CN105789700A - Electrolyte and lithium ion battery - Google Patents
Electrolyte and lithium ion battery Download PDFInfo
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- CN105789700A CN105789700A CN201610189116.3A CN201610189116A CN105789700A CN 105789700 A CN105789700 A CN 105789700A CN 201610189116 A CN201610189116 A CN 201610189116A CN 105789700 A CN105789700 A CN 105789700A
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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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- 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 technical field of lithium ion batteries, in particular to electrolyte of a lithium ion battery and the lithium ion battery containing the electrolyte. The additive contains lithium salt, non-aqueous solvent and additive, wherein the additive contains double-bond-containing cyclic carbonate, boron-containing lithium salt, fluorine-containing lithium sulfimide, cyclic sulfate and double-bond-containing cyclic sultone. The additives of the present application act synergistically to form an effective interfacial film between the anode and cathode, resulting in a battery having good shelf life and low impedance.
Description
Technical field
The application relates to technical field of lithium ion, specifically, relates to the electrolyte of a kind of lithium ion battery and the lithium ion battery containing this electrolyte.
Background technology
The advantage such as lithium ion battery has higher energy density relative to lead-acid battery, Ni-MH battery, nickel-cadmium cell, have extended cycle life, is currently widely used to every field.
For the application of electric automobile, it requires that battery has low internal resistance, long storage calendar life and cycle life.Relatively low internal resistance is conducive to automobile to have good acceleration and power performance, and on hybrid electric vehicle during application, it can recover energy greatly and improve fuel efficiency.Long storage life and cycle life are in order to battery can have long-term reliability, keep good performance in the normal life cycle of automobile.These performances are had large effect by the interaction of electrolyte and anode and cathode.
In consideration of it, special, the application is proposed.
Summary of the invention
The primary goal of the invention of the application is in that to propose a kind of electrolyte.
Second goal of the invention of the application is in that to propose the lithium ion battery containing this electrolyte.
In order to complete the purpose of the application, the technical scheme of employing is:
The application relates to a kind of electrolyte, and containing lithium salts, nonaqueous solvent, additive, described additive includes following component:
Additive A: double bond containing cyclic carbonate；Additive B: boracic lithium salts；Addition of C: fluorine-containing sulfimide lithium；Additive D: cyclic sulfates；Additive E: double bond containing ring-type sultones.
Preferably, described additive A at least one in compound shown in formula I；
Wherein, R1Selected from substituted or unsubstituted C2～6Alkenylene, the C of alkenyl substituted1～6Alkylidene；Substituent group is selected from halogen, C1～3Alkyl.
Preferably, described additive A at least one in vinylene carbonate, vinylethylene carbonate；Preferably, the content of described additive A is the 0.01～0.5% of the quality of described electrolyte.
Preferably, described additive B at least one in difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate, LiBF4；Preferably, the content of described additive B is the 0.01～0.5% of the quality of described electrolyte.
Preferably, described addition of C at least one in compound as shown in Formula II；
Wherein, R21、R22Each independent it is respectively selected from the C that fluorine atom, hydrogen atom are all replaced by fluorine1～6Alkyl；
Preferably, described addition of C is selected from double; two fluorine sulfimide lithium, double; two trifluoromethanesulfonimide lithium, double; two pentafluoroethyl group sulfimide lithium, at least one enjoyed a double blessing in fluoropropyl sulfimide lithium；The content of described addition of C is the 0.01%～6% of the quality of described electrolyte.
Preferably, described additive D at least one in compound as shown in formula III；
Wherein, R3Selected from substituted or unsubstituted C1～6Alkylidene；
Substituent group is selected from C1～6Alkyl, halogen；
Preferably, described additive D at least one in sulfuric acid vinyl ester, sulphuric acid propylene, 4-methylsulfuric acid vinyl acetate；The 0.01%～5% of the quality that content is described electrolyte of described additive D.
Preferably, described additive E at least one in compound as shown in Formulas I V；
Wherein, R4Selected from substituted or unsubstituted C3～6Alkenylene；
Substituent group is selected from C1～6Alkyl, halogen；
Preferably, described additive E at least one in 1,3-propene sultone, Isosorbide-5-Nitrae-butylene sultones；The 0.01～0.5% of the quality that content is described electrolyte of described additive E.
Preferably, described nonaqueous solvent is selected from: at least two in ethylene carbonate, Allyl carbonate, butylene, fluorinated ethylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate and ethyl n-butyrate..
Preferably, described lithium salts at least one in lithium hexafluoro phosphate or difluorophosphate.
The application further relates to a kind of lithium ion battery, and including negative electrode, anode, isolating membrane and electrolyte, electrolyte is the electrolyte of the application, it is preferred that described cathode material is selected from lithium-nickel-manganese-cobalt ternary material, the described preferred LiNi of lithium-nickel-manganese-cobalt ternary material1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2In at least one.
The technical scheme of the application at least has following beneficial effect:
Coordinated between the five kinds of additives added in the application, it is possible to simultaneously improve kinetics and the life-span of battery.
First, additive A, additive B, additive D, additive E synergism improve anode life, additive A, the partially organic film forming of additive E film forming, the degree of polymerization is higher, pliability is better, keeps the integrity of anode film to be beneficial to when tackling the dilation of graphite anode in cyclic process, but its high-temperature stability is slightly worse, additive B, additive D are in the inclined inorganic constituents of anode film forming, it is possible to improve its high-temperature stability.
Secondly, additive B, additive D, additive E synergism improve cathode life, and additive B reduces the quantivalence of surface nickel in the film forming of negative electrode, reduces its oxidation activity；Additive D makes avtive spot contain more element sulphur in the film forming of negative electrode, reduces the catalysis activity of nickel, cobalt, manganese；E has certain degree of polymerization at cathode filming, and it reduces cathode surface and contacts with the direct of electrolyte；The negative electrode side reaction to electrolyte is reduced, thus improving the life-span by the synergism of three.
Further, addition of C improves PF6 -Or PO2F2 -With additive D heat stability in the electrolytic solution, reduce the generation of acid, so that battery can have good storage life.
Finally, additive B, addition of C, additive D coupling, keeping while battery life, make battery have relatively low impedance.The film forming component of additive D is inorganic constituents, is beneficial to lithium ion transmission in interface；Additive B can modification additives A, additive E film forming situation, reduce impedance；Addition of C adds dissociating of negative ions in electrolyte, thus improving electrical conductivity；Above synergism so that battery has relatively low impedance.
Below in conjunction with specific embodiment, the application is expanded on further.Should be understood that these embodiments are merely to illustrate the application rather than restriction scope of the present application.
Detailed description of the invention
The application relates to a kind of electrolyte, containing lithium salts, nonaqueous solvent, additive, wherein, containing following component in additive:
Additive A: double bond containing cyclic carbonate；
Additive B: boracic lithium salts；
Addition of C: fluorine-containing sulfimide lithium；
Additive D: cyclic sulfates；
Additive E: double bond containing ring-type sultones.
Wherein, double bond containing cyclic carbonate refers to have double bond inside circulus or be connected to the compound of double bond containing substituent group on cyclic carbonate；Fluorine-containing sulfimide lithium refers to the compound that part hydrogen atom or whole hydrogen atom are replaced by fluorine on the structural formula of sulfimide lithium；Cyclic sulfates refers to；Double bond containing ring-type sultones refers to the compound inside circulus with double bond.
As a kind of improvement of the application electrolyte, additive A at least one in compound shown in formula I；
Wherein, R1Selected from substituted or unsubstituted C2～6Alkenylene, the C of alkenyl substituted1～6Alkylidene；Substituent group is selected from halogen, C1～3Alkyl.
In this application, carbon number is the alkenylene of 2～6 is straight or branched alkenylene, and in thiazolinyl, the number of double bond is preferably 1.In described alkenylene, the preferred lower limit of carbon number is 3,4, it is preferred that higher limit is 3,4,5,6.Preferably, selecting carbon number is the alkenylene of 2～5.It is furthermore preferred that selecting carbon number is the alkenylene of 2～4.It is further preferred that selecting carbon number is the alkenylene of 2～3.As the example of alkenylene, specifically can enumerate: ethenylidene, acrol, sub-isopropenyl, sub-alkene butyl, sub-alkene amyl group.
In this application, carbon number is the alkylidene of 1～6 is straight or branched alkylidene, and in described alkylidene, the preferred lower limit of carbon number is 2,3, it is preferred that higher limit is 4,5.Preferably, selecting carbon number is the alkylidene of 1～4.It is furthermore preferred that selecting carbon number is the alkylidene of 2～3.As the example of alkyl, specifically can enumerate: methylene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, sub-sec-butyl, pentylidene, hexylidene.
As a kind of improvement of the application electrolyte, R1Selected from ethenylidene, allylidene, butenylidene, inferior pentenyl；Or selected from vinyl, acrylic or the methylene of cyclobutenyl replacement, ethylidene, butylidene.
As a kind of improvement of the application electrolyte, additive A is selected from least one in following compound:
As a kind of improvement of the application electrolyte, additive A is also selected from:
As a kind of improvement of the application electrolyte, the content of additive A is the 0.01～0.5% of the quality of electrolyte；Upper limit value is 0.35%, 0.4%, 0.45%, and lower limit value is 0.02%, 0.05%, 0.1%, 0.2%, 0.25%.The content of additive A can be made up of the content of additive A any number in upper limit value and lower limit value.Additive A content is within the scope of this, and part ensure that film forming and the efficiency first of anode；If content is more than 0.5%, then battery A when high temperature by cathode ternary material oxidation, can cause battery performance to decline.
As a kind of improvement of the application electrolyte, additive B at least one in difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate, LiBF4.
As a kind of improvement of the application electrolyte, the content of described additive B is the 0.01～0.5% of the quality of described electrolyte.Upper limit value is 0.35%, 0.4%, 0.45%, and lower limit value is 0.02%, 0.05%, 0.1%, 0.2%, 0.25%.The content of additive B can be made up of the content of additive B any number in upper limit value and lower limit value.When additive B content is within the scope of this, reducing anode and cathode and become membrane impedance, the life-span is improved at Simultaneous Stabilization interface；If content is more than 0.5%, then battery B when high temperature by cathode ternary material oxidation, can cause battery performance to decline.
As a kind of improvement of the application electrolyte, addition of C at least one in compound as shown in Formula II；
Wherein, R21、R22Each independent it is respectively selected from the C that fluorine atom, hydrogen atom are all replaced by fluorine1～6Alkyl.
As the example of haloalkyl, specifically can enumerate: trifluoromethyl, pentafluoroethyl group, seven fluorine n-pro-pyls, seven fluorine isopropyls, nine fluorine normal-butyls, nine fluorine isobutyl groups, nine fluorine sec-butyls, the nine fluorine tert-butyl groups, 11 fluorine n-pentyls, 11 fluorine isopentyl, 11 fluorine neopentyls, ten trifluoro hexyls.
As a kind of improvement of the application electrolyte, addition of C is selected from least one in following compound:
As a kind of improvement of the application electrolyte, addition of C is further selected from least one in following compound:
As a kind of improvement of the application electrolyte, the content of addition of C is the 0.01%～6% of the quality of described electrolyte.Upper limit value is 4%, 4.5%, 5%, 5.5%, and lower limit value is 0.02%, 0.05%, 0.1%, 0.2%, 0.25%.The content of addition of C can be made up of the content of addition of C any number in upper limit value and lower limit value.When addition of C content is within the scope of this, the electrical conductivity of electrolyte can be improved, improve PF6 -Or PO2F2 -Heat stability.When content is more than 6%, viscosity becomes big, and electrical conductivity reduces on the contrary.
As a kind of improvement of the application electrolyte, additive D at least one in compound as shown in formula III；
Wherein, R3Selected from substituted or unsubstituted C1～6Alkylidene；
Substituent group is selected from C1～6Alkyl, halogen.
As a kind of improvement of the application electrolyte, additive D is selected from least one in following compound:
As a kind of improvement of the application electrolyte, additive D is further selected from least one in following compound:
As a kind of improvement of the application electrolyte, the content of additive D is the 0.01%～5% of the quality of described electrolyte.Upper limit value is 3.5%, 4%, 4.5%, 4.8%, and lower limit value is 0.02%, 0.05%, 0.1%, 0.2%, 0.25%.The content of additive D can be made up of the content of additive D any number in upper limit value and lower limit value.When the content of additive D is within the scope of this, anode and cathode can both film forming, particularly in the film forming on ternary material surface, reduce the reactivity of surface nickel, thus improving the storage life of battery.When content is more than 5%, after long term high temperature storage, the decomposition of D causes battery performance to decline.
As a kind of improvement of the application electrolyte, additive E at least one in compound as shown in formula IV；
Wherein, R4Selected from substituted or unsubstituted C3～6Alkenylene；
Substituent group is selected from C1～6Alkyl, halogen.
Halogen is selected from fluorine, chlorine, bromine；And preferably fluorine, chlorine.
As a kind of improvement of the application electrolyte, additive E is selected from least one in following compound:
As a kind of improvement of the application electrolyte, additive E is further selected from least one in following compound:
As a kind of improvement of the application electrolyte, the content of additive E is the 0.01～0.5% of the quality of described electrolyte.Upper limit value is 0.35%, 0.4%, 0.45%, and lower limit value is 0.02%, 0.05%, 0.1%, 0.2%, 0.25%.The content of additive E can be made up of the content of additive E any number in upper limit value and lower limit value.When additive E is within the scope of this, anode and cathode can both film forming, improve the life-span of battery, especially high temperature service life.But it becomes membrane impedance big, and therefore its content not can exceed that 0.5%.
A kind of improvement as the application electrolyte, nonaqueous solvent is selected from: at least two in ethylene carbonate, Allyl carbonate, butylene, fluorinated ethylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate and ethyl n-butyrate..
As a kind of improvement of the application electrolyte, lithium salts at least one in lithium hexafluoro phosphate or difluorophosphate.
The application further relates to a kind of lithium ion battery, and including negative electrode, anode, isolating membrane and electrolyte, electrolyte is the electrolyte of the application.
Preferably, cathode material is selected from lithium-nickel-manganese-cobalt ternary material.
Preferably, lithium-nickel-manganese-cobalt ternary material is selected from LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2In at least one.
Ternary material surface appearance is different from materials such as cobalt acid lithiums, and Surface Oxygen voltinism is stronger.Additive B reduces the quantivalence of surface nickel in the film forming of negative electrode, reduces its oxidation activity；But during its content height, then unnecessary after film forming additive B generates more gas in negative electrode generation oxidation reaction, causes the decline of performance on the contrary, therefore needs to control its content less than 0.5%；Additive A is prone to, in negative electrode generation oxidation reaction, cause aerogenesis, therefore needs to control its content less than 0.5%；Additive D makes avtive spot contain more element sulphur in the film forming of negative electrode, reduces the catalysis activity of nickel, cobalt, manganese；Additive E has certain degree of polymerization at cathode filming, and it reduces cathode surface and contacts with the direct of electrolyte；Coordinated between five kinds of additives, it is possible to simultaneously improve kinetics and the life-span of battery.
In following embodiment, comparative example and test example, reagent, material and the instrument used be not as having special explanation, all commercially available.
In following experimental example, comparative example and test example, used material is as follows:
Organic solvent: ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), propyl propionate (PP).
Lithium salts: lithium hexafluoro phosphate, difluorophosphate.
Additive A:
Additive A 1: vinylene carbonate；
Additive A 2: vinylethylene carbonate；
Additive B:
Additive B 1: difluorine oxalic acid boracic acid lithium；
Additive B 2: di-oxalate lithium borate；
Additive B 3: LiBF4；
Addition of C:
Addition of C 1: double; two fluorine sulfimide lithium；
Addition of C 2: double; two trifluoromethanesulfonimide lithiums；
Addition of C 3: double; two pentafluoroethyl group sulfimide lithium；
Additive D:
Additive D1:4-methylsulfuric acid vinyl acetate；
Additive D2: sulphuric acid propylene；
Additive D3: sulfuric acid vinyl ester；
Additive E:
Additive E1:1,3-propene sultone；
Additive E2:1,4-butylene sultones；
Lithium battery diaphragm: polypropylene isolating membrane (model is A273, Celgard company provide) 16 microns thick.
The preparation of embodiment 1 lithium ion battery
(1) prepared by cathode sheets
Cathode material is by ternary material (LiNi1/3Co1/3Mn1/3O2), after conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF) 96:2:2 in mass ratio be sufficiently stirred for mix homogeneously in N-Methyl pyrrolidone dicyandiamide solution, be coated on Al paper tinsel, dry, cold pressing, obtain cathode sheets.
(2) prepared by anode strip
Anode material is after being sufficiently stirred for mix homogeneously according to mass ratio 94:2:2:2 by graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickening agent sodium carboxymethyl cellulose (CMC) in deionized water solvent system, be coated on Cu paper tinsel dry, cold pressing, obtain anode strip.
(3) prepared by electrolyte
In water content < in the argon gas atmosphere glove box of 10ppm, by fully dry LiPF6Being dissolved in organic solvent EC and DEC, the mass ratio of the middle EC:DEC of organic solvent is 30:70；Then shown in table 1, additive, mix homogeneously, it is thus achieved that electrolyte are added in organic solvent.Wherein, the concentration of lithium salts is 1mol/L.
(4) preparation of lithium ion battery
Cathode sheets, isolating membrane, anode strip, isolating membrane are placed in order, makes isolating membrane be in the middle of anode and cathode slice to play the effect of isolation, and wind and obtain naked battery core；Naked battery core it is packaged in packaging bag or is placed in metal shell, the electrolyte of above-mentioned preparation being injected in the dried battery removing moisture, the operation such as encapsulation, standing, chemical conversion, shaping, obtain battery.
In the preparation process of above-mentioned battery, the concrete kind of additive used in electrolyte selected in each battery, each electrolyte and content are as shown in Table 1 below.
In Table 1, the content of additive is the percetage by weight that the total weight based on electrolyte obtains.
Table 1:
Prepare comparative example according to the preparation method of embodiment 1, be distinctive in that: the additive of the electrolyte in comparative example is as shown in table 2:
In table 2, the content of additive is the percetage by weight that the total weight based on electrolyte obtains.
Table 2:
Test one, the low temperature direct impedance (DCR) of battery test
The battery prepared is carried out following test respectively:
Adjust the state-of-charge (SOC) of battery during room temperature (25 DEG C) to the 20% of capacity, be placed in the high-low temperature chamber of-25 DEG C, stand 2 hours, make battery temperature reach-25 DEG C.The multiplying power discharging 10s of 0.3C, the voltage before electric discharge is U1, and the voltage after electric discharge is U2, and electric discharge DCR=(U1-U2)/I, the DCR result of each battery is referring to table 3.
Test two, the test of the high-temperature storage performance (calendar life) of battery
The battery prepared is carried out following test respectively:
The capacity of battery is tested during room temperature (25 DEG C), it is designated as initial capacity, then battery 1C is completely charged to 4.1V, constant-voltage charge to electric current is 0.05C, it is subsequently placed in 60 DEG C of baking ovens and stores, store 1 month, take out baking oven, be put in room temperature (25 DEG C) environment more than 3 hours, the temperature making battery core drops to room temperature, then (1C is discharged to by voltage, has a rest 5 minutes, and 1C completely fills to test its reversible capacity, constant-voltage charge to electric current is 0.05C, having a rest 5 minutes, 1C is discharged to by voltage, and this capacity is designated as the reversible capacity of battery core after storage)；After testing, Man Chong, then be placed in 60 DEG C of baking ovens and store, tested a reversible capacity at interval of 1 month, until battery core reversible capacity decays to initial 80%, this time is designated as the calendar life of battery core, and the data of each battery are referring to table 3.
Test three, the test of the cycle life of battery
The battery prepared is carried out following test respectively:
When 25 DEG C, by battery with 1C constant-current charge to 4.1V, then constant-voltage charge to electric current is 0.05C, again with 1C constant-current discharge to 2.8V, now for circulate first, it is circulated charge/discharge according to above-mentioned condition, battery capacity conservation rate is decayed to the cycle life that circulating ring number scale is battery of battery when 80%.Relevant test data obtained in each battery is referring to table 3.
Capability retention after circulation=(discharge capacity after corresponding cycle-index/circulate first discharge capacity) × 100%.
Table 3:
Correlated results from above-mentioned table 3 is it is known that compared to comparative example, the cycle life of embodiment battery and calendar life are all significantly improved, and its resistance value is lower than 50mOhm simultaneously.
Thus it is appreciated that, the electrolyte that the application provides, is applied in ternary system lithium ion battery, it is possible to increase the combination property of lithium ion battery, for instance, it is possible to improve the lithium ion battery calendar life when high temperature, promote cycle performance be maintained with low internal resistance.
In order to further illustrate the beneficial effect of additive coupling, battery in embodiment 4 is carried out comparative illustration with battery D8 in comparative example.
Cyclic sulfates is in anode film forming, if be used alone, along with the increase of its content, its film formation reaction becomes big, causes that impedance increases.We have found through testing that: during by double; two fluorine sulfimide lithium with cyclic sulfates coupling, it is possible to suppress its impedance to increase, find by testing, this is relevant with double; two fluorine sulfimide lithium film forming on graphite anode.
Cyclic sulfates has heat-labile feature, easily decompose during high temperature, the acid content in electrolyte is made to increase, when acid content increases, negative electrode is unfavorable, negative electrode will be destroyed, when the transition metal ions being dissolved down from negative electrode lithium-nickel-manganese-cobalt ternary material deposits to anode, the surface passivated membrane of anode will be destroyed, so that battery performance worsens.We have found through testing that: double; two fluorine sulfimide lithium can improve cyclic sulfates stability in the electrolytic solution, it is suppressed that the growth of the acid content in electrolyte so that it is maintains relatively low level.
Concrete experimental data is as follows:
Battery after test capacity, without the battery of double; two fluorine sulfimide lithium, its acid content is 67.3ppm, and containing the battery of double; two fluorine sulfimide lithium, its acid content is reduced to 32.8ppm.Battery carries out the loop test of 60 DEG C subsequently, and test condition is: 2.8--4.1V, has a rest 5 minutes, and 1C charges to 4.1V, 4.1V constant voltage to 0.05C, has a rest 5 minutes, and 1C is discharged to 2.8V.Loop test, to capacity attenuation to the 80% of initial capacity, takes battery apart, takes out anode diaphragm and obtains electrolyte by the method for centrifugal treating, testing metal ion content therein by ICP (indutively coupled plasma atomic emission spectrum).Result is as shown in table 4 below:
Table 4:
As can be seen from the table, double; two fluorine sulfimide lithium can reduce the anticathode adverse effect of acid content that cyclic sulfates increases, and reduces the dissolution of cathodic metal ion, also reduces the detrimental effect of metal ion antianode SEI simultaneously.
In order to study double; two fluorine sulfimide lithium further, cyclic sulfates is decomposed the inhibitory action of the acid content produced, has carried out the storage test of electrolyte.Electrolyte 4, electrolyte D8 are encapsulated in packaging aluminium plastic film, are placed in 45 DEG C of baking ovens and store one month, then test its acid content (acid base titration is converted into HF numeric representation), colourity (Pt-Co colorimetry).Result is as shown in table 5 below:
Table 5:
| Acidity (ppm) | Colourity (Hazen) | |
| Battery D8 | 152 | 300 |
| Battery 4 | 81 | 100 |
The acidity of the electrolyte 4 in test result display embodiment and colourity are significantly lower than comparative example D8.
When double; two fluorine sulfimide lithium in embodiment battery 4 participate in anode SEI film forming procedure, sulfur nitrogen key disconnects, and sulfonyl group participates in the film forming of anode SEI together with ring-type sulphuric acid.Remaining nitrogenous it is partially left in electrolyte, due to nitrogen electron rich, PF can be made6 -Stable, also improve the heat stability of electrolyte to a certain extent.
To sum up result of study, the collaborative use of additive in embodiment, can be effectively reduced into membrane resistance, simultaneously again can film forming good, this good film forming contributes to the improvement of battery life.
The preparation of embodiment 2 lithium ion battery
Electrolyte and the lithium ion battery containing this electrolyte is prepared according to the method for embodiment 1, it is distinctive in that: lithium salts in battery and organic solvent and cathode material are as shown in table 6, and the ratio of additive and the structural formula of additive compound are respectively as shown in table 7 and table 8:
Table 6:
| Battery is numbered | Cathode material | Lithium salts | Organic solvent |
| Battery 10 | LiNi1/3Co1/3Mn1/3O2 | Lithium hexafluoro phosphate+difluorophosphate | EC/DEC=30/70 |
| Battery 11 | LiNi1/3Co1/3Mn1/3O2 | Lithium hexafluoro phosphate | EC/DEC=30/70 |
| Battery 12 | LiNi1/3Co1/3Mn1/3O2 | Lithium hexafluoro phosphate+difluorophosphate | EC/DEC=30/70 |
| Battery 13 | LiNi0.5Co0.2Mn0.3O2 | Difluorophosphate | EC/DEC=30/70 |
| Battery 14 | LiNi0.5Co0.2Mn0.3O2 | Lithium hexafluoro phosphate | EC/DMC=30/70 |
| Battery 15 | LiNi0.5Co0.2Mn0.3O2 | Lithium hexafluoro phosphate+difluorophosphate | EC/DEC/DMC=30/40/30 |
| Battery 16 | LiNi0.5Co0.2Mn0.3O2 | Lithium hexafluoro phosphate | EC/DEC/PP=30/50/20 |
| Battery 17 | LiNi0.6Co0.2Mn0.2O2 | Difluorophosphate | EC/DEC=30/70 |
| Battery 18 | LiNi0.8Co0.1Mn0.1O2 | Lithium hexafluoro phosphate | EC/DEC=30/70 |
In table 7, the content of additive is the percetage by weight that the total weight based on electrolyte obtains.
Table 7:
Table 8:
Detecting according to the performance of the battery to preparing of the method in embodiment 1, the performance that detection obtains battery 10～18 is similar to above example, repeats no more as space is limited.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. an electrolyte, containing lithium salts, nonaqueous solvent, additive, it is characterised in that described additive includes following component:
Additive A: double bond containing cyclic carbonate；
Additive B: boracic lithium salts；
Addition of C: fluorine-containing sulfimide lithium；
Additive D: cyclic sulfates；
Additive E: double bond containing ring-type sultones.
2. electrolyte according to claim 1, it is characterised in that described additive A at least one in compound shown in formula I；
Wherein, R1Selected from substituted or unsubstituted C2～6Alkenylene, the C of alkenyl substituted1～6Alkylidene；Substituent group is selected from halogen, C1～3Alkyl.
3. electrolyte according to claim 2, it is characterised in that described additive A at least one in vinylene carbonate, vinylethylene carbonate；Preferably, the content of described additive A is the 0.01～0.5% of the quality of described electrolyte.
4. electrolyte according to claim 1, it is characterised in that described additive B at least one in difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate, LiBF4；Preferably, the content of described additive B is the 0.01～0.5% of the quality of described electrolyte.
5. electrolyte according to claim 1, it is characterised in that described addition of C at least one in compound as shown in Formula II；
Wherein, R21、R22Each independent it is respectively selected from the C that fluorine atom, hydrogen atom are all replaced by fluorine1～6Alkyl；
Preferably, described addition of C is selected from double; two fluorine sulfimide lithium, double; two trifluoromethanesulfonimide lithium, double; two pentafluoroethyl group sulfimide lithium, at least one enjoyed a double blessing in fluoropropyl sulfimide lithium；The content of described addition of C is the 0.01%～6% of the quality of described electrolyte.
6. electrolyte according to claim 1, it is characterised in that described additive D at least one in compound as shown in formula III；
Wherein, R3Selected from substituted or unsubstituted C1～6Alkylidene；
Substituent group is selected from C1～6Alkyl, halogen；
Preferably, described additive D at least one in sulfuric acid vinyl ester, sulphuric acid propylene, 4-methylsulfuric acid vinyl acetate；The 0.01%～5% of the quality that content is described electrolyte of described additive D.
7. electrolyte according to claim 1, it is characterised in that described additive E at least one in compound as shown in Formulas I V；
Wherein, R4Selected from substituted or unsubstituted C3～6Alkenylene；
Substituent group is selected from C1～6Alkyl, halogen；
Preferably, described additive E at least one in 1,3-propene sultone, Isosorbide-5-Nitrae-butylene sultones；The 0.01～0.5% of the quality that content is described electrolyte of described additive E.
8. electrolyte according to claim 1, it is characterized in that, described nonaqueous solvent is selected from: at least two in ethylene carbonate, Allyl carbonate, butylene, fluorinated ethylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, propyl propionate, ethyl propionate and ethyl n-butyrate..
9. electrolyte according to claim 1, it is characterised in that described lithium salts at least one in lithium hexafluoro phosphate or difluorophosphate.
10. a lithium ion battery, including negative electrode, anode, isolating membrane and electrolyte, it is characterised in that: electrolyte is the electrolyte described in claim 1 to 9, it is preferred that, described cathode material is selected from lithium-nickel-manganese-cobalt ternary material, the described preferred LiNi of lithium-nickel-manganese-cobalt ternary material1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2In at least one.
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