CN105789701B - Electrolyte and lithium ion battery comprising same - Google Patents
Electrolyte and lithium ion battery comprising same Download PDFInfo
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- CN105789701B CN105789701B CN201610194875.9A CN201610194875A CN105789701B CN 105789701 B CN105789701 B CN 105789701B CN 201610194875 A CN201610194875 A CN 201610194875A CN 105789701 B CN105789701 B CN 105789701B
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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
- 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
Abstract
The application relates to the field of batteries, in particular to electrolyte and a lithium ion battery comprising the electrolyte. The electrolyte of the present application includes an organic solvent, a lithium salt, and an additive including a hydrogenated thiophene-boron trifluoride complex compound and lithium fluorophosphate. Under the common synergistic effect of the electrolyte during hydrogenation of thiophene-boron trifluoride coordination compounds and lithium fluorophosphate, SEI films capable of preventing the electrolyte from being decomposed are formed on the surfaces of a positive plate and a negative plate of the lithium ion battery, and acidic substances generated in the electrolyte can be neutralized, so that the cycle performance and the storage performance of the lithium ion battery are greatly improved.
Description
Technical field
This application involves field of batteries more particularly to a kind of electrolyte and including the lithium ion battery of the electrolyte.
Background technique
Currently, the positive electrode active materials employed in lithium ion battery mainly have LiMn2O4, cobalt acid lithium, ternary material,
LiFePO 4 etc. selects the charge cutoff voltage of the lithium ion battery of the above-mentioned positive electrode being previously mentioned in general
No more than 4.2V, but with advances in technology and the continuous development in market, the energy density of lithium ion battery is promoted increasingly
Seem important and urgent, it is a kind of promoted lithium ion battery energy density effective ways be exploitation high-voltage lithium ion batteries.
However, will lead to conventional electrolyte in the positive electrode surface oxygenolysis of battery, electrolysis under the high voltage of 4.6V
The oxygenolysis of liquid itself can promote the deteriorative reaction of positive electrode active materials simultaneously, further influence the performance of lithium ion battery,
Such as storage performance and cycle performance.
For the defect and deficiency of existing battery, spy releases the application.
Summary of the invention
Primary goal of the invention of the invention is to propose a kind of electrolyte.
Second goal of the invention of the invention is to propose a kind of lithium ion battery.
In order to complete the purpose of the present invention, the technical solution of use are as follows:
This application involves a kind of electrolyte, including organic solvent, lithium salts and additive, the additive includes hydrogenation thiophene
Pheno-boron trifluoride complex and fluorophosphate lithium.
Preferably, in the hydrogenation thiophene-compound of the boron trifluoride complex selected from the structural formula as shown in formula I
It is at least one:
Wherein, R1, R2, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano, substituted or unsubstituted C1~20Alkane
Base, substituted or unsubstituted C2~20Alkenyl, substituted or unsubstituted C6~26Aryl；
Substituent group is selected from halogen, cyano.
Preferably, in the hydrogenation compound of the thiophene-boron trifluoride complex selected from the structural formula as shown in I A of formula
At least one；
Wherein, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano, substituted or unsubstituted C1~20Alkyl, substitution
Or unsubstituted phenyl；Substituent group is selected from halogen, cyano.
Preferably, R3, R4It is each independently selected from hydrogen atom, fluorine atom.
Preferably, the fluorophosphate lithium compound is single at least one of lithium fluophosphate and difluorophosphate.
Preferably, hydrogenation thiophene-boron trifluoride complex content is the 0.05% of the total weight of electrolyte
~10%.
Preferably, the content of the fluorophosphate lithium is the 0.001%~2% of the total weight of electrolyte.
Preferably, the organic solvent is selected from ethylene carbonate, propene carbonate, butylene, fluoro ethylene carbonate
Ester, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, in 1,4- fourth
At least one of ester, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate and ethyl butyrate.
Preferably, the lithium salts is selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro grass
Acid phosphoric acid lithium, LiN (SO2RF)2、LiN(SO2F)(SO2RF), it is double trifluoromethanesulfonimide lithiums, bis- (fluorine sulphonyl) imine lithiums, double
At least one of Lithium bis (oxalate) borate, difluorine oxalic acid boracic acid lithium, wherein RF=-CnF2n+1, the integer that n is 1~10, preferably
LiPF6、LiN(SO2RF)2At least one of；
It is furthermore preferred that the concentration of the lithium salts in the electrolytic solution is 0.5molL-1~2molL-1。
The application further relates to a kind of lithium ion battery, including the positive plate containing positive electrode active materials, contains negative electrode active
Negative electrode tab, isolation film and the electrolyte described herein of material.
The attainable advantageous effects of the application are as follows:
In electrolyte provided by the present application, due to simultaneously including hydrogenation thiophene-boron trifluoride complex and fluoro phosphorus
Sour lithium, therefore the cycle performance and storage performance of lithium ion battery can be improved.The two it is common synergistic effect under, lithium from
The positive and negative plate surface of sub- battery is respectively formed the SEI film that can prevent electrolyte decomposition, is especially formed and is hindered on negative electrode tab surface
Resist small and fine and close solid electrolyte interface (SEI) film；In addition, due to containing hydrogenation thiophene-boron trifluoride in electrolyte simultaneously
Complex and fluorophosphate lithium, can also stablize lithium salts；Additionally it is possible to the acidic materials generated in electrolyte are neutralized,
Such as PF5、HF、CO2Deng effectively reducing corrosion of these acidic materials to SEI film.It thus can be under the synergistic effect of the two, significantly
Improve the cycle performance of lithium ion battery；At the same time, the storage performance of electrolyte is also significantly improved.
Specific embodiment
It is described in detail below by the application, will become more with these explanations the characteristics of the application with advantage
It is clear, clear.
The application's is designed to provide a kind of electrolyte, including organic solvent, lithium salts and additive, the additive packet
Include hydrogenation thiophene-boron trifluoride complex and fluorophosphate lithium.
In above-mentioned electrolyte, hydrogenation thiophene-boron trifluoride complex refers to that hydrogenation thiophene mentioned above is organic
The complex that molecule and boron trifluoride are formed, boron trifluoride are in anion, and hydrogenation thiophene entirely hydrogenates thiophene in cation
Pheno-boron trifluoride complex is in electroneutral.
Hydrogenate at least one of the compound that thiophene-boron trifluoride complex is selected from the structural formula as shown in formula I:
Wherein, R1, R2, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano, substituted or unsubstituted C1~20Alkane
Base, substituted or unsubstituted C2~20Alkenyl, substituted or unsubstituted C6~26Aryl；
Substituent group is selected from halogen, cyano.
Wherein, halogen atom F, Cl, Br, preferably F, Cl；
Wherein, as described below in above-mentioned I substituent group of formula.
The alkyl that carbon atom number is 1~20, alkyl can be chain-like alkyl, can also be naphthenic base, on the ring of naphthenic base
Hydrogen can be replaced by alkyl, in the alkyl the preferred lower limit value of carbon atom number be 2,3,4,5, preferred upper limit value be 3,4,5,
6,8,10,12,14,16,18.Preferably, select carbon atom number for 1~10 alkyl, it is further preferred that selection carbon atom number
For 1~6 chain-like alkyl, carbon atom number is 3~8 naphthenic base, it is further preferred that select carbon atom number for 1~4 chain
Shape alkyl, the naphthenic base that carbon atom number is 5~7.It as the example of alkyl, can specifically enumerate: methyl, ethyl, n-propyl, different
Propyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopenta, cyclohexyl.
The alkenyl that carbon atom number is 2~20 can be cyclic alkenyl radical, can also be chain alkenyl.In addition, in alkenyl double bond
Number preferably 1.The preferred lower limit value of carbon atom number is 3,4,5 in the alkenyl, and preferred upper limit value is 3,4,5,6,8,10,
12,14,16,18.Preferably, select carbon atom number for 2~10 alkenyl, it is further preferred that selecting carbon atom number for 2~6
Alkenyl, it is further preferred that select carbon atom number for 2~5 alkenyl.As the example of alkenyl, can specifically enumerate: second
Alkenyl, allyl, isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base.To the specific choice and alkenyl of alkynyl
It is identical.
Carbon atom number be 6~26 aryl, such as phenyl, benzene alkyl, such as xenyl of the aryl at least containing a phenyl,
Condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and condensed-nuclei aromatics base can also be replaced alkyl or alkenyl.Preferably, it selects
Select carbon atom number be 6~16 aryl, it is further preferred that select carbon atom number for 6~14 aryl, still more preferably
Ground, select carbon atom number for 6~9 aryl.As the example of aryl, can specifically enumerate: phenyl, benzyl, xenyl, to first
Phenyl, o-tolyl, tolyl.
When the carbon atom number being previously mentioned be 1~20 alkyl, carbon atom number be 2~20 alkenyl, carbon atom number be 6~
After 26 aryl is replaced by halogen atom, successively formed accordingly halogenated alkyl, carbon atom number that carbon atom number is 1~20 be 2~
20 halogenated alkenyl, the halogenated aryl that carbon atom number is 6~26；Wherein halogen atom is F, Cl, Br, preferably F, Cl.In institute's shape
At halo groups in, halogen atom replaces part hydrogen atom or whole hydrogen atom, and the number of halogen atom can be 1,2
It is a, 3 or 4.
Preferably, select carbon atom number for 1~10 halogenated alkyl, carbon atom number be 2~10 halogenated alkenyl, carbon atom
The halogenated aryl that number is 6~16；It is further preferred that selecting halogenated chain-like alkyl of the carbon atom number for 1~6, carbon atom number 3
The halogenated aryl that halogenated alkenyl that~8 halogenated cycloalkyl, carbon atom number are 2~6, carbon atom number are 6~14；It is further excellent
Selection of land, select carbon atom number for 1~4 halogenated chain-like alkyl, carbon atom number be 5~7 halogenated cycloalkyl, carbon atom number 2
~5 halogenated alkenyl, the halogenated aryl that carbon atom is 6~10.
It as the example of halo groups, can specifically enumerate: trifluoromethyl (- CF3), 2- fluoro ethyl, 3- fluorine n-propyl, 2-
Fluorine isopropyl, 4- fluorine normal-butyl, 3- fluorine sec-butyl, 5- fluorine n-pentyl, 4- fluorine isopentyl, 1- be fluoride-based, 3- fluorine allyl, 6-
Fluoro- 4- hexenyl, o-fluorophenyl, p-fluorophenyl, fluorophenyl, 4- trifluoromethylphenyl, 2,6- difluoromethyl phenyl, the fluoro- 1- of 2-
Naphthalene.In above-mentioned specific example, F can be replaced by Cl and/or Br.
Preferably, above-mentioned I substituent group of formula is selected from: R1, R2, R3, R4Be each independently selected from hydrogen atom, halogen atom, cyano,
Substituted or unsubstituted C1~12Alkyl, substituted or unsubstituted C1~12Alkenyl, substituted or unsubstituted C6~22Aryl.
As a kind of improvement of the application electrolyte, R1, R2, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyanogen
Base, substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted phenyl.
As a kind of improvement of the application electrolyte, hydrogenates thiophene-boron trifluoride complex and be selected from as shown in I A of formula
At least one of compound of structural formula；
Wherein, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano, substituted or unsubstituted C1~20Alkyl, substitution
Or unsubstituted phenyl；Substituent group is selected from halogen, cyano.
As a kind of improvement of the application electrolyte, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano, substitution
Or unsubstituted C1~12Alkyl；Substituent group is selected from halogen, cyano；
As a kind of improvement of the application electrolyte, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano, substitution
Or unsubstituted C1~6Alkyl；Substituent group is selected from halogen, cyano.
As a kind of improvement of the application electrolyte, R3, R4It is each independently selected from hydrogen atom, fluorine atom.
It is specific as follows shown as hydrogenation thiophene-boron trifluoride complex example:
As a kind of improvement of the application electrolyte, hydrogenates thiophene-boron trifluoride complex and is also selected from:
In this application, the hydrogenation thiophene-boron trifluoride complex being previously mentioned can be according to existing conventional synthesis
Method is synthesized, such as can refer to patent: CN200780033378.X.
In above-mentioned electrolyte, fluorophosphate lithium compound is single at least one of lithium fluophosphate and difluorophosphate.
Wherein, the chemical formula of single lithium fluophosphate is Li2PO3F, the chemical formula of difluorophosphate is LiPO2F2。
In this application, the fluorophosphate lithium being previously mentioned can be synthesized according to existing conventional synthetic method, such as
It can refer to document: Japan Patent JP2008-140767.
In above-mentioned electrolyte, hydrogenation thiophene-boron trifluoride complex content is the total weight of electrolyte
0.05%~10%, preferably the 0.1%~4% of the total weight of electrolyte, the content of fluorophosphate lithium are the gross weight of electrolyte
The 0.001%~2% of amount, preferred content are the 0.01%~1% of the total weight of electrolyte.
If in the electrolytic solution, hydrogenation thiophene-boron trifluoride complex content is excessive, then will lead in positive and negative plate
Surface forms thicker SEI film, reduces the conductive performance of lithium ion, deteriorates the cyclicity of lithium ion battery at ambient and elevated temperatures
Energy and high rate performance；And the content of fluorophosphate lithium is excessive, then will affect the conductivity of electrolyte, reduces the conductibility of lithium ion
Can, deteriorate lithium ion battery cycle performance at ambient and elevated temperatures and storage performance.
If in the electrolytic solution, hydrogenation thiophene-boron trifluoride complex content is too small, lithium-ion electric cannot be effectively improved
The cycle performance of pond at ambient and elevated temperatures, cycle performance especially under high pressure；And the content of fluorophosphate lithium is too small, together
Sample can not play the role of stable lithium salts, not have to the performance of battery.
In above-mentioned electrolyte, organic solvent can be non-aqueous organic solvent, organic solvent be preferably carbon atom number be 1~8,
And the compound containing at least one ester group.
It as the example of organic solvent, can enumerate: ethylene carbonate, propene carbonate, butylene, fluoro carbonic acid second
Enester, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- fourth
Lactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate, ethyl butyrate.
In above-mentioned electrolyte, it can also be inorganic lithium salt, specifically, can contain in lithium salts that lithium salts, which can be organic lithium salt,
At least one of fluorine element, boron element, P elements.Preferably, lithium salts is selected from lithium hexafluoro phosphate (LiPF6), LiBF4
(LiBF4), lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), LiTFOP (tetrafluoro oxalic acid lithium phosphate), LiN (SO2RF)2、
LiN(SO2F)(SO2RF), double trifluoromethanesulfonimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), bis- (fluorine sulphonyl) imines
Lithium Li (N (SO2F)2) (being abbreviated as LiFSI), di-oxalate lithium borate LiB (C2O4)2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium
LiBF2(C2O4At least one of) (being abbreviated as LiDFOB), wherein substituent RF=-CnF2n+1Saturation perfluoroalkyl, n 1
~10 integer, and 2n+1 is greater than zero integer.Particularly preferably LiPF6And/or LiN (SO2RF)2.The lithium salts is in electrolyte
In concentration be 0.5M~2M (M=molL-1)。
In this application, the preparation method of electrolyte selects conventional method, such as by organic solvent, lithium salts and can add
Agent is added to be uniformly mixed.
The another object of the application is the provision of lithium ion battery, and lithium ion battery includes electrolyte, containing positive living
The positive plate of property material, negative electrode tab and isolation film containing negative electrode active material.
In above-mentioned lithium ion battery, it will include positive electrode active materials, viscous that positive plate, which further includes binder and conductive agent,
The anode sizing agent for tying agent and conductive agent is coated on plus plate current-collecting body, obtains positive plate after anode sizing agent is dry.Likewise, will
It include that the negative electrode slurry of negative electrode active material, binder and conductive agent is coated on negative current collector, it is dry to negative electrode slurry
After obtain negative electrode tab.
Preferably, positive electrode active materials are selected from cobalt acid lithium LiCoO2, cobalt nickel lithium manganate ternary material, LiFePO 4, manganese
Sour lithium (LiMnO2At least one of), such as the mixture of cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material can be used as positive-active material
Material.As the example of cobalt nickel lithium manganate ternary material, can specifically enumerate: LiNi1/3Co1/3Mn1/3O2、
LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2。
Preferably, negative electrode active material is carbon material and/or silicon materials.
In above-mentioned lithium ion battery, the specific type of lithium battery diaphragm is not exposed to specific limitation, can be existing
Any diaphragm material used in lithium ion battery, such as polyethylene, polypropylene, Kynoar and their MULTILAYER COMPOSITE
Film, but it is not limited only to these.
Embodiment 1
The application is further described below by way of specific example.But these examples are only exemplary, not to this
The protection scope of application constitutes any restrictions.
In following embodiments, comparative example and test example, reagent, material and the instrument used be not such as special
Explanation, be conventional reagent, conventional material and conventional instrument, it is commercially available, involved in reagent can also lead to
Conventional synthesis process synthesis is crossed to obtain.
In following embodiments, comparative example and test example, used reagent is as follows:
Additive:
Hydrogenate thiophene-boron trifluoride complex: 1~compound of compound 3；
Fluorophosphate lithium: the difluorophosphate being previously mentioned.
Lithium salts: lithium hexafluoro phosphate (LiPF6)。
Organic solvent: ethylene carbonate (EC), methyl ethyl carbonate (EMC).
Positive electrode active materials: cobalt nickel lithium manganate ternary material (LiNi1/3Co1/3Mn1/3O2)。
Isolation film: using PE porous polymer film as isolation film.
The preparation of lithium ion battery (following abbreviation batteries) 1~28
Battery 1~28 is prepared by the following method:
(1) prepared by negative electrode tab
Negative electrode active material graphite, conductive agent acetylene black, binder butadiene-styrene rubber, thickener sodium carboxymethylcellulose are pressed
Be graphite according to weight ratio: acetylene black: butadiene-styrene rubber: sodium carboxymethylcellulose=95:2:2:1 is mixed, and deionized water is added
Afterwards, it is thoroughly mixed, forms uniform negative electrode slurry；This slurry is coated on negative current collector copper foil, then dries, is cold
Pressure, obtains negative electrode tab.
(2) prepared by positive plate
By weight by positive electrode active materials lithium-nickel-manganese-cobalt ternary material, conductive agent acetylene black, binder polyvinylidene fluoride
Than for lithium-nickel-manganese-cobalt ternary material: acetylene black: polyvinylidene fluoride=96:2:2 is mixed, and Solvents N-methyl pyrrolidines is added
Ketone after being thoroughly mixed, forms uniform anode sizing agent；This slurry is coated on plus plate current-collecting body aluminium foil, then dry,
Cold pressing, obtains positive plate.
(3) prepared by electrolyte
Electrolyte 1~28 is prepared by the following method:
In water content < 10ppm argon atmosphere glove box, by EC, EMC according to weight ratio be EC:EMC=3:7 carry out
After mixing, mixed solvent, then the lithium salts LiPF that will sufficiently dry are obtained6It is dissolved in above-mentioned in the mixed solvent, is then added thereto
Enter to hydrogenate thiophene-boron trifluoride complex and difluorophosphate, after mixing evenly, obtains electrolyte, wherein LiPF6It is dense
Degree is 1mol/L.
(4) preparation of battery
Battery 1~28 is prepared by the following method:
Positive plate, isolation film, negative electrode tab are folded in order, isolation film is made to be between positive/negative plate the work for playing isolation
With then winding obtains naked battery core；Naked battery core is placed in outer packing foil, after the above-mentioned electrolyte prepared is injected into drying
Battery in, then by the processes such as Vacuum Package, standing, chemical conversion, shaping, obtain battery.
It is above-mentioned prepare battery during, it is selected electrolyte in each battery, used in each electrolyte
The content for hydrogenating thiophene-boron trifluoride complex type and its content and fluorophosphate lithium, as shown in following table 1.
In following table 1, the content for hydrogenating thiophene-boron trifluoride complex content and fluorophosphate lithium is
The weight percent that total weight based on electrolyte is calculated.
Table 1
Comparative example: lithium ion battery (following abbreviation batteries) 1#~17#Preparation
Battery 1#~17#Prepared by the following method:
The preparation of battery 1 in embodiment 1 is repeated, wherein changing hydrogenation thiophene-boron trifluoride in the preparation of electrolyte and matching
Type, the content of position compound, and/or change the content of difluorophosphate, remaining condition is constant.
It is above-mentioned prepare battery during, it is selected electrolyte in each battery, used in each electrolyte
The content for hydrogenating thiophene-boron trifluoride complex type and its content and difluorophosphate, as shown in following table 2.
In following table 2, hydrogenates thiophene-content of boron trifluoride complex and the content of difluorophosphate is
The weight percent that total weight based on electrolyte is calculated.
Table 2
Note: in table 2, "-" expression is not added with any kind of substance.
Test case
(1) storage performance is tested
The battery being prepared in embodiment and comparative example carries out following tests:
At 25 DEG C, with 0.5C constant current charge to 4.6V, electric current is then charged to battery with the constant voltage of 4.6V
Less than 0.05C, with the constant current of 0.5C to battery discharge to 3.0V；Again with 0.5C constant current charge to 4.6V, then with
The constant voltage of 4.6V charges to electric current less than 0.05C to battery, and then battery is placed at 60 DEG C and is stored 30 days, wait store knot
Shu Hou, with the constant current of 0.5C to battery discharge to 3.0V；Again with 0.5C constant current charge to 4.6V, then with the perseverance of 4.6V
Constant voltage is charged to electric current to battery and is so repeated 3 times less than 0.05C with the constant current of 0.5C to battery discharge to 3.0V,
Take the conduct of last time discharge capacity that can restore capacity.In addition, test result is as follows shown in table 3.
The storage of battery can restore capacity rate (%)=[battery high-temperature storage after restore capacity/battery storage before
Capacity] × 100%
(2) the normal-temperature circulating performance test of battery
The battery being prepared in embodiment and comparative example carries out following tests:
At 25 DEG C, 4.6V is first charged to battery with the constant current of 1C, further extremely with 4.6V constant voltage charging
Electric current is 0.025C, and then with the constant current of 1C by battery discharge to 3.0V, this is a charge and discharge cycles process, this
Discharge capacity is the discharge capacity of the 1st circulation.Battery carries out multiple cyclic charging and discharging test in a manner described, and detection obtains the
The discharge capacity of 100 circulations, and it is calculate by the following formula the circulation volume conservation rate for obtaining battery.In addition, test result is as follows
Shown in table 3.
Battery 100 times circulation after capacity retention ratio (%)=[the 100th time circulation discharge capacity/1st time circulation put
Capacitance] × 100%
(3) the high temperature cyclic performance test of battery
The battery being prepared in embodiment and comparative example carries out following tests:
At 45 DEG C, 4.6V is first charged to battery with the constant current of 1C, further extremely with 4.6V constant voltage charging
Electric current is 0.025C, and then with the constant current of 1C by battery discharge to 3.0V, this is a charge and discharge cycles process, this
Discharge capacity is the discharge capacity of the 1st circulation.Battery carries out multiple cyclic charging and discharging test in a manner described, and detection obtains the
The discharge capacity of 100 circulations, and it is calculate by the following formula the capacity retention ratio after the circulation for obtaining battery.In addition, test result
As shown in Table 3 below.
Battery 100 times circulation after capacity retention ratio (%)=[the 100th time circulation discharge capacity/1st time circulation put
Capacitance] × 100%
Table 3
Related data from above-mentioned table 3, is analyzed as follows:
(1) 60 DEG C of storage performance test result analysis
By to battery 2#, battery 3#And battery 4 and battery 1#It tests obtaining as a result, it is known that when same in electrolyte
When Shi Hanyou difluorophosphoric acid lithium compound and hydrogenation thiophene-boron trifluoride complex, more only addition hydrogenation thiophene-is borontrifluoride
Boron complex only adds difluorophosphate or the case where do not add additive, good rate capability.
It is compared by the test result of the obtained battery of battery 1-8, it is known that the amount of fixed difluorophosphate is 0.5%
When, as hydrogenation thiophene-boron trifluoride complex additive amount increases, battery high rate performance is first improved and is reduced afterwards；
It is compared by the test result of the obtained battery of battery 4 and battery 9-12, it is known that fixed hydrogenation thiophene-three
When the amount of boron fluoride complex is 2%, the additive amount with difluorophosphate complex increases, battery high rate performance
First improve reduces afterwards；
Likewise, analyzing 13~28 high rate performance of battery, there is analysis result same as described above.
(2) test result analysis of cycle performance
Capacity retention ratio and battery 1 after the circulation obtained by battery 1~28#Capacity retention ratio after obtained circulation can
To find out, containing hydrogenation thiophene-boron trifluoride complex and fluorophosphate lithium compound in electrolyte, battery has higher
Capacity retention ratio, battery under high temperature and room temperature have excellent cycle performance.
By battery 1#~9#Capacity retention ratio after obtained circulation, it is known that electrolyte 1#In not any add without being added
Add agent, so that organic solvent can generate more side reaction in pole piece, causes the capacity retention ratio of battery low.
In battery 2#With battery 3#In, respectively in respective electrolyte addition hydrogenation thiophene-boron trifluoride ligand compound
Object, difluorophosphoric acid lithium compound, due to hydrogenation thiophene-boron trifluoride complex is formed by SEI film can't be effective
Ground prevent side reaction between active material and electrolyte or difluorophosphate cannot effective stable lithium salts, to make battery
Cycle performance cannot improve substantially.
Due in battery 4#, battery 5#With battery 7#In, hydrogenate thiophene-boron trifluoride complex and/or difluorophosphoric acid
The weight percentage of lithium compound is very little, due to hydrogenation thiophene-boron trifluoride complex is formed by SEI film cannot
The characteristics of having both compactness and stability can not effectively prevent side reaction or difluoro phosphorus between active material and electrolyte
Sour lithium cannot effective stable lithium salts, improve cycle performance of the battery under high temperature and room temperature cannot effectively.
In battery 6#, battery 8#, battery 9#In, hydrogenate thiophene-boron trifluoride complex and/or difluorophosphoric acid lithiumation
Conjunction object content is excessive, and excessive hydrogenation thiophene-boron trifluoride complex and difluorophosphoric acid lithium compound remain in electrolyte
In, hydrogenation thiophene-boron trifluoride complex will continue to react in pole piece, and interface impedance is caused to become larger；Difluorophosphoric acid
Lithium will lead to the decline of the performances such as the conductivity of electrolyte, to deteriorate cycle performance of the battery under high temperature and room temperature.
In battery 1~8, the content of difluorophosphoric acid lithium compound is 0.5%, and the hydrogen that content is 0.05%~10% is added
Change thiophene-boron trifluoride complex, fine and close, stable SEI film can be formed, prevented between active material and electrolyte
Side reaction, capacity retention ratio with higher after recycling battery under high temperature and room temperature.
In battery 4 and battery 9~12, hydrogenation thiophene-boron trifluoride complex content is 2%, and addition contains
The difluorophosphoric acid lithium compound that amount is 0.1%~2% can form fine and close, stable SEI film, prevent active material and electrolysis
Side reaction between liquid, capacity retention ratio with higher after recycling battery under high temperature and room temperature.Likewise, to battery 15
Capacity retention ratio after~28 circulations is analyzed, and has analysis result same as described above.
In from the above as can be seen that in the electrolyte containing hydrogenated thiophene-boron trifluoride complex and fluorine simultaneously
When for lithium phosphate compound, the capacity retention ratio after battery recycles under high temperature and room temperature is improved, battery is under high temperature and room temperature
With excellent cycle performance.
In summary: in the electrolytic solution, when hydrogenation thiophene-boron trifluoride complex content it is too small or it is excessive with
And when fluorophosphate lithium compound content is too small or excessive, fine and close, stable, the preferable SEI of interface performance cannot be all formed
Film, can not effectively stable lithium salts, so that the battery of the good cycle under high temperature and room temperature can not be obtained simultaneously.When electrolyte contains
There are 0.05%~10% hydrogenation thiophene-boron trifluoride complex and 0.001%~2% fluorophosphate lithium compound,
Especially containing 0.1%~4.0% hydrogenation thiophene-boron trifluoride complex and 0.1%~1% difluorophosphoric acid lithiumation
Object is closed, cycle performance of the battery under high temperature and room temperature is more excellent.
Embodiment 2
Electrolyte is prepared according to the method for embodiment 1, and difference is that additive hydrogenates thiophene-boron trifluoride ligand compound
Object, the structural formula of fluorophosphate lithium and content are as shown in table 4:
In following table 4, thiophene-boron trifluoride complex is hydrogenated, the content of fluorophosphate lithium is based on electrolyte
The weight percent that is calculated of total weight.
Table 4
The electrolyte 29~44 being prepared is prepared into lithium ion battery according to method in above-described embodiment, is prepared
The 60 DEG C of storage performance test results and cycle performance of lithium ion battery are similar to the aforementioned embodiment.
The announcement of book according to the above description, the application those skilled in the art can also carry out above embodiment
Change and modification appropriate.Therefore, the application is not limited to specific embodiment disclosed and described above, to the application's
Some modifications and changes should also be as falling into the protection scope of claims hereof.
Claims (7)
1. a kind of electrolyte, which is characterized in that including organic solvent, lithium salts and additive, the additive includes hydrogenation thiophene-
Boron trifluoride complex and fluorophosphate lithium, wherein the hydrogenation thiophene-boron trifluoride complex is selected from such as formula I
At least one of the compound of shown structural formula:
Wherein, R1, R2, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano, substituted or unsubstituted C1~20Alkyl takes
Generation or unsubstituted C2~20Alkenyl, substituted or unsubstituted C6~26Aryl；Substituent group is selected from halogen, cyano,
Hydrogenation thiophene-boron trifluoride complex content is the 0.05%~10% of the total weight of electrolyte, described
The content of fluorophosphate lithium is the 0.001%~2% of the total weight of electrolyte,
And the fluorophosphate lithium compound is single at least one of lithium fluophosphate and difluorophosphate.
2. electrolyte according to claim 1, which is characterized in that the hydrogenation thiophene-boron trifluoride complex choosing
At least one of the compound of structural formula shown in Formulas I A freely；
Wherein, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano, substituted or unsubstituted C1~20Alkyl, substitution or not
Substituted phenyl；Substituent group is selected from halogen, cyano.
3. electrolyte according to claim 1, which is characterized in that R3, R4It is each independently selected from hydrogen atom, fluorine atom.
4. electrolyte according to claim 1, which is characterized in that the organic solvent is selected from ethylene carbonate, carbonic acid third
Enester, butylene, fluorinated ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbon
Sour first propyl ester, ethyl propyl carbonic acid ester, 1,4- butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate with
And at least one of ethyl butyrate.
5. electrolyte according to claim 1, which is characterized in that
The lithium salts be selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro oxalic acid lithium phosphate,
LiN(SO2RF)2、LiN(SO2F)(SO2RF), bis- (fluorine sulphonyl) imine lithiums, di-oxalate lithium borate, in difluorine oxalic acid boracic acid lithium extremely
Few one kind, wherein RF=-CnF2n+1, n be 1~10 integer；
The concentration of the lithium salts in the electrolytic solution is 0.5molL-1~2molL-1。
6. electrolyte according to claim 5, which is characterized in that the lithium salts is LiPF6、LiN(SO2RF)2In at least
It is a kind of.
7. a kind of lithium ion battery, which is characterized in that including the positive plate containing positive electrode active materials, contain negative electrode active material
Negative electrode tab, isolation film and electrolyte according to any one of claims 1 to 6.
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| CN113045593A (en) * | 2019-12-26 | 2021-06-29 | 北京卫蓝新能源科技有限公司 | Boron-containing organic matter and preparation method and application thereof |
| CN114649583A (en) | 2020-12-17 | 2022-06-21 | 北京卫蓝新能源科技有限公司 | Sulfur-based boron trifluoride salt electrolyte containing unsaturated heterocycle and preparation method and application thereof |
| WO2022160099A1 (en) * | 2021-01-26 | 2022-08-04 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device, and electronic device |
| CN113725485A (en) * | 2021-07-22 | 2021-11-30 | 合肥国轩高科动力能源有限公司 | High-voltage lithium ion battery electrolyte and lithium ion battery |
| EP4287335A1 (en) * | 2022-03-29 | 2023-12-06 | Contemporary Amperex Technology Co., Limited | Electrolyte and secondary battery thereof, battery module, battery pack and electric device |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101425610A (en) * | 2008-10-30 | 2009-05-06 | 上海交通大学 | Alkylthiophene ionic liquid electrolysis solution used for lithium secondary battery |
| CN101512825A (en) * | 2006-09-14 | 2009-08-19 | 国立大学法人静冈大学 | Electrolytic solution for electrochemical device |
| CN102150314A (en) * | 2008-09-11 | 2011-08-10 | 丰田自动车株式会社 | Electrolyte solution and use thereof |
| CN102195082A (en) * | 2010-03-05 | 2011-09-21 | 索尼公司 | Lithium secondary battery, electrolytic solution for lithium secondary battery, electric power tool, electrical vehicle, and electric power storage system |
| CN102332606A (en) * | 2010-07-13 | 2012-01-25 | 比亚迪股份有限公司 | Non-aqueous electrolyte solution and lithium ion battery using same |
| CN103035949A (en) * | 2011-10-07 | 2013-04-10 | 索尼公司 | Electrolytic solution, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic device |
| CN103130783A (en) * | 2011-12-01 | 2013-06-05 | 海洋王照明科技股份有限公司 | Thiophanes ionic liquid containing carbonic ester perssad and preparation method and application thereof |
| CN105098243A (en) * | 2015-08-04 | 2015-11-25 | 宁德时代新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3336998B2 (en) * | 1998-08-28 | 2002-10-21 | 株式会社豊田中央研究所 | Non-aqueous electrolyte secondary battery |
| WO2012090285A1 (en) * | 2010-12-27 | 2012-07-05 | トヨタ自動車株式会社 | Nonaqueous electrolyte solution and use thereof |
| TWI487161B (en) * | 2011-11-16 | 2015-06-01 | Univ Nat Taiwan Science Tech | Lithium-ion battery and method for fabricating the same |
-
2016
- 2016-03-31 CN CN201610194875.9A patent/CN105789701B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101512825A (en) * | 2006-09-14 | 2009-08-19 | 国立大学法人静冈大学 | Electrolytic solution for electrochemical device |
| CN102150314A (en) * | 2008-09-11 | 2011-08-10 | 丰田自动车株式会社 | Electrolyte solution and use thereof |
| CN101425610A (en) * | 2008-10-30 | 2009-05-06 | 上海交通大学 | Alkylthiophene ionic liquid electrolysis solution used for lithium secondary battery |
| CN102195082A (en) * | 2010-03-05 | 2011-09-21 | 索尼公司 | Lithium secondary battery, electrolytic solution for lithium secondary battery, electric power tool, electrical vehicle, and electric power storage system |
| CN102332606A (en) * | 2010-07-13 | 2012-01-25 | 比亚迪股份有限公司 | Non-aqueous electrolyte solution and lithium ion battery using same |
| CN103035949A (en) * | 2011-10-07 | 2013-04-10 | 索尼公司 | Electrolytic solution, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic device |
| CN103130783A (en) * | 2011-12-01 | 2013-06-05 | 海洋王照明科技股份有限公司 | Thiophanes ionic liquid containing carbonic ester perssad and preparation method and application thereof |
| CN105098243A (en) * | 2015-08-04 | 2015-11-25 | 宁德时代新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
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Effective date of registration: 20191219 Address after: 213300 No. 1000 North Avenue, Kunlun Street, Liyang City, Changzhou City, Jiangsu Province Patentee after: CONTEMPORARY AMPEREX TECHNOLOGY Ltd. (JIANGSU) Address before: 352100, Xingang Road, Ningde Town, Jiaocheng District, Fujian, 1 Patentee before: Contemporary Amperex Technology Co.,Ltd. |