CN105845981A - Non-aqueous electrolyte and lithium-ion battery employing same - Google Patents
Non-aqueous electrolyte and lithium-ion battery employing same Download PDFInfo
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- CN105845981A CN105845981A CN201610193163.5A CN201610193163A CN105845981A CN 105845981 A CN105845981 A CN 105845981A CN 201610193163 A CN201610193163 A CN 201610193163A CN 105845981 A CN105845981 A CN 105845981A
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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Abstract
The invention relates to the field of lithium-ion batteries, in particular to a non-aqueous electrolyte and a lithium-ion battery employing the same. The non-aqueous electrolyte comprises a lithium salt, a solvent and an additive, wherein the additive comprises a sulphonate quaternary ammonium salt and an SEI film-forming additive. By the non-aqueous electrolyte, the wettability of the electrolyte on an active material pole piece is significantly improved; a solid electrolyte membrane which is small in impedance, uniform and compact is generated on the surface of the pole piece; and the dynamic performance of the pole piece is improved, so that the battery has good cycle performance when the pole piece is highly compacted or at a low temperature.
Description
Technical field
The application relates to field of lithium ion battery, specifically, relates to a kind of nonaqueous electrolytic solution and uses this nonaqueous electrolytic solution
Lithium ion battery.
Background technology
In recent years, along with developing rapidly that lithium ion battery is applied in portable electronics field, people are to portable for these
Formula electronic equipment provides the demand of small-sized, light, the thin and high performance battery of power supply day by day to increase.Due to the high energy to battery
The continuous pursuit of metric density, using the both positive and negative polarity of high compacted density or the poor negative material of high power capacity cycle performance is current work
A kind of strategy that industry is commonly used.The problem brought therewith is that electrolyte cannot fully infiltrate electrode, causes the charging of battery
Platform raises and discharge platform reduces the output performance affecting battery.When cold cycle, owing to the dynamic performance of battery is owed
Good, easily analyse lithium during low temperature discharge and recharge.
Being analyzed the problems referred to above, battery electrode surface when chemical conversion can generate one layer of SEI film (solid electrolyte film),
This layer of solid electrolyte film controls the passage of ion turnover, is to control the dynamic (dynamical) key factor of electrode reaction.Low
Under temperature environment, if the SEI film formed is the thickest, membrane impedance is higher, then lithium ion cannot migrate through, and will occur to analyse lithium.Another
At high temperature, the SEI film of generation is the most form compact and stable for aspect, then SEI film can gradually dissolve or rupture, and causes the negative pole exposed to continue
Continue and react with electrolyte, while consuming electrolyte so that battery capacity reduces.
It addition, controlling another factor of battery high temperature performance is the electrolyte wetting capacity to pole piece, if increasing eutectic
Point, low viscosity solvent content, the cryogenic property of battery increases really, but its high-temperature behavior can be deteriorated, and both cannot take into account.
For above-mentioned technical problem, special proposition the application.
Summary of the invention
The primary goal of the invention of the application is to propose a kind of nonaqueous electrolytic solution.
Second goal of the invention of the application is 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 lithium salts, solvent and additive, described additive includes sulphonic acid ester quaternary ammonium salt and SEI
Film for additive.
Preferably, the structural formula of described sulphonic acid ester quaternary ammonium salt is as shown in formula I:
Wherein, R1Selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, replacement or unsubstituted
C2～12Alkynyl, substituted or unsubstituted C1～12Alkoxyl, substituted or unsubstituted C1～12Acyloxy；
R2Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C2～12Alkenylene, replacement or unsubstituted
C2～12Alkynylene, substituted or unsubstituted C1～12Alkylene acyl group；
R3Selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C1～12Alkoxyl, substituted or unsubstituted
C1～12Acyloxy, substituted or unsubstituted C6～22Aryl, substituted or unsubstituted C5～22Heterocyclic base；
R4Selected from substituted or unsubstituted C1～3Alkylidene；
Substituent group is cyano group, halogen；
X-Represent anion.
Preferably, R1Selected from substituted or unsubstituted C1～6Alkyl；R2Selected from substituted or unsubstituted C1～12Alkylidene；R3Choosing
From substituted or unsubstituted C1～6Alkyl；R4Selected from substituted or unsubstituted C1～2Alkylidene.
Preferably, the cation group of described sulphonic acid ester quaternary ammonium salt is selected from following structural formula:
Preferably, anion X of described sulphonic acid ester quaternary ammonium salt—Selected from following group:
F-、NO3 -、SO4 2-、PF6 -、BF4 -、AsF6 -、(FSO2)2N-、
Preferably, described SEI film for additive is selected from fluorinated ethylene carbonic ester, vinylene carbonate, vinyl ethylene
At least one in alkene ester, ethylene sulfite, propylene sulfite.
Preferably, described sulphonic acid ester quaternary ammonium salt mass percent in the electrolytic solution is 0.1%～10%.
Preferably, described SEI film for additive mass percent in the electrolytic solution is 0.1%～10%.
Preferably, described lithium salts includes LiPF6。
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, negative plate include negative current collector and
The cathode membrane being coated on negative current collector；Described electrolyte is the nonaqueous electrolytic solution of the application.
The technical scheme of the application at least has a following beneficial effect:
Compared with prior art, the application is by adding the sulphonic acid ester quaternary ammonium salt of formula I in lithium-ion battery electrolytes, aobvious
Write and improve the electrolyte wellability to active substance pole piece, generate little and even compact the solid of impedance in pole piece electric
Solve plasma membrane, improve the dynamic performance of pole piece, so that battery all has good cyclicity under pole piece high-pressure solid or low temperature
Energy.
The cation group of the application sulphonic acid ester quaternary ammonium salt has hydrophilic head and hydrophobic afterbody (in atom N simultaneously
Side chain), thus have amphiphilic.Hydrophobic afterbody can reduce the surface tension of electrolyte, makes the electrolyte can be the most equal
Even infiltrate in pole piece, some sense in polar group containing N heterocycle cation part and pole piece active material surface or SEI film
Group forms hydrogen bond equimolecular intermolecular forces and electrostatic interaction, and the wellability of anticathode improves.The group of the application is hydrophobic
Afterbody is with a sulfonate ester group, during electrochemical redox, easily generates the Lithium perchlorate of good conductivity
RSO3Li, Lithium perchlorate is one layer of fine and close solid electrolyte film, can reduce the impedance of electrode surface.In cation group
Quaternary ammonium salt can be respectively provided with good thermodynamic stability from different anion collocation.When anionicsite is difluoro two grass
When acid phosphoric acid radical ion, tetrafluoro oxalic acid phosphate anion plasma, these materials at higher current potential preferentially at negative electrode active material
The solid electrolyte membrane that matter Surface Creation one layer impedance is low, dense uniform, high temperature performance are excellent, prevents electrolyte and pole piece
Haptoreaction, prevents from generating thicker SEI film.
Hereinafter present context is described further, in the range of purport, implements various deformation be still included in this
In the claim of application, embodiment is only the mode that relatively sharp explanation is implemented, but the concrete side being not limited in embodiment
Formula.
Detailed description of the invention
The application provides a kind of and can generate the good SEI film of even compact dynamic performance at electrode surface, have electrode
There is good wetting capacity, the nonaqueous electrolytic solution of the cold cycle performance of battery can be improved.The application is by the sulphonic acid ester season shown in formula I
Ammonium salt adds in lithium-ion battery electrolytes as additive, it is possible to generate dense uniform when chemical conversion at electrode surface
SEI film, and improve electrolyte wetting capacity in the battery simultaneously, thus improve the pole piece dynamic performance of battery.
As a kind of improvement of the application nonaqueous electrolytic solution, the structural formula such as formula of the sulphonic acid ester quaternary ammonium salt that the application is used
Shown in I:
Wherein, R1Selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, replacement or unsubstituted
C2～12Alkynyl, substituted or unsubstituted C1～12Alkoxyl, substituted or unsubstituted C1～12Acyloxy；
R2Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C2～12Alkenylene, replacement or unsubstituted
C2～12Alkynylene, substituted or unsubstituted C1～12Alkylene acyl group；
R3Selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C1～12Alkoxyl, substituted or unsubstituted
C1～12Acyloxy, substituted or unsubstituted C6～22Aryl, substituted or unsubstituted C5～22Heterocyclic base；
R4Selected from substituted or unsubstituted C1～3Alkylidene；
Substituent group is cyano group, halogen；
X-Represent anion.
In the formula of the application:
Carbon number is the alkyl of 1～12, and alkyl can be chain-like alkyl, it is possible to for cycloalkyl, be positioned on the ring of cycloalkyl
Hydrogen can be replaced by alkyl, in described alkyl, the preferred lower limit of carbon number is 2,3,4,5, preferred higher limit is 3,4,5,
6,8,10.Preferably, the alkyl selecting carbon number to be 1～10, it is further preferred that the chain selecting carbon number to be 1～6
Alkyl, carbon number is the cycloalkyl of 3～8, it is further preferred that the chain-like alkyl selecting carbon number to be 1～4, carbon is former
Subnumber is the cycloalkyl of 5～7.As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, positive fourth
Base, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, hexyl, 2-Methyl pentyl, 3-Methyl pentyl, 1,
1,2-trimethyl-propyl, 3,3 ,-dimethyl-butyl, heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl, different
Heptyl, octyl group, nonyl, decyl.
When in the alkyl that the aforementioned carbon number being previously mentioned is 1～12 containing oxygen atom, it can be alkoxyl.Preferably,
The alkoxyl selecting carbon number to be 1～10, it is further preferred that the alkoxyl selecting carbon number to be 1～6, further
Preferably, the alkoxyl selecting carbon number to be 1～4.As the example of alkoxyl, specifically can enumerate: methoxyl group, ethoxy
Base, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, cyclopentyloxy, ring
Hexyloxy.
When in the alkyl that the aforementioned carbon number being previously mentioned is 1～12 containing oxygen atom, it can be also acyloxy.Preferably
Ground, the acyloxy selecting carbon number to be 1～10, it is further preferred that the acyloxy selecting carbon number to be 1～6, more enters one
Preferably, selection carbon number is the acyloxy of 1～4 to step.As the example of acyloxy, specifically can enumerate: formyloxy, second
Acyloxy, positive propionyloxy, isopropenoxy, positive butyryl acyloxy, secondary butyryl acyloxy, tertiary butyryl acyloxy, positive valeryl epoxide, isoamyl
Acyloxy.
Carbon number be the thiazolinyl of 2～12 can be cyclic alkenyl radical, it is possible to for chain thiazolinyl.It addition, in thiazolinyl double bond
Number is preferably 1.In described thiazolinyl, the preferred lower limit of carbon number is 3,4,5, and preferred higher limit is 3,4,5,6,8,10.
Preferably, the thiazolinyl selecting carbon number to be 2～10, it is further preferred that the thiazolinyl selecting carbon number to be 2～6, more enters one
Preferably, selection carbon number is the thiazolinyl of 2～5 to step.As the example of thiazolinyl, specifically can enumerate: vinyl, pi-allyl,
Isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base.Specifically chosen identical with thiazolinyl to alkynyl.
Carbon number be the alkylidene of 2～12 be straight or branched alkylidene, in described alkylidene, carbon number is preferred
Lower limit is 2,3,4,5, and preferred higher limit is 3,4,5,6,8,10.Preferably, the alkylidene selecting carbon number to be 1～6.
As the example of alkyl, specifically can enumerate: methylene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, Asia
Sec-butyl, pentylidene, hexylidene.
Carbon number be the alkenylene of 2～6 be straight or branched alkenylene, in thiazolinyl, the number of double bond is preferably 1.Institute
Stating the preferred lower limit of carbon number in alkenylene is 3,4,5, and preferred higher limit is 3,4,5,6,8,10.Preferably, select
Carbon number is the alkenylene of 2～6.As the example of alkenylene, specifically can enumerate: ethenylidene, acrol, sub-isopropyl
Thiazolinyl, sub-alkene butyl, sub-alkene amyl group.Specifically chosen identical with alkenylene to alkynylene.
Carbon number is the aryl of 6～26, such as phenyl, benzene alkyl, at least contain a phenyl aryl such as xenyl,
Condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and condensed-nuclei aromatics base also can be replaced by alkyl or thiazolinyl.Preferably, choosing
Select the aryl that carbon number is 6～16, it is further preferred that the aryl selecting carbon number to be 6～14, the most preferably
Ground, the aryl selecting carbon number to be 6～9.As the example of aryl, specifically can enumerate: phenyl, benzyl, xenyl, to first
Phenyl, o-tolyl, a tolyl.
Carbon number is the heterocyclic base of 5～26, is selected from: furyl, thienyl, pyrrole radicals, thiazolyl, imidazole radicals, pyrrole
Piperidinyl, pyrazinyl, pyrimidine radicals, pyridazinyl, indyl, quinolyl etc..
A kind of improvement as the application nonaqueous electrolytic solution: R1Selected from substituted or unsubstituted C1～6Alkyl, replacement or do not take
The C in generation2～6Thiazolinyl, substituted or unsubstituted C2～6Alkynyl, substituted or unsubstituted C1～6Alkoxyl, substituted or unsubstituted C1～6
Acyloxy；
R2Selected from substituted or unsubstituted C1～6Alkylidene, substituted or unsubstituted C2～6Alkenylene, substituted or unsubstituted
C2～6Alkynylene, substituted or unsubstituted C1～6Alkylene acyl group；
R3Selected from substituted or unsubstituted C1～6Alkyl, substituted or unsubstituted C1～6Alkoxyl, substituted or unsubstituted
C1～6Acyloxy, substituted or unsubstituted phenyl, substituted or unsubstituted pyridine radicals；
R4Selected from substituted or unsubstituted C1～2Alkylidene；
Substituent group is cyano group, halogen；
X-Represent anion.
As a kind of improvement of the application nonaqueous electrolytic solution, R1Selected from substituted or unsubstituted C1～6Alkyl；R2Selected from replacing
Or unsubstituted C1～12Alkylidene；R3Selected from substituted or unsubstituted C1～6Alkyl；R4Selected from substituted or unsubstituted C1～2Alkylene
Base.
As a kind of improvement of the application nonaqueous electrolytic solution, R1Selected from C1～6Alkyl；R2Selected from C1～12Alkylidene；R3Selected from taking
Generation or unsubstituted C1～6Alkyl；R4Selected from C1～2Alkylidene.
As a kind of improvement of the application nonaqueous electrolytic solution, the cation group of sulphonic acid ester quaternary ammonium salt is selected from following structure
Formula:
As a kind of improvement of the application nonaqueous electrolytic solution, the cation group of sulphonic acid ester quaternary ammonium salt is also selected from following
Structural formula:
As a kind of improvement of the application nonaqueous electrolytic solution, anion X of sulphonic acid ester quaternary ammonium salt—Selected from following group:
F-、NO3 -、SO4 2-、PF6 -、BF4 -、AsF6 -、(FSO2)2N-、
As a kind of improvement of the application nonaqueous electrolytic solution, SEI film for additive selected from fluorinated ethylene carbonic ester (FEC),
In vinylene carbonate (VC), vinyl ethylene carbonate (VEC), ethylene sulfite (ES), propylene sulfite (PS)
One or more.
As a kind of improvement of the application nonaqueous electrolytic solution, sulphonic acid ester quaternary ammonium salt mass fraction in the electrolytic solution is
0.1%～10%.Upper limit value is 5%, 6%, 7%, 8%, 9%, lower limit value is 0.1%, 0.5%, 1%, 2%,
3wt%.If above-mentioned addition is less than 0.1wt%, inconspicuous to battery wellability and film-formation result；When content is more than 10%,
Electrolyte viscosity increases, and electrical conductivity declines, and dynamic performance declines, limited to cold cycle performance boost.
As a kind of improvement of the application nonaqueous electrolytic solution, SEI film for additive mass fraction in the electrolytic solution is
0.1%～10%.Upper limit value is 5%, 6%, 7%, 8%, 9%, and lower limit value is 0.2%, 0.5%, 1%, 2%, 3%.
SEI film for additive can add with single composition also can mix several interpolation.
As a kind of improvement of the application nonaqueous electrolytic solution, solvent is selected from dimethyl carbonate (DMC), diethyl carbonate
(DEC), Ethyl methyl carbonate (EMC), Ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), methyl formate (MF), Ethyl formate
(EF), methyl acetate (MA), ethyl acetate (EA), propyl propionate (PP), ethyl n-butyrate. (EB), ethyl propionate (EP), butanoic acid third
One or more in ester (PB), also including but not limited to following cyclic ester such as ethylene carbonate (EC), Allyl carbonate
(PC), butylene (BC), vinylene carbonate (VC), ethylene sulfite (ES), propylene sulfite (PS), γ-fourth
At least one in lactone (BL), oxolane (THF).Further, it is also possible to enumerate the ionic liquid different classes of with nonaqueous solvent
Body etc..It addition, for nonaqueous solvent used herein, can be used alone one, it is also possible to according to purposes with arbitrarily
Combination, ratio are used in mixed way two or more.Wherein, from for its redox electrochemical stability and with solute hot, above-mentioned
From the viewpoint of the chemical stability that reaction is relevant, particularly preferably propylene carbonate, ethylene carbonate, diethyl carbonate, carbon
Dimethyl phthalate, Ethyl methyl carbonate.
As a kind of improvement of the application nonaqueous electrolytic solution, lithium salts is except comprising LiPF6Outward, it is also possible to comprise other with
LiPF6Compatible lithium salts, as concrete example, can enumerate: with LiBF4、LiClO4、LiAsF6、LiSbF6、LiCF3SO3、LiN
(CF3SO2)2、LiN(FSO2)2、LiN(C2F5SO2)2、LiN(CF3SO2)(C4F9SO2)、LiC(CF3SO2)3、LiPF3(C3F7)3、
LiB(CF3)4、LiBF3(C2F5)、LiPO2F2、LiPF4(C2O4)、LiPF2(C2O4)2、LiBF2(C2O4)、LiB(C2O4)2Deng for generation
The electrolyte lithium salt of table.For these solutes, can individually a kind of and LiPF6Mixed, it is also possible to according to purposes with arbitrary group
Close, ratio is used in mixed way two or more.
The kind of the nonaqueous solvent used in the nonaqueous electrolytic solution of the application is had no particular limits, it is possible to use arbitrarily
Nonaqueous solvent.As concrete example, can enumerate: dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate
(EMC), Ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), methyl formate (MF), Ethyl formate (EF), methyl acetate (MA),
One or several in ethyl acetate (EA), propyl propionate (PP), ethyl n-butyrate. (EB), ethyl propionate (EP), propyl butyrate (PB)
Kind, also including but not limited to following cyclic ester such as ethylene carbonate (EC), Allyl carbonate (PC), butylene (BC),
Vinylene carbonate (VC), ethylene sulfite (ES), propylene sulfite (PS), gamma-butyrolacton (BL), oxolane
(THF) medium.
For the concentration of solute, have no particular limits, but lower limit be more than 0.5mol/L, be preferably 0.7mol/L with
Upper, more preferably more than 0.9mol/L, additionally, the upper limit is below 2.5mol/L, is preferably below 2.0mol/L, further
It is preferably the scope of below 1.5mol/L.If less than 0.5mol/L, then ionic conductance reduces, and therefore there is nonaqueous electrolytic solution electricity
The tendency that the cycle characteristics in pond, electrical conductivity reduce.On the other hand, if more than 2.5mol/L, then the viscosity of electrolyte rises, battery
Electrical conductivity too low, thus still suffer from making the dynamic performance of battery to there is the risk deteriorated.
Preparation example
The synthesis of [reference example 1] compound A
The first step is reacted:
Second step reacts:
Three-step reaction:
Operating procedure: addition 200ml dichloromethane is as solvent in the flask airtight with stirring, is subsequently adding first sulphur
Acyl chlorides (19.4g, 169.4mmol) is dissolved in 18.3g triethylamine slowly adding as reaction substrate, 15g bromoethanol (121mmol)
Enter in above-mentioned solution.After charging, continuing stirring reaction 3 hours, reaction terminates.Saturated aqueous common salt cleans reactant, point
From upper organic phase, adding heat extraction solvent, obtain head product, (eluting solvent is cyclohexane/ethyl acetate=3/ in silicagel column separation
2) purified product, obtains colorless oil 22.6g, the product compound IL-1-1 reacted as next step.
Above-claimed cpd 13g (64.0mmol) is dissolved in 25ml acetone and puts in the reaction bulb with stirring, then take
5.7g1-methylpyrrole (67.2mmol) joins above-mentioned solution, stirred under nitrogen atmosphere 2 days.After reaction terminates, to reactor
Middle addition 25ml ether, then reduce pressure sucking filtration.Ether cleans solid product repeatedly, is dried to obtain compound IL-1-2
16.5g。
Product 16.5g (57.3mmol) obtained in the previous step is dissolved in 120ml methanol, weighs 11.1gKPF6
Joining in above-mentioned reaction substrate, under nitrogen protection, reaction stirring terminated after 2 days.Product is filtered,
Solid product is cleaned with appropriate methanol and ether.Then the methanol/dichloromethane solution of 8:7 (V/V) is prepared by above-mentioned solid phase
Product dissolves, filtration under diminished pressure, collects filtrate, concentrates and obtains product 13.6g, and this product is target compound A.
The Structural Identification data of compound A:
1H NMR (400MHz, CD3OD-d4): δ 4.74 (bs, 2H), 3.88-3.85 (m, 2H), 3.71-3.61 (m, 4H),
3.23(s,3H),3.18(s,3H),2.28(m,4H).
LCMS(ESI)m/z 208.2(M-145)+.
The synthesis of [reference example 2] compound B
The first step is reacted:
Second step reacts:
Three-step reaction:
Operating procedure: addition 200ml dichloromethane is as solvent in the flask airtight with stirring, is subsequently adding first sulphur
Acyl chlorides (19.4g, 169.4mmol) is dissolved in 18.3g triethylamine slowly adding as reaction substrate, 15g (121mmol) bromoethanol
Enter in above-mentioned solution.After charging, continuing stirring reaction 3 hours, reaction terminates.Saturated aqueous common salt cleans reactant, point
From upper organic phase, adding heat extraction solvent, obtain head product, (eluting solvent is cyclohexane/ethyl acetate=3/ in silicagel column separation
2) purified product, obtains colorless oil 22.6g, the product compound IL-2-1 reacted as next step.
Above-claimed cpd 22g (108.4mmol) is dissolved in 60ml acetone and puts in the reaction bulb with stirring, then take
11.3g 1-methyl piperidine (113.8mmol) joins above-mentioned solution, stirred under nitrogen atmosphere 3 days.After reaction terminates, to reaction
Adding 25ml ether in device, then reduce pressure sucking filtration.Ether cleans solid product repeatedly, is dried to obtain compound IL-2-2
26g。
Product 26g (86.1mmol) obtained in the previous step is dissolved in 280ml methanol, weighs 16.6g KPF6(90.4mmol)
Joining in above-mentioned reaction substrate, under nitrogen protection, reaction stirring terminated after 3 days.Product is filtered, with appropriate
Methanol and ether clean solid product.Then the ethanol/methylene 1.8L solution of 8:7 (V/V) is prepared by above-mentioned solid phase product
Dissolving, filtration under diminished pressure, collect filtrate, concentrate and obtain product 20.5g, this product is target compound B.
The Structural Identification data of compound B:
1H NMR(400MHz,CD3OD-d4):δ4.74(m,2H),3.86(m,2H),3.52-3.48(m,4H),3.22
(s,3H),3.20(s,3H),1.98-1.94(m,4H),1.77-1.69(m,2H).
LCMS(ESI)m/z 208.2(M-145)+。
From the point of view of meeting the building-up process of compound of formula requirement above, it is only necessary to by piperidines and pyrroles and halogenosulfonic acid
Ester reaction can obtain has the various compound described in formula (1) having and modifying functional group.
Such as, as R in formula (1)2During for unsaturated alkane, need synthesizing halogen unsaturation alkane sulfonic acid ester, synthetic method
List of references: Stork G, Baine N H.Vinyl radical cyclization in the synthesis of
natural products:seychellene[J].Tetrahedron Letters,1985,26(48):5927-5930.
R2It is referred to document for synthetic method during alkyl ester group:
(1)Pospisil J.Towards antifungal compounds:total synthesis of
jerangolid D[D].UCL.,2006.
(2)Cheung C W,Ren P,Hu X.Mild and phosphine-free iron-catalyzed
cross-coupling of nonactivated secondary alkyl halides with alkynyl grignard
reagents[J].Organic letters,2014,16(9):2566-2569.
(3) Japan Patent Preparation of optically active 1,3-disubstituted
Azetidinones Jpn.Kokai Tokkyo Koho, 03246274,01, Nov 1991.
R2For referring to Japan Patent with alkyl cyano group side chain:
Preparation of 4-halo-3-hydroxybutanenitrile sulfonate ester,
Jpn.Kokai Tokkyo Koho,03153660,01,Jul 1991.
R3For alkyl except reference example 1, outside 2, reference may also be made to document: Coulomb J, Certal V, Larraufie M H,
et al.Intramolecular homolytic substitution of sulfinates and sulfinamides
[J].Chemistry–A European Journal,2009,15(39):10225-10232.
R3Document is referred to: Quinn R K for synthetic method during phenyl derivatives,Z A,Michalak S E,et
al.Site-Selective Aliphatic C–H Chlorination Using N-Chloroamides Enables a
Synthesis of Chlorolissoclimide[J].Journal of the American Chemical Society,
2015.
The change of anionicsite can be by reacting with corresponding alkali metal salt.
Embodiment 1
By M6S technique, manufacture the most extremely LiCoO2, negative pole is the soft pack cell of graphite, dries to moisture content through 85 DEG C
Below 200ppm, is injected into this battery core by the electrolyte prepared.The compound concrete structure of additive such as table 1 institute in electrolyte
Showing, the composition of electrolyte is as shown in table 2.
Table 1:
Table 2:
Below by way of experimental data, the application lithium-ion battery electrolytes additive it is described and uses the lithium of this additive
The performance of ion battery.
Test one: capability retention is tested, purpose is the improvement of test electrolyte cold cycle performance.
Each embodiment after preparation is completed and the battery core 0.5C charging or discharging current of comparative example difference between 3.0V and 4.35V
25 DEG C and 0 DEG C of repeated charge, write down the capacity of loop ends, and calculate capability retention, the results are shown in Table 3.
Circulation volume conservation rate during 3:25 DEG C and 0 DEG C of table
As seen from Table 3, the electrolyte including the additive described in formula (1) is respectively provided with good following at room temperature and low temperature
Ring performance.Comparative example 1-1, comparative example 1-2, comparative example 1-3 and other embodiments contrast, because of without other additive SEI film forming
Additive, the dense uniform of film forming is deteriorated the most relatively, and cold cycle performance has died down.According to comparative example 1-5 and comparative example
1-6 understands, and sulphonic acid ester quaternary ammonium salt addition is too high or too low, its regulation declines to cold cycle performance.
Test two: low temperature capacity is tested.
By the battery core made according to all embodiments and comparative example after test capacity 25 DEG C, 0.5C is completely charged to 4.35V, so
Rear 25 DEG C of 0.5C are discharged to 3.0V, and 25 DEG C are completely charged to 4.35V, 0 DEG C of 0.5C and are discharged to 3.0V the most again, the 0.5C electric discharge with 25 DEG C
Capacity compares calculating capability retention.Testing-10 DEG C respectively by identical flow process ,-15 DEG C, the discharge capacity of-20 DEG C of batteries is protected
Holdup, the results are shown in Table 4.
Table 4: low temperature capacity conservation rate
As can be seen from Table 4, use the additive of the application can increase the effect of impregnation of electrolyte, thus improve electricity
The low temperature dynamic performance in pond, film for additive also affects the quality of cryogenic property simultaneously, and this is possibly due to film for additive
Prior to electrolyte solvent film forming, and quaternary ammonium salt additive and SEI membrane interaction, it is attached to its surface, prevents entering of SEI film
One step thickens, thus maintains good ion conduction property.
Embodiment 2
Prepare electrolyte and lithium ion battery according to the method for embodiment 1, differ only in, the group of additive in electrolyte
Become as shown in table 5:
Table 5:
The cold cycle capability retention of the lithium ion battery that embodiment 2 prepares and low temperature capacity conservation rate are with above-mentioned
Embodiment is similar, and length is limited, and repeats no more.
Although the application is open as above with preferred embodiment, but is not for limiting claim, any this area skill
Art personnel, on the premise of conceiving without departing from the application, can make some possible variations and amendment, therefore the application
Protection domain should be defined in the range of standard with the application claim.
Claims (10)
1. a nonaqueous electrolytic solution, it is characterised in that described nonaqueous electrolytic solution includes lithium salts, solvent and additive, described interpolation
Agent includes sulphonic acid ester quaternary ammonium salt and SEI film for additive.
Nonaqueous electrolytic solution the most according to claim 1, it is characterised in that the structural formula such as formula I of described sulphonic acid ester quaternary ammonium salt
Shown in:
Wherein, R1Selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted
C2～12Alkynyl, substituted or unsubstituted C1～12Alkoxyl, substituted or unsubstituted C1～12Acyloxy；
R2Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C2～12Alkenylene, substituted or unsubstituted C2～12
Alkynylene, substituted or unsubstituted C1～12Alkylene acyl group；
R3Selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C1～12Alkoxyl, substituted or unsubstituted C1～12Acyl
Epoxide, substituted or unsubstituted C6～22Aryl, substituted or unsubstituted C5～22Heterocyclic base；
R4Selected from substituted or unsubstituted C1～3Alkylidene；
Substituent group is cyano group, halogen；
X-Represent anion.
Nonaqueous electrolytic solution the most according to claim 2, it is characterised in that R1Selected from substituted or unsubstituted C1～6Alkyl；R2
Selected from substituted or unsubstituted C1～12Alkylidene；R3Selected from substituted or unsubstituted C1～6Alkyl；R4Selected from substituted or unsubstituted
C1～2Alkylidene.
Nonaqueous electrolytic solution the most according to claim 2, it is characterised in that the cation group choosing of described sulphonic acid ester quaternary ammonium salt
From following structural formula:
Nonaqueous electrolytic solution the most according to claim 2, it is characterised in that anion X of described sulphonic acid ester quaternary ammonium salt—It is selected from
Following group:
F-、NO3 -、SO4 2-、PF6 -、BF4 -、AsF6 -、(FSO2)2N-、
Nonaqueous electrolytic solution the most according to claim 1, it is characterised in that described SEI film for additive is selected from fluorinated ethylene
At least one in carbonic ester, vinylene carbonate, vinyl ethylene carbonate, ethylene sulfite, propylene sulfite.
Nonaqueous electrolytic solution the most according to claim 1, it is characterised in that described sulphonic acid ester quaternary ammonium salt matter in the electrolytic solution
Amount percent is 0.1%～10%.
Nonaqueous electrolytic solution the most according to claim 1, it is characterised in that described SEI film for additive is in the electrolytic solution
Mass percent is 0.1%～10%.
Nonaqueous electrolytic solution the most according to claim 1, it is characterised in that described lithium salts includes LiPF6。
10. a lithium ion battery, it includes electrolyte, positive plate, negative plate, isolating membrane and package foil；Described positive plate bag
Including plus plate current-collecting body and the positive pole diaphragm being coated on plus plate current-collecting body, negative plate includes negative current collector and is coated on negative pole collection
Cathode membrane on fluid；It is characterized in that: described electrolyte is the nonaqueous electrolytic solution according to any one of claim 1 to 9.
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