CN109037776A - Electrolyte and battery comprising same - Google Patents

Electrolyte and battery comprising same Download PDF

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Publication number
CN109037776A
CN109037776A CN201710433679.7A CN201710433679A CN109037776A CN 109037776 A CN109037776 A CN 109037776A CN 201710433679 A CN201710433679 A CN 201710433679A CN 109037776 A CN109037776 A CN 109037776A
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unsubstituted
substituted
compound
electrolyte
battery
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冯俊敏
张昌明
周艳
付成华
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to CN201710433679.7A priority Critical patent/CN109037776A/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or 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

Abstract

The application relates to the field of batteries, in particular to electrolyte and a battery comprising the electrolyte. The electrolyte comprises an organic solvent, electrolyte salt and an additive, wherein the additive comprises a disulfonyl compound and a cyclic sulfate compound. The application uses the disulfonyl compound and the cyclic sulfate compound in a matching way, so that the cycle performance of the battery under high voltage can be improved obviously, the high-temperature storage performance of the battery can be improved obviously, and the high-temperature safety performance of the battery under high voltage can be improved.

Description

Electrolyte and battery including the electrolyte
Technical field
This application involves field of batteries more particularly to a kind of electrolyte and including the battery of the electrolyte.
Background technique
With the product such as laptop of consumer electronics, mobile phone, handheld device, tablet computer etc. it is universal, greatly Requirement of the family to its battery is also increasingly stringenter；For example require battery should be small and light and high capacity must also be possessed, Long circulating and stable performance.In the secondary battery, lithium ion secondary battery is higher for the battery of other types Energy density advantage makes it inhibit to occupy dominant position on the market.
In these years nonaqueous solvents lithium ion secondary battery is also faced with suitable acid test.It is wanted to meet product (as improved cell voltage) when asking and improving the energy density of battery, it is equivalent to the uncertainty for improving cell safety.Such as When battery is when applied at elevated temperature, at this moment it is anti-violent redox will to occur for the activity raising of electrolyte in anode and cathode It answers, along with the generation of a large amount of side reaction, generates gas, lead to cell expansion.This does not only result in cell damage, while also can The damage for leading to the equipment using battery, since cell expansion deformation causes inside battery that short circuit or electricity occurs when serious Pond packaging, which is burst, causes flammable electrolyte to be revealed, and has the risk for causing the safety accidents such as fire.It would therefore be desirable to have the skills of effect Art solves the problems, such as the decomposition of electrolyte, battery flatulence.
In actual use, although additive can solve the decomposition and battery flatulence of electrolyte, additive reaction is raw At the protective film that electrolyte is reacted with anode and cathode that can effectively completely cut off be often possible to lead to the performance of battery since impedance is excessive It is affected；Especially when the impedance increase of power cell anode-cathode in circulation is too fast, it is very unfavorable often to come to the tape loop of battery Influence；And improve the thick and solid SEI film of cycle performance bring at high temperature it occur frequently that side reaction leads to lithium ion secondary battery There is hidden danger at high temperature.Therefore taking into account high-temperature storage performance, cycle performance and high temperature safety is always that industry is made joint efforts Direction.
In consideration of it, special propose the application.
Summary of the invention
To solve the above-mentioned problems, it is found after the applicant carries out a intensive study: when in electrolyte while including bis sulfone base Compound and cyclic sulfates compound can improve high-temperature storage performance of the battery under high voltage condition, cycle performance simultaneously And high temperature safety, to complete the application.
The application's is designed to provide a kind of electrolyte, including organic solvent, electrolytic salt and additive, the addition Agent includes bis sulfone based compound and cyclic sulfates compound.
The another object of the application is to provide a kind of battery, including the positive plate containing positive electrode active materials, containing negative Negative electrode tab, isolation film and the electrolyte provided herein of pole active material.
The technical solution of the application at least has following beneficial effect:
Include simultaneously bis sulfone based compound and cyclic sulfates compound in the electrolyte of the application, can improve simultaneously secondary High-temperature storage performance, cycle performance and high temperature safety of the battery under high voltage condition.Bis sulfone based compound is added to electrolysis In liquid the high temperature cyclic performance of the secondary cell under high voltage system can be remarkably improved in cathode filming.Cyclic sulfates Compound decomposes during initial charge and discharge process, and formed has low resistance and improved durability jail on the anode surface Solid SEI film, so that high temperature storing stabilization of the secondary cell under high voltage system can be improved.Therefore, two classes in the application Compound is used cooperatively, and is capable of forming low-resistance protective film on positive and negative plate surface, can not only be significantly improved secondary cell Cycle performance under high voltages improves, while can significantly improve high-temperature storage performance；And secondary cell also can be improved in height High temperature safe performance under voltage.
Combined with specific embodiments below, the application is further described.It should be understood that these embodiments are merely to illustrate the application Rather than limitation scope of the present application.
Specific embodiment
The application's is designed to provide a kind of electrolyte, including organic solvent, electrolytic salt and additive, additive packet Include bis sulfone based compound and cyclic sulfates compound.Bis sulfone based compound be added in electrolyte can in cathode filming, from And cathode is protected, reduce and side reaction occurs between electrolyte, and impedance increases less, to be remarkably improved in high voltage body It is the high temperature cyclic performance of lower battery.Cyclic sulfates compound decomposes during initial charge and discharge process, thus in sun Being formed in pole surface has low resistance and the improved firm SEI film of durability, and the high temperature of battery under high pressure can be improved Storage stability.Therefore, two class compound of the application acts synergistically, and is capable of forming low-resistance guarantor on positive and negative plate surface Cuticula, so that the high temperature safe performance of battery under high voltages can be improved.
(bis sulfone based compound)
The bis sulfone based compound of the application electrolyte is selected from least one of such as I compound represented of formula:
Wherein, R11、R12It is each independently selected from substituted or unsubstituted C1~C12Alkyl, substituted or unsubstituted C2~ C12Alkenyl, substituted or unsubstituted C6~C16Aryl, substituted or unsubstituted C1~C12Alkoxy, substituted or unsubstituted C6~ C16Aryloxy group；
R13Selected from substituted or unsubstituted C1~C10Alkylidene, substituted or unsubstituted C2~C10Alkenylene, substitution or not Substituted C6~C16Arlydene；
Substituent group is selected from halogen, C1~C6Alkyl, C2~C6Alkenyl, C6~C12At least one of aryl.
Wherein, alkylidene refers to that divalent alkyl, alkenylene refer to that divalent alkenyl, arlydene refer to divalent aryl.
As a kind of improvement of the application electrolyte, work as R13When for methylene, bis sulfone based compound is selected from such as I A institute of formula At least one of compound shown:
R14Selected from C1~C6Alkyl, C2~C6Alkenyl, C6~C16Aryl.
As the example of bis sulfone based compound, can specifically enumerate:
As the example of bis sulfone based compound, it is also selected from following compound but not limited to this:
As a kind of improvement of the application electrolyte, the content of bis sulfone based compound is the 0.05% of the total weight of electrolyte ~3%.Wherein, bis sulfone based compound in the electrolytic solution content the upper limit be 3%, 2.5%, 2%, 1.5%, 1%, bis sulfone base Close object in the electrolytic solution content lower limit be 0.1%, 0.5%, 1%, 1.5%, 2%；The content range of bis sulfone based compound can It is made of any number of upper and lower bound, as long as meeting lower limit <upper limit.
This is because when the content of bis sulfone based compound is lower than 0.05% complete SEI cannot be formed in cathode surface Film, to not can effectively prevent side reaction caused by the electronics transfer between electrolyte and electrode；And work as bis sulfone based compound When content is greater than 3%, thicker CEI film can be formed in cathode surface, and lithium ion or sodium ion migration resistance is caused to increase, it is unfavorable The positive interface stability of battery in cyclic process.
It is further preferred that the mass fraction of bis sulfone based compound in the electrolytic solution is 0.1%~2%, more preferable 0.1% ~1%.
(cyclic sulfates compound)
Cyclic sulfates compound in the application is selected from least one of such as II compound represented of formula:
Wherein, R21、R22、R23、R24It is each independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C1~C12Alkyl, Substituted or unsubstituted C2~C12Alkenyl, substituted or unsubstituted C6~C16Aryl, substituted or unsubstituted C1~C12Alkoxy, Substituted or unsubstituted C6~C16Aryloxy group；
Substituent group is selected from halogen, cyano, C1~C6At least one of alkoxy.
As a kind of improvement of the application electrolyte, R21、R22、R23、R24It is hydrogen atom.
It is further alternative, R21、R22、R23、R24In at least one group be selected from halogen, cyano, substituted or unsubstituted C1~C12Alkyl, substituted or unsubstituted C2~C12Alkenyl, substituted or unsubstituted C6~C26Aryl, substituted or unsubstituted C1 ~C12Alkoxy, substituted or unsubstituted C6~C26Aryloxy group；Substituent group is selected from halogen, cyano.
It is further alternative, R21、R22、R23、R24In at least one group be selected from halogen, substituted or unsubstituted C1~ C10Alkyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C6~C16Aryl, substituted or unsubstituted C6~ C16Aryloxy group；Substituent group is selected from halogen, cyano.
It is further alternative, R21、R22、R23、R24In at least one group be selected from halogen, substituted or unsubstituted C1~ C6Alkoxy, substituted or unsubstituted C1~C6Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenoxy group；Replace Base is selected from halogen, cyano.
As the example of cyclic sulfates, can specifically enumerate:
As the example of cyclic sulfates, it is also selected from following compound but not limited to this:
As a kind of improvement of the application electrolyte, the content of cyclic sulfates compound is the total weight of electrolyte 0.05%~3%.Wherein, cyclic sulfates compound in the electrolytic solution content the upper limit be 3%, 2.5%, 2%, 1.5%, 1%, cyclic sulfates compound in the electrolytic solution content lower limit be 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%；Ring The content range of shape sulfate compound can be made of any number of upper and lower bound, as long as meeting lower limit <upper limit.
This is because decomposition product is not enough to when the additive amount of sulfate compound in the electrolytic solution is lower than 0.05% Good protective film is formed in anode；And when the content of cyclic acid anhydride is higher than 3%, membrane impedance is increased into, battery is caused to exist Side reaction increases under high temperature.
It is further preferred that the mass fraction of sulfate compound in the electrolytic solution is 0.1%~2%.
It has been investigated that when simultaneously including bis sulfone based compound and cyclic sulfates compound mentioned above in electrolyte When, under the common synergistic effect of the two, positive and negative plate surface is capable of forming low-resistance protective film.Structurally, double Sulfone-based compound is more active compared to the hydrogen atom above single sulphones internal carbon atoms, it is easier to react, and oxygen Changing product is that small molecule segment can effectively participate in forming a film, and only has half effectively to participate in forming a film relative to single sulphones, bis sulfone It is lower that based compound makes into membrane impedance.Meanwhile sulfate compound decomposes during initial charge and discharge process, thus Being formed on anode surface has low resistance and the improved firm SEI film of durability, improves the high temperature storing stabilization of secondary cell Property.Therefore, when two class compounds act synergistically, can significantly improve the cycle performance of secondary cell under high voltages improves, significantly Improve high-temperature storage performance, is also remarkably improved high temperature safe performance under high voltages.
In above-mentioned general formula:
The alkyl that carbon atom number is 1~12, alkyl can be chain-like alkyl, can also be naphthenic base, on the ring of naphthenic base Hydrogen can be replaced by alkyl, in alkyl the preferred lower limit value of carbon atom number be 2,3,4,5, preferred upper limit value be 3,4,5,6,8, 10,12.Preferably, select carbon atom number for 1~10 alkyl, it is further preferred that select carbon atom number for 1~6 chain Alkyl, carbon atom number be 3~8 naphthenic base, it is further preferred that select carbon atom number for 1~4 chain-like alkyl, carbon original The naphthenic base that subnumber is 5~7.It as the example of alkyl, can specifically enumerate: methyl, ethyl, n-propyl, isopropyl, positive fourth Base, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopenta, cyclohexyl.
The alkenyl that carbon atom number is 2~12 can be cyclic alkenyl radical, can also be chain alkenyl.In addition, in alkenyl double bond Number preferably 1.The preferred lower limit value of carbon atom number is 3,4,5 in the alkenyl, and preferred upper limit value is 3,4,5,6,8,10, 12.Preferably, select carbon atom number for 2~10 alkenyl, it is further preferred that select carbon atom number for 2~6 alkenyl, more It is further preferred that select carbon atom number for 2~5 alkenyl.It as the example of alkenyl, can specifically enumerate: vinyl, allyl Base, isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base.
Carbon atom number be 6~16 aryl, such as phenyl, benzene alkyl, such as xenyl of the aryl at least containing a phenyl, Condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and condensed-nuclei aromatics base can also be replaced alkyl or alkenyl.Preferably, it selects Select carbon atom number be 6~14 aryl, it is further preferred that select carbon atom number for 6~12 aryl, still more preferably Ground, select carbon atom number for 6~9 aryl.As the example of aryl, can specifically enumerate: phenyl, benzyl, xenyl, to first Phenyl, o-tolyl, tolyl.
It can be alkoxy when containing oxygen atom in the alkyl that the aforementioned carbon atom number being previously mentioned is 1~12.Preferably, Select carbon atom number for 1~10 alkoxy, it is further preferred that select carbon atom number for 1~6 alkoxy, further Preferably, select carbon atom number for 1~4 alkoxy.It as the example of alkoxy, can specifically enumerate: methoxyl group, ethoxy Base, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, cyclopentyloxy, ring Hexyloxy.
It can be aryloxy group when containing oxygen atom in the aryl that the aforementioned carbon atom number being previously mentioned is 6~16.Preferably, Select carbon atom number for 6~14 aryloxy group, it is further preferred that select carbon atom number for 6~12 aryloxy group, further Preferably, select carbon atom for 6~10 aryloxy group.As the example of aryloxy group, can specifically enumerate: phenoxy group, benzyloxy, 4- methylphenoxy, 3,5- dimethyl phenoxy, 4- methylbenzyloxy, 3- methylbenzyloxy, 2,6- diisopropyl benzyloxy, 1- Naphthoxy.
(organic solvent)
Organic solvent used in nonaqueous electrolytic solution as the application can preferably be enumerated selected from cyclic carbonate One of ester, linear carbonate, chain carboxylate, lactone, ether and amide or two kinds or more.From further increasing high temperature and pressure The angle of cycle performance and storage performance is set out, and at least one in cyclic carbonate, linear carbonate and carboxylate is preferably comprised Kind, more preferably contain cyclic carbonate, linear carbonate and carboxylate simultaneously.
As above-mentioned cyclic carbonate, can enumerate selected from ethylene carbonate (referred to as EC), propene carbonate (referred to as For PC), carbonic acid 1,2- butylene, carbonic acid 2,3- butylene, vinylene carbonate (referred to as VC), vinyl ethylene carbonate (referred to as VEC), 4- acetenyl -1,3- dioxolane -2- ketone (referred to as EEC) etc. have the ring of carbon-to-carbon unsaturated bond Shape carbonic ester；With fluoro- 1, the 3- dioxolane -2- ketone of 4- (i.e. fluorinated ethylene carbonate, referred to as FEC), it is trans- or cis- - 4,5- bis- fluoro- 1,3- dioxolane -2- ketone (the two is referred to as " DFEC " below) etc. have the cyclic carbonate of fluorine atom One of ester or two kinds or more, are more preferably selected from ethylene carbonate, propene carbonate, fluorinated ethylene carbonate, carbonic acid Asia second One of enester and 4- acetenyl -1,3- dioxolane -2- ketone or two kinds or more.
In addition, if organic solvent contains cyclic carbonate, such as ethylene carbonate, propene carbonate and fluoro carbonic acid second The resistance of enester, the then cover film formed on electrode becomes smaller, thus be it is preferred, the content of cyclic carbonate is, relative to having The total volume of solvent is preferably 10 volume % or more, more preferably 20 volume % or more, further preferably 30 volume % with On, in addition, preferably 60 volume % are hereinafter, more preferably 50 volume % or less as its upper limit.
As chain ester, can suitably enumerate selected from methyl ethyl carbonate (referred to as MEC), methyl propyl carbonate (referred to as For one of MPC), methyl isopropyl ester (referred to as MIPC), carbonic acid first butyl ester and ethyl propyl carbonic acid ester or two kinds or more Asymmetric linear carbonate；Selected from dimethyl carbonate (referred to as DMC), diethyl carbonate (referred to as DEC), dipropyl carbonate and The symmetrical linear carbonate of one of dibutyl carbonate or two kinds or more；Selected from methyl pivalate, neopentanoic acid ethyl ester, neopentanoic acid The chain carboxylic of one of the pivalates such as propyl ester, methyl propionate, ethyl propionate, methyl acetate and ethyl acetate or two kinds or more Acid esters.
In addition, it is preferable to use symmetrical linear carbonate when using linear carbonate.
The content of above-mentioned chain ester (linear carbonate, chain carboxylate) is not particularly limited, relative to organic solvent Total volume preferably uses in the range of 30~60 volume %.
Further, the volume ratio of cyclic carbonate and chain ester is preferably 10:90~50:50, and more preferably 20:80~ 50:50.
As other organic solvents, can suitably enumerate selected from acid anhydrides, N-Methyl pyrrolidone, N- methyl formyl Amine, N- methylacetamide, acetonitrile, N,N-dimethylformamide, sulfolane, dimethyl sulfoxide, methyl sulfide, gamma-butyrolacton, tetrahydro furan It one of mutters etc. or two kinds or more.
In order to obtain physical property appropriate, above-mentioned organic solvent uses after usually mixing.A combination thereof can be enumerated suitably Such as the combination of cyclic carbonate and linear carbonate, the combination of cyclic carbonate and chain carboxylate, cyclic carbonate and chain Combination, cyclic carbonate and the linear carbonate of shape carbonic ester and lactone and combination, cyclic carbonate and the linear carbonate of ether With the combination of chain carboxylate etc..
(electrolytic salt)
When battery is lithium ion secondary battery, electrolytic salt is lithium salts, and it can also be inorganic lithium that lithium salts, which can be organic lithium salt, Salt.
Specifically, at least one of fluorine element, boron element, P elements can be contained in lithium salts.Preferably, lithium salts is selected from Lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), tetrafluoro grass Acid phosphoric acid lithium (being abbreviated as LiTFOP), LiN (SO2RF)2、LiN(SO2F)(SO2RF), trifluoromethanesulfonic acid lithium (LiCF3SO3), double three Fluoromethane sulfimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), bis- (fluorine sulphonyl) imine lithium Li (N (SO2F)2) (be abbreviated as LiFSI), di-oxalate lithium borate LiB (C2O4)2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF2(C2O4) (be abbreviated as LiDFOB at least one of), wherein RF=-CnF2n+1, indicate saturation perfluoroalkyl, the integer that n is 1~10, and 2n+1 is greater than Zero integer.
In this application, the concentration of lithium salts in the electrolytic solution is 0.5M~2M (M=mol/L).
In this application, the preparation method of electrolyte selects conventional method, such as by organic solvent, lithium salts and can add Agent is added to be uniformly mixed.
Illustrate the battery according to the embodiment of the present application second aspect below.
According to the battery of the embodiment of the present application, including anode pole piece, cathode pole piece, be placed in anode pole piece and cathode pole piece it Between isolation film and electrolyte.Below by taking lithium ion secondary battery as an example, the battery of the application is further illustrated.
In a lithium ion secondary battery, material of the anode comprising that can deviate from, receive lithium ion, cathode include that can receive, is de- The material of lithium ion out.Specifically, positive electrode active materials can be selected from lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, lithium nickel Mn oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, these lithium transition-metal oxides add other transition metal or The compound that nontransition metal obtains, one or more of mixtures of above-mentioned substance.Negative electrode active material can be soft carbon, hard Carbon, artificial graphite, natural graphite, silicon, silicon oxide compound, silicon-carbon compound, lithium titanate can form the metal etc. of alloy with lithium.
Electrolyte is electrolyte described in above-mentioned first aspect.
In the secondary battery, positive plate further includes binder and conductive agent, will include positive electrode active materials, binder and The anode sizing agent of conductive agent is coated on plus plate current-collecting body, obtains positive plate after anode sizing agent is dry.Likewise, will include The negative electrode slurry of negative electrode active material, binder and conductive agent is coated on negative current collector, is obtained after negative electrode slurry is dry Negative electrode tab.
Specific embodiment
The application is further described below by way of the specific example of lithium ion secondary battery, however, it is not limited to this.But These examples are only exemplary, do not constitute any restrictions to the protection scope of the application.
In following embodiments, comparative example and test example, reagent, material and the instrument used be not such as special Explanation, be conventional reagent, conventional material and conventional instrument, it is commercially available, involved in reagent can also lead to Conventional synthesis process synthesis is crossed to obtain.
In following embodiments, comparative example and test example, used reagent is as follows:
Additive:
Two sulphones: compound I-1~compound I-6, chemical structural formula are as previously shown.
Cyclic sulfates: compound II-8, chemical structural formula are as previously shown.
Lithium salts: lithium hexafluoro phosphate (LiPF6)。
Organic solvent: ethylene carbonate (EC), methyl ethyl carbonate (EMC).
Positive electrode active materials: cobalt acid lithium (LiCoO2)。
Isolation film: using PE porous polymer film as isolation film.
The preparation of 1~13 lithium ion secondary battery of embodiment (following abbreviation batteries) 1~13
Battery 1~13 carries out the preparation of preparation lithium ion secondary battery by the following method:
1) preparation of positive plate: by positive active material cobalt acid lithium (molecular formula LiCoO2), conductive agent acetylene black, bonding Agent polyvinylidene fluoride (being abbreviated as PVDF) is by weight 96:2:2 in suitable N-Methyl pyrrolidone (being abbreviated as NMP) solvent In be thoroughly mixed, form it into uniform anode sizing agent；This slurry is coated on plus plate current-collecting body Al foil, dries, is cold Pressure, obtains positive plate.
2) preparation of negative electrode tab: negative electrode active material graphite, conductive agent acetylene black, binder butadiene-styrene rubber (are abbreviated as SBR), thickener sodium carboxymethylcellulose (being abbreviated as CMC) is according to weight ratio 95:2:2:1 in suitable deionized water solvent It is thoroughly mixed, forms it into uniform negative electrode slurry；This slurry is coated on negative current collector Cu foil, drying, cold pressing, Obtain negative electrode tab.
3) isolation film: using PE porous polymer film as isolation film.
4) preparation of lithium ion secondary battery: positive plate, isolation film, negative electrode tab are folded in order, are in isolation film Play the role of isolation between positive/negative plate, then winding obtains naked battery core；Naked battery core is placed in outer packing foil, by above-mentioned system The electrolyte got ready be injected into it is dry after battery in, by processes such as Vacuum Package, standing, chemical conversion, shapings, i.e., completion lithium from The preparation of sub- secondary cell.
The preparation of electrolyte: in water content < 10ppm argon atmosphere glove box, by ethylene carbonate (being abbreviated as EC), Diethyl carbonate (being abbreviated as DEC), propene carbonate (being abbreviated as PC), ethyl propionate, fluorinated ethylene carbonate (being abbreviated as FEC) According to 20:30:20:25:5 mass ratio after mixing, obtain nonaqueous solvents, then lithium salts LiPF that will be sufficiently dry6Dissolution In above-mentioned nonaqueous solvents, it is made into LiPF6Concentration is the basic electrolyte of 1mol/L.
According to shown in table 1, bis sulfone based compound and cyclic sulfates are added in basic electrolyte.
In table 1, the content of two sulphones and the content of cyclic sulfates are the total weight based on electrolyte Obtained weight percent.
Table 1
1~11 lithium ion secondary battery of comparative example (following abbreviation batteries) 1#~9#Preparation
Comparative example 1~11
Battery 1#~11#Prepared by the following method:
The preparation for repeating battery 1 in embodiment 1, wherein changing the type of additive in the preparation of electrolyte or containing Amount, remaining condition are constant.
It is above-mentioned prepare battery during, it is selected electrolyte in each battery, used in each electrolyte The type and its content of bis sulfone based compound, cyclic sulfates, as shown in table 2.
In table 2, the content of two sulphones and the content of cyclic sulfates are the total weight based on electrolyte Obtained weight percent.
Table 2
Performance survey will be carried out to lithium ion secondary battery made from each comparative example of the application and embodiment as experiment below Examination.
Test one, cycle life test
It with 0.5C constant-current charge to voltage is 4.45V by lithium ion secondary battery, further with 4.45V constant pressure at 60 DEG C Charging to electric current is 0.05C, is then 3.0V with 0.5C constant-current discharge to voltage, this is a charge and discharge cycles process, this time Discharge capacity be the discharge capacity recycled for the first time.Lithium ion secondary battery is carried out according to the method described above 300 cycle chargings/ Discharge test.
Capacity retention ratio (%) after lithium ion secondary battery circulation n times=(discharge capacities of circulation n times/it recycles for the first time Discharge capacity) × 100%.
Test two, high temperature storage test
The lithium ion secondary battery being prepared is subjected to following tests respectively:
With 0.5C electric current constant-current charge to 4.4V at 25 DEG C, 4.4V constant-voltage charge to electric current is 0.025C, is at Then battery is placed in 60 DEG C of high temperature furnace and is kept for 12 days by 4.4V fully charged state, while every 3 days heat is surveyed once；Before storage 100%SOC battery core thickness records the thickness data of battery core as benchmark (0%).
Test three, the test of hot tank security performance
It with 1C constant-current charge to voltage is 4.45V by lithium ion secondary battery, further with 4.45V constant pressure at 25 DEG C Charge to electric current be 0.05C, stop charging, lithium ion secondary battery is placed in hot tank, and by the temperature of hot tank with 5 DEG C/ The speed of min rises to 130 DEG C from 25 DEG C, and temperature remains temperature-resistant after reaching 130 DEG C, starts timing, observes lithium ion after 1h The state of secondary cell.5 lithium ion secondary batteries of every group of test.
The standard that lithium ion secondary battery passes through the test are as follows: without smoldering, without on fire, no explosion.
Experimental result is as shown in table 3.
Table 3
From table 3 it is observed that adding mass percentage content 0.05~3.0% in the electrolyte of lithium ion secondary battery Bis sulfone based compound can improve the high temperature cyclic performance of battery, wherein when bis sulfone based compound additive amount is 0.01%, lithium Battery high-temperature cycle performance improve it is unobvious because additive amount causes not can be well protected cathode very little, cause electrolyte with Cathode reacts, and deteriorates high temperature cyclic performance.When additive amount is 4.0%, since it forms thicker guarantor in cathode surface Cuticula causes impedance to increase, and battery high-temperature cycle performance is caused to decline.From battery 1~6 and battery 1#~9#In it can be seen that formula Bis sulfone based compound optimum addition is 1.0%.
From battery 1~13 and battery 1#~9#In as can be seen that electrolyte in addition mass percentage content be 1% ring When shape sulfuric ester, it can utmostly improve the high-temperature storage performance of battery, the reason is that such compound is decomposed in electrode surface Protective film is formed, the stability under battery high-temperature is improved.
From battery 1~13 and battery 1#~9#In as can be seen that the bis sulfone base chemical combination of certain content is added in electrolyte simultaneously When object and cyclic sulfates, the high temperature safe performance of battery is improved.
As can be seen from the table when bis sulfone based compound and cyclic sulfates addition quality are all 1%, battery High temperature circulation, high-temperature storage performance and high temperature safe performance all reach best.
From battery 1~13 and battery 10#~11#In as can be seen that electrolyte in cyclic sulfates content it is excessive or When the content of bis sulfone based compound is excessive, the high temperature circulation and high-temperature storage performance of battery have certain downward trend.
Embodiment 14~18
Electrolyte is prepared by the method in embodiment 1, difference is, the composition of the additive of electrolyte is as shown in table 4:
Table 4
Lithium ion secondary battery, performance and above embodiments are prepared using the electrolyte that embodiment 14~23 is prepared It is similar, it repeats no more as space is limited.
It is not for limiting claim, any this field skill although the application is disclosed as above with preferred embodiment Art personnel without departing from the concept of this application, can make several possible variations and modification, therefore the application Protection scope should be subject to the range that the claim of this application is defined.

Claims (10)

1. a kind of electrolyte, including organic solvent, electrolytic salt and additive, the additive includes bis sulfone based compound and ring Shape sulfate compound.
2. electrolyte according to claim 1, which is characterized in that the bis sulfone based compound is selected from as shown in formula I At least one of compound:
Wherein, R11、R12It is each independently selected from substituted or unsubstituted C1~C12Alkyl, substituted or unsubstituted C2~C12Alkene Base, substituted or unsubstituted C6~C16Aryl, substituted or unsubstituted C1~C12Alkoxy, substituted or unsubstituted C6~C16Virtue Oxygroup；
R13Selected from substituted or unsubstituted C1~C10Alkylidene, substituted or unsubstituted C2~C10It is alkenylene, substituted or unsubstituted C6~C16Arlydene；
Substituent group is selected from halogen, C1~C6Alkyl, C2~C6Alkenyl, C6~C12At least one of aryl.
3. electrolyte according to claim 1, which is characterized in that the bis sulfone based compound is selected from as shown in I A of formula At least one of compound:
R14Selected from hydrogen atom, C1~C6Alkyl, C2~C6Alkenyl, C6~C16Aryl.
4. electrolyte according to claim 1, which is characterized in that the cyclic sulfates compound is selected from such as II institute of formula At least one of compound shown:
Wherein, R21、R22、R23、R24It is each independently selected from hydrogen atom, halogen, cyano, substituted or unsubstituted C1~C12Alkyl, Substituted or unsubstituted C2~C12Alkenyl, substituted or unsubstituted C6~C16Aryl, substituted or unsubstituted C1~C12Alkoxy, Substituted or unsubstituted C6~C16Aryloxy group；
Substituent group is selected from halogen, cyano, C1~C6At least one of alkoxy.
5. electrolyte according to claim 1, which is characterized in that the bis sulfone based compound is selected from shown in following structural formula At least one of compound:
6. electrolyte according to claim 1, which is characterized in that the cyclic sulfates compound is selected from following structural formula At least one of shown compound:
7. described in any item electrolyte according to claim 1~6, which is characterized in that the content of the bis sulfone based compound is The 0.05%~3% of the total weight of the electrolyte.
8. described in any item electrolyte according to claim 1~6, which is characterized in that the cyclic sulfates compound contains Amount is the 0.05%~3% of the total weight of the electrolyte.
9. described in any item electrolyte according to claim 1~6, which is characterized in that the organic solvent is selected from cyclic carbonate At least one of ester, linear carbonate and carboxylate.
10. a kind of battery, which is characterized in that including described in any one of positive plate, negative electrode tab, isolation film and claim 1~9 Electrolyte.
CN201710433679.7A 2017-06-09 2017-06-09 Electrolyte and battery comprising same Pending CN109037776A (en)

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