CN110148776A - A kind of lithium secondary cell electrolyte and lithium secondary battery reducing battery impedance - Google Patents
A kind of lithium secondary cell electrolyte and lithium secondary battery reducing battery impedance Download PDFInfo
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- CN110148776A CN110148776A CN201910478962.0A CN201910478962A CN110148776A CN 110148776 A CN110148776 A CN 110148776A CN 201910478962 A CN201910478962 A CN 201910478962A CN 110148776 A CN110148776 A CN 110148776A
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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
- H01M10/0567—Liquid materials characterised by the additives
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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
Abstract
The present invention relates to lithium secondary cell electrolyte fields, and in particular to a kind of additive containing phenyl ring and the electrolyte containing the additive.Using the lithium secondary battery of the electrolyte there is lower impedance under room temperature use condition, is provided simultaneously with better cryogenic property, high-temperature behavior and cycle life.Meanwhile the invention also discloses the lithium ion batteries using the electrolyte.
Description
Technical field
The present invention relates to lithium secondary cell electrolyte fields, and in particular to a kind of additive containing phenyl ring and contains the additive
Electrolyte.
Background technique
Lithium secondary battery makes it in consumer electricity due to having the characteristics that energy density is high, having extended cycle life, pollution-free
It has broad application prospects on son, power vehicle battery and on accumulation power supply.
In recent years, with the failure of the Global Oil energy and the development of new energy technology, applied on automobile power
Lithium secondary battery technology rapidly develops.To the performance of lithium secondary battery, more stringent requirements are proposed.As battery need it is longer
Service life, needs can use in extreme temperatures, it is desirable to be able to carry out quick charge and discharge (high magnification), need preferably
Safety.
The battery pack of electric vehicle is usually to be connected or composed in parallel by multiple batteries, and battery can produce in normal work
Raw certain heat, entire battery pack will use a set of battery thermal management system and carry out heat management to battery.The quantity of heat production of battery
Related with the charge-discharge magnification of battery and internal resistance, in the case that internal resistance is certain, charge-discharge magnification is higher, and thermal discharge is bigger, and fills
In the case that discharge-rate is certain, internal resistance is bigger, and thermal discharge is bigger.It is being able to carry out quick charge and discharge (high magnification), is being needed
Under the driving for having better security requirement, charge-discharge magnification cannot be sacrificed, therefore wants control in reasonable thermal discharge, to the greatest extent
Under the conditions of possible powerful charge and discharge, it is desirable that reduce itself internal resistance.
Also, since battery pack is made of multiple batteries, the consistency of single battery determines making for entire battery pack
Battery with two side terminals can be largely improved, to improve the service life of battery as can reducing the impedance of battery with the service life.
In addition, if the internal resistance of battery is excessive, voltage can be rapidly during the charging process for battery in terms of the safety of battery
Rise, battery has the risk overcharged, and battery once overcharges, it is possible that on fire, explosion.Solving the problems, such as over-charging of battery
On, current most solution is that anti-overcharge additive is added in battery electrolyte, and battery once overcharges, anti-overcharge to add
Add agent that polymerization reaction can occur, increase the internal resistance of battery, blocks inside battery electric current, prevent battery catches fire from exploding.But pass through
The mode of anti-overcharge additive is added in electrolyte, although security performance can be promoted to a certain extent, once battery mistake
It fills, the damage to battery is irreversible.
In conclusion needing fundamentally to reduce battery impedance, inhibit the phenomenon that battery is overcharged from source, to electricity
The service life in pond, safety can be more preferable.
CN106450438A improves the electrode/electro of lithium ion battery by adding phosphoric acid ester additive in the electrolytic solution
Solve liquid interfacial property, improve its stability, reduce interface impedance, thus improve lithium ion battery cyclical stability and high temperature,
High voltage capability, gas caused by inhibiting organic solvent to decompose generate, and reduce the expansion of battery.But its reduce be electrode and
The impedance of electrolyte interface, and the overall impedance of non-battery.
WO03083972A1 disclose a kind of non-aqueous electrolyte include poly- (siloxanes-g-3 ethylene oxide) and its
Synthesis.The electrolyte provides significant safety, improves electrochemical stability, improves conductivity, lower impedance, and reduce system
Cause this.But poly- (siloxanes-g-3 ethylene oxide) is nv polymer electrolyte, synthesis is complex, and on boundary
There is also a certain distance with liquid electrolyte in the electric conductivity of face.
It is to improve high-nickel material cycle performance of battery, inhibit battery that CN107834110A, which discloses additive A main function,
Internal resistance increases in high-temperature storage and cyclic process, and additive A includes methyl phenyl carbonate (MPC), carbonic acid phenethyl ester (EPC), uncle
Butyl phenyl carbonic ester, diphenyl carbonate (DPC), bis- (pentafluorophenyl group) carbonic esters (DPFPC), triphenyl phosphite, tricresyl phosphate
At least one of phenyl ester (TPP).But totally investigate be the internal resistance under charge status variation it is smaller, be not concerned with room temperature
Under the conditions of battery itself smaller internal resistance.
Therefore, based on above consideration, it is necessary to provide a kind of electrolyte of lithium secondary battery for reducing battery impedance, especially
It is that while having at low cost under room temperature use condition, is easy to compound with existing electrolyte system, high temperature performance and circulation
Service life such as can also be guaranteed at the characteristics simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of lithium secondary cell electrolytes, using the lithium secondary battery of the electrolyte in room temperature
There is lower impedance under use condition, be provided simultaneously with better cryogenic property, high-temperature behavior and cycle life.Meanwhile this hair
The bright lithium ion battery also disclosed using the electrolyte.
It has surprisingly been found that when adding lithium secondary cell electrolyte shown in structural formula 1 in lithium secondary cell electrolyte
After additive, the impedance of battery is greatly lowered.
Wherein, R1、R2、R3、R4、R5、R6It is independently the phenyl ring that H, F, methyl, phenyl ring, 1-3 F replace.It is preferred that
Ground, R1-R6In at least there are three be F or R1-R6In at least one for 1-3 F substitution phenyl ring.
The present invention also protects the application of the above-mentioned lithium secondary cell electrolyte additive with above structure, is used for non-water body
It is lithium secondary cell electrolyte, the non-aqueous system lithium secondary cell electrolyte, including lithium salts, nonaqueous solvents and adding containing phenyl ring
Add agent and weight percent that the 1 lithium secondary cell electrolyte additive of structural formula is shared in lithium-ion battery electrolytes
For 0.01%-5%.
The nonaqueous solvents is dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl acetate, carbon
Sour first propyl ester, fluorinated ethylene carbonate, 2,2- bis-fluoro ethyls acetic acid esters, propionic acid trifluoroethyl ester, propionic acid bis-fluoro ethyls ester, fluoro
At least one of propene carbonate, methyl propyl carbonate, gamma-butyrolacton and gamma-valerolactone.
The lithium salts is lithium hexafluoro phosphate, bis- (trimethyl fluoride sulfonyl) imine lithiums, at least one in double fluorine sulfimide lithiums
Kind.
The present invention also protects the lithium secondary cell electrolyte of the lithium secondary cell electrolyte additive containing structural formula 1, packet
Lithium salts, nonaqueous solvents, 1 lithium secondary cell electrolyte additive of the structural formula are included, the mass percent of the lithium salts is 5%-
25%；The mass percent of the nonaqueous solvents is 70%-95%；1 lithium secondary cell electrolyte of the structural formula addition
The mass percent of agent is 0.01%-5%.
The lithium secondary cell electrolyte can also include vinylene carbonate, fluorinated ethylene carbonate, difluorophosphoric acid
Lithium, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, 1,3- propane sultone, Triallyl isocyanurate, methane-disulfonic acid
Methylene ester, sulfuric acid vinyl ester, triallyl phosphate, three propinyl phosphates, diphenyl disulfide, tetrabromo cyclooctane, tetrabromo are double
At least one of phenol A, isothiocyanic acid trimethylsilyl group Second addition, the mass percent for accounting for electrolyte is 0.01-10%.
Inventor by many experiments find, 1 lithium secondary cell electrolyte additive of structural formula provided by the invention with above-mentioned addition
When agent is used in combination, superior effect when being used alone than them can be obtained, thus it is speculated that have synergistic effect between them, that is, exist
When being used together with 1 compound of structural formula, the impedance of electrolyte at normal temperature can be further decreased.
The present invention also protects a kind of lithium secondary battery, which includes above-mentioned lithium secondary cell electrolyte.
Beneficial effects of the present invention are as follows:
The present invention accounts for the structural formula 1 of electrolyte gross mass 0.01%-5% by adding in the electrolyte of lithium secondary battery
Compound can reduce the internal resistance of battery as additive, be provided simultaneously with better cryogenic property, high-temperature behavior, high rate performance
And cycle life.
Specific embodiment
It is to further explanation of the invention, rather than limiting the invention below.
The particular compound structural formula being related in embodiment is as follows:
Embodiment 1
(1) preparation of the positive plate of lithium secondary battery
By positive electrode active materials nickle cobalt lithium manganate (LiNi1/3Co1/3Mn1/3O2), conductive agent Super-P, bonding agent PVDF press
Mass ratio 96:2.0:2.0, which is dissolved in being uniformly mixed in solvent N-methyl pyrilidone, is made anode sizing agent, later that anode sizing agent is equal
It is even to be coated in current collector aluminum foil, coating weight 0.018g/cm2, then at 85 DEG C dry after be cold-pressed, trimming, cut-parts,
Slitting, the positive plate of the lithium secondary battery met the requirements is made in dry 4h, soldering polar ear under 85 DEG C of vacuum conditions later.
(2) preparation of the negative electrode tab of lithium secondary battery
By negative electrode active material graphite, conductive agent Super-P, thickener CMC, bonding agent SBR 96.5:1.0 in mass ratio:
1.0:1.5, which is dissolved in being uniformly mixed in solvent deionized water, is made negative electrode slurry, and negative electrode slurry is uniformly coated on collector later
On copper foil, coating weight 0.0089g/cm2, it is cold-pressed after then being dried at 85 DEG C, trimming, cut-parts, slitting, Zhi Hou
The negative electrode tab of the lithium secondary battery met the requirements is made in dry 4h, soldering polar ear under 110 DEG C of vacuum conditions.
(3) preparation of the electrolyte of lithium secondary battery
The electrolyte of lithium secondary battery is to account for the lithium hexafluoro phosphate of electrolyte gross mass 12.5% as lithium salts, with ethylene carbonate
Ester, methyl ethyl carbonate, diethyl carbonate mixture be non-aqueous organic solvent, account for the 81.5% of electrolyte gross mass, wherein with
Ethylene carbonate, methyl ethyl carbonate, diethyl carbonate mass ratio be 3:5:2.In addition, also containing addition in lithium re-electrolysis liquid
Agent, additive are the compound 1 for accounting for lithium secondary cell electrolyte gross mass 3.0%.Second addition be vinylene carbonate, 1,
3- propane sultone accounts for 1.0%, the 2.0% of electrolyte gross mass respectively.
(4) preparation of lithium secondary battery
Positive plate, negative electrode tab and the isolation film of the lithium secondary battery prepared according to previous process are passed through into winding process system
Be made the battery core for being 130mm with a thickness of 8mm, width 60mm, length, and at 75 DEG C vacuum bakeout 10h, injection electrolyte,
It stands for 24 hours, is then dropped to later with the constant current charging of 0.1C (160mA) to 4.2V with 4.2V constant-voltage charge to electric current
0.05C (80mA) is then discharged to 3.0V with the constant current of 0.1C (160mA), charge and discharge is repeated 2 times, finally with 0.1C
The constant current charging of (160mA) completes preparation of the lithium from battery to 3.8V.
Embodiment 2
Lithium secondary battery is prepared according to the method for embodiment 1, the difference is that the electrolyte of lithium secondary battery is to account for electrolyte
The lithium hexafluoro phosphate of gross mass 10.0% is lithium salts, and non-aqueous organic solvent is ethylene carbonate, methyl ethyl carbonate, and it is total to account for electrolyte
The 87.0% of quality, mass ratio 1:2.Compound 2 is added, the 1.0% of electrolyte gross mass is accounted for.Second addition is difluoro phosphorus
Sour lithium accounts for the 1.0% of electrolyte gross mass.Positive electrode used in lithium secondary battery is LiNi0.8Co0.1Mn0.1O2。
Embodiment 3
Lithium secondary battery is prepared according to the method for embodiment 1, the difference is that non-aqueous organic solvent is ethylene carbonate, carbonic acid
Methyl ethyl ester accounts for the 83.0% of electrolyte gross mass, mass ratio 1:3.Compound 3 is added, the 1.0% of electrolyte gross mass is accounted for.
Second addition is vinylene carbonate, fluorinated ethylene carbonate, accounts for 0.5%, the 3.0% of electrolyte gross mass respectively.Lithium two
Positive electrode used in primary cell is LiNi0.8Co0.15Al0.05O2。
Embodiment 4
Lithium secondary battery is prepared according to the method for embodiment 1, the difference is that non-aqueous organic solvent is ethylene carbonate, carbonic acid
Diethylester accounts for the 84.0% of electrolyte gross mass, mass ratio 1:2.Compound 4 is added, the 2.5% of electrolyte gross mass is accounted for.
Second addition is difluorine oxalic acid boracic acid lithium, fluorinated ethylene carbonate, accounts for 0.5%, the 5.0% of electrolyte gross mass respectively.Lithium
Positive electrode used in secondary cell is LiCoO2, negative electrode material is Si-C composite material.
Embodiment 5
Lithium secondary battery is prepared according to the method for embodiment 1, the difference is that the electrolyte of lithium secondary battery is to account for electrolyte
The lithium hexafluoro phosphate of gross mass 15% be lithium salts, non-aqueous organic solvent be ethylene carbonate, propene carbonate, diethyl carbonate,
Account for the 81.5% of electrolyte gross mass, mass ratio 4:1:5.Compound 5 is added, the 1.0% of electrolyte gross mass is accounted for.Second adds
Adding agent is vinylene carbonate, three propinyl phosphates, accounts for 0.5%, the 2.0% of electrolyte gross mass respectively.Lithium secondary battery
Positive electrode used is LiNi0.8Co0.15Al0.05O2, negative electrode material is lithium titanate.The charge cutoff voltage of lithium secondary battery is
2.7V。
Embodiment 6
Lithium secondary battery is prepared according to the method for embodiment 1, the difference is that with ethylene carbonate, methyl ethyl carbonate, carbonic acid
The mixture of diethylester is non-aqueous organic solvent, accounts for the 83.5% of electrolyte gross mass, mass ratio 3:5:2.Add compound
6, account for the 0.01% of electrolyte gross mass.Second addition is triallyl phosphate, fluorinated ethylene carbonate, accounts for electrolysis respectively
1.0%, the 3.0% of liquid gross mass.Positive electrode used in lithium secondary battery is LiCoO2。
Embodiment 7
Lithium secondary battery is prepared according to the method for embodiment 1, the difference is that the electrolyte of lithium secondary battery is to account for electrolyte
The lithium hexafluoro phosphate of gross mass 17.5% is lithium salts, is non-with the mixture of ethylene carbonate, methyl ethyl carbonate, diethyl carbonate
Aqueous organic solvent, accounts for the 78.0% of electrolyte gross mass, and mass ratio 3:5:2 adds compound 7, accounts for electrolyte gross mass
4.0%.Second addition is difluorophosphate, accounts for the 0.5% of electrolyte gross mass.Positive electrode used in lithium secondary battery is
LiMn2O4, negative electrode material is lithium titanate.
Embodiment 8
Lithium secondary battery is prepared according to the method for embodiment 1, the difference is that with ethylene carbonate, methyl ethyl carbonate, carbonic acid
The mixture of diethylester is non-aqueous organic solvent, accounts for the 83.5% of electrolyte gross mass, and mass ratio 3:5:2 adds compound
8, account for the 1.0% of electrolyte gross mass.Second addition is Triallyl isocyanurate, difluorophosphate, accounts for electrolysis respectively
0.5%, the 3.0% of liquid gross mass.Positive electrode used in lithium secondary battery is LiMnO2。
Embodiment 9
Lithium secondary battery is prepared according to the method for embodiment 1, the difference is that the electrolyte of lithium secondary battery is to account for electrolyte
The lithium hexafluoro phosphate of gross mass 15% be lithium salts, non-aqueous organic solvent be ethylene carbonate, propene carbonate, diethyl carbonate,
Account for the 77.5% of electrolyte gross mass, mass ratio 4:1:5.Compound 9 is added, the 5.0% of electrolyte gross mass is accounted for.Second adds
Adding agent is vinylene carbonate, three propinyl phosphates, accounts for 0.5%, the 2.0% of electrolyte gross mass respectively.Lithium secondary battery
Positive electrode used is LiNi0.8Co0.15Al0.05O2, negative electrode material is lithium titanate.The charge cutoff voltage of lithium secondary battery is
2.7V。
Embodiment 10
Lithium secondary battery is prepared according to the method for embodiment 2, the difference is that not adding Second addition.
Embodiment 11
Lithium secondary battery is prepared according to the method for embodiment 1, the difference is that with ethylene carbonate, methyl ethyl carbonate, carbonic acid
The mixture of diethylester is non-aqueous organic solvent, accounts for the 86.5% of electrolyte gross mass, mass ratio 3:5:2.Add compound
6, account for the 0.01% of electrolyte gross mass.Second addition is diphenyl disulfide, accounts for the 1.0% of electrolyte gross mass respectively.Lithium
Positive electrode used in secondary cell is LiCoO2。
Embodiment 12
Lithium secondary battery is prepared according to the method for embodiment 1, the difference is that the electrolyte of lithium secondary battery is to account for electrolyte
The lithium hexafluoro phosphate of gross mass 17.5% is lithium salts, is non-with the mixture of ethylene carbonate, methyl ethyl carbonate, diethyl carbonate
Aqueous organic solvent, accounts for the 77.0% of electrolyte gross mass, and mass ratio 3:5:2 adds compound 1, accounts for electrolyte gross mass
4.0%.Second addition is tetrabromo cyclooctane, difluorophosphate, accounts for 0.5%, the 1% of electrolyte gross mass respectively.Lithium is secondary
The positive electrode of used in battery is LiMn2O4, negative electrode material is lithium titanate.
Embodiment 13
Lithium secondary battery is prepared according to the method for embodiment 1, the difference is that non-aqueous organic solvent is ethylene carbonate, carbonic acid
Methyl ethyl ester accounts for the 83.0% of electrolyte gross mass, mass ratio 1:3.Compound 3 is added, the 1.0% of electrolyte gross mass is accounted for.
Second addition is isothiocyanic acid trimethylsilyl group, tetrabromobisphenol A, accounts for 0.5%, the 3.0% of electrolyte gross mass respectively.Lithium two
Positive electrode used in primary cell is LiNi0.8Co0.15Al0.05O2。
Comparative example 1
Lithium secondary battery is prepared according to the method for embodiment 1, does not add compound in lithium secondary cell electrolyte only
1。
Comparative example 2
Lithium secondary battery is prepared according to the method for embodiment 2, does not add compound in lithium secondary cell electrolyte only
2。
Comparative example 3
Lithium secondary battery is prepared according to the method for embodiment 3, does not add compound in lithium secondary cell electrolyte only
3。
Comparative example 4
Lithium secondary battery is prepared according to the method for embodiment 4, does not add compound in lithium secondary cell electrolyte only
4。
Comparative example 5
Lithium secondary battery is prepared according to the method for embodiment 5, does not add compound in lithium secondary cell electrolyte only
5。
Comparative example 6
Lithium secondary battery is prepared according to the method for embodiment 6, does not add compound in lithium secondary cell electrolyte only
6。
Comparative example 7
Lithium secondary battery is prepared according to the method for embodiment 7, does not add compound in lithium secondary cell electrolyte only
7。
Comparative example 8
Lithium secondary battery is prepared according to the method for embodiment 8, does not add compound in lithium secondary cell electrolyte only
8。
Comparative example 9
Lithium secondary battery is prepared according to the method for embodiment 9, does not add compound in lithium secondary cell electrolyte only
9。
Finally illustrate the test process and test result of lithium secondary battery and its electrolyte according to the present invention.
All comparative examples 1~9 and 1~13 gained battery of all embodiments are tested as follows:
Circulation experiment: comparative example 1~9 and 1~13 gained battery of embodiment are being tested into battery at 25 DEG C of room temperature respectively
Internal resistance；Charge and discharge are carried out with the multiplying power of 2CC/0.5CD at 25 DEG C；It is carried out at -10 DEG C of low temperature with the multiplying power of 0.5CC/0.2CD
Charge and discharge；Charge and discharge cycles test is carried out with the charge-discharge magnification of 0.5CC/0.5CD at 55 DEG C of high temperature, records last respectively
Secondary cyclic discharge capacity and divided by the 1st cyclic discharge capacity up to capacity retention ratio, record result such as table 1.
High temperature storage experiment: by first the filling with 0.5C/0.5C at room temperature of the battery of comparative example 1~9 and embodiment 1~13
Discharge-rate charges to 4.2V at 3.0~4.2V charge and discharge 3 times, then with 0.5C, records the thickness of battery.Battery is placed on 60
It is stored 15 days in DEG C baking oven, records the thickness of battery.The thickness of battery is recorded for the second time divided by the thickness of first record battery
As cell expansion rate.As a result record such as table 1.
The test result of 1 embodiment and comparative example of table:
By above data, it is apparent that 1 compound of structural formula is to can be substantially reduced the internal resistance of cell, battery it is low
Temperature circulation, big multiplying power room temperature cycles, high temperature circulation, the expansion after high temperature storage are all significantly improved.Embodiment 1-13 is obvious
Better than its comparative example, while embodiment 10, the results show that immediately in the case where being free of Second addition, battery also has very low
Internal resistance, good low-temperature circulating, big multiplying power room temperature cycles, high temperature circulation, and the obvious expansion inhibited after high temperature storage.Cause
This can obtain lower internal resistance, better low-temperature circulating, big multiplying power room temperature cycles using battery prepared by electrolyte of the invention,
High temperature circulation, lower high temperature storage expansion.
Above-described is only presently preferred embodiments of the present invention, all made within the scope of the spirit and principles in the present invention
What modifications, equivalent substitutions and improvements etc., should all be included in the protection scope of the present invention.
Claims (10)
1. lithium secondary cell electrolyte additive shown in structural formula 1:
Wherein, R1、R2、R3、R4、R5、R6It is independently the phenyl ring that H, F, methyl, phenyl ring, 1-3 F replace, it is preferable that R1-
R6In at least there are three be F or R1-R6In at least one for 1-3 F substitution phenyl ring.
2. a kind of lithium secondary cell electrolyte, the lithium secondary cell electrolyte includes lithium salts, nonaqueous solvents and claim 1 institute
The lithium secondary cell electrolyte additive for the structural formula 1 stated.
3. lithium secondary cell electrolyte according to claim 2, which is characterized in that 1 lithium secondary battery of structural formula
Electrolysis additive weight percent shared in lithium secondary cell electrolyte is 0.01%-5%.
4. lithium secondary cell electrolyte according to claim 2, which is characterized in that the lithium salts is electrolysed in lithium secondary battery
Weight percent is 5%-25% in liquid；The weight percent of the nonaqueous solvents is 70%-95%；The structural formula 1
The weight percent of lithium secondary cell electrolyte additive is 0.01%-5%.
5. the lithium secondary cell electrolyte according to one of claim 2 to 4, which is characterized in that the nonaqueous solvents is carbon
Dimethyl phthalate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl acetate, methyl propyl carbonate, fluorinated ethylene carbonate,
2,2- bis-fluoro ethyls acetic acid esters, propionic acid trifluoroethyl ester, propionic acid bis-fluoro ethyls ester, fluoropropylene carbonate, methyl propyl carbonate,
At least one of gamma-butyrolacton and gamma-valerolactone.
6. the lithium secondary cell electrolyte according to one of claim 2 to 4, which is characterized in that the lithium salts is hexafluoro phosphorus
At least one of sour lithium, bis- (trimethyl fluoride sulfonyl) imine lithiums, double fluorine sulfimide lithiums.
7. the lithium secondary cell electrolyte according to one of claim 2 to 6, which is characterized in that can also add including second
Add agent, the mass percent for accounting for electrolyte is 0.01-10%, and the Second addition is selected from vinylene carbonate, fluoro carbonic acid
Vinyl acetate, difluorophosphate, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, 1,3- propane sultone, triallyl isocyanide urea
Acid esters, methane-disulfonic acid methylene ester, sulfuric acid vinyl ester, triallyl phosphate, three propinyl phosphates, diphenyl disulfide, four
At least one of bromine cyclooctane, tetrabromobisphenol A, isothiocyanic acid trimethylsilyl group.
8. a kind of lithium secondary battery, which is characterized in that the lithium secondary battery includes the secondary electricity of lithium described in one of claim 2-7
Pond electrolyte.
9. the lithium secondary cell electrolyte additive described in claim 1 with structural formula 1 reduces resistance in the lithium secondary battery
Anti- purposes.
10. purposes according to claim 9, it is further characterized in that the lithium secondary battery with structural formula 1
The cooperation of electrolysis additive and Second addition uses at normal temperature, the Second addition include selected from vinylene carbonate,
Fluorinated ethylene carbonate, difluorophosphate, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, 1,3- propane sultone, three allyls
Base isocyanuric acid ester, methane-disulfonic acid methylene ester, sulfuric acid vinyl ester, triallyl phosphate, three propinyl phosphates, hexichol two
At least one of thioether, tetrabromo cyclooctane, tetrabromobisphenol A, isothiocyanic acid trimethylsilyl group.
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| PCT/CN2019/128446 WO2020238191A1 (en) | 2019-05-31 | 2019-12-25 | Lithium secondary battery electrolyte capable of reducing battery impedence, and lithium secondary battery |
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Cited By (6)
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| CN110994026A (en) * | 2019-12-24 | 2020-04-10 | 河南省法恩莱特新能源科技有限公司 | Wide-temperature-range electrolyte for ternary manganese-doped lithium battery and preparation method thereof |
| CN111244551A (en) * | 2020-03-16 | 2020-06-05 | 电子科技大学 | Electrolyte additive and application thereof in lithium ion battery |
| WO2020238191A1 (en) * | 2019-05-31 | 2020-12-03 | 广州天赐高新材料股份有限公司 | Lithium secondary battery electrolyte capable of reducing battery impedence, and lithium secondary battery |
| CN113429259A (en) * | 2020-07-31 | 2021-09-24 | 中国科学院上海有机化学研究所 | Fluorine-containing compound and application thereof |
| CN114188604A (en) * | 2021-11-19 | 2022-03-15 | 惠州市豪鹏科技有限公司 | Electrolyte and battery thereof |
| CN115954542A (en) * | 2022-11-28 | 2023-04-11 | 九江天赐高新材料有限公司 | Lithium ion battery electrolyte and lithium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101142705A (en) * | 2005-02-03 | 2008-03-12 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
| CN102473962A (en) * | 2010-03-29 | 2012-05-23 | 松下电器产业株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same |
| CN103996872A (en) * | 2014-05-20 | 2014-08-20 | 珠海市赛纬电子材料有限公司 | Lithium ion battery non-aqueous electrolyte with functions of overcharging prevention and flame retardancy |
| CN104979588A (en) * | 2015-07-09 | 2015-10-14 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN105977525A (en) * | 2016-07-08 | 2016-09-28 | 深圳新宙邦科技股份有限公司 | Lithium ion battery employing non-aqueous electrolyte |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110148776A (en) * | 2019-05-31 | 2019-08-20 | 广州天赐高新材料股份有限公司 | A kind of lithium secondary cell electrolyte and lithium secondary battery reducing battery impedance |
-
2019
- 2019-05-31 CN CN201910478962.0A patent/CN110148776A/en active Pending
- 2019-12-25 WO PCT/CN2019/128446 patent/WO2020238191A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101142705A (en) * | 2005-02-03 | 2008-03-12 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
| CN102473962A (en) * | 2010-03-29 | 2012-05-23 | 松下电器产业株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same |
| CN103996872A (en) * | 2014-05-20 | 2014-08-20 | 珠海市赛纬电子材料有限公司 | Lithium ion battery non-aqueous electrolyte with functions of overcharging prevention and flame retardancy |
| CN104979588A (en) * | 2015-07-09 | 2015-10-14 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN105977525A (en) * | 2016-07-08 | 2016-09-28 | 深圳新宙邦科技股份有限公司 | Lithium ion battery employing non-aqueous electrolyte |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020238191A1 (en) * | 2019-05-31 | 2020-12-03 | 广州天赐高新材料股份有限公司 | Lithium secondary battery electrolyte capable of reducing battery impedence, and lithium secondary battery |
| CN110994026A (en) * | 2019-12-24 | 2020-04-10 | 河南省法恩莱特新能源科技有限公司 | Wide-temperature-range electrolyte for ternary manganese-doped lithium battery and preparation method thereof |
| CN110994026B (en) * | 2019-12-24 | 2021-03-09 | 河南省法恩莱特新能源科技有限公司 | Wide-temperature-range electrolyte for ternary manganese-doped lithium battery and preparation method thereof |
| CN111244551A (en) * | 2020-03-16 | 2020-06-05 | 电子科技大学 | Electrolyte additive and application thereof in lithium ion battery |
| CN111244551B (en) * | 2020-03-16 | 2022-05-03 | 电子科技大学 | Electrolyte additive and application thereof in lithium ion battery |
| CN113429259A (en) * | 2020-07-31 | 2021-09-24 | 中国科学院上海有机化学研究所 | Fluorine-containing compound and application thereof |
| CN114188604A (en) * | 2021-11-19 | 2022-03-15 | 惠州市豪鹏科技有限公司 | Electrolyte and battery thereof |
| CN115954542A (en) * | 2022-11-28 | 2023-04-11 | 九江天赐高新材料有限公司 | Lithium ion battery electrolyte and lithium ion battery |
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| WO2020238191A1 (en) | 2020-12-03 |
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