CN104269576B - A kind of electrolyte and the lithium ion battery using the electrolyte - Google Patents
A kind of electrolyte and the lithium ion battery using the electrolyte Download PDFInfo
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- CN104269576B CN104269576B CN201410528776.0A CN201410528776A CN104269576B CN 104269576 B CN104269576 B CN 104269576B CN 201410528776 A CN201410528776 A CN 201410528776A CN 104269576 B CN104269576 B CN 104269576B
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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
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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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 is related to a kind of nonaqueous electrolytic solution and the lithium ion battery using the nonaqueous electrolytic solution, and the electrolyte contains organic solvent, lithium salts and additive.In the organic solvent, the weight/mass percentage composition of ethylene carbonate in organic solvent is 0~10%；Contain fluorinated ethylene carbonate and carboxylic acid ester compound in the additive；Weight/mass percentage composition of the fluorinated ethylene carbonate in nonaqueous electrolytic solution is 5%~30%, and weight/mass percentage composition of the carboxylic acid ester compound in nonaqueous electrolytic solution is 0.1%~50%.The electrolyte by control in solvent the content of easy aerogenesis solvent ethylene carbonate and into electrolyte addition can improve the carboxylic acid esters additive at electrode/electrolyte interface, inhibit the decomposition of electrolyte, the gas production of battery is reduced, so as to improve the high-temperature storage performance of lithium ion battery.
Description
Technical field
The invention belongs to the field of lithium ion battery, being related to a kind of improves the electrolysis of high-temperature storage performance of lithium ion battery
Liquid and the lithium ion battery containing the electrolyte.
Background technology
High-energy-density, long circulation life, wide operating temperature range and the environmental protection of lithium ion battery caused its into
For the main energy sources of current mobile electronic device.But, mobile electronic device particularly smart mobile phone was (lighter, more in recent years
It is thin) develop rapidly, also the energy density to lithium ion battery proposes higher demand.
In order to improve the energy density of lithium ion battery, conventional two methods are the work for improving positive electrode respectively at present
Make voltage and using the negative material with more high discharge capacity.Wherein, Si or Sn and its alloy material of cathode are because it is remote high
It is caused to turn into an important development side of raising lithium ion battery energy density in the theoretical specific capacity (4200mAh/g) of graphite
To.But compared with graphite anode system, Si or Sn and its alloy anode system are very easy to aerogenesis under the high temperature conditions, mainly
Reason is probably that the SEI films on Si or Sn and its alloy anode surface are easily destroyed during high temperature storage：On the one hand
The destruction of SEI films result in reduction decomposition aerogenesis of the solvent in anode surface；On the other hand some cathodic protection additives are in sun
The reduction on pole surface causes negative electrode not to be effectively protected so that electrolyte oxidation decomposes aerogenesis.
In view of this, Si or Sn and its alloy anode high-temperature lithium ion battery storage can be improved it is necessory to provide one kind
The electrolyte of energy.
The content of the invention
According to the one side of the application there is provided a kind of nonaqueous electrolytic solution, the nonaqueous electrolytic solution can be improved in anode
High-temperature storage performance of lithium ion battery containing element silicon and/or tin element.
The nonaqueous electrolytic solution, contains organic solvent, lithium salts and additive, it is characterised in that：
The ethylene carbonate that the weight/mass percentage composition that the organic solvent contains in organic solvent is 0~10%；
Contain fluorinated ethylene carbonate and carboxylic acid ester compound in the additive；
Weight/mass percentage composition of the fluorinated ethylene carbonate in nonaqueous electrolytic solution is 5%~30%, the carboxylate
Weight/mass percentage composition of the class compound in nonaqueous electrolytic solution is 0.1%~50%.
In the application, the weight/mass percentage composition=100% × (matter of ethylene carbonate of ethylene carbonate in organic solvent
Amount/organic solvent quality)；Weight/mass percentage composition=100% × (fluoro carbonic acid of the fluorinated ethylene carbonate in nonaqueous electrolytic solution
The gross mass of quality/nonaqueous electrolytic solution of vinyl acetate)；Weight/mass percentage composition of the carboxylic acid ester compound in nonaqueous electrolytic solution=
100% × (gross mass of quality/nonaqueous electrolytic solution of carboxylic acid ester compound).
Preferably, the nonaqueous electrolytic solution is made up of organic solvent, lithium salts and additive.
Weight/mass percentage composition of the additive in nonaqueous electrolytic solution is 10%~85%.Preferably, the additive
Weight/mass percentage composition range limit in nonaqueous electrolytic solution is optionally from 60%, 40%, 30%, 29%, 22%, and lower limit is optionally certainly
16%th, 18%, 20%.It is further preferred that weight/mass percentage composition of the additive in nonaqueous electrolytic solution be 10%~
40%.
Weight/mass percentage composition of the organic solvent in nonaqueous electrolytic solution is 10%~80%.Preferably, it is described organic
The upper limit of weight/mass percentage composition scope of the solvent in nonaqueous electrolytic solution is optionally from 78%, 75%, 72%, and lower limit is optionally certainly
40%th, 50%, 55%, 60%, 65%.It is further preferred that quality percentage of the organic solvent in nonaqueous electrolytic solution contains
Measure as 50%~80%.
Weight/mass percentage composition of the lithium salts in nonaqueous electrolytic solution is 5%~20%.Preferably, the lithium salts is non-aqueous
The upper limit of weight/mass percentage composition scope in electrolyte is optionally from 18%, 15%, 12%, and lower limit is optionally from 5%, 7%, 9%.
Preferably, weight/mass percentage composition of the fluorinated ethylene carbonate in nonaqueous electrolytic solution is 10%~20%.
Preferably, in the organic solvent, the weight/mass percentage composition of ethylene carbonate in organic solvent is 0~5%.
Weight/mass percentage composition of the carboxylic acid ester compound in nonaqueous electrolytic solution is 0.1%~50%.If too low
It not can effectively improve high-temperature storage performance；Its passivation to both positive and negative polarity of Ruo Taigaozeyin, significantly increases anode and cathode interface
Impedance, deteriorates other performances of battery.Preferably, weight/mass percentage composition of the carboxylic acid ester compound in nonaqueous electrolytic solution
Range limit is optionally from 10%, 5%, and lower limit is optionally from 0.1%, 2%.It is further preferred that the carboxylic acid ester compound exists
Weight/mass percentage composition in nonaqueous electrolytic solution is 1~10%.
Preferably, ethylene carbonate is free of in the organic solvent.
Preferably, at least one of carbonate products in the organic solvent containing carbon number no less than 4.It is excellent
Selection of land, the ethylene carbonate and weight/mass percentage composition that the organic solvent is 0~10% by weight/mass percentage composition be 90%~
Carbonate products of 100% carbon number no less than 4 are constituted.
It is further preferred that in the organic solvent containing in propene carbonate, diethyl carbonate, methyl ethyl carbonate extremely
Few one kind.It is further preferred that the organic solvent is propene carbonate and/or diethyl carbonate.
Preferably, carboxylic acid ester compound described in additive is selected from chain carboxylic acid esters compound or cyclic carboxylic acids esters
At least one of compound.It is further preferred that carboxylic acid ester compound described in additive, which is selected from, has chemistry shown in Formulas I
The compound of structural formula, the compound with chemical structural formula shown in Formula II, the chemical combination with chemical structural formula shown in formula III
At least one of thing, compound with chemical structural formula shown in formula IV：
Wherein, R1、R2The alkyl halide that the alkyl or carbon number for being separately 1~6 selected from carbon number are 1~6
Alkyl；
R3~R14The alkyl for being optionally separately 1~6 from hydrogen, halogen, carbon number, carbon number are 1~6
The haloalkene alkyl that the alkylene or carbon number that alkyl halide alkyl, carbon number are 1~6 are 1~6.
Preferably, R in Formulas I1、R2The alkyl or carbon number for being separately 1~4 selected from carbon number are 1~4
Alkyl halide alkyl.
Preferably, the R in Formula II~formula IV3~R14Separately optionally from hydrogen, halogen, the alkane that carbon number is 1~3
The halo that the alkylene or carbon number that alkyl halide alkyl that alkyl, carbon number are 1~3, carbon number are 1~6 are 1~3
Alkylene.
Compound with chemical structural formula shown in Formulas I~formula IV can be effectively improved the high temperature storage of lithium ion battery
Can, reason be it is at least following in one kind：(1) have in the compound of chemical structural formula shown in Formulas I~formula IV and contain carboxylate
With the intermediate product in SEI film forming processes certain chemical reaction may occur for base, the group, and film forming is participated in indirectly, and
The SEI films generated have extraordinary heat endurance so that it can effectively suppress the reduction decomposition of solvent, particularly be electrolysed
The reduction decomposition of cathodic protection additive in liquid, so as to it also avoid oxidation Decomposition of the solvent in positive pole；(2) relative to conventional carbon
For acid esters solvent, the oxidizing potential of carboxylate is relatively low so that it can be aoxidized so as to modifying positive pole interface in positive pole, also can be one
Determine the oxidation Decomposition aerogenesis of suppression electrolyte in degree.
With in the compound of chemical structural formula shown in Formulas I~formula IV, R1~R14The selection of group is moderate.If these bases
The carbon number of group is excessive, and on the one hand causing the viscosity of electrolyte increases, and electrical conductivity declines, and can not only influence low temperature performance
And high rate performance, can also be because of polarization increase influence cycle performance；On the other hand the space steric effect of each functional group can cause
It, which does not reach, improves the purpose of high-temperature storage performance.
Preferably, the additive contains vinylene carbonate (being abbreviated as VC), vinylethylene carbonate and (is abbreviated as
VEC), fluorinated ethylene carbonate (being abbreviated as FEC), sulfuric acid vinyl ester (being abbreviated as DTD), sulfuric acid vinylene (being abbreviated as ES),
At least one of 1,3- propane sultones (being abbreviated as 1,3-PS), succinonitrile (being abbreviated as SN), adiponitrile (being abbreviated as AND).
Preferably, carboxylic acid ester compound described in additive is selected from ethyl acetate, ethyl propionate, propyl propionate, γ-fourth
At least one of lactone, gamma-valerolactone, δ-valerolactone, 6-caprolactone.
Preferably, Isosorbide-5-Nitrae-butyl sulfonic acid lactone and/or 1,3- propyl sulfonic acid lactone are contained in the additive.
Preferably, contain in the additive with the compound shown in Formula V：
Wherein, n is selected from any positive integer between 1~6.
Preferably, adiponitrile and/or succinonitrile are contained in the additive.
Preferably, the weight/mass percentage composition with the compound shown in Formula V in nonaqueous electrolytic solution is 0.1%~5%.Enter
Preferably, the weight/mass percentage composition with the compound shown in Formula V in nonaqueous electrolytic solution is 1%~3% to one step.
The addition of additive, during being conducive to battery initial charge (chemical conversion) process and following cycle, in anode and cathode table
Face forms passivating film, improves the cycle performance and high-temperature storage performance of battery.
The lithium salts is optionally from least one of organic lithium salt or inorganic lithium salt.
Preferably, at least one of fluorine element, boron element, P elements are contained in the lithium salts.
Preferably, the lithium salts is selected from lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4, double trifluoromethanesulfonimides
Lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), 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).
Preferably, the concentration of lithium salts is 0.9M~1.2M in the nonaqueous electrolytic solution.
According to the another aspect of the application, there is provided a kind of lithium ion battery, it is characterised in that：Contain above-mentioned nonaqueous electrolytic solution
At least one of.
Preferably, the negative pole of the lithium ion battery contains element silicon and/or tin element.
Preferably, the negative material of the lithium ion battery is selected from silicon based anode material, tin base cathode material, contains silicon
At least one of alloy material of cathode, alloy material of cathode containing tin.It is further preferred that the lithium ion battery is negative
Pole material is silicon-composite cathode material of silicon/carbon/graphite and/or tin-graphite composite negative pole material.
Preferably, the positive electrode active materials of the lithium ion battery are selected from lithium and cobalt oxides, lithium nickel oxide, the oxidation of lithium manganese
At least one of thing, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminum oxide.
Herein described technical scheme has the beneficial effect that：
(1) electrolyte provided herein, by the content for controlling easy aerogenesis solvent ethylene carbonate (EC) in solvent
And addition can improve the carboxylic acid esters additive at electrode/electrolyte interface into electrolyte, it is suppressed that the decomposition of electrolyte, reduce
The gas production of battery, so as to improve the high-temperature storage performance of lithium ion battery.
(2) electrolyte provided herein is used for lithium ion battery, and the charge cutoff of resulting lithium ion battery is electric
Pressure is not less than 4.4V.
Embodiment
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
If not being otherwise indicated, the content in embodiment is weight/mass percentage composition.Wherein, in organic solvent each component matter
Measure the quality of percentage composition=100% × organic solvent each component quality/organic solvent；The percentage composition of each component in additive
The gross mass of=100% × additive each component quality/nonaqueous electrolytic solution.
Comparative example 1
The preparation of electrolyte：By ethylene carbonate (being abbreviated as EC), propene carbonate (being abbreviated as PC) and diethyl carbonate
(being abbreviated as DEC) is with mass ratio EC:PC:DEC=20:20:60 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6), make
Its concentration in the electrolytic solution is 1mol/L；In addition also added with the fluoro carbonic acid that mass percentage content is 15% in electrolyte
Vinyl acetate (is abbreviated as FEC), and mass percentage content is 5% PS (being abbreviated as 1,3-PS).
The preparation of anode pole piece：Cobalt acid lithium, conductive carbon black (Super P), binding agent polyvinylidene fluoride (PVDF) are pressed
Mass ratio 97:1.4:1.6 are made lithium ion battery anode glue size with 1-METHYLPYRROLIDONE (NMP) mixing, are coated on collector
On aluminium foil；It is cold-pressed after being dried at 85 DEG C；Then carry out after trimming, cut-parts, slitting, dried under 85 DEG C of vacuum condition
Anode slice of lithium ion battery is made in 4h, soldering polar ear.
The preparation of cathode pole piece：The graphite of active material of positive electrode and SiOx (75 will be used as：25) with conductive carbon black (Super
P), thickener sodium carboxymethylcellulose (being abbreviated as CMC), bonding agent polyacrylic acid (being abbreviated as PAA) in mass ratio 92:1.0:
1.0:5 are made slurry with pure water mixing, are coated on copper foil of affluxion body and are dried at 85 DEG C；Then carry out trimming, cut-parts,
After slitting, 12h is dried under 120 DEG C of vacuum conditions, lithium ion battery negative electrode is made in soldering polar ear.
The preparation of lithium ion battery：Barrier film is used as using polyethylene (being abbreviated as PE) porous polymer film；By obtained positive pole
Piece, barrier film, negative plate are folded in order, barrier film is in the middle of positive/negative plate, and winding obtains naked battery core；Naked battery core is placed in outer
In packaging, the electrolyte of above-mentioned preparation is injected into dried battery, encapsulates, stand, (0.02C constant-current charges are arrived for chemical conversion
3.4V, then with 0.1C constant-current charges to 3.85V), shaping, volume test, complete the preparation (thickness of soft-package battery of lithium ion battery
Spend 4.2mm, width 32mm, length 82mm).
Comparative example 2
The preparation of electrolyte：By ethylene carbonate (being abbreviated as EC), propene carbonate (being abbreviated as PC) and diethyl carbonate
(being abbreviated as DEC) is with mass ratio EC:PC:DEC=15:20:65 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6), make
Its concentration in the electrolytic solution is 1mol/L；In addition also added with the fluoro carbonic acid that mass percentage content is 15% in electrolyte
Vinyl acetate (is abbreviated as FEC), 5% PS (being abbreviated as 1,3-PS).
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Comparative example 3
The preparation of electrolyte：By ethylene carbonate (being abbreviated as EC), propene carbonate (being abbreviated as PC) and diethyl carbonate
(being abbreviated as DEC) is with mass ratio EC:PC:DEC=10:20:70 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6), make
Its concentration in the electrolytic solution is 1mol/L；In addition also added with the fluoro carbonic acid that mass percentage content is 15% in electrolyte
Vinyl acetate (is abbreviated as FEC), 5% PS (being abbreviated as 1,3-PS).
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Comparative example 4
The preparation of electrolyte：By ethylene carbonate (being abbreviated as EC), propene carbonate (being abbreviated as PC) and diethyl carbonate
(being abbreviated as DEC) is with mass ratio EC:PC:DEC=5:20:75 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6), make
Its concentration in the electrolytic solution is 1mol/L；In addition also added with the fluoro carbonic acid that mass percentage content is 15% in electrolyte
Vinyl acetate (is abbreviated as FEC), 5% PS (being abbreviated as 1,3-PS).
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Comparative example 5
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS).
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Comparative example 6
The preparation of electrolyte：Propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are with mass ratio EC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS).
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Embodiment 1
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 5% ethyl acetate.
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Embodiment 2
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 5% ethyl propionate.
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Embodiment 3
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 5% propyl propionate.
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Embodiment 4
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 5% gamma-butyrolacton.
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Embodiment 5
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 5% gamma-valerolactone.
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Embodiment 6
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 5% δ-valerolactone.
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Embodiment 7
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 5% 6-caprolactone.
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Embodiment 8
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 0.1% gamma-butyrolacton.
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Embodiment 9
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 2% gamma-butyrolacton.
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Embodiment 10
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 10% gamma-butyrolacton.
Embodiment 11
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition in electrolyte also added with mass percentage content be 15% fluorinated ethylene carbonate (being abbreviated as FEC), 3% oneself two
Nitrile (ADN), 5% gamma-butyrolacton.
Embodiment 12
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, 1% sulfuric acid in electrolyte
Vinyl acetate (DTD), 5% gamma-butyrolacton.
Embodiment 13
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 3% adiponitrile (ADN), 5% gamma-butyrolacton.
Embodiment 14
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 3% adiponitrile (ADN), 1% sulfuric acid vinyl ester (DTD), 5% γ-Ding Nei
Ester.
Embodiment 15
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 5%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 50% gamma-butyrolacton.
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Embodiment 16
The preparation of electrolyte：By propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) with mass ratio PC:
DEC=20:80 mixing, add the lithium hexafluoro phosphate (LiPF of certain mass6) so that its concentration in the electrolytic solution is 1mol/
L；In addition also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 30%, the 1,3- of 5% in electrolyte
Propane sultone (is abbreviated as 1,3-PS), 50% gamma-butyrolacton.
The preparation of positive plate, the preparation of negative plate and the preparation of lithium ion battery are with comparative example 1.
Table 1 lists the parameter based on comparative example 1-6 and embodiment 1-10.
Table 1
High-temperature storage performance of lithium ion battery is tested
Battery prepared by comparative example 1~6, embodiment 1~16 is respectively taken 5, at normal temperatures with the constant electricity of 0.5C multiplying powers
Current charge to voltage is 4.4V, and electric current is further charged under 4.4V constant voltages for 0.025C, expiring for 4.4V is at
Fill state.Test storage before full charge pond thickness and be designated as D0.The battery of fully charged state is placed in 60 DEG C of baking ovens again and stored
21 days, an every 3 days thickness of test were simultaneously designated as D1, the thickness swelling before being calculated as follows relative to storage.
Thickness swelling=(D1-D0)/D0× 100%
The average thickness expansion rate of every group of 5 batteries is calculated, the cell thickness expansion rate result that changes with time is shown in
Table 2.
Table 2
Analyze comparative example 1~5 to understand, by reducing ethylene carbonate in electrolyte solvent (EC) content, can significantly drop
Thickness swelling during low 60 DEG C of storages of battery.When the component of ethylene carbonate (EC) in electrolyte solvent drops to 0 by 20, electricity
Thickness swelling after pond is stored 6 days drops to 11.9% by 63.3%, and its thickness swelling only has after storing 21 days
27.4%.Analyze comparative example 1,5,6 to understand, the content of the propene carbonate (PC) in reduction electrolyte solvent is to high temperature storage
Improve unobvious.Because ethylene carbonate (EC) is stable without propene carbonate (PC), easy oxidation Decomposition aerogenesis.In order to
Improve the high-temperature storage performance of lithium ion battery, it is necessary to reduce ethylene carbonate in electrolyte solvent (EC) content, take into account simultaneously
To other electrical properties, ethylene carbonate (EC) content can be controlled below 10 in solvent.
Analyze comparative example 5, embodiment 1-7 to understand, can be entered by the carboxylic acid esters additive for introducing 5% in the electrolytic solution
One step significantly reduces thickness swelling during 60 DEG C of storages of battery.Thickness swelling after the battery of comparative example 1 is stored 9 days at 60 DEG C
Just up to 17.1%, and embodiment 1-7 battery has been due to having introduced carboxylic acid ester compound in electrolyte, its 60 DEG C store 21 days
Thickness swelling is below 15% afterwards, with good storage performance.The wherein propyl propionate (embodiment 3) of addition 4%
The thickness swelling of battery improves the most obvious, and after storing 21 days, thickness swelling is only 5.8%.
Analyze embodiment 4, embodiment 8~10 and understand that the concentration of gamma-butyrolacton in the electrolytic solution can also influence battery
High-temperature storage performance.When additive capacity is 0.1% (embodiment 8), thickness swelling of the battery storage after 21 days reaches
28.9%；When addition is 10% (comparative example 10), it is 5.3% that thickness swelling of the battery storage after 21 days, which reaches,.This explanation
Gamma-butyrolacton content not can effectively improve electrode/electrolyte interface when too low, although and it is too high when can significantly improve it is high gentle
Performance is stored up, but in order to take into account other electrical properties, its content can be controlled between 1%~10%.
Embodiment 4 is analyzed, 11-14 is understood, adiponitrile (AND) or sulfuric acid vinyl ester (DTD) etc. are added in the electrolytic solution
High temperature protection additive substitution PS (1,3-PS) or the combination of a variety of high temperature protection additives, to high temperature storage
The improvement of performance is also clearly.
It is not for limiting claim, any this area skill although the application is disclosed as above with preferred embodiment
Art personnel can make some possible variations and modification on the premise of the application design is not departed from, therefore the application
The scope that protection domain should be defined by the application claim is defined.
Claims (9)
1. a kind of nonaqueous electrolytic solution, contains organic solvent, lithium salts and additive, it is characterised in that：
The ethylene carbonate that the weight/mass percentage composition that the organic solvent contains in organic solvent is 0~10%；
Contain sulfuric acid vinyl ester, fluorinated ethylene carbonate and carboxylic acid ester compound in the additive；
Weight/mass percentage composition of the fluorinated ethylene carbonate in nonaqueous electrolytic solution is 5%~30%, the carboxylic acid esters
Weight/mass percentage composition of the compound in nonaqueous electrolytic solution is 0.1%~50%.
2. nonaqueous electrolytic solution according to claim 1, it is characterised in that：In the organic solvent, ethylene carbonate is having
Weight/mass percentage composition in machine solvent is 0~5%；Weight/mass percentage composition of the carboxylic acid ester compound in nonaqueous electrolytic solution
For 1~10%.
3. nonaqueous electrolytic solution according to claim 1, it is characterised in that：Ethylene carbonate is free of in the organic solvent.
4. nonaqueous electrolytic solution according to claim 1, it is characterised in that：Carboxylic acid ester compound is selected from described in additive
Compound with chemical structural formula shown in Formulas I, the compound with chemical structural formula shown in Formula II, with shown in formula III change
At least one of the compound of structural formula, compound with chemical structural formula shown in formula IV：
Wherein, R1、R2The halogenated alkane that the alkyl or carbon number for being separately 1~6 selected from carbon number are 1~6
Base；
R3~R14The halo that the alkyl for being optionally separately 1~6 from hydrogen, halogen, carbon number, carbon number are 1~6
The haloalkene alkyl that the alkylene or carbon number that alkyl, carbon number are 1~6 are 1~6.
5. nonaqueous electrolytic solution according to claim 1, it is characterised in that：Carboxylic acid ester compound is selected from described in additive
At least one of ethyl acetate, ethyl propionate, propyl propionate, gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, 6-caprolactone.
6. nonaqueous electrolytic solution according to claim 1, it is characterised in that：Containing in 1,4- butyl sulfonic acids in the additive
Ester and/or 1,3- propyl sulfonic acid lactones.
7. nonaqueous electrolytic solution according to claim 1, it is characterised in that：Containing in the additive has shown in Formula V
Compound：
Wherein, n is selected from any positive integer between 1~6.
8. a kind of lithium ion battery, it is characterised in that：Contain nonaqueous electrolytic solution any one of claim 1-7.
9. lithium ion battery according to claim 8, it is characterised in that：The negative pole of the lithium ion battery contains element silicon
And/or tin element.
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| CN105633457B (en) * | 2014-10-27 | 2018-05-29 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and electrolyte thereof |
| CN104868096B (en) * | 2015-05-04 | 2017-04-05 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
| CN105140562B (en) * | 2015-07-23 | 2018-04-24 | 东莞市凯欣电池材料有限公司 | A kind of electrolyte containing benzene dinitrile and the lithium ion battery using the electrolyte |
| CN111416145B (en) * | 2015-10-16 | 2022-02-25 | 宁德新能源科技有限公司 | Lithium ion battery |
| CN105261790A (en) * | 2015-11-03 | 2016-01-20 | 宁德新能源科技有限公司 | Electrolyte and lithium-ion battery including same |
| CN108206299B (en) * | 2016-12-19 | 2020-10-09 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and electrolyte thereof |
| CN106654242A (en) * | 2017-01-20 | 2017-05-10 | 广州天赐高新材料股份有限公司 | High-voltage lithium battery with silicon-based negative electrode |
| CN112331914A (en) * | 2019-08-05 | 2021-02-05 | 杉杉新材料（衢州）有限公司 | Non-aqueous electrolyte of lithium ion battery without ethylene carbonate solvent and battery |
| CN112490497A (en) * | 2019-09-11 | 2021-03-12 | 杉杉新材料（衢州）有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same |
| CN112993414A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Lithium ion battery electrolyte and battery thereof |
| CN111509298B (en) * | 2020-06-01 | 2022-04-12 | 蜂巢能源科技股份有限公司 | Electrolyte functional additive for lithium ion battery, lithium ion battery electrolyte and lithium ion battery |
| CN112234270B (en) * | 2020-11-19 | 2021-12-28 | 广州市云通磁电股份有限公司 | Formation method of lithium iron phosphate battery |
| CN112582676A (en) * | 2020-12-09 | 2021-03-30 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN112864466A (en) * | 2021-01-28 | 2021-05-28 | 苏州酷卡环保科技有限公司 | Preparation method of lithium ion battery |
| CN112864468A (en) * | 2021-01-28 | 2021-05-28 | 苏州酷卡环保科技有限公司 | Formation method of power lithium ion battery |
| CN116864811B (en) * | 2023-08-30 | 2023-11-28 | 香河昆仑新能源材料股份有限公司 | Battery electrolyte with excellent high-temperature performance and lithium ion battery |
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| US20140017526A1 (en) * | 2011-03-31 | 2014-01-16 | Sanyo Electric Co., Ltd. | Non-aqueous electrolyte secondary battery system |
| CN103000944B (en) * | 2012-12-03 | 2015-02-25 | 湖州创亚动力电池材料有限公司 | Lithium ion battery electrolyte with high-temperature and low-temperature properties |
| CN103078141A (en) * | 2013-01-25 | 2013-05-01 | 宁德新能源科技有限公司 | Lithium-ion secondary battery and electrolyte thereof |
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