CN105633467B - Electrolyte and lithium ion battery adopting same - Google Patents
Electrolyte and lithium ion battery adopting same Download PDFInfo
- Publication number
- CN105633467B CN105633467B CN201610192975.8A CN201610192975A CN105633467B CN 105633467 B CN105633467 B CN 105633467B CN 201610192975 A CN201610192975 A CN 201610192975A CN 105633467 B CN105633467 B CN 105633467B
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- boron trifluoride
- lithium
- substituted
- lithium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application relates to the field of lithium ion batteries, in particular to electrolyte and a lithium ion battery adopting the electrolyte. The electrolyte of the present application comprises a non-aqueous organic solvent, a lithium salt and an additive comprising an N-substituted pyrrolidone-boron trifluoride complex compound. The electrolyte can form a good interface film on the surfaces of the anode and the cathode, can reduce the reaction activity of the surface of the anode, and inhibits the oxidative decomposition of the electrolyte on the surface of the anode; meanwhile, the acidic components and transition metal ions generated in the electrolyte are captured by utilizing the characteristic of the Lewis base of the compound, so that the high-temperature storage performance and the cycle performance of the battery under high voltage are improved.
Description
Technical field
This application involves field of lithium ion battery, specifically, are related to a kind of electrolyte and the lithium ion using the electrolyte
Battery.
Background technology
The electronic mobile devices such as laptop, mobile phone, handheld device, tablet computer can realize more and more work(
Can, the application technology of electric vehicle, intelligent grid etc. also reaches its maturity.People to the lithium as its main drive energy from
The cruising ability of sub- battery requires also higher and higher.Improving energy density becomes the research hotspot of lithium ion battery.
For the lithium ion battery that positive electrode is nickel-cobalt-manganese ternary material, it is to increase battery energy to promote charging by voltage
The effective ways of metric density.However when improving the voltage of lithium ion battery, when especially charging voltage reaches 4.35V or more, by
Increase in de- lithium ratio, the structural stability of positive electrode reduces, and easily undergoes phase transition reduction positive electrode capacity；Transition metal is molten simultaneously
Solution aggravation moves to cathode and destroys SEI, generate a large amount of reducibility gas, consumes electrolyte.Since voltage has exceeded electrolyte
Oxidation reaction will occur on anode, quickly consume electrolyte for redox window, electrolyte, generate a large amount of by-products or gas
Body.Due to the presence of both the above effect, lithium ion battery is in charging charge and discharge when voltage is higher than 4.35V, inducing capacity fading
It is significantly accelerated.
In actual use, electronic product is also faced with such as the lasting use environment temperature liter for using fever or lithium ion battery
High all lithium ion battery to be made to be in the condition of high temperature, and at high temperature, electrolyte is by by tightened up test, when serious
Cause since the dilatancy of lithium ion battery causes inside lithium ion cell generation short circuit or lithium ion battery packaging to be burst
Flammable electrolyte leakage, so as to cause safety accidents such as fire.Therefore it needs to further increase the oxidation potential of electrolyte,
Effective technology solves the problems, such as the decomposition of electrolyte, lithium ion battery flatulence.In consideration of it, it is necessary to develop a kind of high temperature circulation
High-voltage electrolyte.
Invention content
The primary goal of the invention of the application is to propose a kind of electrolyte.
The second goal of the invention of the application is to propose a kind of lithium ion battery using the electrolyte.
In order to complete the purpose of the application, the technical solution used for：
A kind of electrolyte, including non-aqueous organic solvent, lithium salts and additive, the additive include N substituted pyrrolidones-
Boron trifluoride complex.
Preferably, the N substituted pyrrolidones-boron trifluoride complex is selected from the chemical combination of structural formula shown in formula I
At least one of object：
Wherein, R is selected from substituted or unsubstituted C1~30Alkyl, substituted or unsubstituted C2~30Alkenyl, substitution or unsubstituted
C2~30Alkynyl, substituted or unsubstituted C6~26Aryl；
Substituent group is selected from halogen.
Preferably, R is selected from substituted or unsubstituted C1~20Alkyl, substituted or unsubstituted C2~20Alkenyl；R is preferably straight chain
Or the C of branch1~12Alkyl, C2~12Alkenyl, C3~12Naphthenic base.
Preferably, the N substituted pyrrolidones-boron trifluoride complex is selected from boron trifluoride-N- crassitudes
Ketone, boron trifluoride-N- ethyl pyrrolidones, boron trifluoride-N- propyl pyrroles alkanone, boron trifluoride-N- isopropylpyrrolidines ketone,
Boron trifluoride-n-vinyl pyrrolidone, boron trifluoride-N- acrylic pyrrolidones, boron trifluoride-N- isopropenyl pyrrolidines
At least one of ketone, boron trifluoride-n-octylpyrrolidone, boron trifluoride-N- cyclohexyl pyrrolidones；It is preferred that borontrifluoride
At least one in boron-N-Methyl pyrrolidone, boron trifluoride-N- ethyl pyrrolidones, boron trifluoride-n-vinyl pyrrolidone
Kind.
Preferably, the quality of the N substituted pyrrolidones-boron trifluoride complex is the electrolyte of lithium ion battery
Gross mass 0.1%~5%.
Preferably, the organic solvent is selected from ethylene carbonate, propene carbonate, butylene, fluoro ethylene carbonate
Ester, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, in 1,4- fourths
At least one of ester, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate and ethyl butyrate.
Preferably, the lithium salts is selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro oxalic acid
Lithium phosphate, double trifluoromethanesulfonimide lithiums, bis- (fluorine sulphonyl) imine lithiums, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, LiN
(SO2RF)2、LiN(SO2F)(SO2RFAt least one of), wherein RF=-CnF2n+1, n be 1~10 integer；It is preferred that LiPF6、
LiN(SO2RF)2At least one of.
Preferably, a concentration of 0.3M~1.8M of the lithium salts in the electrolyte of lithium ion battery.
This application involves a kind of lithium ion batteries, including：Positive plate, including plus plate current-collecting body and it is set to anode collection
The positive diaphragm containing positive electrode active materials on body；Negative plate, including negative current collector and be set on negative current collector
The cathode membrane containing negative electrode active material；Isolation film is interval between adjacent positive/negative plate；Electrolyte；And package foil；
It is characterized in that, the electrolyte is the electrolyte of the application.
The technical solution institute of the application is attainable to be had the beneficial effect that：
N substituted pyrrolidones-boron trifluoride complex is added in lithium-ion battery electrolytes by the application, can
Improve the high temperature circulation and storage performance of high-voltage lithium ion batteries.The electrolysis additive of the application can pass through boron trifluoride
Boron atom interacts with positive oxygen atom in structure, while the ketonic oxygen of N substituted pyrrolidones and nitrogen-atoms are capable of providing electricity
Son promotes the surface stability of positive electrode under high voltage with the coordination of transition metal；Solid electrolytic is participated in negative terminal surface
The formation of plasma membrane.N substituted pyrrolidones-boron trifluoride complex is respectively formed good interfacial film in positive and negative pole surface, drop
The reactivity of low positive electrode surface improves the oxidizing potential of electrolyte, inhibits electrolyte in the oxygenolysis of positive electrode surface, changes
It has been apt to high temperature storage voltage drop and aerogenesis.
The ketonic oxygen and nitrogen-atoms of the N substituted pyrrolidones of the application are capable of providing the coordination of electronics and transition metal
The transition metal ions that anode dissolution in the electrolytic solution can also be captured, prevents transition metal ions from destroying cathode solid electrolyte
Film, boron trifluoride can also dissolve the lithium fluoride being deposited in electrode duct, form solvable lithium salts, reduce the fluorination of electrode surface
Lithium deposits, and alleviates the blocking in electrode duct, these characteristics are all conducive to promote high-temperature cycle life and storage performance.
In addition, the additive of the application can effectively promote the wellability of electrode slice, this is because N substituted pyrrolidone packets
Containing hydrophobic side chain (substituent group on nitrogen-atoms) and hydrophilic head (pyrrolidone ring), hydrophobic side chain and carbon material used as anode phase interaction
With reduction negative terminal surface tension.The interaction of hydrophilic head and positive electrode promotes the wellability of electrolyte.
With reference to specific embodiment, the application is expanded on further.It should be understood that these embodiments are merely to illustrate the application
Rather than limitation scope of the present application.
Specific implementation mode
This application involves a kind of electrolyte, including non-aqueous organic solvent, lithium salts and additive, additive includes N substitution pyrroles
Pyrrolidone-boron trifluoride complex.
N substituted pyrrolidones-boron trifluoride complex refers to that N substituted pyrrolidones molecule and boron trifluoride are formed
Complex, boron trifluoride are in anion, and N substituted pyrrolidones are in cation, entire N substituted pyrrolidones-boron trifluoride
Complex is in electroneutral.
As a kind of improvement of the application electrolyte, N substituted pyrrolidones-boron trifluoride complex is selected from such as formula II
At least one of the compound of shown structural formula：
Wherein, R is selected from substituted or unsubstituted C1~30Alkyl, substituted or unsubstituted C2~30Alkenyl, substitution or unsubstituted
C2~30Alkynyl, substituted or unsubstituted C6~26Aryl；
R ', R ", R " ' separate it is respectively selected from hydrogen atom, halogen, C1~6Alkyl, C1~6Alkoxy, C1~6Acyloxy；
Substituent group is selected from halogen.
Halogen in the application is selected from fluorine, chlorine, bromine；Preferably fluorine.
As a kind of improvement of the application electrolyte, N substituted pyrrolidones-boron trifluoride complex is selected from such as formula I
At least one of the compound of shown structural formula：
Wherein, R is selected from substituted or unsubstituted C1~30Alkyl, substituted or unsubstituted C2~30Alkenyl, substitution or unsubstituted
C2~30Alkynyl, substituted or unsubstituted C6~26Aryl；
Substituent group is selected from halogen.
As a kind of improvement of the application electrolyte, R is selected from substituted or unsubstituted C1~20It is alkyl, substituted or unsubstituted
C2~20Alkenyl；R is preferably the C of linear chain or branched chain1~12Alkyl, C2~12Alkenyl, C3~12Naphthenic base.
In this application, the alkyl that carbon atom number is 1~30, alkyl can be chain-like alkyl or naphthenic base, be located at ring
The ring hydrogen of alkyl can be replaced by alkyl, and the preferred lower limiting value of carbon atom number is 2,3,4,5 in the alkyl, the preferred upper limit
Value is 3,4,5,6,8,10,12,14,16,18,20,22,24,26,28.Preferably, select carbon atom number for 1~20 alkyl,
It is further preferred that selecting carbon atom number for 1~12 chain-like alkyl, the naphthenic base that carbon atom number is 3~12 is further excellent
Selection of land selects carbon atom number for 1~6 chain-like alkyl, the naphthenic base that carbon atom number is 5~7.As the example of chain-like alkyl,
It can specifically enumerate：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl, isoamyl
Base, neopentyl, hexyl, 2- Methyl pentyls, 3- Methyl pentyls, 1,1,2- trimethyl-propyls, 3,3 ,-dimethyl-butyl, just
Heptyl, 2- heptyl, 3- heptyl, 2- methylhexyls, 3- methylhexyls, octyl, nonyl, decyl.As the example of naphthenic base, specifically
It can enumerate：Cyclopenta, cyclohexyl, cyclooctyl.
In this application, the alkenyl that carbon atom number is 2~30 can be cyclic alkenyl radical or chain alkenyl.In addition, alkenyl
The number of middle double bond is 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,
4,5,6,8,10,12,14,16,18,20,22,24,26,28.Preferably, select carbon atom number for 2~20 alkenyl, further
Preferably, select carbon atom number for 2~12 alkenyl, it is further preferred that select carbon atom number for 2~6 alkenyl.As
The example of alkenyl can specifically be enumerated：Vinyl, allyl, isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, ring are pungent
Alkenyl.
In this application, carbon atom number be 6~26 aryl, such as phenyl, benzene alkyl, at least contain there are one phenyl virtue
Base such as xenyl, condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and condensed-nuclei aromatics base can also be taken by alkyl or alkenyl
Generation.Preferably, select carbon atom number for 6~16 aryl, it is further preferred that select carbon atom number for 6~14 aryl, more
It is further preferred that select carbon atom number for 6~9 aryl.As the example of aryl, can specifically enumerate：Phenyl, benzyl,
Xenyl, p-methylphenyl, o-tolyl, tolyl.
As a kind of improvement of the application electrolyte, N substituted pyrrolidones-boron trifluoride complex is selected from followingization
Close at least one of object：
Boron trifluoride-N-Methyl pyrrolidone；
Boron trifluoride-N- ethyl pyrrolidones；
Boron trifluoride-N- propyl pyrrole alkanones；
Boron trifluoride-N- isopropylpyrrolidine ketone；
Boron trifluoride-n-vinyl pyrrolidone；
Boron trifluoride-N- acrylic pyrrolidones；
Boron trifluoride-N- isopropenyl pyrrolidones；Boron trifluoride-
N-octylpyrrolidone；
Boron trifluoride-N- cyclohexyl pyrrolidones.
And preferably：Boron trifluoride-N-Methyl pyrrolidone, boron trifluoride-N- ethyl pyrrolidones, boron trifluoride-N- second
At least one of vinyl pyrrolidone.
As a kind of improvement of the application electrolyte, N substituted pyrrolidones-boron trifluoride complex is also selected from
At least one of following compound：
As a kind of improvement of the application electrolyte, the quality of N substituted pyrrolidones-boron trifluoride complex is electricity
Solve the 0.1%~5% of the gross mass of liquid.
When boron trifluoride-N-Methyl pyrrolidone complex content is more than 5%, electrolyte system viscosity is caused to become larger,
The interfacial film formed simultaneously in positive and negative pole surface is blocked up, affects the cycle performance of lithium ion battery, however storage performance still into
One step improves, this is because the boron trifluoride of high-content-N-Methyl pyrrolidone complex on the one hand can be in positive and negative pole surface
Good interfacial film is formed, the reactivity of positive electrode surface is reduced, meanwhile, N substituted pyrrolidones-boron trifluoride ligand compound
Object contains lewis base, can neutralize the sour gas generated in storing process, such as PF5、HF、CO2Deng.When boron trifluoride-N- first
The mass percentage of base pyrrolidones complex in the electrolytic solution<When 0.1%, then very few boron trifluoride-N- methylpyrroles
Improvement unobvious of the alkanone complex to performance of lithium ion battery.
In above-mentioned electrolyte, non-aqueous organic solvent is selected from at least one of carbonate products, carboxylate compound,
In, carbonate products can be linear carbonate or cyclic carbonate.
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, 1,4- fourths
At least one of lactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate, ethyl butyrate.
Non-aqueous organic solvent is also selected from methyl acrylate, dimethyl sulfite, diethyl sulfite, acid anhydrides, N-
Methyl pyrrolidone, N-METHYLFORMAMIDE, N- methylacetamides, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, methyl sulfide,
One or more of tetrahydrofuran.In above-mentioned electrolyte, lithium salts can be organic lithium salt or inorganic lithium salt, it is specific and
It says, at least one of fluorine element, boron element, P elements can be contained in lithium salts.Preferably, 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, and 2n+1 be more than zero integer.Particularly preferably LiPF6And/or LiN
(SO2RF)2.A concentration of 0.5M~2M (the M=molL 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 to provide a kind of lithium ion battery, which includes the electrolysis of the application
Liquid, the positive plate containing positive electrode active materials, negative plate and isolation film containing negative electrode active material.
In above-mentioned lithium ion battery, positive plate further includes binder and conductive agent, will include positive electrode active materials, viscous
The anode sizing agent for tying agent and conductive agent is coated on plus plate current-collecting body, and positive plate is obtained after anode sizing agent drying.Likewise, will
Include negative electrode active material, binder and conductive agent negative electrode slurry be coated in negative current collector on, wait for negative electrode slurry dry
After obtain negative plate.
Preferably, positive electrode active materials are selected from cobalt acid lithium LiCoO2, cobalt nickel lithium manganate ternary material, LiFePO 4, manganese
Sour lithium (LiMnO2At least one of), such as the mixture of cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material can be used as positive-active material
Material.As the example of cobalt nickel lithium manganate ternary material, can specifically enumerate：LiNi1/3Co1/3Mn1/3O2、
LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2。
Preferably, negative electrode active material is carbon material 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.
The charging upper limit blanking voltage of the lithium ion battery of the application is 4.35V~4.6V.
Examples 1 to 30
(1) preparation of the positive plate of lithium ion battery
By positive electrode active materials nickle cobalt lithium manganate (LiNi0.6Co0.2Mn0.2O2), conductive agent Super-P, bonding agent PVDF press
Mass ratio 97.2:1.3:1.5 be dissolved in solvent N-methyl pyrilidone be uniformly mixed anode sizing agent is made, later by anode sizing agent
It is uniformly coated on the tow sides of current collector aluminum foil, coating weight 0.0102g/cm2, carried out after then being dried at 85 DEG C cold
Pressure, trimming, cut-parts, slitting, the positive plate of lithium ion battery is made in dry 4h, soldering polar ear under 85 DEG C of vacuum conditions later.
(2) preparation of the negative plate of lithium ion battery
By negative electrode active material artificial graphite, conductive agent Super-P, thickener CMC, bonding agent SBR in mass ratio 95.4：
1.2：1.2：2.2 be dissolved in solvent deionized water be uniformly mixed negative electrode slurry is made, negative electrode slurry is uniformly coated on collection later
On the tow sides of fluid copper foil, coating weight 0.0071g/cm2, then at 85 DEG C dry after be cold-pressed, trimming, sanction
Piece, slitting, the negative plate of lithium ion battery is made in dry 4h, soldering polar ear under 110 DEG C of vacuum conditions later.
(3) preparation of the electrolyte of lithium ion battery
The electrolyte of lithium ion battery is with the LiPF of 1mol/L6For lithium salts, with ethylene carbonate (EC), methyl ethyl carbonate
(EMC) mixture is non-aqueous organic solvent, wherein electrolyte solvent part EC：The mass ratio of EMC is 30：70.In addition, lithium from
Also contain additive in the electrolyte of sub- battery, the content and title of additive are as shown in table 1.
(4) preparation of lithium ion battery
By the positive plate, negative plate and isolation film of the lithium ion battery prepared according to previous process, (PE films contain ceramics
Coating) by winding process be fabricated to the battery core that thickness is 5.7mm, width 16mm, length are 33mm, wherein the battery core there are
Long airbag, to observe its aerogenesis.And vacuum bakeout 14h (vacuum degree < -0.08MPa), injection electrolyte, standing at 85 DEG C
For 24 hours, use the constant current charge of 0.05C (11mA) to 3.4V later, remove battery then first carry out a vacuum it is pre-packaged with
Just degasification；Again with the constant current charge of 0.05C (11mA) to 4.5V, then battery is removed again and carries out second of degasification；So
3V is discharged to the constant current of 0.5C (110mA) afterwards, is repeated 2 times charge and discharge, is finally filled with the constant current of 0.5C (110mA)
Electricity completes the preparation of lithium ion battery to 3.85V.
Comparative example 1~14
In comparative example 1, lithium ion battery is prepared according to the method for embodiment 1, only in the electrolyte of lithium ion battery
Preparation (i.e. step (3)) in, do not add any additive；In comparative example 2~14, in the system of the electrolyte of lithium ion battery
In standby (i.e. step (3)), it is also added with additive, the content and title of additive are as shown in table 1.
The test process and test result of electrolyte and its lithium ion battery in the application.
(1) the high temperature cyclic performance test of lithium ion battery
At 45 DEG C, 4.5V is first charged to lithium ion battery with the constant current of 0.5C, further with the constant electricity of 4.5V
It is 0.025C that pressure, which charges to electric current, is then discharged to 2.8V to lithium ion battery with the constant current of 0.5C, this is a charge and discharge
Electric cyclic process, this discharge capacity are the discharge capacity of 1 cycle of formula.Lithium ion battery is recycled in a manner described
Charge-discharge test takes the discharge capacity of the 100th cycle.
Capacity retention ratio (%) after the cycle of lithium ion battery 100 times=(discharge capacity/formula of the 100th cycle is followed for 1 time
The discharge capacity of ring) × 100%.
(2) the high-temperature storage performance test of lithium ion battery
At 25 DEG C, 4.5V is first charged to lithium ion battery with the constant current of 0.5C, further with the constant electricity of 4.5V
It is 0.025C that pressure, which charges to electric current, and lithium ion battery has then been surveyed initial volume with drainage in deionized water and has been placed on 60
It is stored 30 days at DEG C, after to be stored, the volume change of test lithium ion battery after storage at high temperatures.
Volume change (%)=(volume/lithium after high-temperature lithium ion battery storage after high-temperature lithium ion battery storage
Volume before ion battery high temperature storage) × 100%.
The performance test results of embodiment and comparative example are as shown in table 1：
Table 1：
The performance test results of lithium ion battery are analyzed：
As can be seen that addition boron trifluoride-N-Methyl pyrrolidone is matched from comparisons of the embodiment 1-6 with comparative example 1-3
The lithium ion battery for closing object has preferable high temperature circulation than not adding the lithium ion battery of comparative example 1 of any additive
Energy and high-temperature storage performance.
When boron trifluoride-N-Methyl pyrrolidone complex content is more than 5% (comparative example 3), cycle performance occurs
Deteriorate, it may be possible to because boron trifluoride-N-Methyl pyrrolidone complex occupies the excessive ratio of non-aqueous organic solvent and causes
Electrolyte system viscosity becomes larger, while blocked up in the interfacial film that positive and negative pole surface is formed, and affects the cyclicity of lithium ion battery
Can, however storage performance still further improves, this is because the boron trifluoride of high-content-one side of N-Methyl pyrrolidone complex
Face can form good interfacial film in positive and negative pole surface, reduce the reactivity of positive electrode surface, while boron trifluoride-N- first
Base pyrrolidones complex contains lewis base, can neutralize the sour gas generated in storing process, such as PF5、HF、CO2Deng.
When boron trifluoride-mass percentage of the N-Methyl pyrrolidone complex in the electrolyte of lithium ion battery<0.1% is (right
Ratio 2) when, then improvement unobvious of the very few boron trifluoride-N-Methyl pyrrolidone complex to the performance of lithium ion battery.
Similarly, from embodiment 7-30 in the comparison of comparative example 4-10 it can be seen that similar result.
As can be seen that N used in this application takes in comparison from embodiment 4,10,16,22 and 28 with comparative example 11 and 12
There are better high temperature circulation and high-temperature storage performance than ether or dimethyl carbonate for pyrrolidones.May be because N takes
There is lewis base for pyrrolidones, the acidic components generated in cycle storing process can be neutralized, capture the mistake of anode dissolution
Metal ion is crossed, prevents cathode solid electrolyte film from wrecking, so as to improve cycle storage stability.
As can be seen that presoma R used in this application from the comparison of embodiment 4,10,16,22 and 28 and comparative example 13
Base pyrrolidones has better high temperature circulation and high-temperature storage performance than n,N-dimethylacetamide.May be because N replaces
The cyclic structure of pyrrolidones can participate in the generation of cathode solid electrolyte film, and N substituted azoles in cathode ring-opening polymerisation
There is no hydrogen atom in alkanone on nitrogen-atoms, reduce the presence of active hydrogen in electrolyte in this way, reduces the generation of the substances such as HF
May, it protects positive electrode not to be corroded, improves the cycle performance of battery.
As can be seen that the application uses boron trifluoride-methyl pyrrolidone ratio from the comparison of embodiment 4 and comparative example 14
Independent methyl pyrrolidone has better high temperature circulation.May be boron trifluoride-methyl pyrrolidone can be formed it is more stable
Positive solid electrolyte film, protection positive electrode surface is stablized, while can dissolve the lithium fluoride for being deposited on positive and negative pole surface, alleviates just
The blocked situation in cathode duct, extends the cycle life of battery.
Embodiment 31~36
According to the preparation method of embodiment 1, lithium ion battery is prepared with the compound and content of additive shown in table 2,
It is as shown in table 2 to test the capacity retention ratio after obtained high temperature circulation, the cubical expansivity after high temperature storage.
Table 2：
It can be seen that a kind of lithium ion battery provided herein and its electrolyte and new additive agent, it can be just
Negative terminal surface forms good interfacial film, can reduce the reactivity of positive electrode surface, inhibits electrolyte in the oxygen of positive electrode surface
Change and decomposes；The acidic components that are generated in the electrolytic solution using the characteristic capture of the lewis base contained in the compound simultaneously and
Transition metal ions, to improve battery high-temperature storage performance under high voltages and cycle performance.
It is illustrating for the preferred embodiment of the application above, but the application is not limited to the embodiment, Mou Xiebian
Shape or replacement compound are all contained in the application claim limited range.In addition, the application used it is certain specific
Term, these terms are merely for convenience of description, not to the application constitute any restrictions.
Claims (10)
1. a kind of electrolyte, including non-aqueous organic solvent, lithium salts and additive, which is characterized in that the additive includes N substitutions
Pyrrolidones-boron trifluoride complex；
At least one in the N substituted pyrrolidones-compound of the boron trifluoride complex selected from structural formula shown in formula I
Kind：
Wherein, R is selected from substituted or unsubstituted C1~30Alkyl, substituted or unsubstituted C2~30It is alkenyl, substituted or unsubstituted
C2~30Alkynyl, substituted or unsubstituted C6~26Aryl；
Substituent group is selected from halogen；
The quality of the N substituted pyrrolidones-boron trifluoride complex is the 0.1%~5% of electrolyte gross mass.
2. electrolyte according to claim 1, which is characterized in that R is selected from substituted or unsubstituted C1~20Alkyl, substitution or
Unsubstituted C2~20Alkenyl.
3. electrolyte according to claim 1, which is characterized in that R is selected from the C for linear chain or branched chain1~12Alkyl, C2~12Alkene
Base, C3~12Naphthenic base.
4. electrolyte according to claim 1, which is characterized in that the N substituted pyrrolidones-boron trifluoride ligand compound
Object is selected from boron trifluoride-N-Methyl pyrrolidone, boron trifluoride-N- ethyl pyrrolidones, boron trifluoride-N- propyl pyrrole alkane
Ketone, boron trifluoride-N- isopropylpyrrolidines ketone, boron trifluoride-n-vinyl pyrrolidone, boron trifluoride-N- acrylic pyrroles
Alkanone, boron trifluoride-N- isopropenyls pyrrolidones, boron trifluoride-n-octylpyrrolidone, boron trifluoride-N- cyclohexyl pyrroles
At least one of pyrrolidone.
5. electrolyte according to claim 1, which is characterized in that the non-aqueous organic solvent is selected from ethylene carbonate, carbon
Acid propylene ester, butylene, fluorinated ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid dipropyl
Ester, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propionic acid
At least one of propyl ester and ethyl butyrate.
6. 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, bis- (fluorine sulphonyl) imine lithiums, di-oxalate lithium borate, difluoro oxalate boric acid
Lithium, LiN (SO2RF)2、LiN(SO2F)(SO2RFAt least one of), wherein RF=-CnF2n+1, n be 1~10 integer.
7. electrolyte according to claim 6, which is characterized in that the lithium salts is double trifluoromethanesulfonimide lithiums.
8. electrolyte according to claim 1, which is characterized in that the lithium salts a concentration of 0.3M in the electrolytic solution~
1.8M。
9. a kind of lithium ion battery, including：Positive plate, including plus plate current-collecting body and be set on plus plate current-collecting body containing just
The positive diaphragm of pole active material；Negative plate, including negative current collector and be set on negative current collector containing cathode live
The cathode membrane of property material；Isolation film is interval between adjacent positive/negative plate；Electrolyte；And package foil；It is characterized in that,
The electrolyte is electrolyte according to any one of claims 1 to 8.
10. lithium ion battery according to claim 9, which is characterized in that the positive electrode active materials are selected from cobalt acid lithium, nickel
At least one of cobalt manganic acid lithium ternary material, LiFePO 4 and LiMn2O4, the negative electrode active material be carbon material and/
Or silicon materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610192975.8A CN105633467B (en) | 2016-03-30 | 2016-03-30 | Electrolyte and lithium ion battery adopting same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610192975.8A CN105633467B (en) | 2016-03-30 | 2016-03-30 | Electrolyte and lithium ion battery adopting same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105633467A CN105633467A (en) | 2016-06-01 |
| CN105633467B true CN105633467B (en) | 2018-11-06 |
Family
ID=56048168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610192975.8A Active CN105633467B (en) | 2016-03-30 | 2016-03-30 | Electrolyte and lithium ion battery adopting same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105633467B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023102793A1 (en) | 2021-12-08 | 2023-06-15 | 宁德时代新能源科技股份有限公司 | Secondary battery and electrical apparatus comprising same |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110504415B (en) * | 2018-05-17 | 2021-05-07 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
| CN109037778A (en) * | 2018-08-01 | 2018-12-18 | 桑德集团有限公司 | A kind of electrolysis additive and electrolyte, lithium ion battery and equipment containing it |
| CN109360938A (en) * | 2018-09-11 | 2019-02-19 | 天津市捷威动力工业有限公司 | A kind of high safety structure lithium battery |
| CN111146497B (en) * | 2018-11-06 | 2021-02-19 | 深圳市比克动力电池有限公司 | Additive for battery electrolyte, lithium ion battery electrolyte and lithium ion battery |
| CN113135947B (en) * | 2021-03-11 | 2022-08-16 | 常德市大度新材料有限公司 | Lithium acetylsulfanilate complex, preparation method thereof and application thereof in non-aqueous electrolyte |
| CN113299489B (en) * | 2021-05-24 | 2022-12-23 | 南通江海电容器股份有限公司 | Preparation process and device of low-temperature lithium ion capacitor electrolyte |
| CN114497738B (en) * | 2022-01-13 | 2023-08-25 | 珠海冠宇电池股份有限公司 | High-temperature high-voltage electrolyte and battery containing same |
| CN116706252B (en) * | 2023-07-28 | 2023-12-26 | 宁德时代新能源科技股份有限公司 | Secondary battery, electricity utilization device and preparation method |
| CN117638082B (en) * | 2024-01-24 | 2024-04-09 | 宁德新能源科技有限公司 | Lithium ion battery and electronic device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1551401A (en) * | 2003-05-13 | 2004-12-01 | 三星Sdi株式会社 | Non-aqueous electrolyte and a lithium secondary battery comprising the same |
| CN103151560A (en) * | 2013-02-05 | 2013-06-12 | 东莞新能源科技有限公司 | Lithium ion battery electrolyte solution and its additive |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2215756C (en) * | 1997-09-18 | 2006-04-04 | Moli Energy (1990) Limited | Additives for improving cycle life of non-aqueous rechargeable lithium batteries |
| JP3336998B2 (en) * | 1998-08-28 | 2002-10-21 | 株式会社豊田中央研究所 | Non-aqueous electrolyte secondary battery |
| WO2008032795A1 (en) * | 2006-09-14 | 2008-03-20 | National University Corporation Shizuoka University | Electrolytic solution for electrochemical device |
| JP2011187232A (en) * | 2010-03-05 | 2011-09-22 | Sony Corp | Lithium secondary battery, electrolytic solution for lithium secondary battery, electric power tool, electrical vehicle, and electric power storage system |
| KR101889118B1 (en) * | 2010-12-28 | 2018-08-16 | 세키스이가가쿠 고교가부시키가이샤 | Lithium ion secondary battery |
| CN102916220B (en) * | 2011-08-05 | 2015-10-14 | 丰田自动车株式会社 | Magnesium battery electrolyte |
| CN105006594B (en) * | 2015-08-14 | 2018-11-23 | 东莞市凯欣电池材料有限公司 | A kind of high stability lithium-ion battery electrolytes |
-
2016
- 2016-03-30 CN CN201610192975.8A patent/CN105633467B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1551401A (en) * | 2003-05-13 | 2004-12-01 | 三星Sdi株式会社 | Non-aqueous electrolyte and a lithium secondary battery comprising the same |
| CN103151560A (en) * | 2013-02-05 | 2013-06-12 | 东莞新能源科技有限公司 | Lithium ion battery electrolyte solution and its additive |
Non-Patent Citations (1)
| Title |
|---|
| Mengyun Nie et al..A Comparative Study of Pyridine-Boron Trifluoride, Pyrazine-(BF3)2 and Triazine-( BF3)3 as Electrolyte Additives for Lithium-Ion Cells.《Journal of The Electrochemical Society》.2015,第162卷(第10期), * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023102793A1 (en) | 2021-12-08 | 2023-06-15 | 宁德时代新能源科技股份有限公司 | Secondary battery and electrical apparatus comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105633467A (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105633467B (en) | Electrolyte and lithium ion battery adopting same | |
| CN109546219A (en) | A kind of lithium-ion battery electrolytes and the lithium ion battery using the electrolyte | |
| EP2833468B1 (en) | Non-aqueous electrolyte solution for secondary batteries, and lithium-ion secondary battery | |
| KR100751205B1 (en) | Electrolyte for improving performance of battery and lithium secondary battery comprising the same | |
| CN104269576B (en) | A kind of electrolyte and the lithium ion battery using the electrolyte | |
| EP2876723B1 (en) | Lithium secondary battery | |
| KR101947059B1 (en) | Electrolyte for non-aqueous electrolyte battery and non-aqueous electrolyte lithium battery | |
| KR20160136686A (en) | Lithium metal battery | |
| CN106159325B (en) | A kind of low temperature electrolyte for lithium ion battery and low-temperature lithium ion battery | |
| JP2003151623A (en) | Nonaqueous secondary battery | |
| JP2009176534A (en) | Non-aqueous electrolyte secondary battery | |
| JP2011222193A (en) | Electrolyte for non-aqueous electrolyte battery and non-aqueous electrolyte battery using it | |
| WO2021015264A1 (en) | Nonaqueous electrolyte solution, nonaqueous electrolyte battery and compound | |
| CN109888384B (en) | Electrolyte and battery containing the same | |
| JP7168851B2 (en) | Electrolyte for non-aqueous electrolyte battery and non-aqueous electrolyte battery using the same | |
| CN104022310A (en) | Lithium ion secondary battery electrolyte and lithium ion battery containing electrolyte | |
| JP2004022336A (en) | Electrolyte for secondary battery and secondary battery using it | |
| EP2413418A1 (en) | Electrolyte solution for electrical energy storage devices, and electrical energy storage device | |
| CN105789684A (en) | Lithium ion secondary battery and electrolyte thereof | |
| JPWO2015080102A1 (en) | Secondary battery electrolyte and secondary battery using the same | |
| CN105742701A (en) | Electrolyte and lithium secondary battery | |
| KR20120091627A (en) | Lithium ion battery including the same | |
| CN109659612A (en) | A kind of high-voltage electrolyte and the lithium ion battery containing the electrolyte | |
| JP2016051600A (en) | Nonaqueous electrolytic solution for power storage device | |
| JP2022126851A (en) | Nonaqueous electrolyte solution for batteries, and lithium secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201119 Address after: 213300 No. 1000 North Avenue, Kunlun Street, Liyang City, Changzhou City, Jiangsu Province Patentee after: CONTEMPORARY AMPEREX TECHNOLOGY Ltd. (JIANGSU) Address before: 352100, Xingang Road, Ningde Town, Jiaocheng District, Fujian, 1 Patentee before: Contemporary Amperex Technology Co.,Ltd. |