CN109687022A - The electrolyte of a kind of fluoride solvent and pyridined additives and lithium ion battery using the electrolyte - Google Patents
The electrolyte of a kind of fluoride solvent and pyridined additives and lithium ion battery using the electrolyte Download PDFInfo
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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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- H01M10/0569—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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses the lithium ion batteries of a kind of fluoride solvent and the electrolyte and use of the pyridined additives electrolyte.The electrolyte includes lithium salts, organic solvent and additive, and the organic solvent includes one of fluorinated organic solvent, linear carbonate class, cyclic carbonates, carboxylic acid esters or a variety of, and the additive includes the pyridine compounds and their of nitrile group-containing.Compared to the conventional lithium ion battery of unused electrolyte of the present invention, due to being added to the pyridine compounds and their of nitrile group-containing in electrolyte of the present invention, and with the use of the fluorinated organic solvent with preferable wellability, electrode interface can be optimized, reduce the impedance between interface, improves cryogenic property；The property that electrode/electrolyte interfacial film can be improved simultaneously, inhibits the dissolution of transition metal, slows down the flatulence speed of battery at high temperature under high pressure, improves the cycle life of lithium ion battery at high temperature under high pressure.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to the electrolyte of a kind of fluoride solvent and pyridined additives and
Use the lithium ion battery of the electrolyte.
Background technique
Currently, lithium ion battery due to its energy density is big, have extended cycle life, memory-less effect, it is environmentally protective the advantages that
It is widely used in the fields such as electric car, electric tool, aerospace, continuous renewal and people however as electronic equipment
Concern to electric tool, people propose the energy density of lithium ion battery, cycle performance, high temperature performance etc. higher
Requirement.
At present, it has been reported that high-voltage anode material have LiCoPO4、LiNiPO4And LiNi0.5Mn1.5Deng charging electricity
Flattening bench is close to or higher than 5V, but the development of matching non-aqueous organic electrolyte seriously lags behind high-voltage anode material,
Limit the application of lithium ion secondary battery.Conventional electrolyte easily decomposes between battery plus-negative plate, generates gas, makes battery
Internal pressure increase, inside heating and it is unstable, especially in the case where high temperature and pressure, the safety of battery and cycle life are tight
Ghost image is rung.For example, decomposing the H generated2O makes LiPF6Self-catalyzed reaction occurs for/carbonate electrolyte system, and intermediate product HF can be led
The dissolution of metal ions M n, Ni in positive electrode is caused, so that positive and negative electrode material degradation, reduces battery capacity and cycle life.And
Electrolyte is the important component of lithium ion battery, is known as the ion conductor for playing conduction between battery positive and negative electrode
" blood " of lithium ion battery is improved the performance of electrolyte by the discussion to new additive agent and solvent, has become lithium
The hot spot of ion battery research.
Summary of the invention
The inventors found that fluorine has very strong electronegativity and low pole, fluorinated solvents have low melting point, high sudden strain of a muscle
The advantages that point and high oxidation decomposition voltage, by being fluorinated to carbonic ester or carboxylic acid esters solvent, the oxidation of electrolyte whole
Decomposition voltage is enhanced.Meanwhile fluorinated solvents have preferable wellability, can optimize electrode interface, reduce between interface
Impedance improves the cryogenic property of battery, and therefore, fluorinated organic solvent has very big hair as lithium-ion battery electrolytes solvent
Exhibition prospect.
Pyridine manifests themselves as alkalescent, can with acid neutralize, and itrile group can with complexing of metal ion, inhibit metal from
The dissolution of son, patent WO2015088052 promotes additive to the complexing power of metal ion by introducing itrile group, however mistake
More itrile groups will increase positive impedance while promoting positive protective capability, so that cycle performance of battery reduces, recycle and low
Temp effect is deteriorated.Based on the aforementioned research to fluorinated solvents of the present invention, the present inventor utilizes fluorinated solvents and nitrile group-containing
Pyridine compounds and their matches, and has prepared high-voltage lithium-ion battery electrolyte of the invention, which can change
Kind electrode/electrolyte interface film character while guaranteeing cryogenic property, slows down flatulence speed when battery stores at high temperature under high pressure
Degree improves lithium ion battery cycle life under high voltages and high temperature cyclic performance and high-temperature storage performance.
In order to reach the purpose of the present invention, the present invention provides a kind of high voltage of fluoride solvent and pyridined additives electricity
Liquid is solved, which includes lithium salts, organic solvent and additive, wherein the organic solvent includes fluorinated organic solvent, chain
One of carbonate based organic solvent, cyclic carbonates organic solvent, carboxylic acid esters organic solvent are a variety of, in additive
Include pyridine compounds and their.
Further, the fluorinated organic solvent such as formula (I) or formula (II) are shown:
In formula (I), R1And R2Respectively indicate alkyl or alkoxy containing 1-6 carbon atom, or containing 1-6 carbon atom
Fluoro-alkyl or fluoroalkyl, and R1And R2In at least one be fluoro-alkyl or fluoro alcoxyl containing 1-6 carbon atom
Base；In formula (II), M1And M2Respectively indicate alkyl or alkoxy containing 1-6 carbon atom, or the fluoro containing 1-6 carbon atom
Alkyl or fluoroalkyl, and M1And M2In at least one be fluoro-alkyl or fluoroalkyl containing 1-6 carbon atom.
Further, according to certain embodiments of the present invention, compound shown in formula (I) includes but is not limited to following chemical combination
Object:
Further, according to certain embodiments of the present invention, compound shown in formula (II) includes but is not limited to following
Compound:
Preferably, the fluorinated organic solvent of the formula (I) or formula (II) accounts for the 2-30% of solvent quality, it is highly preferred that institute
The fluorinated organic solvent for stating formula (I) or formula (II) accounts for the 5-15% of solvent quality.
Further, shown in pyridine compounds and their of the present invention such as formula (III):
Wherein, X1、X2、X3、X4And X5It is independently selected from alkyl, the 1-5 carbon atom of hydrogen atom, 1-5 carbon atom
Alkoxy, halogen atom, itrile group or 1-5 carbon atom alkoxy itrile group, and X1、X2、X3、X4And X5In, at least one
For itrile group or the alkoxy itrile group of 1-5 carbon atom.
Further, according to certain embodiments of the present invention, compound shown in formula (III) includes but is not limited to following
Compound:
Preferably, compound shown in formula (III) accounts for the 0.5-10% of electrolyte quality, such as 1-2%.
Further, also comprising being selected from 1,3 propane sultones (1,3-PS), difluorophosphate in the additive
(LiPO2F2), vinylene carbonate (VC), vinylethylene carbonate (VEC), sulfuric acid vinyl ester (DTD), fluorinated ethylene carbonate
One of (FEC) or multiple additives, it is preferable that the mass percent of aforementioned additive in the electrolytic solution is 0.1-15%.
Preferably, vinylene carbonate (VC), 1,3 propane sulfonic acid lactones (1,3-PS) and fluoro are included in the additive
Ethylene carbonate (FEC).
It is highly preferred that vinylene carbonate (VC), 1,3 propane sulfonic acid lactones (1,3-PS) and fluoro carbon in the additive
The mass ratio of vinyl acetate (FEC) is (0.5-1.5): (2-4): (9-11), such as 1:3:10.
Further, the linear carbonate class organic solvent can be selected from dimethyl carbonate (DMC), diethyl carbonate
(DEC), one of methyl ethyl carbonate (EMC), dipropyl carbonate (DPC) or a variety of；The cyclic carbonates organic solvent
One of ethylene carbonate (EC), vinylene carbonate (VC), propene carbonate (PC) or a variety of can be selected from；The carboxylic acid
Based organic solvent can be selected from ethyl acetate (EA), ethyl propionate (EP), methyl acetate (MA), propyl acetate (PE), propionic acid
One of methyl esters (MP), methyl butyrate (MB), ethyl butyrate (EB) are a variety of.
Preferably, ethylene carbonate (EC), methyl ethyl carbonate (EMC) and diethyl carbonate are included in the organic solvent
(DEC), it is highly preferred that the mass ratio of the ethylene carbonate (EC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) is
(1-3): (4-6): (2-4), such as 2:5:3.
Further, the lithium salts can be selected from LiPF6、LiBF4、LiClO4、LiBOB、LiODFB、LiAsF6、LiN
(SO2CF3)2、LiN(SO2F)2One of or it is a variety of, and based on lithium ion, the concentration of the lithium salts in the electrolytic solution is 0.5-
2M, such as 1-1.5M.
The present invention also provides a kind of lithium ion batteries for having used electrolyte of the present invention, it is preferable that the lithium ion battery
Preparation method include the nickel cobalt being injected into high-voltage lithium-ion battery electrolyte of the invention by sufficiently dry 4.35V
LiMn2O4/silicon-carbon soft-package battery is shelved by 45 DEG C, high-temperature clamp is melted into and secondary sealing process.
Fluoride solvent of the present invention and the high-voltage lithium-ion battery electrolyte of pyridined additives can effectively inhibit metal
Dissolution reduces electrolyte decomposition production gas, protection anode, improves the high-temperature storage performance of battery, while can reduce the increasing of impedance
Add, improves the cryogenic property of lithium ion battery.Compared to the conventional lithium ion battery of unused high-voltage electrolyte of the present invention, by
The pyridine compounds and their of nitrile group-containing is added in electrolyte of the present invention, and organic with the use of the fluoro with preferable wellability
Solvent can optimize electrode interface, reduce the impedance between interface, improve cryogenic property；Electrode/electrolyte can be improved simultaneously
The property of interfacial film inhibits the dissolution of transition metal, slows down the flatulence speed of battery at high temperature under high pressure, improves lithium ion battery
Cycle life at high temperature under high pressure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.Additional aspect and advantage of the invention will be set forth in part in the description, partially will be under
Become obvious in the description in face, or practice through the invention is recognized.It is only used to explain this hair it should be appreciated that being described below
It is bright, it is not intended to limit the present invention.
Term "comprising" used herein, " comprising ", " containing " or its any other deformation, it is intended that covering non-exclusionism
Include.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those elements, but
It may include not expressly listed other elements or such composition, step, method, product or the intrinsic element of device.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
Indefinite article "an" before element or component of the present invention (goes out the quantitative requirement of element or component with "one"
Occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and singular
Element or component also include plural form, unless the quantity obviously only refers to singular.
Moreover, technical characteristic involved in each embodiment of the present invention as long as they do not conflict with each other can
To be combined with each other.
Comparative example 1
The high-voltage lithium-ion battery electrolyte is prepared as follows: in glove box, by ethylene carbonate (EC),
Methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the ratio of weight ratio 2:5:3, and hexafluoro phosphorus is then added
Sour lithium is dissolved, and the electrolyte that hexafluorophosphoric acid lithium concentration is 1M is prepared.Later, mass fraction is added into electrolyte is
0.5% vinylene carbonate (VC), 1.5% 1,3 propane sulfonic acid lactones (1,3-PS) and 5% fluorinated ethylene carbonate
(FEC)。
Prepared high-voltage lithium-ion battery electrolyte is injected into the nickel cobalt mangaic acid by sufficiently dry 4.35V
Lithium/silicon-carbon soft-package battery is shelved by 45 DEG C, after the processes such as high-temperature clamp chemical conversion and secondary sealing, carries out battery performance test,
Obtain battery used in comparative example 1.
Embodiment 1
The high-voltage lithium-ion battery electrolyte is prepared as follows: in glove box, by ethylene carbonate (EC),
Methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the ratio of weight ratio 2:5:3, then to mixed solvent
The middle fluorinated organic solvent (1) that mass fraction 5% is added；Lithium hexafluoro phosphate is added to be dissolved, hexafluorophosphoric acid lithium concentration is prepared
For the electrolyte of 1M.Later, it is 0.5% vinylene carbonate (VC), the 1,3 of 1.5% that mass fraction is added into electrolyte
Propane sulfonic acid lactones (1,3-PS) and 5% fluorinated ethylene carbonate (FEC), it is another plus 1% pyridine compounds and their (5).
Prepared lithium ion battery is injected into the nickel cobalt mangaic acid of the 4.35V by sufficiently drying with high-voltage electrolyte
Lithium/silicon-carbon soft-package battery is shelved by 45 DEG C, after the processes such as high-temperature clamp chemical conversion and secondary sealing, carries out battery performance test,
Obtain battery used in embodiment 1.
In the present invention, for the preparation method of other comparative examples and embodiment referring to comparative example 1 and embodiment 1, table 1 is each implementation
The electrolyte prescription table of example and comparative example.
The electrolyte prescription of each embodiment and comparative example of table 1
Performance of lithium ion battery test
1. high temperature cyclic performance
Under the conditions of high temperature (45 DEG C), above-mentioned lithium ion battery is charged to 4.35V in 1C constant current constant voltage, then in 1C constant current
Under the conditions of be discharged to 3.0V.After charge and discharge 300 circulations, the capacity retention ratio after recycling is calculated the 300th time:
2. high-temperature storage performance
Under the conditions of room temperature (25 DEG C), carrying out a 1C/1C charging and discharging to lithium ion battery, (discharge capacity is denoted as
DC0), battery is then charged into 4.35V under the conditions of 1C constant current constant voltage；Lithium ion battery is placed in 60 DEG C of high-temperature cabinets and is saved
1 month, after taking-up, carrying out 1C electric discharge under normal temperature conditions, (discharge capacity was denoted as DC1)；Then 1C/ is carried out under normal temperature conditions
(discharge capacity is denoted as DC for 1C charging and discharging2), it is extensive using the capacity retention ratio and capacity of following formula calculating lithium ion battery
Multiple rate:
3. low-temperature circulating performance
Under the conditions of low temperature (10 DEG C), above-mentioned lithium ion battery is charged to 4.35V in 0.5C constant current constant voltage, then in 0.5C
3.0V is discharged under constant current conditions.After charge and discharge 50 circulations, the capacity retention ratio after recycling is calculated the 50th time:
The results are shown in Table 2 for the battery performance of above-mentioned each specific comparative example and embodiment.
The battery performance result of each specific embodiment of table 2
It can be seen that in comparative example 1 from upper table data, nickle cobalt lithium manganate/silicon-carbon Soft Roll applied to high voltage 4.35V
When battery, addition mass fraction be 0.5% vinylene carbonate (VC), 1.5% 1,3 propane sulfonic acid lactones (1,3-PS) and
After 5% fluorinated ethylene carbonate (FEC), since the cathode film formation of VC primarily forms organic polymer film, under the condition of high temperature intolerant to
High temperature, be easy decompose, though and positive electrode surface can polymerization film formation, its thermal stability is poor, while VC oxidizing potential itself is lower,
Decomposition is oxidized easily under high potential, thus the high temperature cyclic performance of battery is bad, high-temperature storage performance is general, and battery has
Certain production gas, leads to cell expansion, and the cycle performance of battery under cryogenic is general.
After adding the novel fluorinated solvents of 5% content in the electrolytic solution (i.e. comparative example 2,3,4,5), it can be seen that electricity
The low-temperature circulating performance in pond has a certain upgrade, thus it is speculated that and it is the wellability for increasing electrolyte to pole piece due to fluorinated solvents, drop
The low impedance of battery, so that the low-temperature circulating performance of battery is greatly improved, especially novel fluorinated solvents are to change
When closing object (1) and compound (3), promotes effect and become apparent from.
When not adding novel fluorinated solvents of the present invention, and individually add the pyridine compounds of the nitrile group-containing of 1% content
After (i.e. comparative example 6,8), it can be found that the high temperature cyclic performance of battery is significantly improved.Be presumably due to itrile group battery just
Pole surface polymerization film formation, it is suppressed that positive activity, to reduce the generation of side reaction, while on the nitrogen-atoms in Pyridine Molecules
Lone pair electrons play the effect of lewis base, the PF generated after capable of being decomposed with lithium hexafluoro phosphate under hot conditions5Or POF3Change
It closes object and forms complex, reduce the high-temperature behavior that acidic materials improve battery to the broken ring of battery system；But by
The increase of impedance after film forming, so that low-temperature circulating poor effect, especially when the amount of nitrile group-containing pyridine compounds and their is promoted to 2%
(i.e. comparative example 7,9) afterwards, may be due to excessive at membrane impedance, cycle performance bust.
Novel fluorinated solvents and nitrile group-containing pyridine compounds and their are used in combination, in this hair in high-voltage electrolyte of the invention
In bright some embodiments, compound (1), compound (2), compound (3), compound (4) these four novel fluoro are used
Solvent, and its additive amount be solvent gross mass 5% or 15% when, adjust two kinds of nitrile group-containing pyridine compounds and their (compounds
(5), compound (6)) additive amount be respectively the 1% or 2% of electrolyte gross mass, carry out mix and match, be prepared for 32 kinds of height
Potential electrolysis liquid, and prepare corresponding lithium ion battery and carry out electric performance test, pass through the experiment number to embodiment and comparative example
It is analyzed according to being compared, available such as to draw a conclusion:
1. on the whole, novel fluorinated solvents (2-30% that additive amount is solvent quality) and nitrile group-containing pyridines
Being used cooperatively for object (0.5-15% that additive amount is electrolyte quality) is closed, it can be on the basis for guaranteeing battery low-temperature circulating performance
On, significantly improve the high temperature circulation and high-temperature storage performance of battery；
2. either chain fluoro carbonic ether or chain fluorocarboxylic acid esters compound, can improve to a certain extent
The cryogenic property of battery, this may be caused by having preferable wellability pole piece as fluorinated solvents, however, when fluoro is molten
When agent additive amount is more, the dissolubility of lithium salts is reduced, the increase of viscosity and the reduction of conductivity are caused, it is all more or less
Impedance is improved, cycle performance is reduced；
3. nitrile group-containing pyridine compounds and their shown in formula (III) can make electricity when additive amount is 1% as additive
The high-temperature storage performance of solution matter is significantly improved, but when additive amount is 2%, performance at high temperature declines instead；
Although 4. being had when novel fluorinated solvents or nitrile group-containing pyridine compounds and their is used alone in certain aspect of performance
More preferably effect, but being used in mixed way novel fluorinated solvents and nitrile group-containing pyridine compounds and their makes high-voltage battery comprehensive performance all
There is a degree of promotion, a kind of high-voltage electrolyte having great potential can be obtained.
As it will be easily appreciated by one skilled in the art that the above description is only an embodiment of the present invention, not to limit
The present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in this
Within the protection scope of invention.
Claims (10)
1. the electrolyte of a kind of fluoride solvent and pyridined additives, which includes lithium salts, organic solvent and additive,
It is characterized in that, the organic solvent is organic molten comprising fluorinated organic solvent, linear carbonate class organic solvent, cyclic carbonates
One of agent, carboxylic acid esters organic solvent are a variety of, include pyridine compounds and their in additive.
2. the electrolyte of fluoride solvent according to claim 1 and pyridined additives, which is characterized in that the fluoro has
Shown in solvent such as formula (I) or formula (II):
In formula (I), R1And R2Respectively indicate alkyl or alkoxy containing 1-6 carbon atom, or the fluoro containing 1-6 carbon atom
Alkyl or fluoroalkyl, and R1And R2In at least one be fluoro-alkyl or fluoroalkyl containing 1-6 carbon atom；?
In formula (II), M1And M2Respectively indicate alkyl or alkoxy containing 1-6 carbon atom, or the fluoro-alkyl containing 1-6 carbon atom or
Fluoroalkyl, and M1And M2In at least one be fluoro-alkyl or fluoroalkyl containing 1-6 carbon atom.
3. the electrolyte of fluoride solvent according to claim 2 and pyridined additives, which is characterized in that the formula (I)
Shown compound includes but is not limited to following compound:
Compound shown in the formula (II) includes but is not limited to following compound:
Preferably, the fluorinated organic solvent of the formula (I) or formula (II) accounts for the 2-30% of solvent quality, it is highly preferred that the formula
(I) or the fluorinated organic solvent of formula (II) accounts for the 5-15% of solvent quality.
4. the electrolyte of fluoride solvent according to claim 1 and pyridined additives, which is characterized in that the pyridines
Shown in compound such as formula (III):
Wherein, X1、X2、X3、X4And X5It is independently selected from the alkane of hydrogen atom, the alkyl of 1-5 carbon atom, 1-5 carbon atom
Oxygroup, halogen atom, itrile group or 1-5 carbon atom alkoxy itrile group, and X1、X2、X3、X4And X5In, at least one is nitrile
The alkoxy itrile group of base or 1-5 carbon atom.
5. the electrolyte of fluoride solvent according to claim 4 and pyridined additives, which is characterized in that the formula
(III) compound shown in includes but is not limited to following compound:
Preferably, compound shown in the formula (III) accounts for the 0.5-10% of electrolyte quality, such as 1-2%.
6. the electrolyte of fluoride solvent according to claim 1 and pyridined additives, which is characterized in that the additive
In also comprising selected from 1,3 propane sultones, difluorophosphate, vinylene carbonate, vinylethylene carbonate, sulfuric acid vinyl ester,
One of fluorinated ethylene carbonate or multiple additives, it is preferable that the mass percent of aforementioned additive in the electrolytic solution is
0.1-15%；
It preferably, include vinylene carbonate, 1,3 propane sulfonic acid lactones and fluorinated ethylene carbonate in the additive；
It is highly preferred that vinylene carbonate, 1 in the additive, the mass ratio of 3 propane sulfonic acid lactones and fluorinated ethylene carbonate
For (0.5-1.5): (2-4): (9-11), such as 1:3:10.
7. the electrolyte of fluoride solvent according to claim 1 and pyridined additives, which is characterized in that the chain carbon
Esters of gallic acid organic solvent is selected from one of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate or a variety of；
The cyclic carbonates organic solvent is selected from one of ethylene carbonate, vinylene carbonate, propene carbonate or a variety of；
The carboxylic acid esters organic solvent is selected from ethyl acetate, ethyl propionate, methyl acetate, propyl acetate, methyl propionate, butyric acid first
One of ester, ethyl butyrate are a variety of.
8. the electrolyte of fluoride solvent according to claim 7 and pyridined additives, which is characterized in that described organic molten
It include ethylene carbonate, methyl ethyl carbonate and diethyl carbonate in agent, it is highly preferred that the ethylene carbonate, methyl ethyl carbonate
Mass ratio with diethyl carbonate is (1-3): (4-6): (2-4), such as 2:5:3.
9. the electrolyte of fluoride solvent according to claim 1 and pyridined additives, which is characterized in that the lithium salts choosing
From LiPF6、LiBF4、LiClO4、LiBOB、LiODFB、LiAsF6、LiN(SO2CF3)2、LiN(SO2F)2One of or it is a variety of,
And based on lithium ion, the concentration of the lithium salts in the electrolytic solution is 0.5-2M, such as 1-1.5M.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery has used to be contained described in claim any one of 1-9
The electrolyte of fluorous solvent and pyridined additives, it is preferable that the preparation method of the lithium ion battery includes by claim 1-9
The electrolyte of any one fluoride solvent and pyridined additives is injected into the nickel cobalt mangaic acid by sufficiently dry 4.35V
Lithium/silicon-carbon soft-package battery is shelved by 45 DEG C, high-temperature clamp is melted into and secondary sealing process.
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| CN201811594554.3A CN109687022B (en) | 2018-12-25 | 2018-12-25 | Electrolyte containing fluorine solvent and pyridine additive and lithium ion battery using electrolyte |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111313091A (en) * | 2020-03-03 | 2020-06-19 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
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| CN114300746A (en) * | 2021-12-15 | 2022-04-08 | 惠州锂威新能源科技有限公司 | Electrolyte additive, electrolyte and energy storage device |
| CN114520371A (en) * | 2022-02-18 | 2022-05-20 | 香河昆仑新能源材料股份有限公司 | Non-aqueous electrolyte and lithium ion battery comprising same |
| CN114628787A (en) * | 2022-03-28 | 2022-06-14 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| CN114649589A (en) * | 2020-12-18 | 2022-06-21 | 张家港市国泰华荣化工新材料有限公司 | Electrolyte and lithium secondary battery |
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1172878A2 (en) * | 2000-07-14 | 2002-01-16 | Mitsubishi Chemical Corporation | Non-aqueous electrolytic solution and secondary battery containing same |
| CN101030661A (en) * | 2006-03-24 | 2007-09-05 | 松下电器产业株式会社 | Non-aqueous electrolyte secondary battery |
| CN101673852A (en) * | 2008-09-11 | 2010-03-17 | 比亚迪股份有限公司 | Electrolyte additive and electrolyte and lithium ion battery containing same |
| CN102088111A (en) * | 2009-12-02 | 2011-06-08 | 索尼公司 | Nonaqueous electrolyte battery |
| US20140045032A1 (en) * | 2012-08-09 | 2014-02-13 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
| US20140050991A1 (en) * | 2012-08-16 | 2014-02-20 | Samsung Sdi Co., Ltd. | Electrolyte for high voltage lithium rechargeable battery and lithium rechargeable battery comprising the same |
| CN103647110A (en) * | 2013-12-06 | 2014-03-19 | 华瑞(新乡)化工有限公司 | Ultralow temperature discharge electrolyte of novel lithium ion battery |
| US20150325880A1 (en) * | 2014-05-09 | 2015-11-12 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
| CN105390748A (en) * | 2015-12-14 | 2016-03-09 | 苏州华一新能源科技有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN106532117A (en) * | 2016-11-17 | 2017-03-22 | 张家港市国泰华荣化工新材料有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN107658503A (en) * | 2017-10-23 | 2018-02-02 | 华南师范大学 | A kind of lithium secondary cell electrolyte and lithium secondary battery |
| CN107706455A (en) * | 2017-09-20 | 2018-02-16 | 惠州亿纬锂能股份有限公司 | A kind of high voltage multiplying power electrolyte for taking into account high temperature performance and the lithium ion battery using the electrolyte |
-
2018
- 2018-12-25 CN CN201811594554.3A patent/CN109687022B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1172878A2 (en) * | 2000-07-14 | 2002-01-16 | Mitsubishi Chemical Corporation | Non-aqueous electrolytic solution and secondary battery containing same |
| CN101030661A (en) * | 2006-03-24 | 2007-09-05 | 松下电器产业株式会社 | Non-aqueous electrolyte secondary battery |
| CN101673852A (en) * | 2008-09-11 | 2010-03-17 | 比亚迪股份有限公司 | Electrolyte additive and electrolyte and lithium ion battery containing same |
| CN102088111A (en) * | 2009-12-02 | 2011-06-08 | 索尼公司 | Nonaqueous electrolyte battery |
| US20140045032A1 (en) * | 2012-08-09 | 2014-02-13 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
| US20140050991A1 (en) * | 2012-08-16 | 2014-02-20 | Samsung Sdi Co., Ltd. | Electrolyte for high voltage lithium rechargeable battery and lithium rechargeable battery comprising the same |
| CN103647110A (en) * | 2013-12-06 | 2014-03-19 | 华瑞(新乡)化工有限公司 | Ultralow temperature discharge electrolyte of novel lithium ion battery |
| US20150325880A1 (en) * | 2014-05-09 | 2015-11-12 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
| CN105390748A (en) * | 2015-12-14 | 2016-03-09 | 苏州华一新能源科技有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN106532117A (en) * | 2016-11-17 | 2017-03-22 | 张家港市国泰华荣化工新材料有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN107706455A (en) * | 2017-09-20 | 2018-02-16 | 惠州亿纬锂能股份有限公司 | A kind of high voltage multiplying power electrolyte for taking into account high temperature performance and the lithium ion battery using the electrolyte |
| CN107658503A (en) * | 2017-10-23 | 2018-02-02 | 华南师范大学 | A kind of lithium secondary cell electrolyte and lithium secondary battery |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021031647A1 (en) * | 2019-08-20 | 2021-02-25 | Techtronic Cordless Gp | Lithium ion battery for power tools |
| CN112448033A (en) * | 2019-09-05 | 2021-03-05 | 杉杉新材料（衢州）有限公司 | High-voltage lithium ion battery electrolyte and long-cycle-life high-voltage lithium ion battery |
| CN111313091A (en) * | 2020-03-03 | 2020-06-19 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| CN111313091B (en) * | 2020-03-03 | 2021-08-06 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| CN112368872A (en) * | 2020-03-31 | 2021-02-12 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device |
| US12119446B2 (en) | 2020-03-31 | 2024-10-15 | Ningde Amperex Technology Limited | Electrolyte and electrochemical device |
| CN114649589A (en) * | 2020-12-18 | 2022-06-21 | 张家港市国泰华荣化工新材料有限公司 | Electrolyte and lithium secondary battery |
| CN114649589B (en) * | 2020-12-18 | 2024-04-30 | 张家港市国泰华荣化工新材料有限公司 | Electrolyte and lithium secondary battery |
| CN113506914A (en) * | 2021-07-14 | 2021-10-15 | 国家纳米科学中心 | Ternary lithium ion battery electrolyte and lithium ion battery containing same |
| CN114024027A (en) * | 2021-10-29 | 2022-02-08 | 湖南法恩莱特新能源科技有限公司 | High-concentration electrolyte and preparation method and application thereof |
| CN114024027B (en) * | 2021-10-29 | 2024-04-19 | 湖南法恩莱特新能源科技有限公司 | High-concentration electrolyte and preparation method and application thereof |
| CN114300746A (en) * | 2021-12-15 | 2022-04-08 | 惠州锂威新能源科技有限公司 | Electrolyte additive, electrolyte and energy storage device |
| CN114284557A (en) * | 2021-12-17 | 2022-04-05 | 上海瑞浦青创新能源有限公司 | Electrolyte for battery and battery using same |
| CN114156539A (en) * | 2021-12-21 | 2022-03-08 | 华南师范大学 | Sodium secondary battery electrolyte and sodium secondary battery |
| CN114520371A (en) * | 2022-02-18 | 2022-05-20 | 香河昆仑新能源材料股份有限公司 | Non-aqueous electrolyte and lithium ion battery comprising same |
| CN114520371B (en) * | 2022-02-18 | 2024-04-05 | 香河昆仑新能源材料股份有限公司 | Nonaqueous electrolyte and lithium ion battery comprising same |
| CN114628787A (en) * | 2022-03-28 | 2022-06-14 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| CN114628787B (en) * | 2022-03-28 | 2024-04-05 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device, and electronic device |
| CN114725513A (en) * | 2022-04-01 | 2022-07-08 | 华中科技大学 | Electrolyte containing fluoro additive, preparation method thereof and lithium secondary battery |
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