CN104269576A - Electrolyte and lithium ion battery adopting same - Google Patents
Electrolyte and lithium ion battery adopting same Download PDFInfo
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- CN104269576A CN104269576A CN201410528776.0A CN201410528776A CN104269576A CN 104269576 A CN104269576 A CN 104269576A CN 201410528776 A CN201410528776 A CN 201410528776A CN 104269576 A CN104269576 A CN 104269576A
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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
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Abstract
The invention relates to non-aqueous hydrolyte and a lithium ion battery adopting the same. The electrolyte contains an organic solvent, lithium salt and an additive, wherein the mass content of ethylene carbonate in the organic solvent is 0 to 10 percent; the additive contains fluoroethylene carbonate and a carboxylate compound; the mass content of the fluoroethylene carbonate in the non-aqueous hydrolyte is 5 to 30 percent, and the mass content of the carboxylate compound in the non-aqueous hydrolyte is 0.1 to 50 percent. According to the electrolyte, the content of the solvent ethylene carbonate with high gas producing rate in the solvent is controlled, the carboxylic acid ester additive for improving an electrode/electrolyte interface can be added, so that the decomposition of the electrolyte is suppressed, the gas yield of the battery is reduced, and the high-temperature storage performance of the lithium ion battery is further improved.
Description
Technical field
The invention belongs to the field of lithium ion battery, relate to a kind of improve high-temperature storage performance of lithium ion battery electrolyte and lithium ion battery containing this electrolyte.
Background technology
The high-energy-density of lithium ion battery, long circulation life, wide operating temperature range and environmental protection have made it become the main energy sources of current mobile electronic device.But the develop rapidly of mobile electronic device particularly smart mobile phone (gentlier, thinner), also proposed higher demand to the energy density of lithium ion battery in recent years.
In order to improve the energy density of lithium ion battery, two kinds of conventional at present methods are the operating voltage of raising positive electrode respectively and use the negative material with more high discharge capacity.Wherein, Si or Sn and alloy material of cathode thereof are because its theoretical specific capacity far above graphite (4200mAh/g) makes it become an important development direction of improving lithium ion battery energy density.But compared with graphite anode system, Si or Sn and alloy anode system thereof are very easy to aerogenesis under the high temperature conditions, and main cause may be that the SEI film on Si or Sn and alloy anode surface thereof is very easily destroying in high temperature storage process: the destruction of SEI film result in the reduction decomposition aerogenesis of solvent at anode surface on the one hand; Some cathodic protection additives cause negative electrode to be effectively protected in the reduction of anode surface on the other hand, make electrolyte oxidation decompose aerogenesis.
In view of this, necessaryly a kind of electrolyte improving Si or Sn and alloy anode high-temperature storage performance of lithium ion battery thereof is provided.
Summary of the invention
According to an aspect of the application, provide a kind of nonaqueous electrolytic solution, this nonaqueous electrolytic solution can improve the high-temperature storage performance of lithium ion battery containing element silicon and/or tin element in anode.
Described nonaqueous electrolytic solution, containing organic solvent, lithium salts and additive, is characterized in that:
The described organic solvent mass percentage contained in organic solvent is the ethylene carbonate of 0 ~ 10%;
Containing fluorinated ethylene carbonate and carboxylic acid ester compound in described additive;
The mass percentage of described fluorinated ethylene carbonate in nonaqueous electrolytic solution is 5% ~ 30%, and the mass percentage of described carboxylic acid ester compound in nonaqueous electrolytic solution is 0.1% ~ 50%.
In the application, ethylene carbonate mass percentage=100% in organic solvent × (quality/organic solvent quality of ethylene carbonate); Mass percentage=100% of fluorinated ethylene carbonate in nonaqueous electrolytic solution × (gross mass of the quality/nonaqueous electrolytic solution of fluorinated ethylene carbonate); Mass percentage=100% of carboxylic acid ester compound in nonaqueous electrolytic solution × (gross mass of the quality/nonaqueous electrolytic solution of carboxylic acid ester compound).
Preferably, described nonaqueous electrolytic solution is made up of organic solvent, lithium salts and additive.
The mass percentage of described additive in nonaqueous electrolytic solution is 10% ~ 85%.Preferably, the mass percentage range limit of described additive in nonaqueous electrolytic solution is optionally from 60%, 40%, 30%, 29%, 22%, and lower limit is optionally from 16%, 18%, 20%.Further preferably, the mass percentage of described additive in nonaqueous electrolytic solution is 10% ~ 40%.
The mass percentage of described organic solvent in nonaqueous electrolytic solution is 10% ~ 80%.Preferably, the upper limit of the mass percentage scope of described organic solvent in nonaqueous electrolytic solution is optionally from 78%, 75%, 72%, and lower limit is optionally from 40%, 50%, 55%, 60%, 65%.Further preferably, the mass percentage of described organic solvent in nonaqueous electrolytic solution is 50% ~ 80%.
The mass percentage of described lithium salts in nonaqueous electrolytic solution is 5% ~ 20%.Preferably, the upper limit of the mass percentage scope of described lithium salts in nonaqueous electrolytic solution is optionally from 18%, 15%, 12%, and lower limit is optionally from 5%, 7%, 9%.
Preferably, the mass percentage of described fluorinated ethylene carbonate in nonaqueous electrolytic solution is 10% ~ 20%.
Preferably, in described organic solvent, ethylene carbonate mass percentage is in organic solvent 0 ~ 5%.
The mass percentage of described carboxylic acid ester compound in nonaqueous electrolytic solution is 0.1% ~ 50%.If too low, effectively high-temperature storage performance can not be improved; Ruo Taigaozeyin its to the passivation of both positive and negative polarity, enlarge markedly the impedance at anode and cathode interface, worsen other performances of battery.Preferably, the mass percentage range limit of described carboxylic acid ester compound in nonaqueous electrolytic solution optionally from 10%, 5%, lower limit optionally from 0.1%, 2%.Further preferably, the mass percentage of described carboxylic acid ester compound in nonaqueous electrolytic solution is 1 ~ 10%.
Preferably, ethylene carbonate is not contained in described organic solvent.
Preferably, at least one in the carbonate products of 4 is no less than in described organic solvent containing carbon number.Preferably, described organic solvent by mass percentage be 0 ~ 10% ethylene carbonate and mass percentage be that the carbonate products that 90% ~ 100% carbon number is no less than 4 forms.
Further preferably, at least one in propene carbonate, diethyl carbonate, methyl ethyl carbonate is contained in described organic solvent.Further preferably, described organic solvent is propene carbonate and/or diethyl carbonate.
Preferably, carboxylic acid ester compound described in additive is selected from least one in chain carboxylic acid ester compound or cyclic carboxylic acids ester type compound.Further preferably, carboxylic acid ester compound described in additive is selected from the compound with chemical structural formula shown in formula I, the compound with chemical structural formula shown in formula II, the compound with chemical structural formula shown in formula III, at least one had in the compound of chemical structural formula shown in formula IV:
Wherein, R
1, R
2separately be selected from carbon number be 1 ~ 6 alkyl or carbon number be 1 ~ 6 alkyl halide alkyl;
R
3~ R
14separately optional from hydrogen, halogen, the carbon number alkyl that is 1 ~ 6, the carbon number alkyl halide alkyl that is 1 ~ 6, carbon number be 1 ~ 6 alkylene or carbon number be 1 ~ 6 haloalkene alkyl.
Preferably, R in formula I
1, R
2separately be selected from carbon number be 1 ~ 4 alkyl or carbon number be 1 ~ 4 alkyl halide alkyl.
Preferably, the R in formula II ~ formula IV
3~ R
14separately optional from hydrogen, halogen, the carbon number alkyl that is 1 ~ 3, the carbon number alkyl halide alkyl that is 1 ~ 3, carbon number be 1 ~ 6 alkylene or carbon number be 1 ~ 3 haloalkene alkyl.
The compound with chemical structural formula shown in formula I ~ formula IV effectively can improve the high-temperature storage performance of lithium ion battery, reason is the one at least following: (1) has in the compound of chemical structural formula shown in formula I ~ formula IV containing carboxylic acid ester groups, certain chemical reaction may be there is in this group with the intermediate product in SEI film forming process, indirect participation film forming, and the SEI film generated has extraordinary thermal stability, make it effectively can suppress the reduction decomposition of solvent, the particularly reduction decomposition of cathodic protection additive in electrolyte, thus it also avoid the oxidation Decomposition of solvent at positive pole, (2) for conventional carbonate solvent, the oxidizing potential of carboxylate is on the low side makes it to be oxidized at positive pole thus to modify positive pole interface, also can suppress the oxidation Decomposition aerogenesis of electrolyte to a certain extent.
Have in the compound of chemical structural formula shown in formula I ~ formula IV, R
1~ R
14choosing of group is moderate.If the carbon number of these groups is too much, cause the viscosity of electrolyte to increase on the one hand, conductivity declines, and not only can affect low temperature performance and high rate performance, and also can increase because of polarization affects cycle performance; The space steric effect of each functional group can make it not reach the object improving high-temperature storage performance on the other hand.
Preferably, described additive contains vinylene carbonate (being abbreviated as VC), vinylethylene carbonate (being 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), 1, at least one in 3-N-morpholinopropanesulfonic acid lactone (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 least one in ethyl acetate, ethyl propionate, propyl propionate, gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, 6-caprolactone.
Preferably, Isosorbide-5-Nitrae-butyl sulfonic acid lactone and/or 1,3-propyl sulfonic acid lactone is contained in described additive.
Preferably, in described additive containing having the compound shown in formula V:
Wherein, n is selected from any positive integer between 1 ~ 6.
Preferably, adiponitrile and/or succinonitrile is contained in described additive.
Preferably, having the mass percentage of the compound shown in formula V in nonaqueous electrolytic solution is 0.1% ~ 5%.Further preferably, having the mass percentage of the compound shown in formula V in nonaqueous electrolytic solution is 1% ~ 3%.
Adding of additive, be conducive in battery initial charge (changing into) process and following cycle process, form passivating film on anode and cathode surface, improve cycle performance and the high-temperature storage performance of battery.
At least one of described lithium salts optionally in organic lithium salt or inorganic lithium salt.
Preferably, at least one in fluorine element, boron element, P elements is contained in described lithium salts.
Preferably, described lithium salts is selected from lithium hexafluoro phosphate LiPF
6, LiBF4 LiBF
4, two trifluoromethanesulfonimide lithium LiN (CF
3sO
2)
2(being abbreviated as LiTFSI), di-oxalate lithium borate LiB (C
2o
4)
2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF
2(C
2o
4) at least one in (being abbreviated as LiDFOB).
Preferably, in described nonaqueous electrolytic solution, the concentration of lithium salts is 0.9M ~ 1.2M.
According to the another aspect of the application, a kind of lithium ion battery is provided, it is characterized in that: containing at least one in above-mentioned nonaqueous electrolytic solution.
Preferably, the negative pole of described lithium ion battery contains element silicon and/or tin element.
Preferably, the negative material of described lithium ion battery be selected from silicon based anode material, tin base cathode material, alloy material of cathode containing silicon, containing at least one in the alloy material of cathode of tin.Further preferably, the negative material of described lithium ion battery is silicon-composite cathode material of silicon/carbon/graphite and/or tin-graphite composite negative pole material.
Preferably, the positive electrode active materials of described lithium ion battery is selected from least one in lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminum oxide.
The beneficial effect of technical scheme described in the application is:
(1) electrolyte that provides of the application, by controlling the content of easily aerogenesis solvent ethylene carbonate (EC) in solvent and add the carboxylic acid esters additive that can improve electrode/electrolyte interface in electrolyte, inhibit the decomposition of electrolyte, decrease the gas production of battery, thus improve the high-temperature storage performance of lithium ion battery.
(2) what the application provided is used for electrolyte in lithium ion battery, and the charge cutoff voltage of the lithium ion battery obtained is not less than 4.4V.
Embodiment
Below in conjunction with embodiment, set forth the application further.Should be understood that these embodiments are only not used in the scope of restriction the application for illustration of the application.
As nothing specializes, the content in embodiment is mass percentage.Wherein, the quality of each constituent mass/organic solvent of the mass percentage=100% × organic solvent of each component in organic solvent; The gross mass of each constituent mass/nonaqueous electrolytic solution of the percentage composition=100% × additive of each component in additive.
Comparative example 1
The preparation of electrolyte: ethylene carbonate (being abbreviated as EC), propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio EC:PC:DEC=20:20:60, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition be also added with the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% in electrolyte, mass percentage content is the PS (being abbreviated as 1,3-PS) of 5%.
The preparation of anode pole piece: by cobalt acid lithium, conductive carbon black (Super P), binding agent polyvinylidene fluoride (PVDF) in mass ratio 97:1.4:1.6 and 1-METHYLPYRROLIDONE (NMP) mix and make lithium ion battery anode glue size, be coated in current collector aluminum foil; Cold pressing after drying at 85 DEG C; Then, after carrying out trimming, cut-parts, itemize, under the vacuum condition of 85 DEG C, dry 4h, soldering polar ear, makes anode slice of lithium ion battery.
The preparation of cathode pole piece: using as the graphite of active material of positive electrode and SiOx (75:25) and 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 and pure water mix and make slurry, to be coated on copper foil of affluxion body and oven dry at 85 DEG C; Then, after carrying out trimming, cut-parts, itemize, under 120 DEG C of vacuum conditions, dry 12h, soldering polar ear, make lithium ion battery negative electrode.
The preparation of lithium ion battery: using polyethylene (being abbreviated as PE) porous polymer film as barrier film; Obtained positive plate, barrier film, negative plate are folded in order, make barrier film be in the middle of positive/negative plate, winding obtains naked battery core; Naked battery core is placed in external packing, the electrolyte of above-mentioned preparation is injected in dried battery, encapsulate, leave standstill, change into that (0.02C constant current charge is to 3.4V, again with 0.1C constant current charge to 3.85V), shaping, volume test, complete the preparation (the thickness 4.2mm of soft-package battery, width 32mm, length 82mm) of lithium ion battery.
Comparative example 2
The preparation of electrolyte: ethylene carbonate (being abbreviated as EC), propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio EC:PC:DEC=15:20:65, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Comparative example 3
The preparation of electrolyte: ethylene carbonate (being abbreviated as EC), propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio EC:PC:DEC=10:20:70, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Comparative example 4
The preparation of electrolyte: ethylene carbonate (being abbreviated as EC), propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio EC:PC:DEC=5:20:75, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Comparative example 5
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Comparative example 6
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) mix with mass ratio EC:DEC=20:80, add the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Embodiment 1
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the ethyl acetate of 5%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Embodiment 2
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the ethyl propionate of 5%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Embodiment 3
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the propyl propionate of 5%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Embodiment 4
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the gamma-butyrolacton of 5%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Embodiment 5
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the gamma-valerolactone of 5%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Embodiment 6
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the δ-valerolactone of 5%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Embodiment 7
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the 6-caprolactone of 5%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Embodiment 8
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the gamma-butyrolacton of 0.1%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Embodiment 9
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the gamma-butyrolacton of 2%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Embodiment 10
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the gamma-butyrolacton of 10%.
Embodiment 11
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the adiponitrile (ADN) of 3%, the gamma-butyrolacton of 5%.
Embodiment 12
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the sulfuric acid vinyl ester (DTD) of 1%, the gamma-butyrolacton of 5%.
Embodiment 13
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the adiponitrile (ADN) of 3%, the gamma-butyrolacton of 5%.
Embodiment 14
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 15% is also added with in electrolyte, 5% 1,3-N-morpholinopropanesulfonic acid lactone (is abbreviated as 1,3-PS), the adiponitrile (ADN) of 3%, the sulfuric acid vinyl ester (DTD) of 1%, the gamma-butyrolacton of 5%.
Embodiment 15
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 5% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the gamma-butyrolacton of 50%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is with comparative example 1.
Embodiment 16
The preparation of electrolyte: propene carbonate (being abbreviated as PC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio PC:DEC=20:80, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1mol/L; In addition the fluorinated ethylene carbonate (being abbreviated as FEC) that mass percentage content is 30% is also added with in electrolyte, the PS (being abbreviated as 1,3-PS) of 5%, the gamma-butyrolacton of 50%.
The preparation of the preparation of positive plate, the preparation of negative plate and lithium ion battery is 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 got 5, at normal temperatures with 0.5C multiplying power constant current charge to voltage for 4.4V, under 4.4V constant voltage, charging to electric current is further 0.025C, makes it be in the fully charged state of 4.4V.Full charge pond thickness before test storage is also designated as D
0.The battery of fully charged state is placed in 60 DEG C of baking ovens again and stores 21 days, every 3 days test thickness are also designated as D
1, be calculated as follows the thickness swelling before relative to storage.
Thickness swelling=(D
1-D
0)/D
0× 100%
Calculate and often organize the average thickness expansion rate of 5 batteries, by cell thickness expansion rate over time result be shown in table 2.
Table 2
Analyzing comparative example 1 ~ 5 known, by reducing ethylene carbonate (EC) content in electrolyte solvent, significantly can reduce thickness swelling when 60 DEG C, battery stores.When the component of ethylene carbonate in electrolyte solvent (EC) drops to 0 by 20, the thickness swelling of battery storage after 6 days drops to 11.9% by 63.3%, and after storing 21 days, its thickness swelling only has 27.4%.Analyze comparative example 1,5,6 is known, and the improvement of content to high temperature storage reducing the propene carbonate (PC) in electrolyte solvent is not obvious.This is because ethylene carbonate (EC) does not have propene carbonate (PC) to stablize, easy oxidation Decomposition aerogenesis.In order to improve the high-temperature storage performance of lithium ion battery, must reduce ethylene carbonate in electrolyte solvent (EC) content, taking into account other electrical properties simultaneously, in solvent, ethylene carbonate (EC) content can control below 10.
Analyze comparative example 5, embodiment 1-7 is known, significantly can reduce thickness swelling when 60 DEG C, battery stores further by the carboxylic acid esters additive introducing 5% in the electrolytic solution.After the battery of comparative example 1 stores 9 days at 60 DEG C, thickness swelling is just up to 17.1%, and the battery of embodiment 1-7 is owing to having introduced carboxylic acid ester compound in electrolyte, its 60 DEG C store thickness swelling after 21 days and, all below 15%, have good memory property.The thickness swelling wherein adding the battery of the propyl propionate (embodiment 3) of 4% improves the most obvious, and store after 21 days, thickness swelling is only 5.8%.
Analyze embodiment 4, embodiment 8 ~ 10 is known, gamma-butyrolacton concentration in the electrolytic solution also can affect the high-temperature storage performance of battery.When additive capacity is 0.1% (embodiment 8), the thickness swelling of battery storage after 21 days reaches 28.9%; When addition is 10% (comparative example 10), it is 5.3% that the thickness swelling of battery storage after 21 days reaches.This illustrates that gamma-butyrolacton content can not effectively improve electrode/electrolyte interface time too low, although and too high time significantly can improve high-temperature storage performance, in order to take into account other electrical properties, its content can control between 1% ~ 10%.
Analyze embodiment 4; 11-14 is known; add the high temperature protection additive such as adiponitrile (AND) or sulfuric acid vinyl ester (DTD) in the electrolytic solution and replace 1; 3-N-morpholinopropanesulfonic acid lactone (1; 3-PS) or the coupling of multiple high temperature protection additive, to the improvement of high-temperature storage performance also clearly.
Although the application with preferred embodiment openly as above; but be not for limiting claim; any those skilled in the art are under the prerequisite not departing from the application's design; can make some possible variations and amendment, the scope that therefore protection range of the application should define with the application's claim is as the criterion.
Claims (9)
1. a nonaqueous electrolytic solution, containing organic solvent, lithium salts and additive, is characterized in that:
The described organic solvent mass percentage contained in organic solvent is the ethylene carbonate of 0 ~ 10%;
Containing fluorinated ethylene carbonate and carboxylic acid ester compound in described additive;
The mass percentage of described fluorinated ethylene carbonate in nonaqueous electrolytic solution is 5% ~ 30%, and the mass percentage of described carboxylic acid ester compound in nonaqueous electrolytic solution is 0.1% ~ 50%.
2. nonaqueous electrolytic solution according to claim 1, is characterized in that: in described organic solvent, and ethylene carbonate mass percentage is in organic solvent 0 ~ 5%; The mass percentage of described carboxylic acid ester compound in nonaqueous electrolytic solution is 1 ~ 10%.
3. nonaqueous electrolytic solution according to claim 1, is characterized in that: not containing ethylene carbonate in described organic solvent.
4. nonaqueous electrolytic solution according to claim 1, is characterized in that: carboxylic acid ester compound described in additive is selected from the compound with chemical structural formula shown in formula I, the compound with chemical structural formula shown in formula II, the compound with chemical structural formula shown in formula III, at least one had in the compound of chemical structural formula shown in formula IV:
Wherein, R
1, R
2separately be selected from carbon number be 1 ~ 6 alkyl or carbon number be 1 ~ 6 alkyl halide alkyl;
R
3~ R
14separately optional from hydrogen, halogen, the carbon number alkyl that is 1 ~ 6, the carbon number alkyl halide alkyl that is 1 ~ 6, carbon number be 1 ~ 6 alkylene or carbon number be 1 ~ 6 haloalkene alkyl.
5. nonaqueous electrolytic solution according to claim 1, is characterized in that: carboxylic acid ester compound described in additive is selected from least one in ethyl acetate, ethyl propionate, propyl propionate, gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, 6-caprolactone.
6. nonaqueous electrolytic solution according to claim 1, is characterized in that: containing Isosorbide-5-Nitrae-butyl sulfonic acid lactone and/or 1,3-propyl sulfonic acid lactone in described additive.
7. nonaqueous electrolytic solution according to claim 1, is characterized in that: containing having the compound shown in formula V in described additive:
Wherein, n is selected from any positive integer between 1 ~ 6.
8. a lithium ion battery, is characterized in that: containing nonaqueous electrolytic solution according to any one of claim 1-7.
9. lithium ion battery according to claim 8, is characterized in that: the negative pole of described lithium ion battery contains element silicon and/or tin element.
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