CN105655640A - Non-aqueous electrolyte and lithium-ion battery containing same - Google Patents
Non-aqueous electrolyte and lithium-ion battery containing same Download PDFInfo
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- CN105655640A CN105655640A CN201610183641.4A CN201610183641A CN105655640A CN 105655640 A CN105655640 A CN 105655640A CN 201610183641 A CN201610183641 A CN 201610183641A CN 105655640 A CN105655640 A CN 105655640A
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
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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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- 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 invention belongs to the field of lithium-ion batteries and particularly relates to a non-aqueous electrolyte and a lithium-ion battery containing the same. The non-aqueous electrolyte comprises non-aqueous organic solvent, lithium salt and additives. The additives contain a silicon-based sulfate compound and 3, 9-divinyl-2, 4, 8, 10-tetraoxaspiro [5.5] alkylate. The non-aqueous electrolyte has the advantages that by the synergic effect of the silicon-based sulfate compound and the 3, 9-divinyl-2, 4, 8, 10-tetraoxaspiro [5.5] alkylate, a stable composite passivation membrane is formed on the surface of a cathode, the passivation membrane is low in impedance and beneficial to lithium ion conduction, the membrane impedance increasing of the battery during a circulation process is small, battery capacity fading is small, and the hot box performance and overcharging resistance of the battery can be improved evidently.
Description
Technical field
The application belongs to field of lithium ion battery, and specifically, the application relates to a kind of nonaqueous electrolytic solution and uses the lithium ion battery of this nonaqueous electrolytic solution.
Background technology
Lithium ion battery because having specific energy height, have extended cycle life, the advantage such as self discharge is little, be widely used in consumer electronics product and energy storage and electrokinetic cell. Along with the extensive use of lithium ion battery, it uses environment also to tend to varied already, requires more and more higher to the rate of charge of battery, battery life and security performance. Such as, when battery needs urgent charging to use, more electricity can be had in the short time; Battery needs to improve the life-span of battery when big multiplying power quick charge; Battery uses under the high temperature conditions and is required for ensureing the use safety of client in the process that overcharges, it is therefore desirable to improve battery hot tank and anti-over-charging performance.
The rate of charge of lithium ion battery, life-span and high-temperature storage performance are subject to the impact of factors, and wherein, it, as the important component part of lithium ion battery, is had great impact by electrolyte. Can being improved the dynamic performance of battery by electrolyte, reduce the polarization of big multiplying power, the increase of both positive and negative polarity interface impedance in cyclic process median surface stability, reduction cyclic process, thus reaching to improve the purpose of rate of charge, life-span, hot tank and anti-over-charging performance.
Summary of the invention
The primary goal of the invention of the application is in that to propose a kind of nonaqueous electrolytic solution.
Second goal of the invention of the application is in that the lithium ion battery proposing to use this nonaqueous electrolytic solution.
In order to complete the purpose of the application, the technical scheme of employing is:
A kind of nonaqueous electrolytic solution, including non-aqueous organic solvent, lithium salts and additive, containing, for example the silica-based sulfate compound shown in formula I and 3,9-divinyl-2 in described additive, 4,8,10-tetra-oxaspiro [5.5] alkyl compounds,
Wherein, R1��R6It is each independently selected from hydrogen atom, halogen atom, substituted or unsubstituted C1��20Alkyl, substituted or unsubstituted C1��20Alkylene, substituted or unsubstituted C6��26Aryl, substituted or unsubstituted C1��20Alkoxyl, substituted or unsubstituted C6��26Aryloxy group;
Substituent group is selected from halogen, C1��6Alkyl.
Preferably, R1��R6In have at least a substituent group selected from halogen, substituted or unsubstituted C1��12Alkoxyl, substituted or unsubstituted C1��12Alkyl, substituted or unsubstituted C6��26Aryl.
Preferably, R1��R6In have at least a substituent group selected from halogen, substituted or unsubstituted C1��6Alkoxyl, substituted or unsubstituted C1��6Alkyl, substituted or unsubstituted phenyl.
Preferably, R1��R6For identical group.
Preferably, described silica-based sulfate compound at least one in double; two (trimethyl silicon based) sulfuric ester, double; two (triethyl group is silica-based) sulfuric ester, double; two (triphenyl is silica-based) sulfuric ester, double; two (trifluoro is silica-based) sulfuric esters.
Preferably, described 3,9-divinyl-2, the structural formula of 4,8,10-tetra-oxaspiro [5.5] alkyl compounds is such as shown in formula II:
Wherein, R21��R30It is each independently selected from hydrogen atom, C1��12Alkyl;
Preferably, R21��R30It is hydrogen atom.
Preferably, described silica-based sulfate compound mass percentage content in nonaqueous electrolytic solution is 0.05%��3%, it is preferred to 0.1%��2%.
Preferably, described 3,9-divinyl-2,4,8,10-tetra-oxaspiro [5.5] alkyl compounds mass percentage content in nonaqueous electrolytic solution is 0.01%��3%, it is preferred to 0.1%��2%.
Preferably, described non-aqueous organic solvent at least one in ethylene carbonate, Allyl carbonate, butylene, fluorinated ethylene carbonate, Ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl n-butyrate.;
Described lithium salts at least one in lithium hexafluoro phosphate, double; two trifluoromethanesulfonimide lithium, double; two (fluorine sulphonyl) imine lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium.
The application further relates to a kind of lithium ion battery, and it includes electrolyte, positive plate, negative plate, isolating membrane and package foil; Described positive plate includes plus plate current-collecting body and the positive pole diaphragm being coated on plus plate current-collecting body, and negative plate includes negative current collector and the cathode membrane being coated on negative current collector; It is characterized in that, described electrolyte is nonaqueous electrolytic solution described herein.
The application can reach Advantageous Effects and include following aspect, but is not limited to this:
The application passes through 3,9-divinyl-2,4,8,10-tetra-oxaspiro [5.5] alkyl compounds and silica-based sulfate compound synergism, form stable composite passivation film in negative terminal surface, and this passivating film impedance is low, being conducive to the conduction of lithium ion, and battery membrane impedance increase in cyclic process is also less, battery capacity decay is little. And the silicon atom and 3 in silica-based sulfuric ester; 9-divinyl-2; 4; 8; in 10-tetra-oxaspiro [5.5] alkyl compound, oxygen atom is easily formed at electrode interface in charge and discharge process and leads ionic strong silicon-oxygen polymer and carry out shield electrode material, significantly improves hot tank performance and the anti-over-charging performance of battery.
Below in conjunction with specific embodiment, the application is expanded on further. Should be understood that these embodiments are merely to illustrate the application rather than restriction scope of the present application.
Detailed description of the invention
Present invention purpose is in that to provide one can significantly provide lithium ion battery rate of charge, improves the nonaqueous electrolytic solution of cycle performance of lithium ion battery and high-temperature storage performance, and provides the lithium ion battery using this nonaqueous electrolytic solution.
In order to realize foregoing invention purpose, this application provides a kind of nonaqueous electrolytic solution, including non-aqueous organic solvent, lithium salts and additive, containing silica-based sulfate compound and 3,9-divinyl-2 in additive, 4,8,10-tetra-oxaspiro [5.5] alkyl compounds;
Wherein, the structural formula of silica-based sulfate compound is such as shown in formula I:
Wherein, R1��R6It is each independently selected from hydrogen atom, halogen atom, substituted or unsubstituted C1��20Alkyl, substituted or unsubstituted C1��20Alkylene, substituted or unsubstituted C6��26Aryl, substituted or unsubstituted C1��20Alkoxyl, substituted or unsubstituted C6��26Aryloxy group;
Substituent group is selected from halogen, C1��6Alkyl, halogen is selected from F or Cl.
Preferably, R1��R6In have at least a substituent group selected from halogen, substituted or unsubstituted C1��12Alkoxyl, substituted or unsubstituted C1��12Alkyl, substituted or unsubstituted C6��26Aryl, it is preferred that have at least 2 substituent groups selected from above-mentioned group, more preferably at having 3 substituent groups selected from above-mentioned group;
Preferably, R1��R6In have at least a substituent group selected from halogen, substituted or unsubstituted C1��6Alkoxyl, substituted or unsubstituted C1��6Alkyl, substituted or unsubstituted phenyl.
Preferably, R1��R6For identical group.
The preferred upper limit value of the carbon number of abovementioned alkyl is followed successively by 16,12,8,6,4,3; Such as, when the higher limit of carbon number is 16, the carbon atom number range of alkyl refers to 1��16; The most preferably carbon number of alkyl is 1��3. Alkyl can be alkyl group or cycloalkyl: alkyl group comprises straight chained alkyl and the alkyl with side chain; Cycloalkyl is the saturated alkyl containing alicyclic structure, and alicyclic ring can contain or not contain substituent group.
Example as alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, cyclobutyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, cyclopenta, 2,2-dimethyl propyl, 1-ethyl propyl, 1-methyl butyl, 2-methyl butyl, n-hexyl, isohesyl, 2-hexyl, 3-hexyl, cyclohexyl, 2-methyl amyl, 3-methyl amyl, 1,1,2-thmethylpropyl, 3,3-dimethylbutyls, n-heptyl, n-octyl, n-nonyl, positive decyl.
The preferred upper limit value of the carbon number of above-mentioned alkoxyl is followed successively by 16,12,8,6,4,3; Such as, when the higher limit of carbon number is 16, the carbon atom number range of alkoxyl refers to 1��16; The most preferably carbon number of alkoxyl is 1��3. Alkoxyl comprises unbranched alkoxy and the alkoxyl with side chain.
Example as alkyl, specifically can enumerate: methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, tertiary amoxy, neopentyl oxygen, cyclopentyloxy, 2, 2-dimethyl propoxyl group, 1-ethylpropoxy, 1-methylbutoxy group, 2-methylbutoxy group, positive hexyloxy, different hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl amoxy, 3-methyl amoxy, 1, 1, 2-trimethyl propoxyl group, 3, 3-dimethyl butoxy, positive heptan oxygen base, n-octyloxy, positive ninth of the ten Heavenly Stems oxygen base, n-decyloxy.
As the example of aryl, specifically can enumerate: phenyl, naphthyl etc.
Substituent group in the application is selected from halogen, C1��6Alkyl, described halogen is selected from F or Cl.
Preferably, R1��R6For identical group. I.e. R1��R6Can be halogen, substituted or unsubstituted C simultaneously1��12Alkoxyl, substituted or unsubstituted C1��12Alkyl, substituted or unsubstituted C6��26Aryl; Preferably, R1��R6Can be halogen, substituted or unsubstituted C simultaneously1��6Alkyl, substituted or unsubstituted phenyl.
As a kind of improvement of the application nonaqueous electrolytic solution, silica-based sulfate compound is selected from least one in double; two (triphenyl the is silica-based) sulfuric esters shown in double; two (trifluoro is silica-based) sulfuric ester, the formula I d shown in double; two (triethyl group is silica-based) sulfuric ester, the formula I c shown in double; two (trimethyl silicon based) sulfuric ester, the formula I b shown in formula I a:
Wherein, silica-based sulfate compound is also selected from least one in following compound:
As a kind of improvement of the application nonaqueous electrolytic solution, 3,9-divinyl-2, the structural formula of 4,8,10-tetra-oxaspiro [5.5] alkyl compounds is such as shown in formula II:
Wherein, R21��R30It is each independently selected from hydrogen atom, C1��12Alkyl.
It is further preferred that R21��R30It is each independently selected from hydrogen atom, C1��6Alkyl.
It is further preferred that R23��R30It is hydrogen atom, R23��R30It is each independently selected from hydrogen atom, C1��6Alkyl.
It is furthermore preferred that R21��R30Being hydrogen atom, its structural formula is such as shown in formula II a, called after 3,9-divinyl-2,4,8,10-tetra-oxaspiro [5.5] hendecanes:
Wherein, 3,9-divinyl-2,4,8,10-tetra-oxaspiro [5.5] alkyl compounds are also selected from least one in following compound:
As a kind of improvement of the application nonaqueous electrolytic solution, silica-based sulfate compound mass fraction in nonaqueous electrolytic solution is 0.05%��3%. This is because when the content of silica-based sulfate compound is lower than 0.05%, it is impossible to form complete SEI film in negative terminal surface, thus the side reaction caused by electron transfer between electrolyte and electrode can not effectively be stoped; And when silica-based sulfate compound content is more than 3%, thicker SEI film can be formed in negative terminal surface, cause that lithium ion mobility resistance increases, the cathode interface stability being unfavorable in cyclic process battery.
It is further preferred that the preferred upper limit of the mass fraction scope that silica-based sulfate compound is in nonaqueous electrolytic solution is followed successively by 2.8%, 2.5%, 2.0%, 1.5%, 1.0%, it is preferable that lower limit is followed successively by 0.08%, 0.1%, 0.3%, 0.5%, 0.6%. It is further preferred that the mass fraction that silica-based sulfate compound is in nonaqueous electrolytic solution is 0.1%��2%.
As a kind of improvement of the application nonaqueous electrolytic solution, 3,9-divinyl-2,4,8,10-tetra-oxaspiro [5.5] alkyl compounds mass fraction in nonaqueous electrolytic solution is 0.01%��3%. This is because when 3,9-divinyl-2, when 4,8,10-tetra-oxaspiro [5.5] alkyl compounds addition in the electrolytic solution is lower than 0.01%, it is impossible to being effectively formed stable SEI film, the cycle performance of battery is without improvement; And when 3,9-divinyl-2, when the content of 4,8,10-tetra-oxaspiro [5.5] alkyl compounds is higher than 3%, adds the viscosity of electrolyte, slow down the migration of lithium ion. It is further preferred that 3,9-divinyl-2,4,8,10-tetra-oxaspiro [5.5] alkyl compounds mass fraction in nonaqueous electrolytic solution is 0.1%��2%.
As a kind of improvement of the application nonaqueous electrolytic solution, non-aqueous organic solvent is carbon number is 1��8 and the compound containing at least one ester group.
A kind of improvement as the application nonaqueous electrolytic solution, non-aqueous organic solvent at least one in ethylene carbonate, Allyl carbonate, butylene, fluorinated ethylene carbonate, Ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl n-butyrate..
As a kind of improvement of the application nonaqueous electrolytic solution, lithium salts is at least one in organic lithium salt or inorganic lithium salt optionally.
As a kind of improvement of the application nonaqueous electrolytic solution, containing at least one in fluorine element, boron element, P elements in lithium salts.
As a kind of improvement of the application nonaqueous electrolytic solution, lithium salts is selected from lithium hexafluoro phosphate LiPF6, double; two trifluoromethanesulfonimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), double; two (fluorine sulphonyl) imine 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(C2O4) at least one in (being abbreviated as LiDFOB).
In order to realize foregoing invention purpose, present invention also provides a kind of lithium ion battery, it includes electrolyte, positive plate, negative plate, isolating membrane and package foil; Described positive plate includes plus plate current-collecting body and the positive pole diaphragm being coated on plus plate current-collecting body, and negative plate includes negative current collector and the cathode membrane being coated on negative current collector; Described electrolyte is the nonaqueous electrolytic solution described in any of the above-described paragraph.
As a kind of improvement of the application lithium ion battery, described positive pole diaphragm includes positive electrode active materials, binding agent and conductive agent.
As a kind of improvement of the application lithium ion battery, positive electrode active materials is optionally from cobalt acid lithium LiCoO2, lithium-nickel-manganese-cobalt ternary material, LiFePO 4, at least one in LiMn2O4, or the mixture of cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material.
As a kind of improvement of the application lithium ion battery, cathode membrane includes negative active core-shell material, binding agent and conductive agent.
As a kind of improvement of the application lithium ion battery, negative active core-shell material is graphite and/or silicon.
In order to make present invention purpose, technical scheme and technique effect become apparent from, below in conjunction with embodiment, the application is further elaborated. It should be appreciated that the embodiment described in this specification is merely to explain the application, it is not intended to limit the application.
Embodiment 1��10
The preparation of electrolyte: in water content < in the argon gas atmosphere glove box of 10ppm, by ethylene carbonate (being abbreviated as EC), diethyl carbonate (being abbreviated as DEC), Allyl carbonate (being abbreviated as PC), ethyl propionate, fluorinated ethylene carbonate (being abbreviated as FEC) according to the quality ratio of 20:30:20:25:5 after mix homogeneously, obtain nonaqueous solvent, then by fully dry lithium salts LiPF6It is dissolved in above-mentioned nonaqueous solvent, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.
Shown in table 1, basic electrolyte adds silica-based sulfate compound (I a, I b, I c, I d) and 3,9-divinyl-2,4,8,10-tetra-oxaspiro [5.5] hendecane compounds (II a).
The preparation of lithium ion battery:
1) preparation of positive plate: (molecular formula is LiCoO by positive active material cobalt acid lithium2), conductive agent acetylene black, binding agent polyvinylidene fluoride (being abbreviated as PVDF) in appropriate N-Methyl pyrrolidone (being abbreviated as NMP) solvent, be sufficiently stirred for mixing by weight 96:2:2 so that it is form uniform anode sizing agent;This slurry is coated on plus plate current-collecting body Al paper tinsel, dries, cold pressing, obtain positive plate.
2) preparation of negative plate: negative electrode active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (being abbreviated as SBR), thickening agent sodium carboxymethyl cellulose (being abbreviated as CMC) are sufficiently stirred for mixing according to weight ratio 95:2:2:1 in appropriate deionized water solvent so that it is form uniform cathode size; This slurry is coated on negative current collector Cu paper tinsel, dries, cold pressing, obtain negative plate.
3) isolating membrane: using PE porous polymer film as isolating membrane.
4) preparation of lithium ion battery: positive plate, isolating membrane, negative plate are folded in order, makes isolating membrane be between positive/negative plate to play the effect of isolation, and then winding obtains naked battery core; Naked battery core is placed in outer package paper tinsel, the above-mentioned electrolyte prepared is injected in dried battery, through operations such as Vacuum Package, standing, chemical conversion, shapings, namely completes the preparation of lithium ion battery.
Comparative example 1��6
Preparing basic electrolyte according to the method for embodiment 1, comparative example 1 is without additive, and in comparative example 2��3, electrolysis additive and respective addition are as shown in table 1.
Electrolysis additive and respective addition in embodiment 1��8 and comparative example 1��6 are as shown in table 1.
Table 1: electrolysis additive compound mode in each comparative example and embodiment and addition
Hereinafter the lithium ion battery by experiment each comparative example of the application and embodiment prepared is carried out performance test.
Test one, loop test
The lithium ion battery prepared is carried out following test respectively:
At 25 DEG C, by lithium ion battery, with 1C constant-current charge to 4.4V, then constant-voltage charge to electric current is 0.05C, then with 1C constant-current discharge to 3.0V, now for circulate first, carry out time so repeatedly cycle charging/electric discharge according to above-mentioned condition, calculate lithium ion battery respectively and circulate the capability retention after 50 times, 100 times, 200 times, 300 times and 500 times, often organize each 5 batteries, wherein, the capability retention after circulation is calculated according to the following formula. Electrolyte selected in each lithium ion battery and the relevant test data that obtains are referring to table 3.
Capability retention after circulation=(discharge capacity of corresponding circulation/circulate first discharge capacity) �� 100%, the result of loop test is as shown in table 2.
Table 2: the capability retention test result after circulation
| Group | 50 times | 100 times | 200 times | 300 times | 500 times |
| Embodiment 1 | 98.2% | 95.9% | 94.1% | 91.8% | 87.3% |
| Embodiment 2 | 97.5% | 95.5% | 93.7% | 91.4% | 86.5% |
| Embodiment 3 | 97.4% | 95.3% | 93.4% | 91.3% | 85.9% |
| Embodiment 4 | 97.1% | 94.8% | 93.3% | 91.0% | 85.8% |
| Embodiment 5 | 96.4% | 93.8% | 92.2% | 88.3% | 84.0% |
| Embodiment 6 | 96.4% | 93.6% | 91.1% | 86.5% | 82.3% |
| Embodiment 7 | 97.4% | 93.4% | 91.8% | 86.6% | 82.8% |
| Embodiment 8 | 96.3% | 92.2% | 89.1% | 86.2% | 80.1% |
| Embodiment 9 | 95.3% | 90.2% | 85.1% | 80.2% | 74.1% |
| Embodiment 10 | 95.1% | 89.2% | 84.5% | 79.0% | 73.1% |
| Comparative example 1 | 95.3% | 91.5% | 83.5% | 73.7% | 62.7% |
| Comparative example 2 | 96.2% | 93.1% | 87.4% | 79.2% | 70.6% |
| Comparative example 3 | 95.0% | 92.2% | 85.6% | 77.5% | 68.8% |
| Comparative example 4 | 95.8% | 92.5% | 86.4% | 78.9% | 69.2% |
| Comparative example 5 | 95.8% | 92.5% | 87.4% | 79.4% | 67.0% |
| Comparative example 6 | 95.9% | 91.4% | 83.5% | 74.3% | 61.3% |
Associative list 1 with in table 2 it can be seen that compared with comparative example 1, the electrolyte of comparative example 2��3 is individually added into 2%3,9-divinyl-2,4,8, when 10-tetra-oxaspiro [5.5] hendecane or 2% silica-based sulfate compound, the cycle performance of lithium ion battery slightly improves.In embodiment 1��10, being simultaneously introduced 3,9-divinyl-2 that mass fraction is 1% in electrolyte, when 4,8,10-tetra-oxaspiro [5.5] hendecanes and silica-based sulfate compound that mass fraction is 1%, the cycle performance of battery is obviously improved. But, when 3,9-divinyl-2 in electrolyte, 4,8,10-tetra-oxaspiro [5.5] hendecanes are more than 3% or 3, when the content of 4-ethylene dialkoxy thiophene compound is more than 3%, not only the cycle performance of battery does not improve, and even can worsen, particularly electrolyte adds 4%3,9-divinyl-2,4,8, the comparative example 6 of 10-tetra-oxaspiro [5.5] hendecane and 4% silica-based sulfate compound, the circulation conservation rate of its battery is far below other groups.
Hot tank test after test two, circulation
By carried out 500 times 25 DEG C circulation after battery, with 0.5C electric current constant-current charge to 4.4V, 4.4V constant-voltage charge to electric current for 0.025C at 25 DEG C so that it is be in 4.4V fully charged state, then battery is placed in the high temperature furnace of 150 DEG C and keeps 1 hour, observe the state of battery after testing.
The result of circulation rear hot box test is as shown in table 3.
Table 3: circulation rear hot box test result
| Group | Hot tank is tested |
| Embodiment 1 | 5/5OK |
| Embodiment 2 | 5/5OK |
| Embodiment 3 | 5/5OK 8 --> |
| Embodiment 4 | 5/5OK |
| Embodiment 5 | 5/5OK |
| Embodiment 6 | 5/5OK |
| Embodiment 7 | 5/5OK |
| Embodiment 8 | 5/5OK |
| Embodiment 9 | 5/5OK |
| Embodiment 10 | 5/5OK |
| Comparative example 1 | 5/5fire |
| Comparative example 2 | 1/5OK,4/5fire |
| Comparative example 3 | 1/5OK,4/5fire |
| Comparative example 4 | 1/5OK,4/5fire |
| Comparative example 5 | 1/5OK,4/5fire |
| Comparative example 6 | 5/5fire |
It can be seen that work as 3,9-divinyl-2 in associative list 1 and table 3, when the content of 4,8,10-tetra-oxaspiro [5.5] hendecane compounds is higher than 3%, after will causing circulation, the test of battery hot tank is caught fire, and its reason can consider to be because 3,9-too much divinyl-2,4,8,10-tetra-oxaspiro [5.5] hendecanes membrane impedance in cyclic process increases, and causes that battery lithium metal in cyclic process precipitates out, worsen the heat stability of battery cathode, worsen the hot tank performance after circulating battery. By contrast, the composite passivation film adding the formation of silica-based sulfate compound in electrolyte has good thermostability, improves the hot tank performance of battery after circulating. Therefore, silica-based sulfate compound and 3,9-divinyl-2,4,8,10-tetra-oxaspiro [5.5] hendecanes arrange in pairs or groups as electrolysis additive simultaneously use time, it is possible to significantly improve battery hot tank performance after cycling.
Test three, anti-over-charging test
The battery partly filling state is discharged to 3.0V with 0.5C at 25 DEG C, then with 0.4C constant-current charge to 10V, then 10V constant-voltage charge 2h, observe the state of battery.
The result of anti-over-charging test is as shown in table 4.
Table 4: anti-over-charging test result
| Group | Anti-over-charging is tested |
| Embodiment 1 | 5/5OK |
| Embodiment 2 | 5/5OK |
| Embodiment 3 | 5/5OK |
| Embodiment 4 | 5/5OK |
| Embodiment 5 | 5/5OK |
| Embodiment 6 | 5/5OK |
| Embodiment 7 | 5/5OK |
| Embodiment 8 | 5/5OK |
| Embodiment 9 | 5/5OK |
| Embodiment 10 | 5/5OK |
| Comparative example 1 | 5/5fire |
| Comparative example 2 | 1/5OK,4/5fire 9 --> |
| Comparative example 3 | 1/5OK,4/5fire |
| Comparative example 4 | 1/5OK,4/5fire |
| Comparative example 5 | 1/5OK,4/5fire |
| Comparative example 6 | 5/5fire |
It can be seen that work as 3,9-divinyl-2 in associative list 1 and table 4, when the content of 4,8,10-tetra-oxaspiro [5.5] hendecane compounds is higher than 3%, will causing that battery catches fire in anti-over-charging process, its reason can consider to be because 3,9-too much divinyl-2,4,8,10-tetra-oxaspiro [5.5] hendecanes membrane impedance in lasting charging process increases, and causes that lithium metal precipitates out, lasting lithium is easily caused battery short circuit, cells burst in negative terminal surface deposition. By contrast, adding silica-based sulfate compound and can form stable and that impedance is low composite passivation film in electrolyte, this passivating film is not easily destroyed in lasting charging process, is not therefore easily formed micro-short circuit, thus improving battery anti-over-charging performance. Therefore, silica-based sulfate compound and 3,9-divinyl-2,4,8,10-tetra-oxaspiro [5.5] hendecanes arrange in pairs or groups as electrolysis additive simultaneously use time, it is possible to significantly improve the anti-over-charging performance of battery.
By all above description, the application is by being simultaneously introduced mass fraction 3 not higher than 3% in the electrolytic solution, 9-divinyl-2,4,8,10-tetra-oxaspiro [5.5] hendecane and the mass fraction silica-based sulfate compound not higher than 3%, it is possible to significantly improve the rate of charge of lithium ion battery, life-span, anti-over-charging and circulation rear hot box performance.
Embodiment 11��18
Preparing basic electrolyte according to the method for embodiment 1, the composition differing only in additive is different, specifically as shown in table 5.
Table 5: electrolysis additive compound mode in embodiment 11��18 and addition
Capability retention after the circulation of the basic electrolyte prepared by embodiment 11��18, the hot tank test result after circulation are similar to the test result of embodiment 1��10 with anti-over-charging test result.
The announcement of book and instruction according to the above description, above-mentioned embodiment can also be carried out suitable change and amendment by the application those skilled in the art. Therefore, the application is not limited to detailed description of the invention disclosed and described above, should also be as some modifications and changes of the application falling in the protection domain of claims hereof. Although additionally, employ some specific terms in this specification, but these terms are intended merely to convenient explanation, and the application does not constitute any restriction.
Claims (10)
1. a nonaqueous electrolytic solution, including non-aqueous organic solvent, lithium salts and additive, it is characterised in that, containing, for example the silica-based sulfate compound shown in formula I and 3,9-divinyl-2 in described additive, 4,8,10-tetra-oxaspiro [5.5] alkyl compounds
Wherein, R1��R6It is each independently selected from hydrogen atom, halogen atom, substituted or unsubstituted C1��20Alkyl, substituted or unsubstituted C1��20Alkylene, substituted or unsubstituted C6��26Aryl, substituted or unsubstituted C1��20Alkoxyl, substituted or unsubstituted C6��26Aryloxy group;
Substituent group is selected from halogen, C1��6Alkyl.
2. nonaqueous electrolytic solution according to claim 1, it is characterised in that R1��R6In have at least a substituent group selected from halogen, substituted or unsubstituted C1��12Alkoxyl, substituted or unsubstituted C1��12Alkyl, substituted or unsubstituted C6��26Aryl.
3. nonaqueous electrolytic solution according to claim 1, it is characterised in that R1��R6In have at least a substituent group selected from halogen, substituted or unsubstituted C1��6Alkoxyl, substituted or unsubstituted C1��6Alkyl, substituted or unsubstituted phenyl.
4. the nonaqueous electrolytic solution according to Claims 2 or 3, it is characterised in that R1��R6For identical group.
5. nonaqueous electrolytic solution according to claim 4, it is characterised in that: described silica-based sulfate compound at least one in double; two (trimethyl silicon based) sulfuric ester, double; two (triethyl group is silica-based) sulfuric ester, double; two (triphenyl is silica-based) sulfuric ester, double; two (trifluoro is silica-based) sulfuric esters.
6. nonaqueous electrolytic solution according to claim 1, it is characterised in that described 3,9-divinyl-2, the structural formula of 4,8,10-tetra-oxaspiro [5.5] alkyl compounds is such as shown in formula II:
Wherein, R21��R30It is each independently selected from hydrogen atom, C1��12Alkyl;
Preferably, R21��R30It is hydrogen atom.
7. nonaqueous electrolytic solution according to claim 1, it is characterised in that described silica-based sulfate compound mass percentage content in nonaqueous electrolytic solution is 0.05%��3%, it is preferred to 0.1%��2%.
8. nonaqueous electrolytic solution according to claim 1, it is characterised in that described 3,9-divinyl-2,4,8,10-tetra-oxaspiro [5.5] alkyl compounds mass percentage content in nonaqueous electrolytic solution is 0.01%��3%, it is preferred to 0.1%��2%.
9. nonaqueous electrolytic solution according to claim 1, it is characterized in that, described non-aqueous organic solvent at least one in ethylene carbonate, Allyl carbonate, butylene, fluorinated ethylene carbonate, Ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl n-butyrate.;
Described lithium salts at least one in lithium hexafluoro phosphate, double; two trifluoromethanesulfonimide lithium, double; two (fluorine sulphonyl) imine lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium.
10. a lithium ion battery, it includes electrolyte, positive plate, negative plate, isolating membrane and package foil; Described positive plate includes plus plate current-collecting body and the positive pole diaphragm being coated on plus plate current-collecting body, and negative plate includes negative current collector and the cathode membrane being coated on negative current collector; It is characterized in that, described electrolyte is the nonaqueous electrolytic solution according to any one of claim 1��9.
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