CN105489935B - Electrolyte and the lithium ion battery including the electrolyte - Google Patents

Electrolyte and the lithium ion battery including the electrolyte Download PDF

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CN105489935B
CN105489935B CN201610017858.8A CN201610017858A CN105489935B CN 105489935 B CN105489935 B CN 105489935B CN 201610017858 A CN201610017858 A CN 201610017858A CN 105489935 B CN105489935 B CN 105489935B
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carbon atom
atom number
electrolyte
lithium
boron trifluoride
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CN105489935A (en
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史松君
王耀辉
谢岚
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Dongguan 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
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    • 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

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Abstract

This application involves a kind of electrolyte and the lithium ion battery including the electrolyte, wherein electrolyte includes organic solvent, lithium salts and additive, the additive includes nitrogen heterocyclic ring boron trifluoride complex, and the nitrogen heterocyclic ring is selected from least one of the heterocycle containing pyridyl group, the heterocycle containing pyridazinyl, the heterocycle containing pyrimidine radicals, the heterocycle containing pyrazinyl, the heterocycle containing pyrrole radicals, the heterocycle of pyrazolyl containing and heterocycle containing imidazole radicals.The electrolyte that the application provides, due to including the nitrogen heterocyclic ring boron trifluoride complex, can improve the storage performance under the cycle performance and high temperature of lithium ion battery at high temperature.

Description

Electrolyte and the lithium ion battery including the electrolyte
Technical field
This application involves field of batteries more particularly to a kind of electrolyte and the lithium ion battery including the electrolyte.
Background technology
At present, the positive electrode active materials employed in lithium ion battery mainly have LiMn2O4, cobalt acid lithium, ternary material, LiFePO 4 etc. in general, selects the charge cutoff voltage of the lithium ion battery of the above-mentioned positive electrode being previously mentioned No more than 4.2V, but with advances in technology and the continuous development in market, the energy density of lithium ion battery is promoted increasingly Seem important and urgent, a kind of effective ways for the energy density for promoting lithium ion battery are exploitation high-voltage lithium ion batteries.
However, under the high voltage of 4.4V, conventional electrolyte can be caused in the positive electrode surface oxygenolysis of battery, electrolysis The oxygenolysis of liquid itself can promote the deteriorative reaction of positive electrode active materials simultaneously, further influence the performance of lithium ion battery, Such as storage performance and cycle performance.
Invention content
To solve the above-mentioned problems, the applicant has carried out sharp study, as a result, it has been found that：When in electrolyte while including containing Azacyclo--boron trifluoride complex is capable of providing under the cycle performance and high temperature at high temperature of lithium ion battery Storage performance, so as to complete the application.
The application's is designed to provide a kind of electrolyte, including organic solvent, lithium salts and additive, the additive packet Nitrogen heterocyclic ring-boron trifluoride complex is included, wherein, the nitrogen heterocyclic ring is selected from the heterocycle containing pyridyl group, containing pyridazinyl Heterocycle, the heterocycle containing pyrimidine radicals, the heterocycle containing pyrazinyl, the heterocycle containing pyrrole radicals, the heterocycle of pyrazolyl containing and containing imidazole radicals At least one of heterocycle.
The another object of the application is to provide a kind of lithium ion battery, including the positive plate containing positive electrode active materials, Negative plate, isolation film and electrolyte provided herein containing negative electrode active material.
In the electrolyte that the application provides, due to simultaneously including nitrogen heterocyclic ring mentioned above-boron trifluoride ligand compound Object, therefore the storage performance under the cycle performance and high temperature of lithium ion battery at high temperature can be improved.
Specific embodiment
It is described in detail below by the application, will become more with these explanations with advantage the characteristics of the application It is clear, clear and definite.
The application's is designed to provide a kind of electrolyte, including organic solvent, lithium salts and additive, the additive packet Nitrogen heterocyclic ring-boron trifluoride complex is included, wherein, the nitrogen heterocyclic ring is selected from the heterocycle containing pyridyl group, containing pyridazinyl Heterocycle, the heterocycle containing pyrimidine radicals, the heterocycle containing pyrazinyl, the heterocycle containing pyrrole radicals, the heterocycle of pyrazolyl containing and containing imidazole radicals At least one of heterocycle.
In above-mentioned electrolyte, " heterocycle containing pyridyl group, the heterocycle containing pyrimidine radicals, contains the heterocycle containing pyridazinyl described It is pyridyl group, pyridazinyl, phonetic in the heterocycle of pyrazinyl, the heterocycle containing pyrrole radicals, the heterocycle of pyrazolyl containing, the heterocycle containing imidazole radicals " Piperidinyl, pyrazinyl, pyrrole radicals, pyrazolyl, imidazole radicals can be replaced by other groups, such as can be by halogen atom, hydrogen atom, alkane Base etc. is replaced.
In above-mentioned electrolyte, in the nitrogen heterocyclic ring-boron trifluoride complex, boron trifluoride is in anion, For nitrogen heterocyclic ring in cation, entire azacyclo--boron trifluoride complex is in electroneutral.
Preferably, the nitrogen heterocyclic ring-boron trifluoride complex be selected from following formula I, Formula II, formula III, formula IV, At least one of Formula V, Formula IV and Formula VII compound represented：
In above-mentioned Formulas I, Formula II, formula III, formula IV, Formula V, Formula IV and Formula VII, R11、R12、R13、R14、R15、R21、R22、 R23、R24、R31、R32、R33、R34、R41、R42、R43、R44、R51、R52、R53、R54、R61、R62、R63、R71、R72、R73Each independently It is 2~20 to be selected from alkyl, carbon atom number that hydrogen atom, halogen atom, cyano, sulfonic group, sulfonyl, carbon atom number are 1~20 Alkenyl, carbon atom number be 6~26 aryl, carbon atom number be 1~20 alkoxy, carbon atom number be 6~26 aryloxy group, And above-mentioned carbon atom number be 1~20 alkyl, carbon atom number be 2~20 alkenyl, carbon atom number be 6~26 aryl, carbon The aryloxy group that alkoxy that atomicity is 1~20, carbon atom number are 6~26 replaces institute's shape by halogen atom, sulfonic group or sulfonyl Into group in one kind, wherein, halogen atom F, Cl, Br, preferably F, Cl.In addition, alkyl mentioned above, alkenyl, aryl It can be replaced by the group containing pyridyl group or the group of thienyl-containing.
In above-mentioned Formulas I, Formula II, formula III, formula IV, Formula V, Formula IV and Formula VII, substituent group is as described below.
Carbon atom number is 1~20 alkyl, and alkyl can be chain-like alkyl or cycloalkyl, on the ring of cycloalkyl Hydrogen can be replaced by alkyl, in the alkyl the preferred lower limiting value of carbon atom number be 2,3,4,5, preferred upper limit value be 3,4,5, 6,8,10,12,14,16,18.Preferably, select carbon atom number for 1~10 alkyl, it is further preferred that selection carbon atom number For 1~6 chain-like alkyl, carbon atom number is 3~8 cycloalkyl, it is further preferred that select carbon atom number for 1~4 chain Shape alkyl, carbon atom number are 5~7 cycloalkyl.As the example of alkyl, can specifically enumerate：It is methyl, ethyl, n-propyl, different Propyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl, isopentyl, neopentyl, cyclopenta, cyclohexyl.
Carbon atom number is 2~20 alkenyl, can be cyclic alkenyl radical or chain alkenyl.In addition, in alkenyl double bond Number preferably 1.The preferred lower limiting value of carbon atom number is 3,4,5 in the alkenyl, and preferred upper limit value is 3,4,5,6,8,10, 12,14,16,18.Preferably, select carbon atom number for 2~10 alkenyl, it is further preferred that selecting carbon atom number as 2~6 Alkenyl, it is further preferred that select carbon atom number for 2~5 alkenyl.As the example of alkenyl, can specifically enumerate：Second Alkenyl, pi-allyl, isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base.
Carbon atom number be 6~26 aryl, such as phenyl, benzene alkyl, at least contain there are one phenyl aryl such as xenyl, Condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and condensed-nuclei aromatics base can also be replaced by alkyl or alkenyl.Preferably, it selects Select carbon atom number be 6~16 aryl, it is further preferred that select carbon atom number for 6~14 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.
When containing oxygen atom in the alkyl that the aforementioned carbon atom number being previously mentioned is 1~20, alkoxy can be formed.It is preferred that Ground, select carbon atom number for 1~10 alkoxy, it is further preferred that select carbon atom number for 1~6 alkoxy, more into one Step preferably, select carbon atom number for 1~4 alkoxy.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.
When containing oxygen atom in the aryl that the aforementioned carbon atom number being previously mentioned is 6~26, aryloxy group can be formed.It is preferred that Ground, select carbon atom number for 6~16 aryloxy group, it is further preferred that select carbon atom number for 6~14 aryloxy group, more into One step preferably, select carbon atom for 6~10 aryloxy group.As the example of aryloxy group, can specifically enumerate：Phenoxy group, benzyl Oxygroup, 4- methylphenoxies, 3,5- dimethyl phenoxies, 4- methylbenzyloxies, 3- methylbenzyloxies, 2,6- diisopropyl benzyloxies Base, 1- naphthoxys.
When alkenyl that alkyl that the carbon atom number being previously mentioned is 1~20, carbon atom number are 2~20, carbon atom number be 6~ After the aryloxy group that alkoxy that 26 aryl, carbon atom number are 1~20, carbon atom number are 6~26 is replaced by halogen atom, phase successively Halogenated alkenyl that halogenated alkyl that the formation carbon atom number answered is 1~20, carbon atom number are 2~20, carbon atom number are 6~26 The haloaryloxy that halogenated alkoxy that halogenated aryl, carbon atom number are 1~20, carbon atom number are 6~26, wherein halogen atom are F, Cl, Br, preferably F, Cl.In the halo groups formed, halogen atom carries out part hydrogen atom or whole hydrogen atoms Substitution, the number of halogen atom can be 1,2,3 or 4.
Preferably, select carbon atom number for 1~10 halogenated alkyl, carbon atom number be 2~10 halogenated alkenyl, carbon atom The haloaryloxy that the halogenated aryl for 6~16, the halogenated alkoxy that carbon atom number is 1~10, carbon atom number are 6~16 is counted, It is further preferred that select carbon atom number for 1~6 halogenated chain-like alkyl, carbon atom number be 3~8 halogenated cycloalkyl, carbon it is former Halogenated alkoxy that halogenated aryl that halogenated alkenyl that subnumber is 2~6, carbon atom number are 6~14, carbon atom number are 1~6, carbon Atomicity is 6~14 haloaryloxy, it is further preferred that selecting halogenated chain-like alkyl, carbon of the carbon atom number for 1~4 Halogenated aryl that halogenated alkenyl that halogenated cycloalkyl that atomicity is 5~7, carbon atom number are 2~5, carbon atom are 6~10, carbon The haloaryloxy that halogenated alkoxy that atomicity is 1~4, carbon atom are 6~10.
As the example of halo groups, can specifically enumerate：Trifluoromethyl (- CF3), 2- fluoro ethyls, 3- fluorine n-propyl, 2- Fluorine isopropyl, 4- fluorine normal-butyl, 3- fluorine sec-butyl, 5- fluorine n-pentyl, 4- fluorine isopentyl, 1- are fluoride-based, 3- fluorine pi-allyl, 6- Fluoro- 4- hexenyls, o-fluorophenyl, p-fluorophenyl, fluorophenyl, 4- trifluoromethylphenyls, 2,6- difluoromethyls phenyl, the fluoro- 1- of 2- Naphthalene, fluoro-methoxy, 1- fluorine ethyoxyl, the fluoro- positive propoxies of 2-, the fluoro- isopropoxies of 1-, the fluoro- n-butoxies of 3-, 4- are fluoro- just Amoxy, 2,2- difluoromethyls propoxyl group, the fluoro- positive hexyloxies of 5-, 1,1,2- trifluoromethyl propoxyl group, the fluoro- n-heptyl oxygroups of 6-, The fluoro- n-octyl oxygroups of 7-, the fluoro- cyclopentyloxies of 3-, the fluoro- 2- methylcyclopentoxies of 4-, the fluoro- cyclohexyloxies of 3-, 3- fluorine cycloheptyls oxygroup, The fluoro- 2- methyl cycloheptyl oxygroups of 4-, 3- fluorine rings octyloxy, 4- fluorophenoxies, 3- fluorophenoxies, 2- fluorophenoxies, 3,5- difluorobenzenes Oxygroup, 2,6- difluoros phenoxy group, 2,3- difluoros phenoxy group, 2,6-, bis- fluoro- 4- methylphenoxies, 3- (2- fluoro ethyls) phenoxy group, 2- (1- fluoro ethyls) phenoxy group, 3,5- difluoros benzyloxy, 2- fluorine benzyloxy, the fluoro- 1- naphthoxys of 2-.In above-mentioned specific example In, F can be replaced by Cl and/or Br.
The aryl that carbon atom number is 1~20 alkyl, carbon atom number is 2~20 alkenyl, carbon atom number are 6~26 is by sulphur It is corresponding to form sulfonic group alkyl, sulfonic group alkenyl, sulfonic group aryl, alkyl sulphonyl, alkenyl after acidic group or sulfonyl substitution Sulfonyl, aryl sulfonyl.Sulfonic group can to the part hydrogen atom in abovementioned alkyl, alkenyl, aryl or whole hydrogen atom into Row substitution, sulfonic number can be 1 or 2, likewise, sulfonyl can be to the part hydrogen in abovementioned alkyl, alkenyl, aryl Atom or whole hydrogen atoms are replaced, and the number of sulfonyl can be 1 or 2.
As containing sulfonyl example, can specifically enumerate：It is methyl sulphonyl, ethylsulfonyl, n-propyl sulfonyl, different Sulfonyl propyl base, normal-butyl sulfonyl, iso-butylsulfonyl, tert. butylsulfonyl, n-pentyl sulfonyl, isopentyl sulfonyl, Neopentyl sulfonyl, 2,3- dimethyl propyls sulfonyl, 1- ethyl propyls sulfonyl, n-hexyl sulfonyl, Cyclopentylsulfonyl, Cyclohexylsulfonyl, suberyl sulfonyl, cyclooctyl sulfonyl, n-heptyl sulfonyl, n-octyl sulfonyl, suberyl sulphonyl Base, cyclooctyl sulfonyl, acrylic sulfonyl, cyclobutenyl sulfonyl, pentenyl sulfonyl, hexenyl sulfonyl, heptenyl sulphur Acyl group, octenyl sulfonyl, phenyl sulfonyl, 4- Methyl benzenesulfonyl bases.In addition it containing sulfonic example, can specifically enumerate： Sulfonomethyl, 2- sulfonic groups ethyl, 3- sulfonic groups n-propyl, 4- sulfonic groups normal-butyl, sulfonic group tertiary butyl, 2- sulfonic groups are just Amyl, 3- sulfonic groups isopentyl, 6- sulfonic groups n-hexyl, 2- sulfonic acid cyclopentyl, 4- sulfonic acid butylcyclohexyl, sulfonic group propylene Base, sulfonic group cyclobutenyl, sulfonic group pentenyl, sulfonic group hexenyl, sulfonic group heptenyl, sulfonic group octenyl, sulfonic benzo Base, 4- sulfonic acid methyl phenyl.
In addition, in above-mentioned Formulas I~Formula VII compound represented, R11、R12、R13、R14、R15At least one of be halogen Atom, preferably F or Cl, R21、R22、R23、R24At least one of be halogen atom, preferably F or Cl, R31、R32、R33、R34In It is at least one be halogen atom, preferably F or Cl, R41、R42、R43、R44At least one of for halogen atom, preferably F or Cl, R51、R52、R53、R54At least one of be halogen atom, preferably F or Cl, R61、R62、R63At least one of for halogen atom, it is excellent It is selected as F or Cl, R71、R72、R73At least one of be halogen atom, preferably F or Cl.
It is specific as follows shown as the example of nitrogen heterocyclic ring-boron trifluoride complex：
In this application, the nitrogen heterocyclic ring being previously mentioned-boron trifluoride complex can be according to existing conventional synthesis Method is synthesized, such as can refer to document：CN200780033378.X.
It has been investigated that when electrolyte includes nitrogen heterocyclic ring mentioned above-boron trifluoride complex, inhibit Electrolyte effectively reduces corrosion of the acidic materials generated in electrolyte to solid electrolyte plasma membrane in the decomposition of electrode surface, The storage performance under the cycle performance and high temperature of lithium ion battery at high temperature can be improved, such as lithium ion battery is at 45 DEG C There is down and under 4.4V high pressures excellent cycle performance, there is excellent storage performance at 85 DEG C.
In above-mentioned electrolyte, the content of the nitrogen heterocyclic ring-boron trifluoride complex is the total weight of electrolyte 0.05%~10%, the content of the nitrogen heterocyclic ring-boron trifluoride complex is preferably the total weight of electrolyte 0.1%~4%.
It, can be in positive and negative plate surface shape if the content of nitrogen heterocyclic ring-boron trifluoride complex is excessive in electrolyte Into thicker and fine and close passivating film, the conductive performance of lithium ion is reduced, so as to deteriorate the cycle of lithium ion battery at high temperature Performance.
In above-mentioned electrolyte, the organic solvent can be non-aqueous organic solvent, and the organic solvent is selected from carbonic ester At least one of compound and carboxylate compound, wherein, carbonate products can be linear carbonate or cyclic annular carbon Acid esters.
As the example of organic solvent, can enumerate：Ethylene carbonate, propene carbonate, butylene, fluoro carbonic acid second Enester, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, Isosorbide-5-Nitrae-fourth Lactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl butyrate.
In above-mentioned electrolyte, the lithium salts can be organic lithium salt or inorganic lithium salt, specifically, the lithium salts In can contain fluorine element, boron element, at least one of P elements.Preferably, the lithium salts is selected from lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), tetrafluoro oxalic acid lithium phosphate (LiTFOP)、LiN(SO2RF)2、LiN(SO2F)(SO2RF), double trifluoromethanesulfonimide lithium LiN (CF3SO2)2It (is abbreviated as LiTFSI), bis- (fluorine sulphonyl) imine lithium Li (N (SO2F)2) (being abbreviated as LiFSI), di-oxalate lithium borate LiB (C2O4)2It (is abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF2(C2O4At least one of) (being abbreviated as LiDFOB), wherein, substituent RF=- CnF2n+1Saturation perfluoroalkyl, n be 1~10 integer, preferably 1~4 integer, and 2n+1 be more than zero integer.It is especially excellent It is selected as LiPF6And/or LiN (SO2RF)2.A concentration of 0.5M~2M (the M=mol L of the lithium salts in the electrolytic solution-1)。
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.
The another object of the application is the provision of lithium ion battery, and the lithium ion battery includes electrolyte, containing just The positive plate of pole active material, negative plate and isolation film containing negative electrode active material.
In above-mentioned lithium ion battery, the positive plate further includes binding agent and conductive agent, will include positive-active material The anode sizing agent of material, binding agent and conductive agent is coated on plus plate current-collecting body, and positive plate is obtained after anode sizing agent drying.Equally , the negative electrode slurry for including negative electrode active material, binding agent and conductive agent is coated on negative current collector, treats negative electrode slurry Negative plate is obtained after drying.
Preferably, the positive electrode active materials are selected from cobalt acid lithium LiCoO2, cobalt nickel lithium manganate ternary material, ferrous phosphate Lithium, LiFePO4 (LiFePO4), LiMn2O4 (LiMnO2At least one of), such as cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material Mixture can be used as positive electrode active materials.As the example of cobalt nickel lithium manganate ternary material, can specifically enumerate：LiNi1/3Co1/ 3Mn1/3O2, nickle cobalt lithium manganate LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2。
Preferably, the negative electrode active material is graphite and/or silicon materials.
In above-mentioned lithium ion battery, the specific type of lithium battery diaphragm is not exposed to specific limitation, can be existing Any diaphragm material used in lithium ion battery, such as polyethylene, polypropylene, Kynoar and their MULTILAYER COMPOSITE Film, but it is not limited only to these.
Embodiment
The application is further described below by way of specific example.But these examples are only exemplary, not to this The protection domain of application forms any restrictions.
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, wherein involved 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：
Nitrogen heterocyclic ring-boron trifluoride complex：1~the compound of compound 7 being previously mentioned.
Lithium salts：Lithium hexafluoro phosphate (LiPF6)。
Organic solvent：Ethylene carbonate (EC), methyl ethyl carbonate (EMC).
Positive electrode active materials：Lithium-nickel-manganese-cobalt ternary material (LiNi1/3Co1/3Mn1/3O2)。
Isolation film：Using PE porous polymer films as isolation film.
The preparation of 0 lithium ion battery of Examples 1 to 3 (following abbreviation batteries) 1~30
Battery 1~30 is prepared by the following method：
(1) prepared by negative plate
Negative electrode active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber, thickener sodium carboxymethylcellulose are pressed It is graphite: acetylene black: butadiene-styrene rubber: sodium carboxymethylcellulose=95: mixed at 2: 2: 1 according to weight ratio, adds in deionized water Afterwards, it is thoroughly mixed, forms uniform negative electrode slurry；This slurry is coated on negative current collector copper foil, then dries, is cold Pressure, obtains negative plate.
(2) prepared by positive plate
By positive electrode active materials lithium-nickel-manganese-cobalt ternary material, conductive agent acetylene black, binding agent polyvinylidene fluoride by weight Than for lithium-nickel-manganese-cobalt ternary material: acetylene black: polyvinylidene fluoride=96: mixed at 2: 2 add in Solvents N-methyl pyrrolidines Ketone after being thoroughly mixed, forms uniform anode sizing agent；This slurry is coated on plus plate current-collecting body aluminium foil, then dry, Cold pressing, obtains positive plate.
(3) prepared by electrolyte
Electrolyte 1~30 is prepared by the following method：
In the argon gas atmosphere glove box of water content ＜ 10ppm, EC, EMC are carried out according to weight ratio for EC: EMC=3: 7 After mixing, mixed solvent, then the lithium salts LiPF that will fully dry are obtained6Above-mentioned in the mixed solvent is dissolved in, is then added thereto Enter nitrogen heterocyclic ring-boron trifluoride complex, after stirring evenly, obtain electrolyte, wherein LiPF6A concentration of 1mol/L.
(4) preparation of battery
Battery 1~30 is prepared by the following method：
Positive plate, isolation film, negative plate are folded in order, isolation film is made to be between positive/negative plate the work for playing isolation With then winding obtains naked battery core；Naked battery core is placed in outer packing foil, after the above-mentioned electrolyte prepared is injected into drying Battery in, then by processes such as Vacuum Package, standing, chemical conversion, shapings, obtain battery.
It is above-mentioned prepare battery during, it is used in selected electrolyte, each electrolyte in each battery The type and its content of nitrogen heterocyclic ring-boron trifluoride complex, as shown in table 1 below.
In table 1 below, the content of nitrogen heterocyclic ring-boron trifluoride complex is calculated for the total weight based on electrolyte Obtained weight percent.
Table 1
1~9 lithium ion battery of comparative example (following abbreviation batteries) 1#~9#Preparation
Comparative example 1~9
Battery 1#~9#Prepared by the following method：
The preparation of battery 1 in embodiment 1 is repeated, wherein in the preparation of electrolyte, changes nitrogen heterocyclic ring-boron trifluoride and matches The type and/or content of position compound, remaining condition are constant.
It is above-mentioned prepare battery during, it is used in selected electrolyte, each electrolyte in each battery The type and its content of nitrogen heterocyclic ring-boron trifluoride complex, as shown in table 2 below.
In table 2 below, the content of nitrogen heterocyclic ring-boron trifluoride complex is calculated for the total weight based on electrolyte Obtained weight percent.
Table 2
Note：In table 2, "-" expression is not added with any kind of substance.
Test case
(1) the high-temperature storage performance test of battery
With the high-temperature storage performance of the volume change characterization battery before and after battery storage.
The battery being prepared in embodiment and comparative example carries out following tests：
At 25 DEG C, 4.4V first charges to battery with the constant current of 0.5C, further with 4.4V constant-potential charges It is 0.025C to electric current, then battery is measured to the initial volume of battery in deionized water with drainage, by the initial of battery Then battery is placed at 85 DEG C as the volume before battery storage and stores 6h, after to be stored, test battery is in height by volume Then the volume change of battery is calculated in volume after gentle storage by following formula.In addition, institute in test result is as follows table 4 Show.
The volume change (%) of battery=[volume before volume/battery storage after battery high-temperature storage] × 100%
(2) the high temperature cyclic performance test of battery
The battery being prepared in embodiment and comparative example carries out following tests：
At 45 DEG C, 4.4V is first charged to lithium rechargeable battery with the constant current of 1C, it is further constant with 4.4V Voltage charges to electric current as 0.025C, and then with the constant current of 1C by battery discharge to 3.0V, this is a charge and discharge cycles Process, this discharge capacity are the discharge capacity of the 1st cycle.Battery carries out multiple cycle charge discharge electrical measurement in a manner described Examination, detection obtains the discharge capacity of the 100th cycle, and passes through the capacity retention ratio that following formula is calculated after the cycle of battery. In addition, test result is as follows shown in table 3.
Capacity retention ratio (%) after the cycle of battery 100 times=[discharge capacity/1st time cycle of the 100th cycle is put Capacitance] × 100%
Table 3
Related data from above-mentioned table 3, is analyzed as follows：
(1) test result analysis of high-temperature storage performance
Volume change and battery 1 as obtained by by battery 1~8#~3#The volume change comparison of gained, can obtain Go out：Contain nitrogen heterocyclic ring-boron trifluoride complex in the electrolyte provided due to the application so that battery has preferable High temperature cyclic performance and high-temperature storage performance；In addition, by battery 3#Test result comparison with 1~8 gained of battery is it is found that work as When the content of nitrogen heterocyclic ring-boron trifluoride complex is more than 10%, the cycle performance of battery deteriorates and by battery 2#It is compared with the test result of 1~8 gained of battery it is found that when the content of nitrogen heterocyclic ring-boron trifluoride complex is less than When 0.05%, the raising of the high-temperature storage performance of battery is not obvious.
Similarly, test result and battery 1 as obtained by by battery 9~30#The comparison of the test result of gained can obtain Know：When in electrolyte contain nitrogen heterocyclic ring-boron trifluoride complex when, battery have preferable high temperature cyclic performance and High-temperature storage performance.
It can be seen that electrolyte provided herein, since good solid electrolytic can be formed on positive and negative electrode surface Matter interfacial film reduces the reactivity on positive and negative electrode surface, and electrolyte is inhibited to carry out redox reaction on positive and negative electrode surface；Together When the application provide electrolyte generate sour gas greatly reduce, improve the high-temperature storage performance of battery under high voltages And high temperature cyclic performance.
The announcement of book according to the above description, the application those skilled in the art can also carry out the above embodiment Appropriate change and modification.Therefore, the application is not limited to specific embodiment disclosed and described above, to the application's Some modifications and changes should also be as falling into the protection domain of claims hereof.

Claims (10)

1. a kind of electrolyte, which is characterized in that including organic solvent, lithium salts and additive, the additive include nitrogen heterocyclic ring- Boron trifluoride complex, wherein, the nitrogen heterocyclic ring-boron trifluoride complex is selected from shown in compound 1, formula IV Compound, the heterocycle containing pyrimidine radicals-boron trifluoride complex, contains the heterocycle containing pyridazinyl-boron trifluoride complex The heterocycle of pyrrole radicals-boron trifluoride complex, heterocycle-boron trifluoride complex of pyrazolyl containing, containing imidazole radicals At least one of heterocycle-boron trifluoride complex：
Wherein, R41、R42、R43、R44It is each independently selected from hydrogen atom, halogen atom, cyano, sulfonic group, sulfonyl, carbon atom It is 1~20 to count aryl, carbon atom number that the alkyl for 1~20, the alkenyl that carbon atom number is 2~20, carbon atom number are 6~26 Alkyl that the aryloxy group and above-mentioned carbon atom number that alkoxy, carbon atom number are 6~26 are 1~20, carbon atom number are 2~20 Alkenyl, carbon atom number be 6~26 aryl, carbon atom number be 1~20 alkoxy, carbon atom number be 6~26 aryloxy group Replaced one kind in formed group, halogen atom F, Cl, Br, and R by halogen atom, sulfonic group or sulfonyl41、R42、R43、 R44At least one of be halogen atom.
2. electrolyte according to claim 1, which is characterized in that the nitrogen heterocyclic ring-boron trifluoride complex is Selected from least one of following formula II, formula III, VII compound represented of formula V, formula VI and formula：
Wherein, R21、R22、R23、R24、R31、R32、R33、R34、R51、R52、R53、R54、R61、R62、R63、R71、R72、R73It is respectively independent Ground be selected from hydrogen atom, halogen atom, cyano, sulfonic group, sulfonyl, carbon atom number be 1~20 alkyl, carbon atom number be 2~ The fragrant oxygen that alkoxy that aryl that 20 alkenyl, carbon atom number are 6~26, carbon atom number are 1~20, carbon atom number are 6~26 Aryl that alkenyl that alkyl that base and above-mentioned carbon atom number are 1~20, carbon atom number are 2~20, carbon atom number are 6~26, The aryloxy group that alkoxy that carbon atom number is 1~20, carbon atom number are 6~26 replaces institute by halogen atom, sulfonic group or sulfonyl One kind in the group of formation, wherein, halogen atom F, Cl, Br.
3. electrolyte according to claim 2, which is characterized in that R21、R22、R23、R24At least one of for halogen atom, R31、R32、R33、R34At least one of for halogen atom, R51、R52、R53、R54At least one of for halogen atom, R61、R62、R63 At least one of for halogen atom, R71、R72、R73At least one of be halogen atom.
4. electrolyte according to claim 2, which is characterized in that R21、R22、R23、R24、R31、R32、R33、R34、R41、R42、 R43、R44、R51、R52、R53、R54、R61、R62、R63、R71、R72、R73It is each independently selected from F, the chain that carbon atom number is 1~4 Aryl that alkenyl that cycloalkyl that alkyl, carbon atom number are 5~7, carbon atom number are 2~5, carbon atom number are 6~9, carbon atom Count the halogenated chain-like alkyl, carbon atom number that the alkoxy for 1~4, the aryloxy group that carbon atom is 6~10, carbon atom number are 1~4 Halogenated aryl that halogenated alkenyl that halogenated cycloalkyl, carbon atom number for 5~7 are 2~5, carbon atom are 6~10, carbon atom number One kind in the haloaryloxy that halogenated alkoxy, carbon atom for 1~4 are 6~10.
5. electrolyte according to claim 1, which is characterized in that the nitrogen heterocyclic ring-boron trifluoride complex is Selected from least one of following compounds：
6. electrolyte according to claim 1, which is characterized in that the nitrogen heterocyclic ring-boron trifluoride complex Content is the 0.05%~10% of the total weight of electrolyte.
7. electrolyte according to claim 1, which is characterized in that the organic solvent is selected from ethylene carbonate, carbonic acid Acrylic ester, butylene, fluorinated ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, Methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate and butyric acid At least one of ethyl ester.
8. electrolyte according to claim 1, which is characterized in that
The lithium salts be selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro oxalic acid lithium phosphate, LiN(SO2RF)2、LiN(SO2F)(SO2RF), double trifluoromethanesulfonimide lithiums, bis- (fluorine sulphonyl) imine lithiums, double oxalic acid boric acid At least one of lithium, difluorine oxalic acid boracic acid lithium, wherein, RF=-CnF2n+1, n is 1~10 integer, and the lithium salts is in electrolyte In a concentration of 0.5mol L-1~2mol L-1。
9. a kind of lithium ion battery, which is characterized in that including the positive plate containing positive electrode active materials, contain negative electrode active material Any one of negative plate, isolation film and claim 1 ~ 8 described in electrolyte.
10. lithium ion battery according to claim 9, which is characterized in that
The positive electrode active materials are selected from cobalt acid lithium, cobalt nickel lithium manganate ternary material, LiFePO 4, LiFePO4 and mangaic acid At least one of lithium,
The negative electrode active material is graphite and/or silicon materials.
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