CN105336987A - Non-aqueous electrolyte of lithium ion battery and lithium ion battery - Google Patents

Non-aqueous electrolyte of lithium ion battery and lithium ion battery Download PDF

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Publication number
CN105336987A
CN105336987A CN201510790253.8A CN201510790253A CN105336987A CN 105336987 A CN105336987 A CN 105336987A CN 201510790253 A CN201510790253 A CN 201510790253A CN 105336987 A CN105336987 A CN 105336987A
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lithium ion
additive
carbonate
aqueous electrolyte
ion cell
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石桥
郑仲天
胡时光
曹朝伟
黄丰良
周雪
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Shenzhen Capchem Technology Co Ltd
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Shenzhen Capchem Technology Co Ltd
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Priority to CN201510790253.8A priority Critical patent/CN105336987A/en
Priority to PCT/CN2015/095387 priority patent/WO2017084109A1/en
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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
    • 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
    • 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
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a non-aqueous electrolyte of a lithium ion battery and the lithium ion battery. The non-aqueous electrolyte of the lithium ion battery comprises a non-aqueous organic solvent, lithium salt and additives, wherein the additives comprise an additive A and an additive B, the additive A is selected from a compound represented as a structural formula 1, R is selected from alkyl with the carbon atom number of 1-3, m is a natural integer in a range of 1-2, and the additive A accounts for 0.1%-2% of the total mass of the non-aqueous electrolyte of the lithium ion battery; the additive B is selected from at least one of vinylene carbonate, vinylethylene carbonate and fluoroethylene carbonate, and the additive B accounts for 0.5%-3% of the total mass of the non-aqueous electrolyte of the lithium ion battery. The high-and-low temperature performance of the non-aqueous electrolyte of the lithium ion battery is excellent.

Description

A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery
Technical field
The present invention relates to lithium-ion battery electrolytes technical field, particularly relate to a kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery.
Background technology
Along with the development of new-energy automobile, non-aqueous electrolyte lithium ion battery has huge application prospect at new-energy automobile dynamic power system.Although these battery with nonaqueous electrolyte are practical, also cannot be satisfactory on durability uses, particularly at high temperature 45 DEG C, useful life is shorter.Especially for power vehicle and energy-storage system, non-aqueous electrolyte lithium ion battery request also can normally work in cold district, more will take into account high temperature performance.
In non-aqueous electrolyte lithium ion battery, nonaqueous electrolytic solution is the key factor affecting battery high temperature performance, and especially, the performance of the additive in nonaqueous electrolytic solution to battery high temperature performance is even more important.In lithium ion battery initial charge process, the lithium ion deintercalation in cell positive material out, is embedded in Carbon anode by electrolyte.Due to its high response, electrolyte produces Li in Carbon anode surface reaction 2cO 3, the compound such as LiO, LiOH, thus form passivating film in negative terminal surface, this passivating film is called solid electrolyte interfacial film (SEI).The SEI film formed in initial charge process, not only stops electrolyte further at Carbon anode Surface disintegration, and plays lithium ion tunneling, only allow lithium ion to pass through.Therefore, SEI film determines the quality of performance of lithium ion battery.
In order to improve the properties of battery, many scientific research persons by adding the quality that different additives improves SEI film in electrolyte, thus improve the performance of battery.Such as, propose in Japanese Unexamined Patent Publication 2000-123867 publication and improve battery behavior by adding vinylene carbonate in the electrolytic solution.The polymer inactivation electrode surface of the method by producing with vinylene carbonate polyisocyanate polyaddition, stops electrolyte to decompose at electrode surface, thus improves the cycle performance of battery.But because lithium ion is difficult to by this passivating film, the internal resistance of cell rises, and makes battery not good in subzero performance.Meanwhile, battery in pyroprocess, easy aerogenesis and cause battery bulging.Chinese patent application CN1385919A discloses a kind of containing RSO 3si (C mh 2m+1) 3the electrolyte of compound, this electrolyte can improve the low temperature performance of battery.But in an experiment, we find containing RSO 3si (C mh 2m+1) 3although the electrolyte of compound can improve the low temperature performance of battery, battery high-temperature behavior is not ideal enough, and battery cannot be practical.
Summary of the invention
The invention provides a kind of non-aqueous electrolyte for lithium ion cell can taking into account battery high temperature performance, a kind of lithium ion battery comprising above-mentioned non-aqueous electrolyte for lithium ion cell is provided further.
According to a first aspect of the invention, the invention provides a kind of non-aqueous electrolyte for lithium ion cell, comprise non-aqueous organic solvent, lithium salts and additive, this additive comprises additive A and additive B, above-mentioned additive A is selected from compound shown in structural formula 1, wherein R is selected from the alkyl that carbon number is 1-3, and m is the natural integer of 1-2
Structural formula 1
The content of above-mentioned additive A is 0.1%-2% relative to above-mentioned non-aqueous electrolyte for lithium ion cell gross mass; Above-mentioned additive B is selected from least one in vinylene carbonate (VC), vinylethylene carbonate (VEC), fluorinated ethylene carbonate (FEC), and the content of above-mentioned additive B is 0.5%-3% relative to above-mentioned non-aqueous electrolyte for lithium ion cell gross mass.
As preferred version of the present invention, wherein R is selected from methyl, ethyl or propyl group.
As preferred version of the present invention, m is 1.
As preferred version of the present invention, additive A is selected from least one in trimethyl silicon based methanesulfonates, trimethyl silicon based esilate, trimethyl silicon based propane sulfonic acid ester.
Scheme as a further improvement on the present invention, above-mentioned non-aqueous organic solvent is the mixture of cyclic carbonate and linear carbonate, above-mentioned cyclic carbonate be selected from ethylene carbonate, propene carbonate and butylene one or more, above-mentioned linear carbonate be selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate one or more.
Scheme as a further improvement on the present invention, above-mentioned lithium salts is selected from LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiN (SO 2cF 3) 2, LiN (SO 2c 2f 5) 2, LiC (SO 2cF 3) 3with LiN (SO 2f) 2in one or more.
Scheme as a further improvement on the present invention, above-mentioned additive also comprise in PS (1,3-PS), Isosorbide-5-Nitrae-butane sultone (BS), 1,3-propene sultone (PST) one or more.
According to a second aspect of the invention, the invention provides a kind of lithium ion battery, the barrier film comprising positive pole, negative pole and be placed between positive pole and negative pole, also comprise the non-aqueous electrolyte for lithium ion cell of first aspect.
Scheme as a further improvement on the present invention, above-mentioned positive pole is selected from LiCoO 2, LiNiO 2, LiMn 2o 4, LiCo 1-ym yo 2, LiNi 1-ym yo 2, LiMn 2-ym yo 4and LiNi xco ymn zm 1-x-y-zo 2in one or more, wherein, M be selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti one or more, and 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
Containing additive A and additive B in non-aqueous electrolyte for lithium ion cell of the present invention, additive A can be decomposed on negative pole, form passivating film, this passivating film impedance is lower, be conducive to lithium ion to pass through, improve the cryogenic property of battery, but this Stability of Passive Film is poor, battery high-temperature behavior is not ideal enough.If now coexist with additive B, additive B can be decomposed to form passivating film in positive pole, negative terminal surface, thus the passivating film that formation additive A and additive B analyte are composited, the high temperature performance that is beyond one's reach when demonstrating each additive individualism takes into account characteristic.
Embodiment
Below by embodiment, the present invention is described in further detail.
One embodiment of the invention provide a kind of non-aqueous electrolyte for lithium ion cell, comprise non-aqueous organic solvent, lithium salts and additive, this additive comprises additive A and additive B, above-mentioned additive A is selected from compound shown in structural formula 1, wherein R is selected from the alkyl that carbon number is 1-3, m is the natural integer of 1-2
Structural formula 1
Above-mentioned additive B is selected from least one in vinylene carbonate (VC), vinylethylene carbonate (VEC), fluorinated ethylene carbonate (FEC).
In the present invention, R is selected from the alkyl that carbon number is 1-3, wherein alkyl can be saturated hydrocarbyl or unsaturated alkyl, namely can be alkyl, alkenyl or alkynyl, example such as methyl, ethyl, propyl group, the isopropyl of alkyl, example such as vinyl, acrylic, the pi-allyl of thiazolinyl, example such as acetenyl, propinyl, the propargyl of alkynyl.
In the present invention, in initial charge process, compound shown in structural formula 1 can have precedence over solvent molecule and decompose in negative terminal surface, its catabolite mainly RSO 3li, this product is conducive to lithium ion to be passed through.Inventor shows through further investigation, and R is selected from the alkyl that carbon number is 1-3, can obtain the above-mentioned excellent effect being beneficial to lithium ion and passing through significantly.But when to be selected from carbon number be the alkyl being greater than 3 to R, because R group is excessive, be unfavorable in catabolite that the composition that lithium ion passes through increases, lithium ion can be hindered on the contrary to pass through, reduce the cryogenic property of battery.Additive B also in initial charge process, can be formed polymer inactivation film on both positive and negative polarity surface, stops the decomposition of solvent molecule further.But this passivating film impedance is comparatively large, and battery cryogenic property is poor, meanwhile, when battery high-temperature stores, aerogenesis is serious, reduces battery high-temperature memory property.When additive A and additive B use simultaneously, can form in negative terminal surface the passivating film that additive A and additive B analyte be composited, the high temperature performance that is beyond one's reach when demonstrating each additive individualism takes into account characteristic.
In a preferred embodiment of the invention, the content of additive A is 0.1%-2% relative to above-mentioned non-aqueous electrolyte for lithium ion cell gross mass.Lower than 0.1% time, be difficult to fully form passivating film in negative terminal surface, thus be difficult to the low temperature performance fully improving battery with nonaqueous electrolyte, and during more than 2%, compound shown in structural formula 1 forms blocked up passivating film on both positive and negative polarity surface, thus reduces battery high-temperature behavior.The content of additive B is 0.5%-3% relative to above-mentioned non-aqueous electrolyte for lithium ion cell gross mass.Lower than 0.5% time, be difficult to fully form passivating film on both positive and negative polarity surface, thus be difficult to the high-temperature behavior fully improving battery with nonaqueous electrolyte, and during more than 3%, additive B forms blocked up passivating film on both positive and negative polarity surface, increase the internal resistance of cell, and produce a large amount of gas, thus reduce battery cryogenic property and high-temperature behavior.
In nonaqueous lithium ion battery electrolytic solution of the present invention, by using additive A and additive B simultaneously, compared with individually adding, high-temperature storage characteristics and the low-temperature characteristics of battery significantly improve, though its mechanism of action is not fully aware of.Infer in addition, when two kinds of additives use jointly, by certain interact (such as acting synergistically), the composite passivation film that these two kinds of additives are formed is more stable, even if be also easy to conducting lithium ions at low temperatures.
In a preferred embodiment of the invention, above-mentioned non-aqueous organic solvent is the mixture of cyclic carbonate and linear carbonate, above-mentioned cyclic carbonate be selected from ethylene carbonate, propene carbonate and butylene one or more, above-mentioned linear carbonate be selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate one or more.
Adopt the cyclic carbonate organic solvent of high-k and the mixed liquor of low viscous linear carbonate organic solvent as the solvent of lithium-ion battery electrolytes, make the mixed liquor of this organic solvent have high ionic conductivity, high dielectric constant and low viscosity simultaneously.
In a preferred embodiment of the invention, above-mentioned lithium salts is selected from LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiN (SO 2cF 3) 2, LiN (SO 2c 2f 5) 2, LiC (SO 2cF 3) 3with LiN (SO 2f) 2in one or more, described lithium salts preferably LiPF 6or LiPF 6with the mixture of other lithium salts.
In a preferred embodiment of the invention, above-mentioned additive also comprises one or more in PS (1,3-PS), Isosorbide-5-Nitrae-butane sultone (BS), 1,3-propene sultone (PST).
Above-mentioned film for additive can form more stable SEI film on graphite cathode surface, thus further increases the performance of lithium ion battery.
One embodiment of the invention provide a kind of lithium ion battery, the barrier film comprising positive pole, negative pole and be placed between positive pole and negative pole, also comprise the non-aqueous electrolyte for lithium ion cell of first aspect.
In a preferred embodiment of the invention, above-mentioned positive pole is selected from LiCoO 2, LiNiO 2, LiMn 2o 4, LiCo 1-ym yo 2, LiNi 1-ym yo 2, LiMn 2-ym yo 4and LiNi xco ymn zm 1-x-y-zo 2in one or more, wherein, M be selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti one or more, and 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
In one embodiment of the invention, positive electrode is LiNi 0.5co 0.2mn 0.3o 2, negative material is Delanium.
Describe the present invention below by way of specific embodiment.Should be appreciated that these embodiments are only exemplary, do not form limiting the scope of the invention.
Embodiment 1
1) preparation of electrolyte
By ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) in mass ratio for EC:DEC:EMC=1:1:1 mixes, then add lithium hexafluoro phosphate (LiPF 6) be 1mol/L to molar concentration, then add the vinylene carbonate (VC) of the trimethyl silicon based methanesulfonates by the gross mass 0.5% of electrolyte and the gross mass 1% by electrolyte.
2) preparation of positive plate
By the quality of 93:4:3 than blended anode active material lithium nickel cobalt manganese oxide LiNi 0.5co 0.2mn 0.3o 2, then they are dispersed in METHYLPYRROLIDONE (NMP), obtain anode sizing agent by conductive carbon black Super-P and binding agent polyvinylidene fluoride (PVDF).Be uniformly coated on by slurry on the two sides of aluminium foil, through drying, calendering and vacuumize, and burn-on after aluminum lead-out wire with supersonic welder and obtain positive plate, the thickness of pole plate is at 120-150 μm.
3) preparation of negative plate
By the mass ratio mixing negative active core-shell material Delanium of 94:1:2.5:2.5, conductive carbon black Super-P, binding agent butadiene-styrene rubber (SBR) and carboxymethyl cellulose (CMC), then by their dispersions in deionized water, obtain cathode size.Be coated on by slurry on the two sides of Copper Foil, through drying, calendering and vacuumize, and burn-on after nickel making outlet with supersonic welder and obtain negative plate, the thickness of pole plate is at 120-150 μm.
4) preparation of battery core
Between positive plate and negative plate, place thickness is that the polyethene microporous membrane of 20 μm is as barrier film, then the sandwich structure that positive plate, negative plate and barrier film form is reeled, square aluminum metal-back is put into after being flattened by coiling body again, the lead-out wire of both positive and negative polarity is welded on the relevant position of cover plate respectively, and with laser-beam welding machine, cover plate and metal-back are welded as a whole, obtain the battery core treating fluid injection.
5) battery core fluid injection and change into
In the glove box that dew point controls below-40 DEG C, the electrolyte of above-mentioned preparation is injected battery core by liquid injection hole, and the amount of electrolyte will ensure the space be full of in battery core.Then change into according to the following steps: 0.05C constant current charge 3min, 0.2C constant current charge 5min, 0.5C constant current charge 25min, after shelving 1hr, shaping is sealed, then further with the electric current constant current charge of 0.2C to 4.2V, after normal temperature shelf 24hr, with the electric current constant-current discharge of 0.2C to 3.0V.
6) high temperature cyclic performance test
Battery is placed in the baking oven of constant temperature 45 DEG C, with the electric current constant current charge of 1C to 4.2V then constant voltage charge drop to 0.1C to electric current, then with the electric current constant-current discharge of 1C to 3.0V, circulation like this 300 weeks, record the discharge capacity of the 1st week and the discharge capacity of the 300th week, be calculated as follows the capability retention of high temperature circulation:
The discharge capacity * 100% of discharge capacity/1st of capability retention=300th week week
7) high-temperature storage performance test
Battery after changing into is charged to 4.2V with 1C constant current constant voltage at normal temperatures, measures battery initial discharge capacity and initial cells thickness, and then 60 DEG C of storages are after 7 days, are discharged to 3V with 1C, measure the maintenance capacity of battery and recover capacity and store rear cell thickness.Computing formula is as follows:
Battery capacity conservation rate (%)=maintenance capacity/initial capacity × 100%;
Capacity resuming rate (%)=recovery capacity/initial capacity × 100%.
Thickness swelling (%)=(after storing cell thickness-initial cells thickness)/initial cells thickness × 100%.
8) cryogenic property test
At 25 DEG C, the battery 1C constant current constant voltage after changing into is charged to 4.2V, then uses 1C constant-current discharge to 3.0V, record discharge capacity.Then 1C constant current constant voltage is charged to 4.2V, after the environment being placed in-20 DEG C shelves 12h, 0.3C constant-current discharge to 3.0V, record discharge capacity.
Low temperature discharging efficiency value=0.3C discharge capacity (-20 DEG C)/1C discharge capacity (25 DEG C) × 100% of-20 DEG C.
Embodiment 2
As shown in table 1, except the trimethyl silicon based esilate in the preparation of electrolyte, the trimethyl silicon based methanesulfonates of 0.5% being changed into 0.5%, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 2.
Embodiment 3
As shown in table 1, except the trimethyl silicon based propane sulfonic acid ester in the preparation of electrolyte, the trimethyl silicon based methanesulfonates of 0.5% being changed into 0.5%, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 2.
Embodiment 4
As shown in table 1, except the fluorinated ethylene carbonate (FEC) in the preparation of electrolyte, the vinylene carbonate (VC) of 1% being changed into 1%, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 2.
Embodiment 5
As shown in table 1, except the vinylethylene carbonate (VEC) in the preparation of electrolyte, the vinylene carbonate (VC) of 1% being changed into 1%, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 2.
Comparative example 1
As shown in table 1, except not adding vinylene carbonate (VC) in the preparation of electrolyte, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 2.
Comparative example 2
As shown in table 1, except not adding except trimethyl silicon based methanesulfonates in the preparation of electrolyte, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 2.
Comparative example 3
As shown in table 1, except not adding except trimethyl silicon based methanesulfonates in the preparation of electrolyte, other is identical with embodiment 5, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 2.
Comparative example 4
As shown in table 1, except not adding except trimethyl silicon based methanesulfonates in the preparation of electrolyte, other is identical with embodiment 4, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 2.
Comparative example 5
As shown in table 1, except not adding trimethyl silicon based methanesulfonates and vinylene carbonate (VC) in the preparation of electrolyte, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 2.
Table 1
Table 2
By contrasting with comparative example 1-comparative example 5, independent interpolation additive A can improve the low temperature performance of battery, but the high-temperature storage of battery and cycle performance poor, independent interpolation additive B can improve circulation and the high-temperature storage performance of battery, but it is serious that battery high-temperature stores aerogenesis, and low temperature performance is deteriorated (except FEC).When additive A and additive B use simultaneously, because both can form composite passivation film, produce synergy, the high-temperature storage of battery can be improved simultaneously, circulation and low temperature performance.Can find out, be increased to 3 with carbon number in additive A from 1, its low temperature performance has the trend of variation simultaneously, and this mainly increases due to carbon number, is unfavorable for that the composition that lithium ion passes through increases, causes the internal resistance of cell to increase in the passivating film of formation.
Embodiment 6
As shown in table 3, except the trimethyl silicon based methanesulfonates in the preparation of electrolyte, the trimethyl silicon based methanesulfonates of 0.5% being changed into 0.1%, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 4.
Embodiment 7
As shown in table 3, except the trimethyl silicon based methanesulfonates in the preparation of electrolyte, the trimethyl silicon based methanesulfonates of 0.5% being changed into 1%, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 4.
Embodiment 8
As shown in table 3, except the trimethyl silicon based methanesulfonates in the preparation of electrolyte, the trimethyl silicon based methanesulfonates of 0.5% being changed into 2%, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 4.
Embodiment 9
As shown in table 3, except the vinylene carbonate (VC) of 1% being changed into except the vinylene carbonate of 0.5% in the preparation of electrolyte, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 4.
Embodiment 10
As shown in table 3, except the vinylene carbonate (VC) in the preparation of electrolyte, the vinylene carbonate (VC) of 1% being changed into 2%, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 4.
Embodiment 11
As shown in table 3, except the vinylene carbonate (VC) in the preparation of electrolyte, the vinylene carbonate (VC) of 1% being changed into 3%, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 4.
Comparative example 6
As shown in table 3, except the trimethyl silicon based methanesulfonates in the preparation of electrolyte, the trimethyl silicon based methanesulfonates of 0.5% being changed into 3%, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 4.
Comparative example 7
As shown in table 3, except the vinylene carbonate (VC) in the preparation of electrolyte, the vinylene carbonate (VC) of 1% being changed into 5%, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 4.
Comparative example 8
As shown in table 3, except the trimethyl silicon based methanesulfonates of 0.5% being changed into the trimethyl silicon based methanesulfonates of 3% in the preparation of electrolyte and the vinylene carbonate (VC) of 1% changes into except the vinylene carbonate (VC) of 5%, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 4.
Table 3
Table 4
By contrasting with comparative example 6-comparative example 8, when additive A content is in 0.1% to 2% scope, additive B content is in 0.5% to 3% scope, and the cycle performance of battery, high-temperature storage performance and low temperature performance are all very excellent.But, when additive A content more than 2% or additive B content more than 3%, the cycle performance of battery, high-temperature storage performance and low temperature performance are obviously deteriorated.
Embodiment 12
As shown in table 5, except additionally adding by outside the PS (1,3-PS) of the gross mass 1% of electrolyte in the preparation of electrolyte, other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 6.
Embodiment 13
As shown in table 5,1 of gross mass 1% by electrolyte is added except extra in the preparation of electrolyte, outside 4-butane sultone (BS), other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 6.
Embodiment 14
As shown in table 5,1 of gross mass 1% by electrolyte is added except extra in the preparation of electrolyte, outside 3-propene sultone (PST), other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 6.
Comparative example 9
As shown in table 5, except not adding 0.5% trimethyl silicon based methanesulfonates in the preparation of electrolyte and extra adding 1 of gross mass 1% by electrolyte, 3-propane sultone (1,3-PS), other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 6.
Comparative example 10
As shown in table 5, except not adding 0.5% trimethyl silicon based methanesulfonates in the preparation of electrolyte and extra adding 1 of gross mass 1% by electrolyte, outside 4-butane sultone (BS), other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 6.
Comparative example 11
As shown in table 5, except not adding 0.5% trimethyl silicon based methanesulfonates in the preparation of electrolyte and extra adding 1 of gross mass 1% by electrolyte, outside 3-propene sultone (PST), other is identical with embodiment 1, tests the data of high temperature cyclic performance, high-temperature storage performance and the cryogenic property obtained in table 6.
Table 5
Table 6
By contrasting with comparative example 9-comparative example 11, VC and other additive combination basis adding trimethyl silicon based methanesulfonates, circulation and the high-temperature storage performance of battery can be improved further.
Above content is in conjunction with concrete execution mode further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.

Claims (9)

1. a non-aqueous electrolyte for lithium ion cell, comprises non-aqueous organic solvent, lithium salts and additive, it is characterized in that, described additive comprises additive A and additive B, and described additive A is selected from compound shown in structural formula 1, and wherein R is selected from the alkyl that carbon number is 1-3, m is the natural integer of 1-2
The content of described additive A is 0.1%-2% relative to described non-aqueous electrolyte for lithium ion cell gross mass; Described additive B is selected from least one in vinylene carbonate, vinylethylene carbonate, fluorinated ethylene carbonate, and the content of described additive B is 0.5%-3% relative to described non-aqueous electrolyte for lithium ion cell gross mass.
2. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, wherein R is selected from methyl, ethyl or propyl group.
3. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, m is 1.
4. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, described additive A is selected from least one in trimethyl silicon based methanesulfonates, trimethyl silicon based esilate, trimethyl silicon based propane sulfonic acid ester.
5. non-aqueous electrolyte for lithium ion cell according to claim 1, it is characterized in that, described non-aqueous organic solvent is the mixture of cyclic carbonate and linear carbonate, described cyclic carbonate be selected from ethylene carbonate, propene carbonate and butylene one or more, described linear carbonate be selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate one or more.
6. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, described lithium salts is selected from LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiN (SO 2cF 3) 2, LiN (SO 2c 2f 5) 2, LiC (SO 2cF 3) 3with LiN (SO 2f) 2in one or more.
7. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, described additive also comprise in PS, Isosorbide-5-Nitrae-butane sultone, 1,3-propene sultone one or more.
8. a lithium ion battery, the barrier film comprising positive pole, negative pole and be placed between positive pole and negative pole, is characterized in that, also comprises the non-aqueous electrolyte for lithium ion cell described in claim 1 to 7 any one.
9. lithium ion battery according to claim 8, is characterized in that, described positive pole is selected from LiCoO 2, LiNiO 2, LiMn 2o 4, LiCo 1-ym yo 2, LiNi 1-ym yo 2, LiMn 2-ym yo 4and LiNi xco ymn zm 1-x-y-zo 2in one or more, wherein, M be selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti one or more, and 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
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