CN105098242A - Electrolyte and lithium ion battery comprising the same - Google Patents

Electrolyte and lithium ion battery comprising the same Download PDF

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Publication number
CN105098242A
CN105098242A CN201510464212.XA CN201510464212A CN105098242A CN 105098242 A CN105098242 A CN 105098242A CN 201510464212 A CN201510464212 A CN 201510464212A CN 105098242 A CN105098242 A CN 105098242A
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lithium
electrolyte
ion battery
lithium ion
carbon number
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CN105098242B (en
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陈培培
冯绍伟
付成华
龙兵
唐超
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The application relates to an electrolyte and a lithium ion battery comprising the electrolyte. The electrolyte comprises a lithium salt, an organic solvent and additives. The additives comprise difluoro lithium phosphate and a cyclic sulphate ester compound. The electrolyte provided by the application is applied to the lithium ion battery. Specifically, after the electrolyte is applied to the lithium ion battery whose pole piece has heavy coating weight at the single-sided active substance layer, not only high-temperature cycle performance of the lithium ion battery is improved, but also the rate capability and the low-temperature discharging performance of the lithium ion battery is improved.

Description

Electrolyte and comprise the lithium ion battery of this electrolyte
Technical field
The application relates to technical field of lithium ion, particularly, relates to a kind of electrolyte and comprises the lithium ion battery of this electrolyte, and especially, this electrolyte is applicable in the high lithium ion battery of the coating weight of the active material on pole piece.
Background technology
In the information age of develop rapidly, the demand of the electronic products such as mobile phone, notebook, camera increases year by year, and lithium ion battery is widely used in these areas.Meanwhile, what lithium ion battery had also enlivened in fields such as electric automobile, hybrid vehicle, energy storage devices grows up.
Lithium ion battery, as the working power of electronic product, has that energy density is high, the high outstanding feature of memory-less effect, operating voltage, just progressively replaces traditional Ni-Cd battery, MH-Ni battery.But along with the development of the expansion of electronics market demand and power, energy storage device, the requirement of people to the energy density of lithium ion battery also improves constantly, and therefore, the lithium ion battery that exploitation has high-energy-density becomes the task of top priority.
At present, the energy density improving lithium ion battery mainly contains following several mode:
One, develop high voltage cathode material, but be applied to the cathode material also imperfection of more than 4.4V at present, and partial electrolyte liquid is unstable under high voltages;
Two, adopt the new material of high power capacity, such as silicon materials, but silicon materials expand serious, first all coulombic efficiencies are low, and cyclical stability is low;
Three, by improving the coating weight of the active material layer on collector, thus the energy density of lithium ion battery is improved.Although this method has higher application feasibility, but it is serious that the raising of the coating weight of the active material on unit collector can cause the dynamics of lithium ion battery to worsen, such as can have a strong impact on the mobility of lithium ion, thus lithium ion battery is occurred phenomenons such as high rate performance is poor, poor performance at low temperatures.
Therefore, need badly now and a kind of electrolyte is provided, after applying under making the high condition of the coating weight of the active material layer on its collector in lithium ion battery, the high temperature cyclic performance of lithium ion battery, high rate performance and low temperature performance can be improved.
Summary of the invention
In order to solve the problem, the applicant has carried out studying with keen determination, found that: the electrolyte including difluorophosphate and cyclic sulfates compounds, be applied in lithium in battery after, after being particularly applied in the high lithium ion battery of the coating weight of the active material layer of the one side be arranged on collector, the high temperature cyclic performance of lithium ion battery, high rate performance and low temperature performance can be improved, thus complete the application.
The object of the application is to provide a kind of electrolyte, comprises lithium salts, organic solvent and additive, and wherein, described additive comprises difluorophosphate and cyclic sulfates compounds.
Especially, described cyclic sulfates compounds is for being selected from by one or more in the compound shown in following formula I and formula II:
wherein,
In described formula I, n is the integer of 1 ~ 3,
In described formula II, m is the integer of 0 ~ 3,
In described formula I and formula II, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8independently of one another for the alkyl being selected from hydrogen atom, halogen atom, cyano group, carboxyl, sulfonic group, carbon number are 1 ~ 20, the carbon number unsaturated alkyl that is 2 ~ 20 and the above-mentioned carbon number alkyl that is 1 ~ 20, the carbon number unsaturated alkyl that is 2 ~ 20 by halogen atom replace the one in the group that formed, wherein, halogen atom is F, Cl, Br, I.
Another object of the application is to provide a kind of lithium ion battery, comprise the electrolyte that positive plate, negative plate, lithium battery diaphragm and the application provide, wherein, described positive plate comprises plus plate current-collecting body and is arranged at the positive electrode active material layer on described plus plate current-collecting body, wherein, described positive electrode active material layer comprises positive electrode active materials; Described negative plate comprises negative current collector and is arranged at the negative electrode active material layer on described negative current collector, and wherein, described negative electrode active material layer comprises negative active core-shell material; Described lithium battery diaphragm is between positive plate and negative plate.
Especially, in above-mentioned lithium ion battery, be positioned at the coating weight of the positive electrode active material layer of the one side on described plus plate current-collecting body at 0.026g/cm 2below, be positioned at the coating weight of the negative electrode active material layer of the one side on described negative current collector at 0.013g/cm 2below.
The electrolyte that the application provides, be applied in lithium ion battery, particularly when after the lithium ion battery that the coating weight of the active material layer being applied to the one side be arranged on pole piece is high, the high temperature cyclic performance of lithium ion battery can not only be improved, and high rate performance and the low temperature performance of lithium ion battery can be improved.
Embodiment
Be described in detail below by the application, the feature of the application and advantage will illustrate along with these and become more clear, clear and definite.
The object of the application is to provide a kind of electrolyte, comprises lithium salts, organic solvent and additive, and wherein, described additive comprises difluorophosphate (LiPO 2f 2) and cyclic sulfates compounds.
In above-mentioned electrolyte, mentioned cyclic sulfates compounds is for containing-O-SO 2the cyclic compound of-O-group.Especially ,-O-SO 2-O-group is positioned on the ring of cyclic compound.
In a preferred embodiment, cyclic compound can be five-membered cyclic compound, six-membered cyclic compound, seven-membered compounds, their, octatomic ring shape compound.Further, be preferably five-membered cyclic compound, six-membered cyclic compound, octatomic ring shape compound, further, be preferably five-membered cyclic compound and/or six-membered cyclic compound.Wherein, ring has several atom, this ring just claims " a few ring ".
In above-mentioned electrolyte, the concrete kind of cyclic sulfates compounds is not subject to concrete restriction, can select according to the actual requirements.
In a preferred embodiment, described cyclic sulfates compounds is for being selected from by one or more in the compound shown in following formula I and formula II:
In above-mentioned formula I, n is the integer of 1 ~ 3, and further, n is preferably 1 ~ 2.
When n chooses the integer of more than 2, except being connected with substituent R 1, R 2carbon atom outside, the substituting group be positioned on the carbon atom of diverse location can be identical, also can be completely different, or be two or more diverse location carbon atom on substituting group identical, be not subject to the restriction of concrete label.Such as, when n is 2, except being connected with substituent R 1, R 2carbon atom outside, four substituting groups remained on two carbon atoms can be identical, also can be completely different, or be in four substituting groups both are above identical arbitrarily.
In above-mentioned formula II, m is the integer of 0 ~ 3, and further, m is preferably 0 ~ 1.
When m chooses the integer of more than 2, except being connected with substituent R 5, R 6carbon atom outside, the substituent type be positioned on the carbon atom of diverse location can be identical, also can be completely different, or be two or more diverse location carbon atom on substituting group identical, be not subject to the restriction of concrete label.Such as, when m is 2, except being connected with substituent R 5, R 6carbon atom outside, four substituting groups remained on two carbon atoms can be identical, also can be completely different, or be in four substituting groups both are above identical arbitrarily.
In above-mentioned formula I and formula II, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8independently of one another for the alkyl being selected from hydrogen atom, halogen atom, cyano group, carboxyl, sulfonic group, carbon number are 1 ~ 20, the carbon number unsaturated alkyl that is 2 ~ 20 and the above-mentioned carbon number alkyl that is 1 ~ 20, the carbon number unsaturated alkyl that is 2 ~ 20 by halogen atom replace the one in the group that formed, wherein, halogen atom is F, Cl, Br, I.
Especially, be in the unsaturated alkyl of 2 ~ 20 at carbon number, unsaturated alkyl is chain unsaturated alkyl.
In above-mentioned formula I, R 1, R 2, R 3, R 4can be different, also can be identical, or R 1, R 2, R 3, R 4in arbitrarily the two is identical, or be R 1, R 2, R 3, R 4in any three identical.
In above-mentioned formula II, R 5, R 6, R 7, R 8can be different, also can be identical, or R 5, R 6, R 7, R 8in arbitrarily the two is identical, or be R 5, R 6, R 7, R 8in any three identical.
When selecting carbon number to be the alkyl of 1 ~ 20, the not special restriction of concrete kind of alkyl, such as chain alkyl, cyclic alkane base.Wherein, chain alkyl comprises linear paraffin base and branched alkane alkyl.Especially, linear paraffin base is selected.
Preferably, select carbon number to be the alkyl of 1 ~ 10, further preferably, select carbon number to be the alkyl of 1 ~ 5, still more preferably, select carbon number to be the alkyl of 1 ~ 3.
As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, cyclopenta, n-hexyl, isohesyl, cyclohexyl, heptyl, suberyl, octyl group, ring octyl group, nonyl, decyl, hendecane alkyl, dodecane alkyl, tridecane alkyl, tetradecane alkyl, pentadecane alkyl, hexadecane alkyl, heptadecane alkyl, octadecane alkyl, nonadecane alkyl, eicosane alkyl.
When selecting carbon number to be the unsaturated alkyl of 2 ~ 20, the not special restriction of concrete kind of unsaturated alkyl, can select according to the actual requirements.Especially, thiazolinyl, alkynyl is selected.Wherein, the not special restriction in the number of unsaturated bond and the position of unsaturated bond, can select the unsaturated alkyl of desired structure according to actual conditions.Such as, the number of unsaturated bond can be 1,2,3 or 4.Especially, unsaturated bond is positioned at the end of unsaturated alkyl, and wherein, described end is the position be connected with ring away from unsaturated alkyl.
When unsaturated bond is 1, especially, unsaturated bond is positioned at the end of selected unsaturated alkyl, and such as, when carbon number is more than or equal to 3, the carbon atom on unsaturated bond is not connected with ring.
In a preferred embodiment, select carbon number to be the unsaturated alkyl of 2 ~ 10, further preferably, select carbon number to be the unsaturated alkyl of 2 ~ 5, still more preferably, select carbon number to be the unsaturated alkyl of 2 ~ 3.
As the example of unsaturated alkyl, specifically can enumerate :-CH=CH 2,-CH 2-CH=CH 2,-CH 2cH 2-CH=CH 2,-CH 2cH 2cH 2-CH=CH 2,-C ≡ CH ,-CH 2-C ≡ CH ,-CH 2cH 2-C ≡ CH ,-CH 2cH 2cH 2-C ≡ CH ,-CH=CH-CH=CH 2.
When the alkyl that carbon number is 1 ~ 20 is replaced by halogen atom, the not special restriction of the replacement number of halogen atom and the position of substitution thereof, can replace the part hydrogen atom on above-mentioned alkyl or whole hydrogen atom according to the actual requirements.Such as, the number of halogen atom can be 1,2,3 or 4.Especially, halogen atom is F, Cl.
When the number that halogen atom replaces is more than 2, the kind of halogen atom can be identical, also can difference completely, or be that the species partial of selected halogen atom is identical.
As alkyl by halogen atom replace the example of group that formed, specifically can enumerate:
wherein, X is the one in F, Cl, Br, I.
When the unsaturated alkyl that carbon number is 2 ~ 20 is replaced by halogen atom, the not special restriction of the replacement number of halogen atom and the position of substitution thereof, can replace the part hydrogen atom on above-mentioned unsaturated alkyl or whole hydrogen atom according to the actual requirements.Such as, the number of halogen atom can be 1,2,3 or 4.Especially, halogen atom is F, Cl.
When the number that halogen atom replaces is more than 2, the kind of halogen atom can be identical, also can difference completely, or be that the species partial of selected halogen atom is identical.
When unsaturated alkyl by halogen atom replace the example of group that formed, specifically can enumerate:
-C ≡ C-X ,-CH 2-C ≡ C-X,--CH 2cH 2-C ≡ C-X ,-CH 2cH 2cH 2-C ≡ C-X, wherein, X is the one in F, Cl, Br, I.
In a preferred embodiment, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8independently of one another for the alkyl being selected from hydrogen atom, fluorine atom, chlorine atom, carbon number are 1 ~ 10, the carbon number unsaturated alkyl that is 2 ~ 10 and the above-mentioned carbon number alkyl that is 1 ~ 10, the carbon number unsaturated alkyl that is 2 ~ 10 by fluorine atom, chlorine atom replace the one in the group that formed.
In further preferred embodiment, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8independently of one another for the alkyl being selected from hydrogen atom, carbon number is 1 ~ 5, the carbon number unsaturated alkyl that is 2 ~ 5 and the above-mentioned carbon number alkyl that is 1 ~ 5, the carbon number unsaturated alkyl that is 2 ~ 5 by fluorine atom, chlorine atom replace the one in the group that formed.
Further preferred embodiment in, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8independently of one another for being selected from hydrogen atom, carbon number be 1 ~ 3 alkyl, carbon number be one in the unsaturated alkyl of 2 ~ 3, especially, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be one that hydrogen atom, the carbon number alkyl that is 1 ~ 3, the carbon number thiazolinyl that is 2 ~ 3, carbon number are in the alkynyl of 2 ~ 3 independently of one another.
As the example of cyclic sulfates compounds, specifically can enumerate:
In this application, the source of described cyclic sulfates compounds and difluorophosphate is not all subject to special restriction, all by commercially available or conventionally carry out synthesis obtain.
Discovery is studied, when including difluorophosphate (LiPO in electrolyte simultaneously through the applicant 2f 2) and cyclic sulfates compounds time, this electrolyte is applied to after in the high lithium ion battery of the coating weight of the active material on pole piece, the high temperature cyclic performance of this lithium ion battery can not only be improved, especially, improve the cycle performance of lithium ion battery at 55 ~ 60 DEG C, but also the high rate performance of lithium ion battery and the low temperature performance of lithium ion battery can be improved, wherein, the low temperature mentioned is-10 ~ 0 DEG C.
Especially, the electrolyte that the application provides also is suitable for the high lithium ion battery of the coating weight of the active material layer of the one side be arranged on collector.Wherein, the upper limit of the coating weight of the active material layer on negative electrode can reach 0.026g/cm 2, the lower limit of the coating weight of the active material layer on negative electrode is not subject to concrete restriction, as long as carry out according to demand applying, the upper limit of the coating weight of the active material layer on anode can reach 0.013g/cm 2, the lower limit of the coating weight of the active material on anode is not subject to concrete restriction, as long as carry out according to demand applying.Above-mentioned mentioned coating weight is the coating weight of the active material layer of the one side be positioned on collector.
Especially, in this application, the coating weight method of testing of positive and negative plate is as follows: get collector foil 20, and wherein the area of every a slice is S, and point its weight of another name, gets its mean value, be designated as M1; At the slurry of the one side coating identical weight of every a slice collector foil, after coating evenly, at 120 DEG C after dry 1 hour, after testing substantially not containing solvent.Then respectively weight is taken to the collector foil of dried one side coating slurry, get its mean value, be designated as M2; The coating weight M3 being then positioned at the active material layer of the one side on collector is calculated by following formula.
M3＝(M2-M1)/S
In this application, on the positive plate that described active material layer is arranged in lithium ion battery or negative plate, wherein, active material layer comprises active material, binding agent and conductive agent, and wherein, active material comprises again positive electrode active materials or negative active core-shell material.
In above-mentioned electrolyte, the not special restriction of content of cyclic sulfates compounds, can select according to the actual requirements.
In a preferred embodiment, the content of cyclic sulfates compounds is 0.01 ~ 3% of the total weight of electrolyte, further, the content of cyclic sulfates compounds is 0.15 ~ 2.5% of the total weight of electrolyte, further, the content of cyclic sulfates compounds is 0.3 ~ 1.5% of the total weight of electrolyte.
Find after deliberation, if when the content of cyclic sulfates compounds is too low, electrolyte is applied to lithium in battery after, the cryogenic property of lithium ion battery can not get improving substantially, and when the too high levels of cyclic sulfates compounds, electrolyte then can be caused to form thicker solid electrolyte interface (solidelectrolyteinterface is called for short SEI) film in pole piece, the cryogenic property of lithium ion battery can be caused on the contrary to worsen further.
In above-mentioned electrolyte, the not special restriction of content of cyclic sulfates compounds, can select according to the actual requirements.
In a preferred embodiment, the content of difluorophosphate is 0.05 ~ 0.8% of the total weight of electrolyte, and further, the content of difluorophosphate is 0.15 ~ 0.55% of the total weight of electrolyte, further, the content of difluorophosphate is 0.2 ~ 0.4% of the total weight of electrolyte.
Find after deliberation, if LiPO 2f 2content too low time, electrolyte to the positive pole of lithium ion battery substantially without improvement result, if LiPO 2f 2too high levels time, electrolyte can passivation positive pole and negative pole, the dynamic performance of lithium ion battery is deteriorated, such as, can reduces the mobility of lithium ion, and reduces the high temperature cyclic performance of lithium ion battery, high rate performance and low temperature performance.
In above-mentioned electrolyte, the not special restriction of concrete kind of lithium salts, can select according to the actual requirements.
In a preferred embodiment, described lithium salts be selected from following compound one or more: lithium hexafluoro phosphate (LiPF 6), two trifluoromethanesulfonimide lithium (LiN (CF 3sO 2) 2, be abbreviated as LiTFSI), lithium perchlorate (LiClO 4), hexafluoroarsenate lithium (LiAsF 6), di-oxalate lithium borate (LiB (C 2o 4) 2, be abbreviated as LiBOB), trifluoromethayl sulfonic acid lithium (LiCF 3sO 3).
In above-mentioned electrolyte, the not special restriction of content of described lithium salts, can carry out selection according to the actual requirements and add, such as, select conventional addition.
Especially, the content of lithium salts is make lithium salts molar concentration in the electrolytic solution be 0.5 ~ 2mol/L, and more particularly, the content of lithium salts is make lithium salts molar concentration in the electrolytic solution be 0.9 ~ 1.3mol/L.
In this application, the not special restriction of concrete kind of organic solvent, can select according to the actual requirements.Especially, select in non-aqueous organic solvent one or more.
As the example of non-aqueous organic solvent, specifically can enumerate: ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, oxolane.
In this application, the not special restriction of preparation method of electrolyte, can conventionally prepare, as long as by the mixing of materials in electrolyte evenly.Such as, lithium salts, difluorophosphate, cyclic sulfates compounds are joined in solvent and mixed, obtained electrolyte.Wherein, the not special restriction of the order of addition of material.Especially, first lithium salts is joined in organic solvent, then difluorophosphate and cyclic sulfates compounds are joined in organic solvent jointly and mix, especially, after mixing, obtain electrolyte.
Another object of the application is to provide a kind of lithium ion battery, comprises positive plate, negative plate, lithium battery diaphragm and electrolyte, wherein, and the electrolyte that electrolyte provides for the application.
In above-mentioned lithium ion battery, described positive plate comprises plus plate current-collecting body and is arranged at the positive electrode active material layer on described plus plate current-collecting body, and wherein, described positive electrode active material layer comprises positive electrode active materials, also comprises bonding agent and conductive agent; Described negative plate comprises negative current collector and is arranged at the negative electrode active material layer on described negative current collector, and wherein, described negative electrode active material layer comprises negative active core-shell material, also comprises bonding agent and conductive agent; Described lithium battery diaphragm is between positive plate and negative plate.Wherein, the concrete kind of plus plate current-collecting body, positive electrode active materials, negative current collector, negative active core-shell material, binding agent, conductive agent and lithium battery diaphragm is not all subject to concrete restriction, is convenient source, can select according to demand.
In above-mentioned lithium ion battery, the upper limit being positioned at the coating weight of the positive electrode active material layer on plus plate current-collecting body can reach 0.026g/cm 2, especially, coating weight is 0.02g/cm 2, the lower limit being positioned at the coating weight of the positive active material on plus plate current-collecting body is not subject to concrete restriction, as long as carry out according to demand applying; The upper limit being positioned at the coating weight of the negative electrode active material layer on negative current collector can reach 0.013g/cm 2, especially, coating weight is 0.01g/cm 2, the lower limit being positioned at the coating weight of the negative electrode active material layer on negative current collector is not subject to concrete restriction, as long as carry out according to demand applying.Wherein, the coating weight of mentioned active material layer is the coating weight of the active material layer of the one side be positioned on collector.
Especially, in above-mentioned lithium ion battery, plus plate current-collecting body can select aluminium foil; Negative current collector can select Copper Foil; Binding agent can select in Kynoar (PVDF), butadiene-styrene rubber (SBR) and sodium carboxymethylcellulose (CMC) one or more; Conductive agent can select in superconduction carbon, carbon nano-tube, Graphene and carbon nano-fiber one or more; Lithium battery diaphragm can select the multilayer complex films of polyethylene, polypropylene, Kynoar and above-mentioned polyethylene, polypropylene, Kynoar; The above-mentioned concrete kind being referred to each material, but be not limited only to above-mentioned enumerated plus plate current-collecting body, negative current collector, binding agent, conductive agent, lithium battery diaphragm material.
In a preferred embodiment, described positive electrode active materials is one or more in cobalt acid lithium, LiFePO4, LiMn2O4 and lithium-nickel-manganese-cobalt ternary material.
In a preferred embodiment, described negative active core-shell material is selected from lithium metal, native graphite, Delanium, mesophase spherule micro-carbon ball (being abbreviated as MCMB), hard carbon, soft carbon, silicon, silico-carbo compound, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO 2, spinel structure lithiumation TiO 2-Li 4ti 5o 12, one or more in Li-Al alloy.
Owing to including the electrolyte that the application provides in lithium ion battery, therefore, the lithium ion battery provided by the application has excellent high temperature cyclic performance, especially, at 55 ~ 60 DEG C, there is excellent high temperature cyclic performance, in addition, the lithium ion battery that the application provides has good high rate performance and the low temperature performance of excellence, wherein, at-10 ~ 0 DEG C, there is excellent low temperature performance.
The preparation method of the lithium ion battery that the application provides is known in the art, can manufacture the lithium ion battery that the application provides by existing preparation method of lithium ion battery.
Embodiment
The application is further described below by way of instantiation.But these examples are only exemplary, do not form any restriction to the protection range of the application.
In following embodiment, comparative example and test example, the reagent used, material and instrument as there is no special explanation, all commercially available acquisition.
In following experimental example, comparative example and test example, used material is as follows:
Organic solvent: ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC).
Lithium salts: LiPF 6, LiAsF 6, LiClO 4, LiB (C 2o 4) 2, LiN (CF 3sO 2) 2, LiCF 3sO 3.
Difluorophosphate (LiPO 2f 2).
Cyclic sulfates compounds:
Lithium battery diaphragm: thickness is the polypropylene barrier film of 12 μm.
Embodiment 1 ~ 20 electrolyte 1 #~ 20 #preparation
All electrolyte 1 is prepared successively according to following preparation method in embodiment 1 ~ 20 #~ 20 #:
In drying shed, in the mixed liquor of EC, PC and DEC, add lithium salts, then add LiPO 2f 2with cyclic sulfates compounds, after mixing, prepare electrolyte, wherein, EC and PP mentions that lithium salts molar concentration is in the electrolytic solution 1mol/L than being EC: PC: DEC=20: 20: 60.
In above-described embodiment 1 ~ 20, the concrete kind of the lithium salts adopted, cyclic sulfates compounds and the content of each material and LiPO 2f 2content as shown in Table 1 below.Wherein, in following table 1, the content of cyclic sulfates compounds is the percetage by weight obtained based on the total weight of electrolyte, LiPO 2f 2content be the percetage by weight obtained based on the total weight of electrolyte.
Table 1
Comparative example 1 ~ 6
In comparative example 1 ~ 6 all according to embodiment in given preparation method prepare electrolyte 1 ~ 6 successively, wherein, the addition of each used material as shown in Table 2 below, in following table 1, the content of cyclic sulfates compounds is the percetage by weight obtained based on the total weight of electrolyte, LiPO 2f 2content be the percetage by weight obtained based on the total weight of electrolyte.
Table 2
Note: any material is not added in "-" expression.
Test example
the preparation of lithium ion battery
By the electrolyte 1 obtained in embodiment and comparative example #~ 20 #, electrolyte 1 ~ 6 prepares lithium ion battery 1 successively according to following step respectively #~ 20 #, lithium ion battery 1 ~ 6:
(1) positive plate preparation
Positive plate 1:
By cobalt acid lithium (LiCoO 2), binding agent (Kynoar), conductive agent (acetylene black) according to mass ratio be cobalt acid lithium: Kynoar: acetylene black=98: mix at 1: 1, add 1-METHYLPYRROLIDONE (NMP), the system that is stirred under de-airing mixer effect becomes transparent and homogeneous shape, obtains anode sizing agent; Anode sizing agent being evenly coated on thickness is on the aluminium foil of 12 μm; Aluminium foil is transferred to after room temperature is dried 120 DEG C of oven drying 1h, anode sizing agent forms positive electrode active material layer, and then obtain positive plate through colding pressing, cutting, wherein, the coating weight being positioned at the positive electrode active material layer of the one side on aluminium foil is 0.0200g/cm 2.
Positive plate 2:
Carry out the preparation of positive plate 2 according to the method for positive plate 1, wherein, the positive electrode active material layer formed after anode sizing agent drying is different, and the coating weight being positioned at the positive electrode active material layer of the one side on aluminium foil is 0.026g/cm 2, all the other conditions are constant.
(2) negative plate preparation
Negative plate 1:
It is Delanium by Delanium, thickener sodium carboxymethylcellulose (CMC) solution, binding agent SBR emulsion according to mass ratio: sodium carboxymethylcellulose: SBR emulsion=98: 1: 1 mixing, after joining deionized water solvent, under the stirring action that de-airing mixer stirs, obtain cathode size; Cathode size being evenly coated in thickness is on 8 μm of Copper Foils; Copper Foil is transferred to after room temperature is dried 120 DEG C of oven drying 1h, cathode size forms negative electrode active material layer, and then obtain negative plate through colding pressing, cutting, wherein, the coating weight being positioned at the negative electrode active material layer of the one side on Copper Foil is 0.010g/cm 2.
Negative plate 2:
Carry out the preparation of negative plate 2 according to the method for negative plate 1, wherein, the negative electrode active material layer formed after cathode size drying is different, and the coating weight being positioned at the negative electrode active material layer of the one side on aluminium foil is 0.0130g/cm 2, all the other conditions are constant.
(3) preparation of lithium ion battery
Above-mentioned positive plate, negative plate lithium battery are separated, then after being wound into square naked battery core, loads aluminum plastic film, then after at 80 DEG C, baking dewaters, injecting corresponding electrolyte, sealing, through leaving standstill, after the operation such as heat is colded pressing, changed into, fixture, partial volume, obtaining the lithium ion battery of finished product.
performance of lithium ion battery is tested
(1) the high temperature cyclic performance test of lithium ion battery
The lithium ion battery prepared is tested respectively by the following method:
After at 55 DEG C under 4.4V constant voltage charge to 0.05C, and leave standstill 5 minutes, afterwards with 0.5C multiplying power constant-current discharge to 3.0V, this is a charge and discharge cycles process, this discharge capacity is the discharge capacity first of lithium ion battery, afterwards according to above-mentioned cycling condition, carry out 40,80,120,200,500 charge and discharge cycles respectively, then the result that the electrolyte in corresponding lithium ion battery, battery and positive and negative plate and test obtain is as shown in table 3.Wherein, circulation conservation rate calculates according to the following formula.
Capability retention (%) after lithium ion battery the N time circulation=(discharge capacity/discharge capacity first of the N time circulation) × 100%
Table 3
(2) lithium ion battery high rate performance test
The lithium ion battery prepared is tested respectively by the following method:
At 25 DEG C, lithium ion battery is left standstill 30 minutes, afterwards with 0.5C multiplying power constant current charge to 4.4V, afterwards under 4.4V constant voltage charge to 0.05C, and leave standstill 5 minutes, then by lithium ion battery respectively to be discharged to 3.0V under the different multiplying of 0.2C, 0.5C, 1.0C, 2.0C, after each electric discharge terminates, leave standstill 5 minutes again, the discharge capacity of record lithium ion battery.Wherein, with discharge capacity during 0.2C multiplying power discharging for benchmark, calculate the discharge capacity ratio of lithium ion battery under different discharge-rate respectively by following formula, then the result that in corresponding lithium ion battery, battery, selected electrolyte and positive and negative plate and test obtain is as shown in table 4.
Multiplying power discharging Capacity Ratio (%)=(discharge capacity under the discharge capacity under corresponding multiplying power/0.2C multiplying power) × 100% of lithium ion battery
(3) the low temperature performance test of lithium ion battery
The lithium ion battery prepared is tested respectively by the following method:
At 25 DEG C, lithium ion battery is left standstill 30 minutes, again with 0.5C constant current charge to 4.4V, under 4.4V, constant voltage charge, to 0.05C, and leaves standstill 5 minutes afterwards, then by lithium ion battery respectively under 25 DEG C, 0 DEG C ,-10 DEG C different temperatures after static 4h, all with 0.5C to be discharged to 3.0V, after each electric discharge terminates, then leave standstill 5 minutes, the discharge capacity of record lithium ion battery.With 25 DEG C of discharge capacities for benchmark, calculate lithium ion battery discharge capacity ratio at different temperatures, then the result that the electrolyte in corresponding lithium ion battery, battery and positive and negative plate and test obtain is as shown in table 4.
Discharge capacity ratio (%) under lithium ion battery different temperatures=(discharge capacity/25 DEG C discharge capacity under relevant temperature) × 100%.
Table 4
Can be learnt by above-mentioned table 3 and table 4, test the capability retention after the circulation obtained compared with lithium ion battery 1 ~ 6, the discharge capacity ratio under different multiplying and the discharge capacity ratio under low temperature, lithium ion battery 1 #~ 20 #combination property be improved, such as, the capability retention after circulation, the discharge capacity ratio under different multiplying and the discharge capacity ratio under low temperature, all obtain lifting by a relatively large margin.
Can learn thus, the electrolyte that the application is provided, be applied in lithium ion battery, particularly be applied to the lithium ion battery that the coating weight of the active material layer of the one side be arranged on pole piece is high, still the combination property of lithium ion battery can be improved, such as cycle performance, high rate performance and low temperature performance.
The announcement of book according to the above description, the application those skilled in the art can also carry out suitable change and amendment to above-mentioned execution mode.Therefore, the application is not limited to embodiment disclosed and described above, also should fall in the protection range of claim of the application some modifications and changes of the application.

Claims (10)

1. an electrolyte, is characterized in that, comprises lithium salts, organic solvent and additive, and wherein, described additive comprises difluorophosphate and cyclic sulfates compounds.
2. electrolyte according to claim 1, is characterized in that, described cyclic sulfates compounds is for being selected from by one or more in the compound shown in following formula I and formula II:
wherein,
In described formula I, n is the integer of 1 ~ 3,
In described formula II, m is the integer of 0 ~ 3,
In described formula I and formula II, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8independently of one another for the alkyl being selected from hydrogen atom, halogen atom, cyano group, carboxyl, sulfonic group, carbon number are 1 ~ 20, the carbon number unsaturated alkyl that is 2 ~ 20 and the above-mentioned carbon number alkyl that is 1 ~ 20, the carbon number unsaturated alkyl that is 2 ~ 20 by halogen atom replace the one in the group that formed, wherein, halogen atom is F, Cl, Br, I.
3. electrolyte according to claim 2, is characterized in that, in described formula I and formula II, and R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8independently of one another for the alkyl being selected from hydrogen atom, halogen atom, cyano group, carboxyl, sulfonic group, carbon number are 1 ~ 10, the carbon number unsaturated alkyl that is 2 ~ 10 and the above-mentioned carbon number alkyl that is 1 ~ 10, the carbon number unsaturated alkyl that is 2 ~ 10 by halogen atom replace the one in the group that formed.
4. electrolyte according to claim 1, is characterized in that, the content of described cyclic sulfates compounds is 0.01 ~ 3% of the total weight of electrolyte.
5. electrolyte according to claim 1, is characterized in that, the content of described difluorophosphate is 0.05 ~ 0.8% of the total weight of electrolyte.
6. electrolyte according to claim 1, is characterized in that, described lithium salts be selected from lithium hexafluoro phosphate, two trifluoromethanesulfonimide lithium, lithium perchlorate, hexafluoroarsenate lithium, di-oxalate lithium borate and trifluoromethayl sulfonic acid lithium one or more.
7. electrolyte according to claim 1, it is characterized in that, described organic solvent be selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, methyl formate, Ethyl formate, ethyl propionate, propyl propionate and oxolane one or more.
8. a lithium ion battery, it is characterized in that, comprise the electrolyte according to any one of positive plate, negative plate, lithium battery diaphragm and claim 1 ~ 7, wherein, described positive plate comprises plus plate current-collecting body and is arranged at the positive electrode active material layer on described plus plate current-collecting body, wherein, described positive electrode active material layer comprises positive electrode active materials; Described negative plate comprises negative current collector and is arranged at the negative electrode active material layer on described negative current collector, and wherein, described negative electrode active material layer comprises negative active core-shell material; Described lithium battery diaphragm is between positive plate and negative plate.
9. lithium ion battery according to claim 8, is characterized in that, is positioned at the coating weight of the described positive electrode active material layer of the one side on described plus plate current-collecting body at 0.026g/cm 2below, the coating weight of the described negative electrode active material layer of the one side on described negative current collector is positioned at 0.013g/cm 2below.
10. lithium ion battery according to claim 8, it is characterized in that, described positive electrode active materials be cobalt acid lithium, LiFePO4, LiMn2O4 and lithium-nickel-manganese-cobalt ternary material in one or more, described negative active core-shell material is selected from lithium metal, native graphite, Delanium, mesophase spherule micro-carbon ball, hard carbon, soft carbon, silicon, silico-carbo compound, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO 2, spinel structure lithiumation TiO 2-Li 4ti 5o 12, one or more in Li-Al alloy.
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