greatlyd improve, in hexafluorophosphoric acid
A small amount of LiBF4 is added in lithium solute, improves the low-temperature characteristics and security feature of electrolyte, is made of the electrolyte
Lithium battery, the especially lithium battery of tertiary cathode system, low temperature performance well, safety are good.The technical scheme is that in this way
It realizes:
A kind of resistance to super-low-temperature lithium-ion cell electrolyte, is made of solute and solvent, and the ratio of the solute and solvent is
(10-16): 1, the solute is binary system, is made of lithium hexafluoro phosphate and LiBF4, and mass ratio is (7 ~ 9): 1,
The solvent is quaternary system, is made of ethylene carbonate, ethyl propionate, ethyl acetate and vinylene carbonate, volume ratio
For (25 ~ 30): (30 ~ 35): (30 ~ 35): (1 ~ 3), the overall density of the electrolyte are 0.9 ~ 1.3mol/L.
In resistance to super-low-temperature lithium-ion cell electrolyte of the invention, the ethylene carbonate, ethyl propionate, acetic acid second
The volume ratio of ester and vinylene carbonate is 25:35:38:2, and the mass ratio of lithium hexafluoro phosphate and LiBF4 is 8:1, described
The overall density of electrolyte is 1.0mol/L.
In resistance to super-low-temperature lithium-ion cell electrolyte of the invention, the ethylene carbonate, ethyl propionate, acetic acid second
The volume ratio of ester and vinylene carbonate is 30:34:35:1, and the mass ratio of lithium hexafluoro phosphate and LiBF4 is 7:1, described
The overall density of electrolyte is 0.9mol/L.
In resistance to super-low-temperature lithium-ion cell electrolyte of the invention, the ethylene carbonate, ethyl propionate, acetic acid second
The volume ratio of ester and vinylene carbonate is 25:30:34:7, and the mass ratio of lithium hexafluoro phosphate and LiBF4 is 9:1, described
The overall density of electrolyte is 1.3mol/L.
Implement this resistance to super-low-temperature lithium-ion cell electrolyte of the invention, has the advantages that
1, electrolyte fusing point is reduced using ethyl acetate as electrolyte solvent, the fusing point of ethyl acetate is -84 DEG C, is greatly mentioned
High electrolyte low-temperature characteristics.
2, since LiBF4 has the advantages that low temperature performance well, thermal stability are good, add in lithium hexafluoro phosphate solute
Add a small amount of LiBF4 material that the low-temperature characteristics and security feature of electrolyte can be improved；
3, the lithium battery low temperature performance well that is made using low-temperature electrolyte provided by the invention, safety are good, and especially ternary is being just
The lithium battery of polar body system.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below.
In an embodiment of the present invention, ethylene carbonate is clear colorless liquid, is crystalline solid when room temperature, for changing
The industries such as fertilizer, fiber, pharmacy and organic synthesis can be used as the fine solvent of lithium battery electrolytes in battery industry.
In an embodiment of the present invention, ethyl propionate, -73.8 DEG C of fusing point, viscosity (0.502mPa.s), fusing point is low, viscosity
It is low, the viscosity and eutectic point of electrolyte system can be reduced, the migration of lithium ion is conducive to, improves the low temperature properties of lithium ion battery
Energy.
In an embodiment of the present invention, ethyl acetate, 77 DEG C of boiling point, has lower fusing point by -83 DEG C of fusing point, can be right
The cryogenic property of lithium ion battery is significantly improved, moderate boiling point, can satisfy the requirement that battery uses, dielectric constant
Height, viscosity is low, does not influence the performance of the high rate performance of battery.
In an embodiment of the present invention, vinylene carbonate, 60 DEG C of x24h of thermal stability, no significant change is a kind of lithium
The novel organic film for additive of ion and additives for overcharge protection additive, have the function of good high temperature performance and anti-inflatable, can
To improve the capacity and cycle life of battery.
In an embodiment of the present invention, lithium hexafluoro phosphate has good conductivity, can form stable solid electrolyte
Interfacial film (SEI film), the advantages that internal resistance is small and charge/discharge speed is fast are the preferred electrolysis of current lithium-ion battery electrolytes
Matter.
In an embodiment of the present invention, LiBF4 has preferable chemical stability and thermal stability, not to moisture
It is too sensitive, mainly as lithium hexafluoro phosphate base electrolyte system additive, improves cycle life, improve lithium ion battery
Can, and it is also quite outstanding to the passivation ability of aluminium foil, therefore as film additive, it is widely used in current electrolyte,
The operating temperature range that lithium ion battery can also be widened improves the high/low temperature discharge performance of battery.
In an embodiment of the present invention, the electrolyte is made of solute and solvent, and the ratio of the solute and solvent is
(10-16): 1, the solute is binary system, is made of lithium hexafluoro phosphate and LiBF4, and mass ratio is (7 ~ 9): 1,
The solvent is quaternary system, is made of ethylene carbonate, ethyl propionate, ethyl acetate and vinylene carbonate, volume ratio
For (25 ~ 30): (30 ~ 35): (30 ~ 35): (1 ~ 3), the overall density of the electrolyte are 0.9 ~ 1.3mol/L.The electrolyte
Configuration can carry out in glove box, after weighing respectively to the solvent and solute, be placed in container, pass through convention stir, shake
It swings, the modes such as ultrasound are uniformly mixed.
Embodiment 1
By ethylene carbonate, ethyl propionate, ethyl acetate and vinylene carbonate, 25:35:38:2 is mixed by volume, after stirring
Electrolyte solvent is formed, then is dissolved in after the ratio that lithium hexafluoro phosphate and LiBF4 are 8:1 in mass ratio is mixed above-mentioned molten
In agent, in glove box after strong stirring, it can be configured to the low-temperature electrolyte that concentration is 1 .0mol/L, as a result as shown in the table:
| Temperature (DEG C) | Discharge-rate (C) | Capacity retention ratio (%, 25 DEG C opposite) |
| 25 | 0.2 | 100 |
| 0 | 0.2 | 92 |
| -20 | 0.2 | 87 |
| -30 | 0.2 | 80 |
Embodiment 2
By ethylene carbonate, ethyl propionate, ethyl acetate and vinylene carbonate, 30:34:35:1 is mixed by volume, after stirring
Electrolyte solvent is formed, then is dissolved in after the ratio that lithium hexafluoro phosphate and LiBF4 are 7: 1 in mass ratio is mixed above-mentioned molten
In agent, in glove box after strong stirring, it can be configured to the low-temperature electrolyte that concentration is 0.9 mol/L, as a result as shown in the table:
| Temperature (DEG C) | Discharge-rate (C) | Capacity retention ratio (%, 25 DEG C opposite) |
| 25 | 0.2 | 100 |
| 0 | 0.2 | 90 |
| -20 | 0.2 | 85 |
| -30 | 0.2 | 78 |
Embodiment 3
By ethylene carbonate, ethyl propionate, ethyl acetate and vinylene carbonate, 25:30:34:7 is mixed by volume, after stirring
Electrolyte solvent is formed, then is dissolved in after the ratio that lithium hexafluoro phosphate and LiBF4 are 9:1 in mass ratio is mixed above-mentioned molten
In agent, in glove box after strong stirring, it can be configured to the low-temperature electrolyte that concentration is 1 .3mol/L, as a result as shown in the table:
| Temperature (DEG C) | Discharge-rate (C) | Capacity retention ratio (%, 25 DEG C opposite) |
| 25 | 0.2 | 100 |
| 0 | 0.2 | 94 |
| -20 | 0.2 | 90 |
| -30 | 0.2 | 81 |
The technical scheme of the present invention is realized as follows: a kind of low temperature electrolytes for Li-ion batteries, includes solvent and solute two
Point, solvent is made of ethylene carbonate, ethyl propionate, ethyl acetate and vinylene carbonate, and the volume ratio of four kinds of materials is (25
~ 30): (30 ~ 35): (30 ~ 35): (1 ~ 3)；Solute is made of lithium hexafluoro phosphate and LiBF4, the mass ratioes of two kinds of materials be (7 ~
9): 1；The overall density of electrolyte is the .3mol/L of 0 .9 ~ 1.Specific electrolyte configuration can carry out in glove box, to solvent
It after weighing respectively with solute, is placed in container, is uniformly mixed by modes such as convention stir, concussion, ultrasounds.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle.
Claims (4)
1. a kind of resistance to super-low-temperature lithium-ion cell electrolyte, which is characterized in that be made of solute and solvent, the solute with it is molten
The ratio of agent is (10-16): 1, the solute is binary system, is made of lithium hexafluoro phosphate and LiBF4, mass ratio
For (7 ~ 9): 1, the solvent is quaternary system, by ethylene carbonate, ethyl propionate, ethyl acetate and vinylene carbonate structure
At volume ratio is (25 ~ 30): (30 ~ 35): (30 ~ 35): (1 ~ 3), and the overall density of the electrolyte is 0.9 ~ 1.3mol/
L。
2. resistance to super-low-temperature lithium-ion cell electrolyte according to claim 1, which is characterized in that the ethylene carbonate
Ester, ethyl propionate, ethyl acetate and vinylene carbonate volume ratio be 25:35:38:2, lithium hexafluoro phosphate and LiBF4
Mass ratio be 8:1, the overall density of the electrolyte is 1.0mol/L.
3. resistance to super-low-temperature lithium-ion cell electrolyte according to claim 1, which is characterized in that the ethylene carbonate
Ester, ethyl propionate, ethyl acetate and vinylene carbonate volume ratio be 30:34:35:1, lithium hexafluoro phosphate and LiBF4
Mass ratio be 7:1, the overall density of the electrolyte is 0.9mol/L.
4. resistance to super-low-temperature lithium-ion cell electrolyte according to claim 1, which is characterized in that the ethylene carbonate
Ester, ethyl propionate, ethyl acetate and vinylene carbonate volume ratio be 25:30:34:7, lithium hexafluoro phosphate and LiBF4
Mass ratio be 9:1, the overall density of the electrolyte is 1.3mol/L.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811478992.3A CN109560324A (en) | 2018-12-05 | 2018-12-05 | A kind of resistance to super-low-temperature lithium-ion cell electrolyte |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811478992.3A CN109560324A (en) | 2018-12-05 | 2018-12-05 | A kind of resistance to super-low-temperature lithium-ion cell electrolyte |
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| Publication Number | Publication Date |
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| CN109560324A true CN109560324A (en) | 2019-04-02 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103500850A (en) * | 2013-10-23 | 2014-01-08 | 山东大学 | Low-temperature electrolyte of lithium iron phosphate battery |
| CN105047996A (en) * | 2015-05-28 | 2015-11-11 | 河南省法恩莱特新能源科技有限公司 | Lithium ion battery low temperature electrolyte and lithium ion battery |
| CN105633463A (en) * | 2016-01-08 | 2016-06-01 | 九江迅通新能源科技有限公司 | Lithium-ion secondary battery electrolyte applicable to low-temperature environment discharging |
| CN106169611A (en) * | 2016-09-17 | 2016-11-30 | 复旦大学 | A kind of low-temperature electrolyte with ethyl acetate as solvent |
| CN107171023A (en) * | 2017-05-17 | 2017-09-15 | 中国第汽车股份有限公司 | A kind of low temperature electrolytes for Li-ion batteries |
-
2018
- 2018-12-05 CN CN201811478992.3A patent/CN109560324A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103500850A (en) * | 2013-10-23 | 2014-01-08 | 山东大学 | Low-temperature electrolyte of lithium iron phosphate battery |
| CN105047996A (en) * | 2015-05-28 | 2015-11-11 | 河南省法恩莱特新能源科技有限公司 | Lithium ion battery low temperature electrolyte and lithium ion battery |
| CN105633463A (en) * | 2016-01-08 | 2016-06-01 | 九江迅通新能源科技有限公司 | Lithium-ion secondary battery electrolyte applicable to low-temperature environment discharging |
| CN106169611A (en) * | 2016-09-17 | 2016-11-30 | 复旦大学 | A kind of low-temperature electrolyte with ethyl acetate as solvent |
| CN107171023A (en) * | 2017-05-17 | 2017-09-15 | 中国第汽车股份有限公司 | A kind of low temperature electrolytes for Li-ion batteries |
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Application publication date: 20190402 |