CN106450453A - Lithium ion battery electrolyte and lithium ion battery containing same - Google Patents
Lithium ion battery electrolyte and lithium ion battery containing same Download PDFInfo
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- CN106450453A CN106450453A CN201610903121.6A CN201610903121A CN106450453A CN 106450453 A CN106450453 A CN 106450453A CN 201610903121 A CN201610903121 A CN 201610903121A CN 106450453 A CN106450453 A CN 106450453A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- 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 invention belongs to the technical field of lithium ion battery materials, and discloses a lithium ion battery electrolyte and a lithium ion battery containing the electrolyte. The electrolyte comprises organic solvents, conductive lithium salts, additives and phenylpyridine compounds. According to the invention, a solid electrolyte protective film formed by the phenylpyridine compounds can inhibit decomposition of the electrolyte, reduce the battery impedance, and slow down the battery gas expansion speed under the condition of high temperature and high pressure, and further can inhibit the dissolution of transition metals, prevent the transition metals from being embedded into cathodes and protect battery anode and cathode materials to greatly improve cycle performances and safety performances of electrodes.
Description
Technical field
The invention belongs to lithium ion battery material technical field and in particular to a kind of lithium-ion battery electrolytes and containing should
The lithium ion battery of electrolyte.
Background technology
In recent years, the lithium rechargeable battery with high-energy-density has obtained sufficient development and application.Can with other
Rechargeable battery is compared, and lithium rechargeable battery has that energy density is big, running voltage is high, have extended cycle life, self discharge is low, green
The advantages of environmental protection.Lithium rechargeable battery is in the portable 3C electronic equipment such as mobile phone, notebook computer and big multiplying power power at present
Battery aspect has preferable application prospect.
As the critical material of lithium secondary battery nonaqueous electrolytic solution be rise between battery positive and negative electrode conduction from
Sub- conductor, itself affects the performance of battery to a great extent.Because lithium ion battery charge and discharge potential is high, and positive pole is embedded with
The lithium of larger activity, therefore electrolyte must is fulfilled for chemical stability height, wider range, safety non-toxic, ionic conductivity
The condition such as high, inert to both positive and negative polarity.At present, by carrying out continuing in depth to study to new lithium salts and solvent it is proposed that being permitted
The method improving cycle performance of battery and security performance, forms solid-state protecting film by additive on positive pole and negative terminal surface more
It is a kind of cost-effective approach.
At present, commercialization lithium rechargeable battery electrolyte is mainly with linear carbonate such as dimethyl carbonate, carbonic acid two
The mixed solvent of ethyl ester and Ethyl methyl carbonate etc. and cyclic carbonate such as ethylene carbonate and Allyl carbonate is solvent, with
LiPF6For conducting salt composition.And electrolyte, in the decomposition of battery plus-negative plate, produces gas, the intrinsic pressure rising of battery can be made, internal
Accumulated heat and loss of stability, especially under high temperature high voltage, will have a strong impact on cycle life and the safety of battery.With market
The raising requiring, lifting performance of lithium ion battery is increasingly urgent, and improving capacity and the key of safety is to solve commercialization electricity
The problem that solution liquid exists, substantial amounts of catabolite can make battery impedance and irreversible capacity increase；The gas producing reduces battery
Safety；The dissolution of positive pole transition metal makes battery plus-negative plate material degradation, reduces battery capacity and cycle life.And pass through to add
Plus agent premature oxidation/reduction forms the well solid electrolyte interface film of densification, the decomposition of electrolyte can be alleviated, thus subtracting
Lack the irreversible capacity of battery and improve its cycle performance.
Content of the invention
In place of solving the shortcoming and defect of above prior art, the primary and foremost purpose of the present invention be to provide a kind of lithium from
Sub- battery electrolyte.
Another object of the present invention is to providing a kind of lithium ion battery containing above-mentioned electrolyte.
The object of the invention is achieved through the following technical solutions：
A kind of lithium-ion battery electrolytes, by organic solvent, electric conducting lithium salt, additive and phenylpyridine class compound structure
Become, described phenylpyridine class compound has the general structure shown in formula (I), (II) or (III)；
In formula, R1, R2, R3, R4, R5 are each independently selected from hydrogen atom, fluorine atom, cyano group, carbon number are 2～15
Alkyl, carbon number are any one in 2～15 fluoro-alkyl.
Preferably, described phenylpyridine class compound is 2- phenylpyridine (a), 2- (4- aminomethyl phenyl) pyridine (b), 2-
(2,4 difluorobenzene base) pyridine (c), 3- phenylpyridine (d), 3- (4- fluorophenyl) pyridine (e), 4- (3- pyridine radicals) cyanophenyl (f),
4- phenylpyridine (g), 4- (4- fluorophenyl) pyridine (h), 4- (3- (trifluoromethyl) phenyl) pyridine (i).Tool counter structure formula is such as
Under：
Preferably, the addition of described phenylpyridine class compound accounts for the 0.1%～5.0% of electrolyte gross mass.
Preferably, described organic solvent refers to cyclic carbonate solvents:The mass ratio of linear carbonate solvent is 1:(1～
3) mixed solvent.
Preferably, described cyclic carbonate solvents are the mixed of one of ethylene carbonate and Allyl carbonate or two kinds
Close；Described linear carbonate solvent is dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), carbonic acid first
One of propyl ester (MPC), ethyl acetate (EA), ethyl propionate (EP) or two or more mixing.
Preferably, described electric conducting lithium salt includes lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), dioxalic acid boric acid
Lithium (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), perfluoro butyl Sulfonic Lithium (LiC4F9SO3), trifluoromethyl sulfonic acid lithium
(LiCF3SO3), double (fluorine sulphonyl) imine lithium (LiFSI), at least one in double trifluoromethanesulfonimide lithium (LiTFSI).
Described electric conducting lithium salt concentration in organic solvent is 0.8～1.5mol/L.
Preferably, described additive is vinylene carbonate, vinylethylene carbonate, fluorinated ethylene carbonate, 1,3- third
At least one in sultone, adiponitrile, succinonitrile, the addition of described additive accounts for the 0.1% of electrolyte gross mass
～5.0%.
A kind of lithium ion battery containing above-mentioned electrolyte, including anode pole piece, cathode pole piece, be placed in both positive and negative polarity pole piece it
Between barrier film and described electrolyte；Described anode pole piece includes plus plate current-collecting body and the cathode film being coated on plus plate current-collecting body
Piece, described cathode pole piece includes negative current collector and the cathode membrane being coated on negative current collector.
Described positive pole diaphragm includes positive electrode active materials, conductive agent and binding agent, and described cathode membrane includes negative electrode active
Material, conductive agent and binding agent.
Preferably, described positive electrode active materials are selected from the transition metal oxide of lithium, wherein, the oxo transition metal of described lithium
Compound is LiCoO2、LiMn2O4、LiMnO2、Li2MnO4、LiFePO4、Li1+aMn1-xMxO2、LiCo1-xMxO2、LiFe1-xMxPO4、
Li2Mn1-xO4, wherein, M is 0≤a selected from one or more of Ni, Co, Mn, Al, Cr, Mg, Zr, Mo, V, Ti, B, F<0.2,
0≤x<1.
Preferably, at least one in graphite, Si-C composite material, lithium titanate for the described negative active core-shell material.
With respect to prior art, the invention has the advantages that and beneficial effect：
The phenylpyridine class compound of the present invention, the solid electrolyte protecting film of formation can suppress electrolyte decomposition, reduces
Battery impedance, slows down battery flatulence speed in the case of High Temperature High Pressure；The dissolution of transition metal can be suppressed simultaneously, prevent transition metal
Excessive embedded negative pole, it is to avoid because solvent molecule embeds altogether, electrode material is damaged, substantially increase the cycle performance of electrode
And safety.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester and diethyl carbonate are with 1:2 quality than mix homogeneously and is stirred continuously, and is slowly added to 1.0mol/L's in mixed solvent
Lithium hexafluoro phosphate, adds the vinylene carbonate that mass fraction is 2.0%, 1.0% succinonitrile, 1.0% 2- phenyl pyrazoline
Pyridine, stirs the electrolyte obtaining the present embodiment to being completely dissolved.
(2) preparation of lithium ion battery：
With LiCoO2It is negative active core-shell material for positive electrode active materials, graphite, add conductive agent, binding agent and solvent abundant
After being uniformly mixed, be coated in drying on aluminium foil, roll-in, cut after respectively be obtained positive and negative electrode pole piece.By both positive and negative polarity pole piece with
Polypropylene diaphragm is wound into rectangular lithium ion battery.It is transferred to glove box fluid injection after 85 DEG C of bakings in 48 hours, be aged after sealing,
Lithium ion battery is obtained after chemical conversion, partial volume.The performance test results of gained lithium ion battery are shown in Table 1.
Embodiment 2
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester and diethyl carbonate are with 1:3 quality than mix homogeneously and is stirred continuously, and is slowly added to 1.2mol/L's in mixed solvent
Lithium hexafluoro phosphate, add the fluorinated ethylene carbonate that mass fraction is 3.0%, 0.5% vinylethylene carbonate, 2.0%
2- (4- aminomethyl phenyl) pyridine, stir the electrolyte obtaining the present embodiment to being completely dissolved.
(2) preparation of lithium ion battery
With LiNi0.8Co0.15Al0.05O2It is negative active core-shell material for positive electrode active materials, graphite, add conductive agent, bonding
After agent and solvent are thoroughly mixed uniformly, be coated in dryings on aluminium foil, roll-in, cut after prepared positive and negative electrode pole piece respectively.Will
Both positive and negative polarity pole piece and polypropylene diaphragm are wound into rectangular lithium ion battery.It is transferred to glove box note after 85 DEG C of bakings in 48 hours
Liquid, ageing, chemical conversion after sealing, obtains lithium ion battery after partial volume.The performance test results of gained lithium ion battery are shown in Table 1.
Embodiment 3
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester and Ethyl methyl carbonate are with 1:1 quality than mix homogeneously and is stirred continuously, and is slowly added to 1.0mol/L's in mixed solvent
Lithium hexafluoro phosphate, add 1, the 3- propane sultone that mass fraction is 1.5%, 2.0% vinylethylene carbonate,
3.0% 2- (2,4 difluorobenzene base) pyridine, stirs the electrolyte obtaining the present embodiment to being completely dissolved.
(2) preparation of lithium ion battery
With LiNi0.5Mn0.3Co0.2O2It is negative active core-shell material for positive electrode active materials, graphite, add conductive agent, binding agent
Be thoroughly mixed after uniformly with solvent, be coated in dryings on aluminium foil, roll-in, cut after prepared positive and negative electrode pole piece respectively.Will just
Cathode pole piece and polypropylene diaphragm are wound into rectangular lithium ion battery.It is transferred to glove box fluid injection after 85 DEG C of bakings in 48 hours,
Ageing, chemical conversion after sealing, obtain lithium ion battery after partial volume.The performance test results of gained lithium ion battery are shown in Table 1.
Embodiment 4
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester and Ethyl methyl carbonate are with 1:2 quality than mix homogeneously and is stirred continuously, and is slowly added to the six of 1mol/L in mixed solvent
Lithium fluophosphate, add 1, the 3- propane sultone that mass fraction is 1.5%, 3.0% fluorinated ethylene carbonate, 0.5%
3- phenylpyridine, stir the electrolyte obtaining the present embodiment to being completely dissolved.
(2) preparation of lithium ion battery
With LiNi0.6Mn0.2Co0.2O2It is negative active core-shell material for positive electrode active materials, graphite, add conductive agent, binding agent
Be thoroughly mixed after uniformly with solvent, be coated in dryings on aluminium foil, roll-in, cut after prepared positive and negative electrode pole piece respectively.Will just
Cathode pole piece and polypropylene diaphragm are wound into rectangular lithium ion battery.It is transferred to glove box fluid injection after 85 DEG C of bakings in 48 hours,
Ageing, chemical conversion after sealing, obtain lithium ion battery after partial volume.The performance test results of gained lithium ion battery are shown in Table 1.
Embodiment 5
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester, diethyl carbonate, Ethyl methyl carbonate are with 1:1:1 quality than mix homogeneously and is stirred continuously, and slowly adds in mixed solvent
Enter the lithium hexafluoro phosphate of 0.9mol/L, add 1, the 3- propane sultone that mass fraction is 2.0%, 2.0% fluoro carbon
Vinyl acetate, 1.5% 3- (4- fluorophenyl) pyridine, stir the electrolyte obtaining the present embodiment to being completely dissolved.
(2) preparation of lithium ion battery is with embodiment 3.The performance test results of gained lithium ion battery are shown in Table 1.
Embodiment 6
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester, diethyl carbonate, Ethyl methyl carbonate are with 1:1:2 quality than mix homogeneously and is stirred continuously, and slowly adds in mixed solvent
Enter the lithium hexafluoro phosphate of 1.4mol/L, add mass fraction be 3.0% fluorinated ethylene carbonate, 1.0% ethylene carbonate sub-
Ethyl ester, 4.5% 4- (3- pyridine radicals) cyanophenyl, stir the electrolyte obtaining the present embodiment to being completely dissolved.
(2) preparation of lithium ion battery
With LiNi0.8Mn0.1Co0.1O2It is negative active core-shell material for positive electrode active materials, graphite, add conductive agent, binding agent
Be thoroughly mixed after uniformly with solvent, be coated in dryings on aluminium foil, roll-in, cut after prepared positive and negative electrode pole piece respectively.Will just
Cathode pole piece and polypropylene diaphragm are wound into rectangular lithium ion battery.It is transferred to glove box fluid injection after 85 DEG C of bakings in 48 hours,
Ageing, chemical conversion after sealing, obtain lithium ion battery after partial volume.The performance test results of gained lithium ion battery are shown in Table 1.
Embodiment 7
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester, Allyl carbonate, diethyl carbonate are with 4:1:5 quality than mix homogeneously and is stirred continuously, and slowly adds in mixed solvent
Enter the lithium hexafluoro phosphate of 0.9mol/L, add the fluorinated ethylene carbonate that mass fraction is 2.0,2.0% ethylene carbonate Asia
Ethyl ester, 0.5% 4- phenylpyridine, stir the electrolyte obtaining the present embodiment to being completely dissolved.
(2) preparation of lithium ion battery is with embodiment 3.The performance test results of gained lithium ion battery are shown in Table 1.
Embodiment 8
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester, Allyl carbonate, diethyl carbonate are with 4:1:10 quality than mix homogeneously and is stirred continuously, and slowly adds in mixed solvent
Enter the lithium hexafluoro phosphate of 1mol/L, add the fluorinated ethylene carbonate that mass fraction is 3.0%, 1.0% ethylene carbonate Asia
Ethyl ester, 1.0% 1,3- propane sultone, 2.0% 4- (4- fluorophenyl) pyridine, stir to being completely dissolved, that is, obtain this
The electrolyte of embodiment.
(2) preparation of lithium ion battery is with embodiment 2.The performance test results of gained lithium ion battery are shown in Table 1.
Embodiment 9
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester, Allyl carbonate, carbonic acid first diethylester, dimethyl carbonate are with 4:1:5:2 quality than mix homogeneously and is stirred continuously, to mixed
Be slowly added to the lithium hexafluoro phosphate of 1.2mol/L in bonding solvent, add mass fraction be 2.0% fluorinated ethylene carbonate,
1.0% vinylene carbonate, 1.0% dintrile, 4.5% 4- [3- (trifluoromethyl) phenyl] pyridine, stir to being completely dissolved,
Obtain the electrolyte of the present embodiment.
(2) preparation of lithium ion battery is with embodiment 1.The performance test results of gained lithium ion battery are shown in Table 1.
Embodiment 10
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester, diethyl carbonate, dimethyl carbonate are with 1:2:1 quality than mix homogeneously and is stirred continuously, and slowly adds in mixed solvent
Enter the lithium hexafluoro phosphate of 1.2mol/L, add the fluorinated ethylene carbonate that mass fraction is 2.0%, 1.0% carbonic acid Asia second
Alkene ester, 1.0% 1,3- propane sultone, 1% 4- (4- pyridine radicals) cyanophenyl, stir to being completely dissolved, that is, obtain this reality
Apply the electrolyte of example.
(2) with LiNi0.6Mn0.2Co0.2O2It is negative active core-shell material for positive electrode active materials, Si-C composite material, addition is led
Electric agent, binding agent and solvent are thoroughly mixed after uniformly, be coated in dryings on aluminium foil, roll-in, cut after prepared positive and negative respectively
Pole pole piece.Both positive and negative polarity pole piece and polypropylene diaphragm are wound into rectangular lithium ion battery.It is transferred to after 85 DEG C of bakings in 48 hours
Glove box fluid injection, ageing, chemical conversion after sealing, obtains lithium ion battery after partial volume.The performance test results of gained lithium ion battery
It is shown in Table 1.
Embodiment 11
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester, Ethyl methyl carbonate, dimethyl carbonate are with 1:2：1 quality than mix homogeneously and is stirred continuously, and slowly adds in mixed solvent
Enter the lithium hexafluoro phosphate of 1.2mol/L, add 1, the 3- propane sultone that mass fraction is 1.0%, 1.0% carbonic acid Asia
Vinyl acetate, 1.0% vinylethylene carbonate, 2.0% 4- [3- fluoro- 5- (trifluoromethyl) phenyl] pyridine, stir to complete
Dissolving, that is, obtain the electrolyte of the present embodiment.
(2) with LiNi0.5Mn0.3Co0.2O2It is negative active core-shell material for positive electrode active materials, Si-C composite material, addition is led
Electric agent, binding agent and solvent are thoroughly mixed after uniformly, be coated in dryings on aluminium foil, roll-in, cut after prepared positive and negative respectively
Pole pole piece.Both positive and negative polarity pole piece and polypropylene diaphragm are wound into rectangular lithium ion battery.It is transferred to after 85 DEG C of bakings in 48 hours
Glove box fluid injection, ageing, chemical conversion after sealing, obtains lithium ion battery after partial volume.The performance test results of gained lithium ion battery
It is shown in Table 1.
Comparative example 1
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester and diethyl carbonate are with 1:2 quality than mix homogeneously and is stirred continuously, and is slowly added to 1.0mol/L's in mixed solvent
Lithium hexafluoro phosphate, adds the vinylene carbonate that mass fraction is 2%, 1% succinonitrile, stirs to being completely dissolved, obtain final product
Electrolyte to this comparative example.
(2) preparation of lithium ion battery is with embodiment 1.The performance test results of gained lithium ion battery are shown in Table 1.
Comparative example 2
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester and diethyl carbonate are with 1:3 quality than mix homogeneously and is stirred continuously, and is slowly added to 1.2mol/L's in mixed solvent
Lithium hexafluoro phosphate, adds the fluorinated ethylene carbonate that mass fraction is 3.0%, 0.5% vinylethylene carbonate, stir to
It is completely dissolved, that is, obtain the electrolyte of this comparative example.
(2) preparation of lithium ion battery is with embodiment 2.The performance test results of gained lithium ion battery are shown in Table 1.
Comparative example 3
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester and Ethyl methyl carbonate are with 1:1 quality than mix homogeneously and is stirred continuously, and is slowly added to 1.0mol/L's in mixed solvent
Lithium hexafluoro phosphate, adds 1, the 3- propane sultone that mass fraction is 1.5%, 2.0% vinylethylene carbonate, stirring
To being completely dissolved, that is, obtain the electrolyte of this comparative example.
(2) preparation of lithium ion battery is with embodiment 3.The performance test results of gained lithium ion battery are shown in Table 1.
Comparative example 4
(1) preparation of electrolyte
In in the glove box full of argon (moisture ＜ 0.1ppm, oxygen content ＜ 0.1ppm), by ethylene carbonate
Ester and Ethyl methyl carbonate are with 1:2 quality than mix homogeneously and is stirred continuously, and is slowly added to the six of 1mol/L in mixed solvent
Lithium fluophosphate, adds 1, the 3- propane sultone that mass fraction is 1.5%, 3.0% fluorinated ethylene carbonate, stir to
It is completely dissolved, that is, obtain the electrolyte of this comparative example.
(2) preparation of lithium ion battery is with embodiment 4.The performance test results of gained lithium ion battery are shown in Table 1.
Test experiments
All comparative examples 1～4 and all embodiments 1～11 gained battery are tested as follows：
Circulation experiment：By comparative example 1～4 and embodiment 1～11 gained battery respectively in 25 DEG C of room temperature and 55 DEG C of high temperature
Under charge and discharge cycles test is carried out in the range of 3.0～4.2V with the charge-discharge magnification of 0.5C/0.5C, respectively record the 300th time
With the 200th cyclic discharge capacity and divided by circulate for the 1st time discharge capacity obtains final product capability retention, record result such as table 1.
High temperature storage is tested：By first for the battery of comparative example 1～4 and embodiment 1～11 filling with 0.5C/0.5C at room temperature
Discharge-rate charges to 4.2V, the thickness of record battery in 3.0～4.25V discharge and recharge 3 times, then with 0.5C.Battery is placed on
Store 15 days in 60 DEG C of baking ovens, the thickness of record battery.The thickness of second record battery is divided by the thickness of first record battery
Degree is cell expansion rate.Result record such as table 1.
Table 1
Correction data understands, adding phenylpyridine class compound in lithium-ion battery electrolytes can make battery obtain more
Normal temperature circulation well, high temperature cyclic performance, reduce thickness swelling during high temperature storage for the battery.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not subject to above-described embodiment
Limit, other any spirit without departing from the present invention and the change made under principle, modification, replacement, combine, simplify,
All should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (9)
1. a kind of lithium-ion battery electrolytes it is characterised in that：Described lithium-ion battery electrolytes are by organic solvent, conductive lithium
Salt, additive and phenylpyridine class compound are constituted, and described phenylpyridine class compound has shown in formula (I), (II) or (III)
General structure；
The alkane that in formula, R1, R2, R3, R4, R5 are each independently selected from hydrogen atom, fluorine atom, cyano group, carbon number are 2～15
Base, carbon number are any one in 2～15 fluoro-alkyl.
2. a kind of lithium-ion battery electrolytes electrolyte according to claim 1 it is characterised in that：Described phenylpyridine class
Compound is 2- phenylpyridine, 2- (4- aminomethyl phenyl) pyridine, 2- (2,4 difluorobenzene base) pyridine, 3- phenylpyridine, 3- (4- fluorine
Phenyl) pyridine, 4- (3- pyridine radicals) cyanophenyl, 4- phenylpyridine, 4- (4- fluorophenyl) pyridine or 4- (3- (trifluoromethyl) phenyl)
Pyridine.
3. a kind of lithium-ion battery electrolytes according to claim 1 and 2 it is characterised in that：Described phenylpyridine class
The addition of compound accounts for the 0.1%～5.0% of electrolyte gross mass.
4. a kind of lithium-ion battery electrolytes according to claim 1 and 2 it is characterised in that：Described organic solvent refers to
Cyclic carbonate solvents:The mass ratio of linear carbonate solvent is 1:The mixed solvent of (1～3)；Described cyclic carbonate solvents
Mixing for one of ethylene carbonate and Allyl carbonate or two kinds；Described linear carbonate solvent be dimethyl carbonate,
One of diethyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, ethyl acetate, ethyl propionate or two or more mixing.
5. a kind of lithium-ion battery electrolytes according to claim 1 it is characterised in that：Described electric conducting lithium salt includes hexafluoro
Lithium phosphate, LiBF4, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, perfluoro butyl Sulfonic Lithium, trifluoromethyl sulfonic acid lithium,
At least one in double (fluorine sulphonyl) imine lithium, double trifluoromethanesulfonimide lithium；Described electric conducting lithium salt is in organic solvent
Concentration is 0.8～1.5mol/L.
6. a kind of lithium-ion battery electrolytes according to claim 1 it is characterised in that：Described additive is carbonic acid Asia second
In alkene ester, vinylethylene carbonate, fluorinated ethylene carbonate, PS, butyl sultone, adiponitrile, succinonitrile
At least one, the addition of described additive accounts for the 0.1%～5.0% of electrolyte gross mass.
7. the electrolyte described in a kind of any one containing claim 1～6 lithium ion battery it is characterised in that：Described lithium from
Sub- battery is included described in anode pole piece, cathode pole piece, the barrier film being placed between both positive and negative polarity pole piece and any one of claim 1～6
Electrolyte；Described anode pole piece includes plus plate current-collecting body and the positive pole diaphragm being coated on plus plate current-collecting body, described negative pole pole
Piece includes negative current collector and the cathode membrane being coated on negative current collector.
8. a kind of lithium ion battery according to claim 7 it is characterised in that：Described positive pole diaphragm includes positive-active material
Material, conductive agent and binding agent, described cathode membrane includes negative active core-shell material, conductive agent and binding agent.
9. a kind of lithium ion battery according to claim 8 it is characterised in that：Described positive electrode active materials are selected from the mistake of lithium
Cross metal-oxide, wherein, the transition metal oxide of described lithium is LiCoO2、LiMn2O4、LiMnO2、Li2MnO4、
LiFePO4、Li1+aMn1-xMxO2、LiCo1-xMxO2、LiFe1-xMxPO4、Li2Mn1-xO4, wherein, M be selected from Ni, Co, Mn, Al,
One or more of Cr, Mg, Zr, Mo, V, Ti, B, F, 0≤a<0.2,0≤x<1；Described negative material is selected from graphite, silicon-carbon
At least one in composite, lithium titanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610903121.6A CN106450453A (en) | 2016-10-17 | 2016-10-17 | Lithium ion battery electrolyte and lithium ion battery containing same |
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| CN108598488A (en) * | 2018-06-08 | 2018-09-28 | 东莞市杉杉电池材料有限公司 | A kind of lithium ion battery with high energy density and its electrolyte |
| CN110867611A (en) * | 2019-10-15 | 2020-03-06 | 湖南博信新能源科技有限公司 | Power lithium ion battery electrolyte of high-nickel ternary cathode material system |
| CN111755747A (en) * | 2019-03-29 | 2020-10-09 | 比亚迪股份有限公司 | Non-aqueous electrolyte, battery containing non-aqueous electrolyte and vehicle containing battery |
| CN114024027A (en) * | 2021-10-29 | 2022-02-08 | 湖南法恩莱特新能源科技有限公司 | High-concentration electrolyte and preparation method and application thereof |
| CN114156533A (en) * | 2022-02-10 | 2022-03-08 | 河南电池研究院有限公司 | Lithium ion battery gel electrolyte and preparation method of lithium ion battery |
| CN115332633A (en) * | 2022-10-13 | 2022-11-11 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN115602940A (en) * | 2022-11-07 | 2023-01-13 | 广东工业大学（Cn） | Additives for interfacial film formation and lithium replenishment and related methods and assemblies |
| CN116936810A (en) * | 2023-09-15 | 2023-10-24 | 天鹏锂能技术(淮安)有限公司 | Positive pole piece of sodium ion battery and sodium ion battery |
| WO2024034887A1 (en) * | 2022-08-08 | 2024-02-15 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108598488B (en) * | 2018-06-08 | 2020-12-01 | 东莞市杉杉电池材料有限公司 | High-energy-density lithium ion battery and electrolyte thereof |
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| CN111755747A (en) * | 2019-03-29 | 2020-10-09 | 比亚迪股份有限公司 | Non-aqueous electrolyte, battery containing non-aqueous electrolyte and vehicle containing battery |
| CN110867611B (en) * | 2019-10-15 | 2023-03-24 | 湖南法恩莱特新能源科技有限公司 | Power lithium ion battery electrolyte of high-nickel ternary cathode material system |
| CN110867611A (en) * | 2019-10-15 | 2020-03-06 | 湖南博信新能源科技有限公司 | Power lithium ion battery electrolyte of high-nickel ternary cathode material system |
| CN114024027A (en) * | 2021-10-29 | 2022-02-08 | 湖南法恩莱特新能源科技有限公司 | High-concentration electrolyte and preparation method and application thereof |
| CN114024027B (en) * | 2021-10-29 | 2024-04-19 | 湖南法恩莱特新能源科技有限公司 | High-concentration electrolyte and preparation method and application thereof |
| CN114156533B (en) * | 2022-02-10 | 2022-04-22 | 河南电池研究院有限公司 | Lithium ion battery gel electrolyte and preparation method of lithium ion battery |
| CN114156533A (en) * | 2022-02-10 | 2022-03-08 | 河南电池研究院有限公司 | Lithium ion battery gel electrolyte and preparation method of lithium ion battery |
| WO2024034887A1 (en) * | 2022-08-08 | 2024-02-15 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| CN115332633B (en) * | 2022-10-13 | 2023-03-24 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN115332633A (en) * | 2022-10-13 | 2022-11-11 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN115602940A (en) * | 2022-11-07 | 2023-01-13 | 广东工业大学（Cn） | Additives for interfacial film formation and lithium replenishment and related methods and assemblies |
| CN116936810A (en) * | 2023-09-15 | 2023-10-24 | 天鹏锂能技术(淮安)有限公司 | Positive pole piece of sodium ion battery and sodium ion battery |
| CN116936810B (en) * | 2023-09-15 | 2023-12-12 | 天鹏锂能技术(淮安)有限公司 | Positive pole piece of sodium ion battery and sodium ion battery |
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Application publication date: 20170222 |