CN105742709A - Electrolyte for lithium-ion battery and lithium-ion battery employing electrolyte - Google Patents
Electrolyte for lithium-ion battery and lithium-ion battery employing electrolyte Download PDFInfo
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- CN105742709A CN105742709A CN201610248812.7A CN201610248812A CN105742709A CN 105742709 A CN105742709 A CN 105742709A CN 201610248812 A CN201610248812 A CN 201610248812A CN 105742709 A CN105742709 A CN 105742709A
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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
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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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 relates to the technical field of lithium-ion batteries, in particular to a high-voltage and high-compaction electrolyte for a lithium-ion battery and the lithium-ion battery employing the electrolyte. The electrolyte comprises a lithium salt, a non-aqueous organic solvent and an additive, wherein the additive comprises fluoroethylene carbonate, a nitrile compound and a compound with a structure shown in the formula I; R1, R2 and R3 in the formula I are independently selected from hydrogen, halogen, hydroxyl, amino, a sulfo group, nitryl, carboxyl, an aldehyde group and alkyl or alkoxy of which the carbon atom number is 1-3 respectively; R4 is selected from hydrogen, amino or alkyl of which the carbon atom number is 1-3; and n is selected from an arbitrary integer between 0 and 2. Compared with the prior art, the battery employing the electrolyte is excellent in infiltration effect and high in development capacity under the conditions of high voltage and high compaction and has excellent cycle performance and high-temperature storage performance through synergistic effects of the fluoroethylene carbonate, the nitrile compound and the compound with the structure shown in the formula I.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of high voltage reality lithium-ion battery electrolytes and use the lithium ion battery of this electrolyte.
Background technology
Since 1991 by Sony success commercialization since, lithium ion battery is applied to the electronics market such as mobile phone, notebook computer, photographing unit, panel computer soon, and advantage progressively occupies leading position so that its specific energy height, voltage height, operating temperature range width, long service life, memory-less effect, self-discharge rate be little etc..Additionally, it is also applied to the fields such as unmanned plane, electric bicycle, electrodynamic balance car, electric automobile as supply module.But along with the corresponding development using field, the energy density of current supply module cannot mate corresponding power consumption module, therefore how to promote the energy density of lithium ion battery and seem and become more and more important.Promoting the mode of lithium ion battery energy density in prior art, be roughly divided into two kinds, one is improve charging voltage to increase the gram volume of positive electrode active materials；Two is that the compacted density strengthening cathode size is to obtain less volume.
Wherein, lithium ion transport, as one of big main component of lithium ion battery four, is played the effect of key by electrolyte.But the lifting of the rising of battery charging voltage, anode compacted density, except the special pre-treatment to respective material, electrolyte be it is also proposed more harsh requirement, do not require nothing more than the electrolyte used and should have broader electrochemical window in theory, to adapt to positive electrode Oxidation under high potential after charging voltage raises, also to keep good infiltration with the positive/negative plate of high-pressure solid, barrier film, with ensure lithium ion without hindrance pass through intercalation.Current domestic lithium ion battery majority adopts LiPF6-EC/EMC/DEC, as main electrolyte system, is aided with the additives such as a small amount of ethylene carbonate, propylene sulfite.Though this electrolyte has excellent cycle performance and high-temperature storage performance at lower voltages, but in the lithium-ion battery system of high voltage real density, its various aspects of performance such as circulation and high-temperature storage all seems not ideal enough, and wetting property is also poor.Therefore it is badly in need of making existing electrolyte further to optimize so that it is the lithium-ion battery system of high voltage real density can be mated.
Summary of the invention
For current electrolysis liquid in the lithium ion battery of high voltage real density, its performance such as circulation and high-temperature storage is not ideal enough, wetting property is the defect such as poor also, an object of the present invention is in that: provides the circulation of battery under a kind of high voltage and high-temperature storage performance excellent, enables the lithium-ion battery electrolytes that high-pressure solid positive/negative plate is fully infiltrated simultaneously.
The two of the purpose of the present invention are in that: for the deficiencies in the prior art, it is provided that a kind of lithium ion battery during use when 4.4V and above high potential high compacted density with good high-temperature storage and cycle performance.
To achieve these goals, the present invention adopts solution below:
A kind of lithium-ion battery electrolytes, including lithium salts, Non-aqueous Organic Solvents and additive, described additive includes fluorinated ethylene carbonate, nitrile compounds and has the compound of structure shown in formula I；
Wherein, the R in formula I1、R2、R3Separately selected from alkyl or alkoxyl that hydrogen, halogen, hydroxyl, amino, sulfonic group, nitro, carboxyl, aldehyde radical, carbon number are 1～3；R4It is the alkyl of 1～3 selected from hydrogen, amino or carbon number；N arbitrary integer between 0～2.
The present invention is by the synergism of fluorinated ethylene carbonate, nitrile compounds and the compound with structure shown in formula I, under high voltage is real, not only effect of impregnation is excellent, it is high to play capacity to make the battery using this electrolyte, and possesses circulation and the high-temperature storage performance of excellence.Wherein, fluorinated ethylene carbonate forms SEI film in negative terminal surface, solvent and negative active core-shell material is effectively isolated, it is ensured that cycle life, and fluorinated ethylene carbonate is in high-pressure solid battery system simultaneously, it is possible to promote the wetting property of battery；Nitrile compounds, transition metal generation complexing with positive pole, it is suppressed that battery is the dissolution of transition metal under high-temperature storage conditions, improves high-temperature behavior, and the complexation film formed can suppress solvent directly to contact and oxidized decomposition with positive electrode active materials, promote cycle performance；There is the 2-Thiophene Carboxylic Acid ester type compound of structure shown in formula I; its unsaturated carbon-carbon double bond contained and the transition metal generation complexing in positive electrode active materials are to protect the not oxidized decomposition of solvent on the one hand; on the other hand; the ester group contained can reduce the overall viscosity of electrolyte; promote the electrolyte wetting property to pole piece so that itself and high-pressure solid pole piece agree with completely.
Preferably, described fluorinated ethylene carbonate weight/mass percentage composition in the electrolytic solution is 1%～8%；Described nitrile compounds weight/mass percentage composition in the electrolytic solution is 0.05%～5%；The described compound with structure shown in formula I weight/mass percentage composition in the electrolytic solution is 0.01%～8%.
Preferably, described lithium salts is at least one in lithium hexafluoro phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, double; two fluorine sulfimide lithium, LiBF4 and double; two trifluoromethanesulfonimide lithium；Described lithium salts weight/mass percentage composition in the electrolytic solution is 10%～20%.
Preferably, described Non-aqueous Organic Solvents is selected from one or more in ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, propyl propionate, ethyl propionate, methyl propyl carbonate, oxolane, dioxy cycloalkanes, gamma-butyrolacton, ethyl acetate, propyl acetate, methyl acetate, methyl butyrate, ethyl n-butyrate., propyl butyrate；Described Non-aqueous Organic Solvents weight/mass percentage composition in the electrolytic solution is 65%～85%.Above-mentioned Non-aqueous Organic Solvents has higher decomposition electric potential, has good heat stability and electrochemical stability under high temperature, high pressure, thus the electrical property for 4.4V and above high voltage reality lithium ion battery provides stable electrochemical environment.
Preferably, described nitrile compounds is at least one in adiponitrile, succinonitrile, glutaronitrile, pimelic dinitrile, 2-methyl cellosolve acetate glutaronitrile and 1,3,6-hexane three nitrile.Cited nitrile compounds can improve anode material for lithium-ion batteries stability under high voltages, it is suppressed that electrolyte decomposes at positive electrode surface, improves memory property and the cycle performance of high-voltage lithium ion batteries.
Preferably, there are described in one or more in 2-thiophenecarboxylate (structural formula is such as shown in formula II), 3-amino-2-thiophenecarboxylate (structural formula is such as shown in formula III), 2-thiophene acetic acid ethyl ester (structural formula is such as shown in formula IV), 2-thiophene acetic acid methyl ester (structural formula is such as shown in formula V) and 2-thiophene ethyl formate (structural formula such as formula VI is shown) of the compound of structure shown in formula I.
Preferably, described additive also includes vinylene carbonate, and described vinylene carbonate weight/mass percentage composition in the electrolytic solution is 0.1%～2%.Vinylene carbonate is a kind of excellent additives for overcharge protection additive; there is good high temperature performance and anti-flatulence function; capacity and the cycle life of battery can be improved; so the addition of this auxiliary additive can optimize electrolyte system further so that this electrolyte has more excellent combination property.
Preferably, having the compound of structure shown in formula I weight/mass percentage composition in the electrolytic solution described in is 0.5%～5%；N is selected from 1 or 2.
The present invention also provides for a kind of lithium ion battery adopting above-mentioned lithium-ion battery electrolytes to prepare, including anode pole piece, barrier film, cathode pole piece and electrolyte, described anode pole piece includes plus plate current-collecting body and is coated in the positive pole diaphragm of anode collection surface, and described cathode pole piece includes negative current collector and is coated in the cathode membrane of negative pole currect collecting surface.
Wherein, described positive pole diaphragm includes positive active material, conductive agent and binding agent and the compacted density >=4.0g/cm of described positive pole diaphragm3。
Described cathode membrane includes negative electrode active material, conductive agent and binding agent and the compacted density >=1.65g/cm of described cathode membrane3。
The charge cutoff voltage of described lithium ion battery is 4.4～4.7V.
The present invention at least has the advantages that
1) one lithium-ion battery electrolytes of the present invention, including lithium salts, Non-aqueous Organic Solvents and additive, described additive includes fluorinated ethylene carbonate, nitrile compounds and has the 2-Thiophene Carboxylic Acid ester type compound of structure shown in formula I；Wherein, fluorinated ethylene carbonate forms SEI film in negative terminal surface, solvent and negative active core-shell material is effectively isolated, it is ensured that cycle life, and fluorinated ethylene carbonate is in high-pressure solid battery system simultaneously, it is possible to promote the wetting property of battery；Nitrile compounds, transition metal generation complexing with positive pole, it is suppressed that battery is the dissolution of transition metal under high-temperature storage conditions, improves high-temperature behavior, and the complexation film formed can suppress solvent directly to contact and oxidized decomposition with positive electrode active materials, promote cycle performance；There is the 2-Thiophene Carboxylic Acid ester type compound of structure shown in formula I; its unsaturated carbon-carbon double bond contained and the transition metal generation complexing in positive electrode active materials are to protect the not oxidized decomposition of solvent on the one hand; on the other hand; the ester group contained can reduce the overall viscosity of electrolyte; promote the electrolyte wetting property to pole piece so that itself and high-pressure solid pole piece agree with completely；
2) the Non-aqueous Organic Solvents system selected by the present invention, comprises the solvent of the high-k such as ethylene carbonate, Allyl carbonate, is conducive to the dissolving of lithium salts and the lifting of battery high-temperature behavior；Additionally, comprise the solvent composition that viscosity is low and electrochemical window is wide, it is possible to do not decomposed by the positive pole of high potential under high voltage condition, and the electrolyte infiltration requirement to pole piece can be met；
3) present invention adjusts produced cooperative effect by the proportioning of fluorinated ethylene carbonate, nitrile compounds and the 2-Thiophene Carboxylic Acid ester type compound with structure shown in formula I, make the lithium ion battery using this electrolyte to prepare when 4.4V and above high voltage real density, not only effect of impregnation is excellent, and possess excellent circulation and high-temperature storage performance, have broad application prospects.
Accompanying drawing explanation
Fig. 1 is the cycle performance figure of battery obtained by the embodiment of the present invention 1～15 and comparative example 1～6.
Detailed description of the invention
Below in conjunction with detailed description of the invention and Figure of description, the present invention and beneficial effect thereof are described in further detail, but, the specific embodiment of the present invention is not limited thereto.
Embodiment 1
The preparation of electrolyte:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding the 2-thiophenecarboxylate that mass fraction is 5%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 1.
The preparation of lithium ion battery:
By positive active material cobalt acid lithium, conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF) in mass ratio 95: 3: 2 in N-Methyl pyrrolidone dicyandiamide solution, be sufficiently stirred for mix homogeneously after, be coated on Al paper tinsel dry, cold pressing, obtaining anode pole piece, its compacted density is 4.0g/cm3。
After negative electrode active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickening agent carboxymethyl cellulose sodium (CMC) are sufficiently stirred for mix homogeneously according to mass ratio 95: 2: 2: 1 in deionized water solvent system, be coated on Cu paper tinsel dry, cold pressing, obtaining cathode pole piece, its compacted density is 1.65g/cm3。
Using polyethylene (PE) for basement membrane (10 μm) and at the nano oxidized aluminized coating of coating on base films (3 μm) as barrier film.
Anode pole piece, barrier film, cathode pole piece are folded in order, makes barrier film be in the middle of positive/negative plate to play the effect of isolation, and wind and obtain naked battery core.Naked battery core is placed in outer package, inject preparation electrolyte and encapsulated, shelve, be melted into, the operation such as aging, secondary encapsulation, partial volume, obtain the lithium ion battery that model is 504848.
Embodiment 2
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding fluorinated ethylene carbonate that mass fraction is 3%, mass fraction is the adiponitrile of 1% and 2-thiophenecarboxylate that mass fraction is 0.5%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 2.
All the other, with embodiment 1, repeat no more here.
Embodiment 3
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding fluorinated ethylene carbonate that mass fraction is 3%, mass fraction is the adiponitrile of 1% and 2-thiophenecarboxylate that mass fraction is 5%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 3.
All the other, with embodiment 1, repeat no more here.
Embodiment 4
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding the 3-amino-2-thiophenecarboxylate that mass fraction is 2%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 4.
All the other, with embodiment 1, repeat no more here.
Embodiment 5
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding fluorinated ethylene carbonate that mass fraction is 5%, mass fraction is the adiponitrile of 3% and 3-amino-2-thiophenecarboxylate that mass fraction is 0.2%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 5.
All the other, with embodiment 1, repeat no more here.
Embodiment 6
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding fluorinated ethylene carbonate that mass fraction is 5%, mass fraction is the adiponitrile of 3% and 3-amino-2-thiophenecarboxylate that mass fraction is 2%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 6.
All the other, with embodiment 1, repeat no more here.
Embodiment 7
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding the 2-thiophene acetic acid ethyl ester that mass fraction is 5%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 7.
All the other, with embodiment 1, repeat no more here.
Embodiment 8
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding fluorinated ethylene carbonate that mass fraction is 3%, mass fraction is the adiponitrile of 1% and 2-thiophene acetic acid ethyl ester that mass fraction is 0.5%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 8.
All the other, with embodiment 1, repeat no more here.
Embodiment 9
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding fluorinated ethylene carbonate that mass fraction is 3%, mass fraction is the adiponitrile of 1% and 2-thiophene acetic acid ethyl ester that mass fraction is 5%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 9.
All the other, with embodiment 1, repeat no more here.
Embodiment 10
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding 2-thiophene acetic acid methyl ester and 1% vinylene carbonate that mass fraction is 5%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 10.
All the other, with embodiment 1, repeat no more here.
Embodiment 11
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding fluorinated ethylene carbonate that mass fraction is 3%, 2-thiophene acetic acid methyl ester and 1% vinylene carbonate that adiponitrile that mass fraction is 1%, mass fraction are 0.5%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 11.
All the other, with embodiment 1, repeat no more here.
Embodiment 12
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding fluorinated ethylene carbonate that mass fraction is 3%, 2-thiophene acetic acid methyl ester and 1% vinylene carbonate that adiponitrile that mass fraction is 1%, mass fraction are 5%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 12.
All the other, with embodiment 1, repeat no more here.
Embodiment 13
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding the 2-thiophene ethyl formate that mass fraction is 5%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 13.
All the other, with embodiment 1, repeat no more here.
Embodiment 14
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding fluorinated ethylene carbonate that mass fraction is 3%, mass fraction is the adiponitrile of 1% and 2-thiophene ethyl formate that mass fraction is 0.5%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 14.
All the other, with embodiment 1, repeat no more here.
Embodiment 15
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding fluorinated ethylene carbonate that mass fraction is 3%, mass fraction is the adiponitrile of 1% and 2-thiophene ethyl formate that mass fraction is 5%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of embodiment 15.
All the other, with embodiment 1, repeat no more here.
Comparative example 1:
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding the fluorinated ethylene carbonate that mass fraction is 3%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of comparative example 1.
All the other, with embodiment 1, repeat no more here.
Comparative example 2:
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding fluorinated ethylene carbonate that mass fraction is 3% and mass fraction is the adiponitrile of 1%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of comparative example 2.
All the other, with embodiment 1, repeat no more here.
Comparative example 3:
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding the adiponitrile that mass fraction is 1%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of comparative example 3.
All the other, with embodiment 1, repeat no more here.
Comparative example 4:
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding the adiponitrile of fluorinated ethylene carbonate that mass fraction is 5% and 1%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of comparative example 4.
All the other, with embodiment 1, repeat no more here.
Comparative example 5:
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding the adiponitrile of fluorinated ethylene carbonate that mass fraction is 3% and 3%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of comparative example 5.
All the other, with embodiment 1, repeat no more here.
Comparative example 6:
The preparation of electrolyte as different from Example 1:
Glove box (moisture < 10ppm at full argon, oxygen content < 1ppm) in, ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate than mix homogeneously and are stirred continuously with the quality of 25:10:30:40:5, in mixed solvent, are slowly added to the LiPF that mass fraction is 12.5%6, adding the adiponitrile of fluorinated ethylene carbonate that mass fraction is 5% and 3%, stirring, to being completely dissolved, namely obtains the lithium-ion battery electrolytes of comparative example 6.
All the other, with embodiment 1, repeat no more here.
Battery made by embodiment 1～15 and comparative example 1～6 carrying out first charge-discharge efficiency, partial volume capacity and capacity of negative plates respectively and plays performance test, test result is in Table 1.
Each the performance test results of table 1 embodiment 1～15 and comparative example 1～6
Additionally, for the advantage embodying the present invention further, respectively same batch of battery obtained by embodiment 1～15 and comparative example 1～6 is carried out following performance test:
Room temperature 0.7C/1C loop test: battery is limited voltage with 0.7C multiplying power constant current charge to 4.4V in 25 ± 1 DEG C of environment, then constant-potential charge is to cut-off current 0.05C, shelves 5min, then carries out constant current electric discharge, discharge-rate 1C, discharge cut-off voltage 3.0V；Finally being circulated test, cycle-index is set to more than 400 times.Test result is as shown in Figure 1.
85 DEG C of high-temperature storage 16h tests: battery is limited voltage with 0.2C multiplying power constant current charge to 4.4V, then constant-potential charge is to cut-off current 0.02C, shelve 5min, carry out 0.2C multiplying power constant-current discharge again to 3.0V blanking voltage, recording this discharge capacity is initial discharge capacity, and measures the cell thickness of original state, internal resistance；The battery of full power state is put in the baking oven of 85 DEG C, 16h is stored with the steady temperatures of 85 ± 2 DEG C, the thickness under battery high-temperature state is tested immediately after having stored, 2h is cooled down under room temperature state, test thickness, internal resistance, test residual capacity, 0.2C multiplying power test recovery capacity with 0.2C multiplying power constant-current discharge；Calculate hot Thickness Measurement by Microwave expansion rate, cold Thickness Measurement by Microwave expansion rate, internal resistance Magnification, residual capacity percentage ratio, recover volume percent.The related data of test gained is as shown in table 2.
Table 2 embodiment 1～15 and comparative example 1～6 storge quality test result at 85 DEG C
The test result of his-and-hers watches 1 is analyzed: play and efficiency test result first from the capacity of battery obtained by comparative example 1～6, adopt five yuan of organic solvent systems of conventional ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate, the theory being extremely difficult to negative material plays gram volume, and first charge-discharge efficiency only has about 85%.Analyze its first charge-discharge efficiency and reduce big reason, one side is the SEI film that the film for additive selected by comparative example 1～6 is formed on cathode membrane surface, it is mainly composed of the compound such as lithium carbonate and alkoxyl lithium, all needs effective lithium that consumption part is deviate from from positive pole；On the other hand, the cyclic carbonates organic solvent used for improving high-temperature storage performance, there is higher viscosity, be difficult to show all good wetting property in the both positive and negative polarity diaphragm of high-pressure solid, cause that effective lithium that first time charging embeds graphite layers does not discharge completely when discharging first.Therefore, select the excellent additive with film forming and infiltration double effects to seem to be even more important.Therefore, the embodiment of the present invention 1～15 is compared with comparative example 1～6, and by adding 2-Thiophene Carboxylic Acid ester type compound in the electrolytic solution, its first charge-discharge efficiency is effectively improved, and all can be maintained at about 90%.
The test result of Fig. 1 is analyzed: it is seen that, when dicyandiamide solution selected by comparative example 1～6 is consistent, when the different additive combination adopted, circulating effect shows certain undulatory property.This is because, solvent ratios is general only can be affected high temperature and cryogenic property to some extent, and additive then becomes the principal element affecting cycle performance comparatively speaking.Find from the test result of comparative example 3 and comparative example 4, the addition of fluorinated ethylene carbonate, the cycle performance improving high voltage reality battery is helpful.This is because: fluorinated ethylene carbonate is many fluorine than ethylene carbonate; fluorine has higher electronegativity and electron-withdrawing power; quantum chemistry calculation shows that the minimum orbital energy (-0.3108eV) that do not occupy of fluorinated ethylene carbonate is far below ethylene carbonate (-0.29512eV); therefore it can reduce under relatively electronegative potential; have precedence over other solvents react formation SEI film, it can protect electrolyte main solvent not to be reduced and have better cycle performance；And the highest occupied molecular orbital of fluorinated ethylene carbonate is also far below other solvents, therefore it can promote the overall resistance to pressure of electrolyte after adding, and is more beneficial for widening the electrochemical window of electrolyte；Additionally, experiment finds that reduction viscosity, increase wellability are played critically important effect by fluorochemical additive in the electrolytic solution, especially the battery system to the little granule positive and negative pole material of high-pressure solid and high-specific surface area, has more excellent chemical property.
Additionally, adiponitrile is a kind of typical nitrile compounds, it contains methylene functional group, it is possible to meet the intersolubility with main solvent；Meanwhile, containing cyano group unsaturated group, have necessarily electron-withdrawing.Analyze the high-temperature storage data of comparative example 2 and comparative example 5, it is seen that, the content increasing adiponitrile makes the high-temperature expansion problem of battery effectively to be controlled further.It should be noted that; battery aerogenesis in high-temperature storage process is mainly derived from three; wherein, would generally selecting the low and low-boiling organic solvent of some viscosity in the electrolytic solution to take into account battery cryogenic property, the volatilization when high-temperature storage of this kind solvent becomes one of aerogenesis source；Secondly, the SEI film formed during Battery formation is not absolute rigidity, in high temperature environments, part alkoxyl lithium and lithium inorganic compound decomposes, produce the gases such as carbon dioxide；Additionally, under full power state, battery anode active material is in high potential for a long time, and high potential and high temperature exacerbate the oxidation decomposition course of organic solvent in electrolyte, it is easy to cause the generation of gas.And possibly together with unsaturated bond in adiponitrile, it in the battery can with the transition metal generation complexing of positive electrode active materials, it is prevented that the dissolution of transition metal；And completely cut off directly contacting of organic solvent and high potential point to a certain extent, prevent the oxidized decomposition of organic solvent further.Additionally, this unsaturated bond with the micro-moisture coordination in electrolyte, can also eliminate portion of water, effectively prevent moisture and lithium hexafluoro phosphate from reacting and generate the Lewis acid destruction positive pole of high activity, highly reduced property.
The comprehensive capacity analyzing comparative example 1～6 plays, efficiency, high-temperature storage and room temperature circulate all data it can be seen that the additive two kinds representative by adjusting fluorinated ethylene carbonate, adiponitrile first, it is difficult to obtain very big breakthrough.Reason is that fluorinated ethylene carbonate no doubt circulates, wellability is excellent and electrochemical window width, but addition increases and can bring high-temperature storage flatulence risk；Adiponitrile is controlling aerogenesis and is preventing positive pole passivation effect obvious, but with negative pole poor compatibility, and cycle performance need to improve further.It is thus desirable to introduce new combination property additive more preferably to make up the deficiency of the two.And the 2-Thiophene Carboxylic Acid ester type compound with structure shown in formula I just disclosure satisfy that requirement, in structure, it contains thiophene heterocycle, can effectively be passivated positive electrode active materials, and oxidizable composition in protection solvent, and limit for height on the electrochemical window of itself, oxidative resistance is strong；Contain ester group simultaneously, electrolyte overall density viscosity can be reduced, the both positive and negative polarity diaphragm of high-pressure solid state is had good effect of impregnation.
And play capacity, first efficiency comparative from the negative pole of the comparative example 2 of table 1 and embodiment 2～3,5～6,8～9,11～12,14～15 it can also be seen that, the 2-Thiophene Carboxylic Acid ester type compound with structure shown in formula I promotes substantially on wetting property, make effective lithium more efficiently deintercalation of energy of embedding graphite cathode interlayer, electric discharge plays capacity to be increased therewith, and first charge-discharge efficiency also significantly increases；Simultaneously because 2-Thiophene Carboxylic Acid ester type compound is obvious to positive pole passivation, the oxidation Decomposition aerogenesis of oxidizable organic solvent in electrolyte can be suppressed so that thickness swelling controls to some extent；Reduce the dissolution of transition metal simultaneously, effectively reduce its probability contacted with cathode membrane, improve the spray charging precipitator in storage process, and residual capacity and recovery capacity all promote substantially, so battery high-temperature storge quality is effectively improved；In addition, circulating with the obvious advantage, the 2-Thiophene Carboxylic Acid ester type compound of addition can form SEI passivating film at positive pole, decreases electrolyte oxidation consumption on positive pole in circulating battery process, maintain effective lithium content of whole battery, be effectively increased the cycle life of battery.
And contrast from the embodiment 1 of Fig. 1 and the circulation of embodiment 2,3, that adds 2-thiophenecarboxylate in the electrolytic solution is simultaneously introduced fluorinated ethylene carbonate and adiponitrile, compared with adding 2-thiophenecarboxylate merely in the electrolytic solution, the cycle life of battery remains basically stable, and illustrates that 2-thiophenecarboxylate joins as additive and can play the effect improving circulating battery in electrolyte equally.
From above-mentioned analysis it is seen that, circulation volume will be kept unattenuated, except positive pole need passivation except, also need negative pole formed passivating film, the therefore addition of 2-thiophenecarboxylate, except having passivation at positive electrode surface, equally exist certain film forming effect in negative terminal surface.And found by the performance capacity in contrast table 1 and first charge-discharge efficiency, the addition of 2-thiophenecarboxylate is when 0.5% and 5%, and both capacity play difference substantially, illustrates that the addition of 0.5% can not fully meet the pole piece requirement to wetting property；And after fluorinated ethylene carbonate addition, efficiency is in a slight decrease first, this is because fluorinated ethylene carbonate can consume part effectively lithium in negative terminal surface film forming.Similarly analyze embodiment 4～15, it is seen that add 3-amino-2-thiophenecarboxylate, 2-thiophene acetic acid ethyl ester, 2-thiophene acetic acid methyl ester and 2-thiophene ethyl formate in the electrolytic solution all can draw corresponding conclusion.Analyze capacity of negative plates and the first charge-discharge efficiency of embodiment 1,4,7,10 again, discovery is more or less the same, this is because mainly thiophene heterocycle and the ester functional groups that play a decisive role in 2-Thiophene Carboxylic Acid ester type compound, the oxidative resistance of electrical conductivity and compound is simply slightly affected by the functional group such as methylene and amino, and general trend is increasing and deaminize and being more beneficial for infiltration of methylene.And be also mainly reflected in effect of impregnation from the cycle performance figure difference of Fig. 1, well then cycle performance performance is more excellent for general wetting property.But it should be noted that increasing of alkyl, have certain expansion risk when high-temperature storage.Reason is that short chain contributes to being formed the big π key of heterocycle in storage process, and compound itself has the more stable more resistant to elevated temperatures macroscopic property of formation.
Comprehensive above analysis is known, the present invention passes through reasonable selection dicyandiamide solution and lithium salt, the ratio of rational allocation fluorinated ethylene carbonate and adiponitrile, and introduce positive pole passivation ability and all good 2-Thiophene Carboxylic Acid ester type compound of wellability, make 4.4V high voltage reality lithium ion battery, possess and play the combination property that capacity is high, high-temperature storage performance is excellent, have extended cycle life, under the overall situation that long circulating high capacity density is constantly pursued in existing digital battery field, it is widely applied prospect.
The announcement of book and instruction according to the above description, above-mentioned embodiment can also be modified and revise by those skilled in the art in the invention.Therefore, the invention is not limited in above-mentioned detailed description of the invention, any conspicuously improved, replacement or modification that every those skilled in the art are done on the basis of the present invention belong to protection scope of the present invention.Although additionally, employ some specific terms in this specification, but these terms are intended merely to convenient explanation, and the present invention does not constitute any restriction.
Claims (12)
1. a lithium-ion battery electrolytes, including lithium salts, Non-aqueous Organic Solvents and additive, it is characterised in that: described additive includes fluorinated ethylene carbonate, nitrile compounds and has the compound of structure shown in formula I；
Wherein, the R in formula I1、R2、R3Separately selected from alkyl or alkoxyl that hydrogen, halogen, hydroxyl, amino, sulfonic group, nitro, carboxyl, aldehyde radical, carbon number are 1～3；R4It is the alkyl of 1～3 selected from hydrogen, amino or carbon number；N arbitrary integer between 0～2.
2. lithium-ion battery electrolytes according to claim 1, it is characterised in that: described fluorinated ethylene carbonate weight/mass percentage composition in the electrolytic solution is 1%～8%；Described nitrile compounds weight/mass percentage composition in the electrolytic solution is 0.05%～5%；The described compound with structure shown in formula I weight/mass percentage composition in the electrolytic solution is 0.01%～8%.
3. lithium-ion battery electrolytes according to claim 1, it is characterised in that: described lithium salts is at least one in lithium hexafluoro phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, double; two fluorine sulfimide lithium, LiBF4 and double; two trifluoromethanesulfonimide lithium；Described lithium salts weight/mass percentage composition in the electrolytic solution is 10%～20%.
4. lithium-ion battery electrolytes according to claim 1, it is characterised in that: described Non-aqueous Organic Solvents is selected from one or more in ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, propyl propionate, ethyl propionate, methyl propyl carbonate, oxolane, dioxy cycloalkanes, gamma-butyrolacton, ethyl acetate, propyl acetate, methyl acetate, methyl butyrate, ethyl n-butyrate., propyl butyrate；Described Non-aqueous Organic Solvents weight/mass percentage composition in the electrolytic solution is 65%～85%.
5. lithium-ion battery electrolytes according to claim 1, it is characterised in that: described nitrile compounds is at least one in adiponitrile, succinonitrile, glutaronitrile, pimelic dinitrile, 2-methyl cellosolve acetate glutaronitrile and 1,3,6-hexane three nitrile.
6. lithium-ion battery electrolytes according to claim 1, it is characterised in that: described in there are one or more in 2-thiophenecarboxylate, 3-amino-2-thiophenecarboxylate, 2-thiophene acetic acid ethyl ester, 2-thiophene acetic acid methyl ester and 2-thiophene ethyl formate of the compound of structure shown in formula I.
7. lithium-ion battery electrolytes according to claim 1, it is characterised in that: described additive also includes vinylene carbonate, and described vinylene carbonate weight/mass percentage composition in the electrolytic solution is 0.1%～2%.
8. lithium-ion battery electrolytes according to claim 2, it is characterised in that: described in have the compound of structure shown in formula I weight/mass percentage composition in the electrolytic solution be 0.5%～5%；N is selected from 1 or 2.
9. a lithium ion battery, including anode pole piece, barrier film, cathode pole piece and electrolyte, described anode pole piece includes plus plate current-collecting body and is coated in the positive pole diaphragm of anode collection surface, described cathode pole piece includes negative current collector and is coated in the cathode membrane of negative pole currect collecting surface, it is characterised in that: described electrolyte is the lithium-ion battery electrolytes described in any one of claim 1～8.
10. lithium ion battery according to claim 9, it is characterised in that: described positive pole diaphragm includes positive active material, conductive agent and binding agent and the compacted density >=4.0g/cm of described positive pole diaphragm3。
11. lithium ion battery according to claim 9, it is characterised in that: described cathode membrane includes negative electrode active material, conductive agent and binding agent and the compacted density >=1.65g/cm of described cathode membrane3。
12. lithium ion battery according to claim 9, it is characterised in that: the charge cutoff voltage of described lithium ion battery is 4.4～4.7V.
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