CN107017433B - Nonaqueous electrolytic solution and lithium ion battery - Google Patents
Nonaqueous electrolytic solution and lithium ion battery Download PDFInfo
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- CN107017433B CN107017433B CN201610058765.XA CN201610058765A CN107017433B CN 107017433 B CN107017433 B CN 107017433B CN 201610058765 A CN201610058765 A CN 201610058765A CN 107017433 B CN107017433 B CN 107017433B
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- electrolytic solution
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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 present invention provides a kind of nonaqueous electrolytic solution and lithium ion battery.The nonaqueous electrolytic solution includes: non-aqueous organic solvent；Lithium salts；And additive.The additive includes: fluorinated ethylene carbonate, LiBF4；And the compound of 1 structure of formula；In formula 1, R1~R4It is independently selected from one of H, halogen, the saturation that carbon atom number is 1~10 or unsaturated alkyl carbochain；The alkyl carbon chain can be replaced by O, halogen, and the halogen is selected from F, Cl, Br.Nonaqueous electrolytic solution of the invention can significantly improve low-temperature circulating performance, multiplying power discharging property and the security performance of lithium ion battery while guaranteeing high-temperature storage performance of lithium ion battery.
Description
Technical field
The present invention relates to field of batteries more particularly to a kind of nonaqueous electrolytic solutions and lithium ion battery.
Background technique
The high-energy density of lithium ion battery, long circulation life, wide operating temperature range and it is environmentally protective made its at
For the main energy sources of current mobile electronic device.With the extensive use of lithium ion battery, to its environmental suitability propose compared with
High requirement, present electronic product sometimes need to use under extreme conditions, the very high or very low environment such as temperature, and one
As for conventional environment, lithium ion battery performance in extreme condition use can deteriorate clearly.
Important component of the nonaqueous electrolytic solution as lithium ion battery has the high-temperature behavior and cryogenic property of battery
Great influence.However under normal circumstances, improve the high-temperature behavior and low temperature properties of lithium ion battery from the angle of nonaqueous electrolytic solution
There can be contradiction.On the one hand, high-temperature behavior can be improved by the way that film for additive passivation positive and negative anodes interface is added, but due to increasing simultaneously
Positive and negative anodes interface impedance is added, so that the cryogenic property severe exacerbation of lithium ion battery.On the other hand, optimize non-aqueous organic solvent
Composition reduces the viscosity under nonaqueous electrolytic solution low temperature, and conductivity improves, and such as by adding a large amount of low viscosity solvents, can be improved
The cryogenic property of lithium ion battery, but the high-temperature behavior of lithium ion battery would generally be deteriorated, and cannot finally solve lithium-ion electric
Pond in the application the problem of.
In view of this, it is low to improve lithium ion battery it is necessory to develop one kind under conditions of not influencing high-temperature behavior
The nonaqueous electrolytic solution and lithium ion battery of warm dynamic performance.
Summary of the invention
In view of the problems in the background art, the purpose of the present invention is to provide a kind of nonaqueous electrolytic solution and lithium-ion electrics
Pond, the nonaqueous electrolytic solution can significantly improve lithium ion battery while guaranteeing high-temperature storage performance of lithium ion battery
Low-temperature circulating performance, multiplying power discharging property and security performance.
In order to achieve the above object, in one aspect of the invention, the present invention provides a kind of nonaqueous electrolytic solutions comprising:
Non-aqueous organic solvent；Lithium salts；And additive.The additive includes: fluorinated ethylene carbonate, LiBF4；And formula 1
The compound of structure；
In formula 1, R1~R4It is independently selected from H, halogen, the saturation that carbon atom number is 1~10 or unsaturated alkyl
One of carbochain；The alkyl carbon chain can be replaced by O, halogen, and the halogen is selected from F, Cl, Br.
In another aspect of this invention, the present invention provides a kind of lithium ion batteries comprising: nonaqueous electrolytic solution；Anode
Piece；Negative electrode tab；And isolation film, positive plate and negative electrode tab is isolated.The nonaqueous electrolytic solution is according to one aspect of the present invention
Nonaqueous electrolytic solution.
Compared with the existing technology, the invention has the benefit that
Nonaqueous electrolytic solution of the invention can while guaranteeing high-temperature storage performance of lithium ion battery, significantly improve lithium from
Low-temperature circulating performance, multiplying power discharging property and the security performance of sub- battery.
Specific embodiment
The following detailed description of nonaqueous electrolytic solution according to the present invention and lithium ion battery.
Illustrate nonaqueous electrolytic solution according to a first aspect of the present invention first.
Nonaqueous electrolytic solution according to a first aspect of the present invention includes: non-aqueous organic solvent；Lithium salts；And additive.It is described
Additive includes: fluorinated ethylene carbonate (FEC), LiBF4 (LiBF4)；And the compound of 1 structure of formula；
In formula 1, R1~R4It is independently selected from H, halogen, the saturation that carbon atom number is 1~10 or unsaturated alkyl
One of carbochain；The alkyl carbon chain can be replaced by O, halogen, and the halogen is selected from F, Cl, Br.
LiBF is individually added into nonaqueous electrolytic solution4When, the high-temperature storage performance and low temperature discharge of battery can be improved
Performance, the reason is that LiBF4The electron deficient of middle boron element makes it be easy to have an effect with the oxygen atom of positive electrode surface, formation
The enough stable positive electrode surface of B-O bond energy is reduced to the oxidation activity of nonaqueous electrolytic solution, to effectively inhibit battery at high temperature swollen
It is swollen.Meanwhile LiBF4Effect with anode advantageously reduces positive electrode reaction resistance, improves the dynamic performance of anode, mentions
The low temperature performance of high battery.However, LiBF4Reduction decomposition can occur in cathode, decomposition product covers negative terminal surface, causes
The embedding lithium impedance of cathode increases, and is unfavorable for the dynamic performance of cathode.When especially charging at low ambient temperatures, higher embedding lithium impedance
The precipitation of negative terminal surface lithium metal is easily caused, to deteriorate the low temperature charging performance and low-temperature circulating performance of lithium ion battery.
Containing LiBF4Nonaqueous electrolytic solution in 1 structure of introduction-type compound and fluorinated ethylene carbonate when, can be negative
Pole surface forms the high SEI film of ionic conductivity, and the formation mechenism of the SEI film is explained as follows, and but it is not limited to this.1 structure of formula
Compound have high reaction activity can be in LiBF during battery initial charge4Before reduction decomposition occurs, first
Electrochemical reduction and ring-opening polymerization occurs, polymerizate forms reticular structure, to fluorinated ethylene carbonate and LiBF4Tool
There is inducing action, keep the two evenly dispersed, and is formed a film by mesh in electrode surface, formed a film dense uniform, and can reduce
The increase of membrane impedance, not only effectively inhibits LiBF in cyclic process4Reduction decomposition, also reduction LiBF4To lithium intercalation
Dynamic (dynamical) adverse effect.The compound of 1 structure of formula can also influence fluorinated ethylene carbonate and form a film in negative terminal surface, 1 knot of formula
S-O key of the compound of structure in film forming procedure on its ring will disconnect, and be formed in the form of free radical with fluorinated ethylene carbonate
Polymer reaction, on the one hand can increase polymer skeleton structure make its stability enhance, on the other hand can be used as poly-
The degree of polymerization for closing the polymerization reaction of the reaction terminating agent limitation fluorinated ethylene carbonate of reaction is not too large, so that SEI film is stablized
And will not be blocked up, to improve the cycle performance of battery.The composite S EI film that three is formed has lower interface impedance, favorably
In the ionic conductivity for increasing SEI film, improve lithium ion intercalation/deintercalation dynamics, so as to improve the low-temperature circulating performance of battery.
In addition, also at positive interface ring-opening reaction can occur for the compound of 1 structure of formula, the decomposition product containing phenyl ring is generated, is conducive to
The interface impedance for reducing anode, effectively improves the multiplying power discharging property and thermal stability of battery.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the compound of 1 structure of formula can be selected from adjacent benzene
Diphenol cyclic sulfates, tetra- fluoro pyrocatechol cyclic sulfates of 2,3,4,5-, 3- methyl pyrocatechol cyclic sulfates, 4- methyl
One or more of catechol cyclic sulfates；
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the compound of 1 structure of formula is in non-aqueous solution electrolysis
Mass percentage in liquid is 0.05%~3%.When mass percentage of the compound in nonaqueous electrolytic solution of 1 structure of formula
When lower than 0.05%, complete SEI film cannot be formed in negative terminal surface, to cannot effectively inhibit LiBF4Reduction decomposition make
With；And when mass percentage of the compound of 1 structure of formula in nonaqueous electrolytic solution is greater than 3%, it can be formed in negative terminal surface
Thicker SEI film causes lithium ion mobility resistance to increase, is unfavorable for the low-temperature circulating performance and multiplying power discharging property of battery.It is excellent
Selection of land, mass percentage of the compound of 1 structure of formula in nonaqueous electrolytic solution can be 0.1%~2%.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, LiBF4Quality percentage in nonaqueous electrolytic solution
Content is 0.01%~2%.LiBF4When mass percentage in nonaqueous electrolytic solution is lower than 0.01%, cannot effectively it press down
Thickness swelling of the battery processed during high temperature storage can not embody its improvement to low temperature performance；And work as LiBF4?
When mass percentage in nonaqueous electrolytic solution is higher than 2%, LiBF4Too strong to the effect of cathode, meeting severe exacerbation cathode moves
Mechanical property causes very detrimental effect to low-temperature circulating performance.Preferably, LiBF4Quality hundred in nonaqueous electrolytic solution
Dividing content can be 0.05%~0.5%.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, fluorinated ethylene carbonate is in nonaqueous electrolytic solution
Mass percentage can be 0.01%~10%, preferably can be 1%~5%.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the additive further include: the nitrile with ehter bond.
The nitrile with ehter bond can be selected from one or both of bis- (propionitrile) ethers of ethylene glycol, 1,2,3- tri- (2- cyanato-) propane.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the nitrile with ehter bond is in nonaqueous electrolytic solution
Mass percentage can be 0.1%~3%.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the additive may also include that vinylene carbonate
One or more of ester (VC), 1,3- propane sultone (1,3-PS), adiponitrile (ADN).
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the non-aqueous organic solvent can be selected from ethylene carbonate
Ester, propene carbonate, butylene, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbonic acid first third
Ester, ethyl propyl carbonic acid ester, 1,4- butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, in ethyl butyrate at least
Two kinds.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the non-aqueous organic solvent is in nonaqueous electrolytic solution
Mass percentage can be 75%~95%, preferably can be 80%~90%.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the lithium salts can be selected from LiPF6、LiTFSI、
LiClO4、LiAsF6、LiBOB、LiDFOB、LiTFOB、LiN(SO2RF)2、LiN(SO2F)(SO2RFOne or more of),
In, RFFor CnF2n+1, n be 1~10 integer.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, concentration of the lithium salts in nonaqueous electrolytic solution can
It preferably can be 0.8M~1.2M for 0.5M~1.5M.
Secondly the lithium ion battery of explanation according to a second aspect of the present invention.
Lithium ion battery according to a second aspect of the present invention includes: nonaqueous electrolytic solution；Positive plate；Negative electrode tab；And isolation
Positive plate and negative electrode tab is isolated in film.The nonaqueous electrolytic solution is the nonaqueous electrolytic solution according to first aspect present invention.
In the lithium ion battery described according to a second aspect of the present invention, the positive plate may include plus plate current-collecting body and painting
Positive diaphragm of the cloth on plus plate current-collecting body.The anode diaphragm may include positive electrode active materials, binder and conductive agent.It is described
Positive electrode active materials can be selected from cobalt acid lithium (LiCoO2), lithium-nickel-manganese-cobalt ternary material, LiFePO 4, one of LiMn2O4 or
It is several.
In the lithium ion battery described according to a second aspect of the present invention, the negative electrode tab may include negative current collector and painting
Cathode membrane of the cloth on negative current collector.The cathode membrane may include negative electrode active material, binder and conductive agent.It is described
Negative electrode active material can be selected from the micro- carbon ball of natural graphite, artificial graphite, interphase (referred to as MCMB), hard carbon, soft carbon, silicon, silicon-
Carbon complex, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO2、SiO、SiO2, spinel structure lithiumation TiO2-
Li4Ti5O12, one or more of Li-Al alloy.
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
Comparative example 1
Prepare nonaqueous electrolytic solution: nonaqueous electrolytic solution is with concentration for 1.15M lithium hexafluoro phosphate (LiPF6) it is lithium salts, with carbonic acid
The mixture of vinyl acetate (EC), propene carbonate (PC) and diethyl carbonate (DEC) is non-aqueous organic solvent, is according to mass ratio
EC:PC:DEC=30:30:40 mixing.Furthermore also contain additive in nonaqueous electrolytic solution, additive is that mass percentage is
4% fluorinated ethylene carbonate (FEC).
Prepare positive plate: by positive electrode active materials LiCoO2, conductive agent SuperP, binder polyvinylidene fluoride (PVDF)
Anode sizing agent is made in 97:1.4:1.6 in mass ratio and N-Methyl pyrrolidone (NMP) mixing, is coated in current collector aluminum foil simultaneously
It is cold-pressed after being dried at 85 DEG C, after then carrying out trimming, cut-parts, slitting, 4h is dried under 85 DEG C of vacuum condition, welded
Positive plate is made in tab.
It prepares negative electrode tab: negative electrode active material graphite, conductive agent SuperP, thickener CMC, bonding agent SBR is pressed into quality
Negative electrode slurry is made than 97:1.0:1.0:1.5 and pure water mixing, is coated on copper foil of affluxion body and is dried at 85 DEG C laggard
Row cold pressing dries 4h, negative electrode tab is made in soldering polar ear after then carrying out trimming, cut-parts, slitting under 110 DEG C of vacuum conditions.
Prepare lithium ion battery: using PE porous polymer film as isolation film；By positive plate obtained, isolation film, cathode
Piece is folded in order, is in isolation film among positive/negative plate, and winding obtains naked battery core；Naked battery core is placed in outer packing, it will
The nonaqueous electrolytic solution of above-mentioned preparation is injected into the naked battery core after drying, and encapsulation, standing, (0.02C constant-current charge arrives for chemical conversion
3.4V, then with 0.1C constant-current charge to 3.85V), shaping, volume test, complete soft bag lithium ionic cell preparation (Soft Roll lithium from
Sub- battery with a thickness of 4.2mm, width 32mm, length 82mm).
Comparative example 2
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.3% LiBF4。
Comparative example 3
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.5% glycol sulfate.
Comparative example 4
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.5% catechol cyclic sulfates.
Comparative example 5
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 3% LiBF4, mass percentage be 0.5% adjacent benzene
Diphenol cyclic sulfates.
Comparative example 6
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.3% LiBF4, mass percentage be 4% adjacent benzene
Diphenol cyclic sulfates.
Comparative example 7
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 3% LiBF4, mass percentage be 4% adjacent benzene two
Phenol cyclic sulfates.
Comparative example 8
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% second
Glycol cyclic sulfates.
Embodiment 1
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% neighbour
Benzenediol cyclic sulfates.
Embodiment 2
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.05%
Catechol cyclic sulfates.
Embodiment 3
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.1% neighbour
Benzenediol cyclic sulfates.
Embodiment 4
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 1% adjacent benzene
Diphenol cyclic sulfates.
Embodiment 5
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 2% adjacent benzene
Diphenol cyclic sulfates.
Embodiment 6
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 3% adjacent benzene
Diphenol cyclic sulfates.
Embodiment 7
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.01% LiBF4, mass percentage be 0.5%
Catechol cyclic sulfates.
Embodiment 8
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.05% LiBF4, mass percentage be 0.5%
Catechol cyclic sulfates.
Embodiment 9
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.1% LiBF4, mass percentage be 0.5% neighbour
Benzenediol cyclic sulfates.
Embodiment 10
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.5% LiBF4, mass percentage be 0.5% neighbour
Benzenediol cyclic sulfates.
Embodiment 11
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 1% LiBF4, mass percentage be 0.5% adjacent benzene
Diphenol cyclic sulfates.
Embodiment 12
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 2% LiBF4, mass percentage be 0.5% adjacent benzene
Diphenol cyclic sulfates.
Embodiment 13
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% neighbour
Benzenediol cyclic sulfates, ethylene glycol (double propionitrile) ether that mass percentage is 0.2%.
Embodiment 14
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% neighbour
Benzenediol cyclic sulfates, ethylene glycol (double propionitrile) ether that mass percentage is 0.5%.
Embodiment 15
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% neighbour
Benzenediol cyclic sulfates, ethylene glycol (double propionitrile) ether that mass percentage is 1%.
Embodiment 16
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% neighbour
Benzenediol cyclic sulfates, ethylene glycol (double propionitrile) ether that mass percentage is 2%.
Embodiment 17
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% neighbour
Benzenediol cyclic sulfates, ethylene glycol (double propionitrile) ether that mass percentage is 3%.
Embodiment 18
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% 2,
Tetra- fluoro pyrocatechol cyclic sulfates of 3,4,5-, ethylene glycol (double propionitrile) ether that mass percentage is 4%.
Embodiment 19
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% 3-
Methyl pyrocatechol cyclic sulfates, 1,2,3- tri- (2- cyanato-) propane that mass percentage is 1%.
Embodiment 20
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% neighbour
Benzenediol cyclic sulfates, the 1,3- propane sultone (1,3-PS) that mass percentage is 1%.
Embodiment 21
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% neighbour
The adiponitrile (ADN) that 1,3-PS that benzenediol cyclic sulfates, mass percentage are 1%, mass percentage are 2%.
Embodiment 22
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% 2,
1,3-PS that tetra- fluoro pyrocatechol cyclic sulfates of 3,4,5-, mass percentage are 1%, mass percentage are oneself of 2%
Dintrile (ADN).
Embodiment 23
Lithium ion battery is prepared referring to the method for comparative example 1, the difference is that, when preparing nonaqueous electrolytic solution, addition
Agent be mass percentage be 4% FEC, mass percentage be 0.2% LiBF4, mass percentage be 0.5% 3-
The adiponitrile that 1,3-PS that methyl pyrocatechol cyclic sulfates, mass percentage are 1%, mass percentage are 2%
(ADN)。
The additive of the nonaqueous electrolytic solution of table 1 comparative example 1-8 and embodiment 1-23 forms and additive amount
Illustrate the test process and test result of lithium ion battery below.
Test one: low-temperature circulating performance test
By the battery of each embodiment and comparative example after the completion of preparation, at 25 DEG C extremely with 0.5C electric current constant-current charge
4.35V, at 4.35V, constant-voltage charge to 0.05C；Battery stands 5 minutes after completely filling, then with 0.2C multiplying power discharging to 3.0V, should
Discharge capacity is denoted as 25 DEG C of discharge capacities of battery.Later at 0 DEG C, battery standing 30 minutes, extremely with 0.2C constant-current charge
4.35V, then constant-voltage charge to 0.05C, stands 5 minutes, then is discharged to 3.0V with 0.2C, stands 5 minutes；Phase is pressed at 0 DEG C
Same condition carries out repeated charge, writes down the discharge capacity of different cycle-indexes, and calculate capacity retention ratio.
Discharge capacity/25 DEG C the discharge capacity of different cycle-indexes under capacity retention ratio (%)=low temperature after low-temperature circulating
× 100%.
Test two: multiplying power discharging property test
By the battery of each embodiment and comparative example after the completion of preparation, at 25 DEG C extremely with 0.5C electric current constant-current charge
4.35V, at 4.35V, constant-voltage charge to 0.05C；Battery stands 5 minutes after completely filling, and then puts according to certain discharge-rate
Electricity is to 3.0V.After electric discharge terminates every time, battery standing 5 minutes, then with the charging of identical condition.The multiplying power of electric discharge is respectively
0.2C, 0.5C, 1.0C, 1.5C, 2.0C record electric discharge of the battery under different multiplying and hold with the capacity of 0.2C electric discharge for 100%
Amount ratio.
Discharge capacity/0.2C discharge capacity under discharge capacitance (%)=different multiplying under different multiplying ×
100%.
Test three: high-temperature storage performance test
By the battery of each embodiment and comparative example after the completion of preparation, at 25 DEG C extremely with 0.5C electric current constant-current charge
4.35V, at 4.35V, constant-voltage charge to 0.05C, then with 0.5C multiplying power discharging to 3.0V.Later, it is filled with 0.5C electric current constant current
Electricity is to 4.35V, then 4.35V constant-voltage charge is at 4.35V fully charged state to 0.05C, thickness before testing battery storage and
Internal resistance；Then, full electric battery is put into 85 DEG C of insulating boxs, takes out the thickness for testing battery and internal resistance after storing 6h.As the following formula
Calculate the thickness increment rate and internal resistance increase rate of battery.
Thickness × 100% before thickness increment rate (%)=(thickness before thickness-storage after storage) ÷ is stored.
Internal resistance × 100% before internal resistance increase rate (%)=(internal resistance before internal resistance-storage after storage) ÷ is stored.
Test four: hot tank performance test
At 25 DEG C, each 5, the battery of comparative example and embodiment are taken respectively, with 0.5C electric current constant-current charge to 4.35V,
Under 4.35V, then battery is put into hot tank by constant-voltage charge to 0.05C, hot tank from room temperature begin to warm to 150 DEG C it is constant
30min, observes the state of battery, and hot tank heating rate is 5 DEG C/min.
The performance test results of table 2 comparative example 1-8 and embodiment 1-23
Comparative example 1 and comparative example 2 are analyzed it is found that being individually added into 0.3% LiBF in the nonaqueous electrolytic solution containing FEC4
To the low-temperature circulating performance of lithium ion battery without improvement, slightly improve the multiplying power discharging property and thermal stability of lithium ion battery,
Significantly improve the high-temperature storage performance of lithium ion battery.Comparative example 1 and comparative example 3-4 are analyzed it is found that in the non-water power containing FEC
When being individually added into 0.5% glycol sulfate in solution liquid, low-temperature circulating performance, the multiplying power that can slightly improve lithium ion battery are put
Electrical property, the slight high-temperature storage performance for improving lithium ion battery, thermal stability；And in the nonaqueous electrolytic solution containing FEC
When 0.5% catechol cyclic sulfates are added, since catechol cyclic sulfates are formed by SEI membrane structure than second two
Alcohol sulfuric ester is stablized, and especially high temperature resistance is good, can improve multiplying power discharging property, the thermal stability of lithium ion battery, slightly
Improve low-temperature circulating performance, the high-temperature storage performance of lithium ion battery, but improvement is limited.
Comparative example 2, comparative example 4 and embodiment 1 are analyzed it is found that by being added simultaneously in the nonaqueous electrolytic solution containing FEC
LiBF4With catechol cyclic sulfates, lithium can be improved significantly while guaranteeing high-temperature storage performance of lithium ion battery
The low-temperature circulating performance and multiplying power discharging property of ion battery, and improve the security performance of lithium ion battery.This is because working as
LiBF4When being added simultaneously with catechol cyclic sulfates, synergistic effect between the two can be further played.LiBF4It can
With the interface stability of positive improved effect anode and nonaqueous electrolytic solution, suitable LiBF4Also help the positive electrochemistry of reduction
Impedance improves the dynamic performance of anode.And simultaneously, on the one hand suitable catechol cyclic sulfates can be formed in cathode
The high SEI film of ionic conductivity is conducive to improve the dynamic performance under cathode low temperature, makes up LiBF4The kinetics of cathode
Also in anode ring-opening reaction occurs for the insufficient defect of energy, another aspect catechol cyclic sulfates, generates point containing phenyl ring
Product is solved, the interface impedance of anode is reduced.
Comparative example 8 and embodiment 1 are analyzed it is found that containing catechol cyclic sulfates and LiBF4In lithium ion battery
It is apparently higher than in terms of low-temperature circulating performance, multiplying power discharging property and high-temperature storage performance containing glycol sulfate and LiBF4
Lithium ion battery, this is because catechol cyclic sulfates be formed by SEI membrane structure than glycol sulfate stablize.
Analysis embodiment 1-12 it is found that when being added mass fraction no more than 2% in the nonaqueous electrolytic solution containing FEC simultaneously
LiBF4When being no more than 3% catechol cyclic sulfates with mass fraction, the capacity after lithium ion battery low-temperature circulating is protected
Holdup is significantly improved, and discharge capacity of the lithium ion battery under different multiplying has promotion, and will not reduce lithium ion
The high-temperature storage performance of battery improves lithium ion in addition, can also significantly improve the percent of pass of lithium ion battery hot tank test simultaneously
The security performance of battery.Comparative example 5-7 is analyzed it is found that as LiBF in nonaqueous electrolytic solution4Content is more than that 2% or catechol are cyclic annular
When the content of sulfuric ester is more than 3%, other than high-temperature storage performance, thermal stability, the low-temperature circulating performance of lithium ion battery and
Multiplying power discharging property deteriorates.
Embodiment 1 and embodiment 13-23 are analyzed it is found that containing FEC, catechol cyclic sulfates and LiBF at the same time4
On the basis of three kinds of additives, bis- (propionitrile) ethers of ethylene glycol, 1,2,3- tri- (2- cyanato-s) third are added again in nonaqueous electrolytic solution
Alkane, 1, the anode passivation additives such as 3-PS, ADN can further improve the high-temperature storage performance of lithium ion battery, this is because this
A little additives can be further formed passivating film by coordinate bond or oxygenolysis, and help to stablize FEC, catechol
Cyclic sulfates and LiBF4The structure of composite membrane of formation prevents composite membrane from decomposing at high temperature and battery performance is caused to decline.
The announcement of book according to the above description, those skilled in the art in the invention can also carry out above embodiment
Change and modification appropriate.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 scope of claims hereof.
Claims (13)
1. a kind of nonaqueous electrolytic solution, comprising:
Non-aqueous organic solvent；
Lithium salts；And
Additive；
It is characterized in that,
The additive includes:
Fluorinated ethylene carbonate, LiBF4；And
The compound of 1 structure of formula；
In formula 1, R1~R4It is independently selected from H, halogen, the saturation or unsaturated alkyl carbochain that carbon atom number is 1~10
One of；The alkyl carbon chain can be replaced by O, halogen, and the halogen is selected from F, Cl, Br；
Mass percentage of the compound of 1 structure of formula in nonaqueous electrolytic solution is 0.05%~3%；
Mass percentage of the LiBF4 in nonaqueous electrolytic solution is 0.01%~2%；
Mass percentage of the fluorinated ethylene carbonate in nonaqueous electrolytic solution is 0.01%~10%.
2. nonaqueous electrolytic solution according to claim 1, which is characterized in that the compound of 1 structure of formula is selected from adjacent benzene two
Phenol cyclic sulfates, tetra- fluoro pyrocatechol cyclic sulfates of 2,3,4,5-, 3- methyl pyrocatechol cyclic sulfates, 4- methyl are adjacent
One or more of benzenediol cyclic sulfates；
3. nonaqueous electrolytic solution according to claim 1, which is characterized in that the compound of 1 structure of formula is in non-aqueous solution electrolysis
Mass percentage in liquid is 0.1%~2%.
4. nonaqueous electrolytic solution according to claim 1, which is characterized in that quality of the LiBF4 in nonaqueous electrolytic solution
Percentage composition is 0.05%~0.5%.
5. nonaqueous electrolytic solution according to claim 1, which is characterized in that fluorinated ethylene carbonate is in nonaqueous electrolytic solution
Mass percentage is 1%~5%.
6. nonaqueous electrolytic solution according to claim 1, which is characterized in that the additive further include: the nitrile with ehter bond.
7. nonaqueous electrolytic solution according to claim 6, which is characterized in that it is double that the nitrile with ehter bond is selected from ethylene glycol
One or both of (propionitrile) ether, 1,2,3- tri- (2- cyanato-) propane.
8. nonaqueous electrolytic solution according to claim 6, which is characterized in that the nitrile with ehter bond is in nonaqueous electrolytic solution
Mass percentage be 0.1%~3%.
9. nonaqueous electrolytic solution according to claim 1 or 6, which is characterized in that the additive further include: vinylene carbonate
One or more of ester, 1,3- propane sultone, adiponitrile.
10. nonaqueous electrolytic solution according to claim 1, which is characterized in that the lithium salts is selected from LiPF6、LiTFSI、
LiClO4、LiAsF6、LiBOB、LiDFOB、LiTFOB、LiN(SO2RF)2、LiN(SO2F)(SO2RFOne or more of),
In, RFFor CnF2n+1, n be 1~10 integer.
11. nonaqueous electrolytic solution according to claim 1, which is characterized in that concentration of the lithium salts in nonaqueous electrolytic solution
For 0.5M~1.5M.
12. nonaqueous electrolytic solution according to claim 11, which is characterized in that concentration of the lithium salts in nonaqueous electrolytic solution
For 0.8M~1.2M.
13. a kind of lithium ion battery, comprising:
Nonaqueous electrolytic solution；
Positive plate；
Negative electrode tab；And
Positive plate and negative electrode tab is isolated in isolation film；
It is characterized in that,
The nonaqueous electrolytic solution is according to nonaqueous electrolytic solution of any of claims 1-12.
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| CN111029655A (en) * | 2019-12-20 | 2020-04-17 | 杉杉新材料（衢州）有限公司 | Lithium ion battery electrolyte and lithium ion battery containing same |
| CN111640981B (en) * | 2020-05-18 | 2021-10-26 | 珠海冠宇电池股份有限公司 | Electrolyte for silicon-carbon system lithium ion battery and silicon-carbon system lithium ion battery |
| CN112271330B (en) * | 2020-10-21 | 2022-06-07 | 广州天赐高新材料股份有限公司 | Electrolyte additive, electrolyte and energy storage device |
| CN113189507A (en) * | 2021-03-23 | 2021-07-30 | 天津力神电池股份有限公司 | Method for rapidly representing stability of SEI (solid electrolyte interface) film of lithium battery |
| CN114597492A (en) * | 2021-04-12 | 2022-06-07 | 深圳市研一新材料有限责任公司 | Nonaqueous electrolyte solution and lithium ion battery using same |
| CN113314773A (en) * | 2021-05-12 | 2021-08-27 | 江苏师范大学 | Aqueous zinc ion battery electrolyte and preparation method and application thereof |
| CN114583268A (en) * | 2021-07-09 | 2022-06-03 | 深圳市研一新材料有限责任公司 | Lithium ion battery electrolyte and application thereof |
| CN115312863A (en) * | 2022-08-25 | 2022-11-08 | 珠海冠宇电池股份有限公司 | Battery electrolyte, preparation method of battery electrolyte and battery |
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