CN109103501A - A kind of lithium-ion battery electrolytes - Google Patents
A kind of lithium-ion battery electrolytes Download PDFInfo
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- CN109103501A CN109103501A CN201810771792.0A CN201810771792A CN109103501A CN 109103501 A CN109103501 A CN 109103501A CN 201810771792 A CN201810771792 A CN 201810771792A CN 109103501 A CN109103501 A CN 109103501A
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- lithium
- ion battery
- battery electrolytes
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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
- H01M10/42—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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- 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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- 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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- General Chemical & Material Sciences (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention discloses a kind of lithium-ion battery electrolytes, including electrolyte lithium salt, organic solvent and functional additive；Functional additive includes Silver hexafluorophosphate, allyloxy trimethylsilane, 1,4,8,11- tetraazacyclododecane tetradecane, Methyl benzenesulfonyl isocyanate and cyclic phosphazene class additive.A kind of lithium-ion battery electrolytes of the invention, with good electrode capacity, rate charge-discharge performance, positive and negative anodes matching performance, cycle performance；And the short-circuit risks of inside battery are reduced, the high-temperature behavior and security performance of battery are significantly improved.
Description
Technical field
The present invention relates to field of lithium ion battery, more particularly to a kind of lithium-ion battery electrolytes.
Background technique
Lithium-ion battery electrolytes are the bridges for connecting positive and negative electrode, play a part of transmitting ion in inside battery, main
It to be made of lithium salts, organic solvent and additive.Voltage, capacity, energy and power of the selection of electrolyte and battery etc. is closely
It is related.Lithium-ion battery electrolytes are referred to as " blood " of battery, and the use of electrolysis additive is equivalent to execution " blood note
Penetrate ", certain performances of battery can be targetedly changed using less dosage, including electrode capacity, multiplying power charge and discharge
Electrical property, positive and negative anodes matching performance, cycle performance and security performance etc..
The electrolyte of lithium ion battery is mostly liquid organic electrolyte, is made of organic solvent and electric conducting lithium salt.It is common
Organic solvent be alkylcarbonic acid esters compound, but its flash-point is all very low, causes the electrolyte solution (electrolysis of lithium ion battery
Liquid) easily burn.When battery occurs short circuit, the safety problems such as overcharges, battery abnormal heating or decomposes and generates a large amount of gas at gasification
Body causes cell fracture on fire.In recent years, a lot of cell safety accidents all had occurred in each state, and this is mainly due to batteries to abuse
Cause safety issue caused by thermal runaway under (thermal shock overcharges, external short circuit etc.) state, it is especially big in electric vehicle etc.
Capacity electric energy application aspect, safety problem are even more important.In addition, also there is many document report flame-retardant additives that can significantly improve
The safety problem of electrolyte.But generate the problem that electrolyte traditional performance such as circulation cryogenic property by serious shadow therewith
It rings, so that it cannot meet actual use demand.Therefore, the safety of battery can be improved it is urgent to provide one kind and assign
Give the lithium-ion battery electrolytes of electrolyte multiple performance.
Summary of the invention
In view of this, can improve the safety of battery the present invention provides a kind of lithium-ion battery electrolytes and assign
Give a variety of property of the electrolyte including improving electrode capacity, rate charge-discharge performance, positive and negative anodes matching performance, cycle performance
Energy.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of lithium-ion battery electrolytes, including electrolyte lithium salt, organic solvent and functional additive；The function addition
Agent includes Silver hexafluorophosphate, allyloxy trimethylsilane, 1,4,8,11- tetraazacyclododecane tetradecane, Methyl benzenesulfonyl isocyanate
With cyclic phosphazene class additive.
By adopting the above technical scheme have the beneficial effect that 1,4,8,11- tetraazacyclododecane tetradecane can with it is positive in electrolyte
Metal ion in the conductive agent SP of material dissolution forms complex, which improves metal ion deposition
Thermodynamical reaction performance, so that deposition reaction be made to need lower potential value；The complex molecules of formation are big ring class knot
Structure has certain steric effect, can also reduce deposition reaction dynamics；1,4,8,11- tetraazacyclododecane is added in the electrolytic solution
In the lithium ion battery of the tetradecane, by Isosorbide-5-Nitrae, the complex that 8,11- tetraazacyclododecane tetradecanes are formed inhibits metal ion
Deposition, significantly improve the high-temperature behavior and security performance of battery, reduce internal short-circuit risks.
Cyclic phosphazene flame-retardant additive has good flame retardant property, which can promote electricity as functional additive
Solution liquid system forms stable interfacial film in positive and negative pole surface, takes into account while improving electrolyte flame-retardant performance and guarantees electrolyte tool
There is measured cycle performance, and the problem of causing low temperature to analyse lithium due to the addition of fire retardant can be improved, effectively improves battery
Comprehensive performance.
Further, the concentration of the electrolyte lithium salt is 0.8-3.5mol/L, and the concentration of the Silver hexafluorophosphate is 0.2-
2mol/L, the concentration of the allyloxy trimethylsilane are 0.2-2mol/L, the Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes it is dense
Degree is 0.02-0.2mol/L, and the dosage of the Methyl benzenesulfonyl isocyanate occupies the 0.2-2% of solvent gross mass, described
The dosage of cyclic phosphazene class additive occupies the 0.2-5% of solvent gross mass.
Preferably, the concentration of the electrolyte lithium salt is 0.8-2.5mol/L, and the concentration of the Silver hexafluorophosphate is 1.1-
1.5mol/L, the concentration of the allyloxy trimethylsilane are 1.1-1.5mol/L, the Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes
Concentration be 0.11-0.15mol/L, the dosage of the Methyl benzenesulfonyl isocyanate occupies the 0.4% of solvent gross mass, institute
The dosage for stating cyclic phosphazene class additive occupies the 0.4% of solvent gross mass.
Further, the electrolyte lithium salt includes lithium hexafluoro phosphate, LiBF4, lithium perchlorate, trifluoromethane sulfonic acid
One of lithium, lithium chloride, lithium iodide, lithium aluminate, hexafluoroarsenate lithium, fluoro sulfimide lithium are a variety of.
Further, the organic solvent is cyclic carbonate or linear carbonate.
Preferably, the organic solvent is ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbonic acid
One of diethylester, ethyl acetate, propyl acetate, methyl propionate and ethyl propionate are a variety of.
Further, the lithium-ion battery electrolytes further include anode protection additive, the anode protection additive
Dosage accounts for the 0.5-4% of electrolyte gross mass.
Preferably, the anode protection additive is one of succinonitrile, adiponitrile, malononitrile, glutaronitrile or a variety of.
It can be seen via above technical scheme that compared with prior art, the present disclosure provides a kind of lithium ion batteries
Electrolyte, with good electrode capacity, rate charge-discharge performance, positive and negative anodes matching performance, cycle performance；And it reduces
The short-circuit risks of inside battery, the high-temperature behavior and security performance of battery are significantly improved.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that
Described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, every other embodiment obtained by those of ordinary skill in the art without making creative efforts belong to
The scope of protection of the invention.
Embodiment 1
A kind of lithium-ion battery electrolytes, including electrolyte lithium salt, organic solvent, Silver hexafluorophosphate, allyloxy front three
Silane, 1,4,8,11- tetraazacyclododecane tetradecane, Methyl benzenesulfonyl isocyanate and cyclic phosphazene class additive；Electrolyte lithium salt
For lithium hexafluoro phosphate and LiBF4, the concentration of lithium hexafluoro phosphate is 0.8mol/L, and the concentration of LiBF4 is 0.8mol/
L；Organic solvent is ethylene carbonate and propene carbonate, and ethylene carbonate occupies the 60% of solvent gross mass, propylene carbonate
Ester occupies the 40% of solvent gross mass；The concentration of Silver hexafluorophosphate is 1.1mol/L, and the concentration of allyloxy trimethylsilane is
The concentration of 1.1mol/L, Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes are 0.11mol/L, and the dosage of Methyl benzenesulfonyl isocyanate accounts for
The dosage of the 0.4% of organic solvent gross mass, the cyclic phosphazene class additive occupies the 0.4% of solvent gross mass.It uses
Cobalt acid lithium material, as negative electrode material, is designed to that capacity is the soft-package battery of 8Ah as positive electrode, artificial graphite.
Embodiment 2
A kind of lithium-ion battery electrolytes, including electrolyte lithium salt, organic solvent, Silver hexafluorophosphate, allyloxy front three
Silane, 1,4,8,11- tetraazacyclododecane tetradecane, Methyl benzenesulfonyl isocyanate and cyclic phosphazene class additive；Electrolyte lithium salt
For lithium perchlorate, trifluoromethyl sulfonic acid lithium and lithium chloride, the concentration of lithium perchlorate is 0.8mol/L, trifluoromethyl sulfonic acid lithium it is dense
Degree is 0.9mol/L, and the concentration of lithium chloride is 1mol/L；Organic solvent is methyl ethyl carbonate, dimethyl carbonate and carbonic acid diethyl
Ester, methyl ethyl carbonate occupy the 20% of solvent gross mass, and dimethyl carbonate occupies the 30% of solvent gross mass, carbonic acid diethyl
Ester occupies the 50% of solvent gross mass；The concentration of Silver hexafluorophosphate is 0.2mol/L, and the concentration of allyloxy trimethylsilane is
The concentration of 0.2mol/L, Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes are 0.02mol/L, and the dosage of Methyl benzenesulfonyl isocyanate accounts for
The dosage of the 0.2% of organic solvent gross mass, the cyclic phosphazene class additive occupies the 0.2% of solvent gross mass.It uses
Cobalt acid lithium material, as negative electrode material, is designed to that capacity is the soft-package battery of 8Ah as positive electrode, artificial graphite.
Embodiment 3
A kind of lithium-ion battery electrolytes, including electrolyte lithium salt, organic solvent, Silver hexafluorophosphate, allyloxy front three
Silane, 1,4,8,11- tetraazacyclododecane tetradecane, Methyl benzenesulfonyl isocyanate and cyclic phosphazene class additive；Electrolyte lithium salt
For fluoro sulfimide lithium, the concentration of fluoro sulfimide lithium is 3mol/L；Organic solvent be ethyl propionate and propyl acetate, third
Acetoacetic ester occupies the 50% of solvent gross mass, and propyl acetate occupies the 50% of solvent gross mass；The concentration of Silver hexafluorophosphate
Concentration for 2mol/L, allyloxy trimethylsilane is 2mol/L, and the concentration of Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes is
0.2mol/L, the dosage of Methyl benzenesulfonyl isocyanate occupy the 2% of solvent gross mass, the cyclic phosphazene class additive
Dosage occupies the 5% of solvent gross mass.Use cobalt acid lithium material as positive electrode, artificial graphite as negative electrode material, if
Count into the soft-package battery that capacity is 8Ah.
A kind of lithium-ion battery electrolytes of comparative example 1, do not contain Silver hexafluorophosphate, allyloxy trimethylsilane, remaining with
The scheme of embodiment 1 is consistent.
A kind of lithium-ion battery electrolytes of comparative example 2 do not contain Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes, remaining and implementation
The scheme of example 1 is consistent.
A kind of lithium-ion battery electrolytes of comparative example 3 do not contain Methyl benzenesulfonyl isocyanate, remaining and embodiment 1
Scheme is consistent.
A kind of lithium-ion battery electrolytes of comparative example 4 do not contain cyclic phosphazene class additive, the side of remaining and embodiment 1
Case is consistent.
A kind of lithium-ion battery electrolytes of comparative example 5 do not contain Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes and cyclic phosphazene class
Additive, remaining is consistent with the scheme of embodiment 1.
The cobalt acid lithium reversible capacity and appearance of the lithium ion battery of embodiment 1-3 and comparative example 1-5 under condition of different temperatures
It is as shown in table 1 to measure conservation rate.
Table 1
Silver hexafluorophosphate, allyloxy trimethylsilane and Methyl benzenesulfonyl isocyanate are significantly improved as functional additive
The electrode capacity of lithium ion battery, rate charge-discharge performance and cycle performance.
500 weeks capacity retention ratios, squeeze test, short-circuit test and the point of embodiment 1-3 and comparative example 1-5 lithium ion battery
It is as shown in table 2 to fire the after-combustion time.
Table 2
The Isosorbide-5-Nitrae added in lithium-ion battery electrolytes, 8,11- tetraazacyclododecane tetradecanes and cyclic phosphazene class additive, association
Same-action, reduces the short-circuit risks of inside lithium ion cell, and the high-temperature behavior and security performance of battery are significantly improved.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (8)
1. a kind of lithium-ion battery electrolytes, which is characterized in that including electrolyte lithium salt, organic solvent and functional additive；Institute
Stating functional additive includes Silver hexafluorophosphate, allyloxy trimethylsilane, 1,4,8,11- tetraazacyclododecane tetradecane, methylbenzene sulphur
Acyl isocyanates and cyclic phosphazene class additive.
2. a kind of lithium-ion battery electrolytes according to claim 1, which is characterized in that the concentration of the electrolyte lithium salt
Concentration for 0.8-3.5mol/L, the Silver hexafluorophosphate is 0.2-2mol/L, and the concentration of the allyloxy trimethylsilane is
The concentration of 0.2-2mol/L, the Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes are 0.02-0.2mol/L, and the Methyl benzenesulfonyl is different
The dosage of cyanate occupies the 0.2-2% of solvent gross mass, and it is total that the dosage of the cyclic phosphazene class additive occupies solvent
The 0.2-5% of quality.
3. a kind of lithium-ion battery electrolytes according to claim 2, which is characterized in that the concentration of the electrolyte lithium salt
For 0.8-2.5mol/L, the concentration of the Silver hexafluorophosphate is 1.1-1.5mol/L, the concentration of the allyloxy trimethylsilane
For 1.1-1.5mol/L, the Isosorbide-5-Nitrae, the concentration of 8,11- tetraazacyclododecane tetradecanes is 0.11-0.15mol/L, the methylbenzene sulphur
The dosage of acyl isocyanates occupies the 0.4% of solvent gross mass, and the dosage of the cyclic phosphazene class additive occupies solvent
The 0.4% of gross mass.
4. a kind of lithium-ion battery electrolytes according to claim 1, which is characterized in that the electrolyte lithium salt includes six
Lithium fluophosphate, LiBF4, lithium perchlorate, trifluoromethyl sulfonic acid lithium, lithium chloride, lithium iodide, lithium aluminate, hexafluoroarsenate lithium,
One of fluoro sulfimide lithium is a variety of.
5. a kind of lithium-ion battery electrolytes according to claim 1, which is characterized in that the organic solvent is cyclic annular carbon
Acid esters or linear carbonate.
6. a kind of lithium-ion battery electrolytes according to claim 1, which is characterized in that the organic solvent is carbonic acid second
Enester, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl acetate, propyl acetate, methyl propionate and
One of ethyl propionate is a variety of.
7. a kind of lithium-ion battery electrolytes according to claim 1, which is characterized in that the lithium-ion battery electrolytes
It further include anode protection additive, the dosage of the anode protection additive accounts for the 0.5-4% of electrolyte gross mass.
8. a kind of lithium-ion battery electrolytes according to claim 1 or claim 7, which is characterized in that the anode protection addition
Agent is one of succinonitrile, adiponitrile, malononitrile, glutaronitrile or a variety of.
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Cited By (2)
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| CN112018442A (en) * | 2019-05-29 | 2020-12-01 | 比亚迪股份有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN117543084A (en) * | 2024-01-10 | 2024-02-09 | 深圳海辰储能科技有限公司 | Electrolyte, energy storage device and electric equipment |
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