CN107017432B - Nonaqueous electrolytic solution and lithium ion battery - Google Patents
Nonaqueous electrolytic solution and lithium ion battery Download PDFInfo
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- CN107017432B CN107017432B CN201610058323.5A CN201610058323A CN107017432B CN 107017432 B CN107017432 B CN 107017432B CN 201610058323 A CN201610058323 A CN 201610058323A CN 107017432 B CN107017432 B CN 107017432B
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- electrolytic solution
- nonaqueous electrolytic
- phosphoric acid
- cyclic anhydride
- carbon atom
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
- C07C255/09—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton containing at least two cyano groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
-
- 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
-
- 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: phosphoric acid cyclic anhydride compound；And the dinitrile compound containing unsaturated bond.Nonaqueous electrolytic solution of the invention can improve the stability of positive electrode active materials under high voltages, inhibit nonaqueous electrolytic solution in positive electrode surface oxygenolysis, improve the chemical property of lithium ion battery under high voltage condition.Lithium ion battery of the invention can be used for high voltage condition for a long time.
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
Lithium ion battery has that energy density is high, operating voltage is high, self-discharge rate is low, has extended cycle life, is pollution-free etc. solely
Special advantage, has been used as power supply to be widely used in the electronic products such as camera, mobile phone.
In recent years, with the fast development of smart electronics product, the cruising ability of lithium ion battery is proposed higher
It is required that.In order to improve the energy density of lithium ion battery, exploitation high-voltage lithium ion batteries are one of effective ways.Currently, work
Make the hot spot that voltage has become numerous R&D institutions and business research in the lithium ion battery of 4.35V or more.However in high voltage
Under, the oxidation activity of positive electrode active materials increases, stability declines, and nonaqueous electrolytic solution is caused to be easy that electrification occurs in positive electrode surface
Oxidation reaction is learned, and then decomposes and generates gas.Meanwhile transition metal element (such as nickel, cobalt, manganese) meeting in positive electrode active materials
Reduction reaction occurs and dissolves out, further deteriorates so as to cause lithium ion battery chemical property.Therefore, overcome nonaqueous electrolytic solution
It is the Important Problems developed in high-voltage lithium ion batteries in the oxygenolysis of positive electrode surface.
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 be used for high voltage condition for a long time, and guarantee that lithium ion battery has excellent chemical property.
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: phosphoric acid cyclic anhydride compound；And contain unsaturated bond
Dinitrile compound.
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 improve the stability of positive electrode active materials under high voltages, inhibit non-aqueous solution electrolysis
Liquid improves the chemical property of lithium ion battery under high voltage condition in positive electrode surface oxygenolysis.
Lithium ion battery of the invention can be used for high voltage condition for a long time.
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 comprising: non-aqueous organic solvent；Lithium salts；And
Additive.The additive includes: phosphoric acid cyclic anhydride compound；And the dinitrile compound containing unsaturated bond.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, phosphoric acid cyclic anhydride compound can be in positive electrode active materials
Surface reaction generates Low ESR passivating film, improves the stability of positive electrode active materials structure under high voltages, inhibits crystal structure
It collapses, improves the stability of oxygen atom in positive electrode active materials under high voltages；Dinitrile compound containing unsaturated bond can be
Multiple tooth complex reaction occurs for the transition metal element in positive electrode surface and positive electrode active materials, and polymerization reaction occurs and generates densification
Positive-pole protective layer, play the role of stable transition metal element, so as under high voltages effectively inhibit nonaqueous electrolytic solution exist
The reaction of positive electrode surface inhibits transition metal element dissolution.The dinitrile compound of unsaturated bond is prior to phosphoric acid cyclic anhydride compound
Protective film is formed in positive electrode surface, and does not need specific reaction potential, and it passes through multiple tooth complexing and positive-active material
The protective layer that transition metal element in material is formed is in reticular structure, has to the formation of the passivating film of phosphoric acid cyclic anhydride compound and lures
Effect is led, it is made to be uniformly dispersed on reticular structure, complex protection membrane structure even compact, the electrolyte resistance being ultimately formed are rotten
Erosion, thermal stability might as well.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the phosphoric acid cyclic anhydride compound can be selected from it is a kind of or
Several compounds with formula (I) structure,
In formula (I), R1、R2、R3Be each independently selected from the alkyl, carbon atom number that carbon atom number is 1~7 be 6~15 and
Group containing at least one phenyl ring.The alkyl is to lose any one hydrogen atom on alkane molecule to be formed by group.Institute
Stating alkane can be selected from linear paraffin, branched paraffin, any one in cycloalkane.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, R1、R2、R3Carbon atom can be each independently selected from
Alkyl, phenyl of the number for 1~3.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, R1、R2、R3It can be identical.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the phosphoric acid cyclic anhydride compound can be selected from tripropyl
One or more of phosphoric acid cyclic anhydride, trimethyl phosphoric acid cyclic anhydride, triethyl group phosphoric acid cyclic anhydride and triphenyl phosphoric acid cyclic anhydride.Under correspondence
Formula (1)~(4) in face, wherein R1、R2、R3It is identical, respectively n-propyl, methyl, ethyl, phenyl.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the dinitrile compound containing unsaturated bond can
There are the compounds of formula (II) structure selected from one or more,
In formula (II), A1The alkylene for being 1~10 selected from carbon atom number, A2The sub- hydrocarbon for being 1~10 selected from carbon atom number
Base, A3The alkyl for being 1~10 selected from H or carbon atom number, A4The alkyl for being 1~10 selected from H or carbon atom number.The alkyl is hydrocarbon
Any one hydrogen atom is lost on class compound molecule is formed by group.The alkylene is to lose on hydrocarbon molecules
Any two hydrogen atom is formed by group.The hydrocarbon compound may include alkane, cycloalkane, alkene, alkynes, in aromatic hydrocarbon
Any one.The alkane can be selected from linear paraffin, branched paraffin, any one in cycloalkane.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, A1It can be selected from the alkylene that carbon atom number is 1~5
Base.A2It can be selected from the alkylidene that carbon atom number is 1~5.A3It can be selected from H, the alkyl that carbon atom number is 1~5 or carbon atom number are 6
~10 aryl.A4It can be selected from H, the alkyl that carbon atom number is 1~5 or the aryl that carbon atom number is 6~10.The alkylidene is
Any two hydrogen atom is lost on alkane molecule is formed by group.The alkyl is that any one hydrogen original is lost on alkane molecule
Son is formed by group.The aryl loses any one hydrogen atom on the aromatic rings for fragrant hydrocarbon molecule and is formed by group.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the dinitrile compound containing unsaturated bond can
With symmetrical structure.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the dinitrile compound containing unsaturated bond can
One in 1,4- dicyano -2- butylene, 1,6- dicyano -3- hexene and 1,4- dicyano -2,3- dimethyl -2- butylene
Kind is several.Corresponding following formula (5)~(7).
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the phosphoric acid cyclic anhydride compound is in nonaqueous electrolytic solution
In mass percentage can be 0.1%~3%.When mass percentage mistake of the phosphoric acid cyclic anhydride compound in nonaqueous electrolytic solution
When low, it is not enough in the reaction for the Low ESR passivating film that surface of positive electrode active material generates, to the electrification of lithium ion battery
The improvement result for learning performance is unobvious；When mass percentage of the phosphoric acid cyclic anhydride compound in nonaqueous electrolytic solution is excessively high,
It is thickeied in the Low ESR passivating film that surface of positive electrode active material generates, impedance increases, and is unfavorable for the circulation of lithium ion battery instead
Performance.Preferably, the upper limit of mass percentage range of the phosphoric acid cyclic anhydride compound in nonaqueous electrolytic solution can be selected from
2%, 1%, lower limit can be selected from 0.1%, 0.2%, 0.5%.It is further preferred that the phosphoric acid cyclic anhydride compound is in non-aqueous solution electrolysis
Mass percentage in liquid can be 0.5%~2%.It is further preferred that the phosphoric acid cyclic anhydride compound is in non-aqueous solution electrolysis
Mass percentage in liquid can be 0.5%~1%.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the dinitrile compound containing unsaturated bond exists
Mass percentage in nonaqueous electrolytic solution can be 0.1%~4%.When the dinitrile compound containing unsaturated bond is in non-aqueous solution electrolysis
When mass percentage in liquid is too low, the chelation structure formed with transition metal element in positive electrode active materials is not enough caused
It is close, and unsaturated bond polymerization crosslinking degree is lower, fine and close protective layer cannot be effectively formed, can not effectively inhibit nonaqueous electrolytic solution with
Redox reaction between positive electrode active materials, to be unable to improve the chemical property of lithium ion battery；When containing insatiable hunger
When excessively high with the mass percentage of the dinitrile compound of key in nonaqueous electrolytic solution, with the transition gold in positive electrode active materials
It is too strong to belong to the complexing that element is formed, and polymerization crosslinking degree is high, the protective layer of formation is very thick, is unfavorable for lithium ion and passes through, draws
It plays positive impedance to dramatically increase, the cycle performance that will lead to lithium ion battery is deteriorated.Preferably, two containing unsaturated bond
The upper limit of mass percentage range of the nitrile compound in nonaqueous electrolytic solution can be selected from 3%, 2%, lower limit can be selected from 0.1%,
0.2%, 0.5%.It is further preferred that quality percentage of the dinitrile compound containing unsaturated bond in nonaqueous electrolytic solution
Content can be 0.2%~3%.It is further preferred that quality percentage of the phosphoric acid cyclic anhydride compound in nonaqueous electrolytic solution
Content can be 0.5%~2%.
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 (being abbreviated as EC), propene carbonate (being abbreviated as PC), dimethyl carbonate (being abbreviated as DMC), diethyl carbonate (are abbreviated as
DEC), methyl ethyl carbonate (being abbreviated as EMC), gamma-butyrolacton (being abbreviated as BL), methyl formate (being abbreviated as MF), Ethyl formate (letter
Be written as MA), ethyl propionate (being abbreviated as EP), one of propyl propionate (being abbreviated as PP) and tetrahydrofuran (being abbreviated as THF)
Or it is several.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the lithium salts can be selected from organic lithium salt, inorganic lithium
Salt or combinations thereof.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, in the lithium salts can containing fluorine element, boron element,
One or more of P elements.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, the lithium salts can be selected from lithium hexafluoro phosphate LiPF6、
Double trifluoromethanesulfonimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), bis- (fluorine sulphonyl) imine lithium Li (N (SO2F)2) (letter
Be written as LiFSI), di-oxalate lithium borate LiB (C2O4)2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF2(C2O4) (be abbreviated as
LiDFOB), hexafluoroarsenate lithium LiAsF6, lithium perchlorate LiClO4, trifluoromethanesulfonic acid lithium LiCF3SO3One or more of.
In the nonaqueous electrolytic solution described according to a first aspect of the present invention, in the nonaqueous electrolytic solution, the concentration of lithium salts
It can be 0.5M~1.5M.Preferably, the concentration of lithium salts can be 0.8M~1.2M.
Secondly illustrate the lithium ion battery described according to a second aspect of the present invention comprising: nonaqueous electrolytic solution；Positive plate；
Negative electrode tab；And isolation film, positive plate and negative electrode tab is isolated.The nonaqueous electrolytic solution is according to first aspect present invention
Nonaqueous electrolytic solution.
In the lithium ion battery described according to a second aspect of the present invention, the end of charge voltage of the lithium ion battery can
Not less than 4.35V.It is further preferred that the end of charge voltage of the lithium ion battery is 4.35V~5V.Lithium of the invention from
Sub- battery can be used for the high voltage condition of 4.35V or more for a long time.
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, nickle cobalt lithium manganate, one or more of LiMn2O4.
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 graphite and/or silicon.
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
(1) preparation of nonaqueous electrolytic solution: in drying shed, by ethylene carbonate (EC), propene carbonate (PC) and carbonic acid
Diethylester (DEC) ratio of EC:PC:DEC=1:1:1 in mass ratio is uniformly mixed, and obtains non-aqueous organic solvent.To non-aqueous organic
LiPF is added in solvent6, obtain LiPF6Concentration is the solution of 1mol/L, as nonaqueous electrolytic solution.
(2) 1.42kg Solvents N-methyl -2-Pyrrolidone (being abbreviated as NMP), 1.2kg bonding the preparation of positive plate: are weighed
Agent polyvinylidene fluoride (be abbreviated as PVDF, the mass percentage of polyvinylidene fluoride be 10%), 0.16kg conductive agent it is conductive
Graphite and 7.2kg positive electrode active materials cobalt acid lithium (LiCoO2), it is sufficiently mixed and is uniformly mixing to obtain anode sizing agent.Anode is starched
Material is uniformly coated on the plus plate current-collecting body aluminium foil with a thickness of 16 μm, is obtained positive diaphragm in 120 DEG C of baking 1h, is passed through later
Compacting, cutting obtain positive plate.
(3) it the preparation of negative electrode tab: weighs 1.2kg thickener sodium carboxymethylcellulose and (is abbreviated as CMC, carboxymethyl cellulose
The mass percentage of sodium be 1.5%), (mass percentage of butadiene-styrene rubber is 0.07kg binder SBR emulsion
50%), 2.4kg negative electrode active material powdered graphite, is sufficiently mixed and is uniformly mixing to obtain negative electrode slurry.Equably by negative electrode slurry
Be coated on the negative current collector copper foil with a thickness of 12 μm, obtain cathode membrane in 120 DEG C of baking 1h, later through overcompaction, point
It cuts to obtain negative electrode tab.
(4) preparation of lithium ion battery: using the polypropylene film with a thickness of 12 μm as isolation film.By positive plate, isolation
Film, negative electrode tab are folded in order, are in isolation film among positive and negative anodes and are played the role of isolation, and the naked electricity of squarely is then wound
Core.Naked battery core is packed into aluminum foil sack, after 80 DEG C of bakings remove water, inject nonaqueous electrolytic solution, by Vacuum Package, standing,
The processes such as chemical conversion, shaping complete the preparation of lithium ion battery.
Comparative example 2
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride, is added LiPF after mixing6, obtaining tripropyl phosphoric acid cyclic anhydride mass percentage is 1%, LiPF6Concentration
For the solution of 1mol/L, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Comparative example 3
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.1 is added into non-aqueous organic solvent,
4- dicyano -2- butylene, is added LiPF after mixing6, obtain Isosorbide-5-Nitrae-dicyano -2- butylene mass percentage be 1%,
LiPF6Concentration is the solution of 1mol/L, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Comparative example 4
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality hundred
Point content is 4%, 1,4- dicyano -2- butylene mass percentage is 1%, LiPF6Concentration is the solution of 1mol/L, as non-
Water electrolysis liquid.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Comparative example 5
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality hundred
Point content is 1%, 1,4- dicyano -2- butylene mass percentage is 5%, LiPF6Concentration is the solution of 1mol/L, as non-
Water electrolysis liquid.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 1
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality hundred
Point content is 0.2%, 1,4- dicyano -2- butylene mass percentage is 1%, LiPF6Concentration is the solution of 1mol/L, as
Nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 2
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality hundred
Point content is 0.5%, 1,4- dicyano -2- butylene mass percentage is 1%, LiPF6Concentration is the solution of 1mol/L, as
Nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 3
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality hundred
Point content is 1%, 1,4- dicyano -2- butylene mass percentage is 1%, LiPF6Concentration is the solution of 1mol/L, as non-
Water electrolysis liquid.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 4
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality hundred
Point content is 2%, 1,4- dicyano -2- butylene mass percentage is 1%, LiPF6Concentration is the solution of 1mol/L, as non-
Water electrolysis liquid.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 5
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and bis- (propionitrile) ethers of ethylene glycol, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality percentage
Content is 3%, 1,4- dicyano -2- butylene mass percentage is 1%, LiPF6Concentration is the solution of 1mol/L, as non-aqueous
Electrolyte.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 6
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality hundred
Point content is 1%, 1,4- dicyano -2- butylene mass percentage is 0.2%, LiPF6Concentration is the solution of 1mol/L, as
Nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 7
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality hundred
Point content is 1%, 1,4- dicyano -2- butylene mass percentage is 0.5%, LiPF6Concentration is the solution of 1mol/L, as
Nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 8
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality hundred
Point content is 1%, 1,4- dicyano -2- butylene mass percentage is 1%, LiPF6Concentration is the solution of 1mol/L, as non-
Water electrolysis liquid.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 9
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality hundred
Point content is 1%, 1,4- dicyano -2- butylene mass percentage is 2%, LiPF6Concentration is the solution of 1mol/L, as non-
Water electrolysis liquid.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 10
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality hundred
Point content is 1%, 1,4- dicyano -2- butylene mass percentage is 3%, LiPF6Concentration is the solution of 1mol/L, as non-
Water electrolysis liquid.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 11
(1) preparation of nonaqueous electrolytic solution: in drying shed, ethylene carbonate, propene carbonate and diethyl carbonate are pressed
The ratio of mass ratio EC:PC:DEC=1:1:1 is uniformly mixed, and obtains non-aqueous organic solvent.Three are added into non-aqueous organic solvent
Propyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene, are added LiPF after mixing6, obtain tripropyl phosphoric acid cyclic anhydride quality hundred
Point content is 1%, 1,4- dicyano -2- butylene mass percentage is 4%, LiPF6Concentration is the solution of 1mol/L, as non-
Water electrolysis liquid.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Table 1 provides the composition of the nonaqueous electrolytic solution of comparative example 1-5 and embodiment 1-11.
1 nonaqueous electrolytic solution of table composition
The test process of lithium ion battery will be illustrated next.
(1) the high-temperature storage performance test of lithium ion battery
The high-temperature storage performance of the lithium ion battery prepared in comparative example 1-5 and embodiment 1-11 is tested respectively,
Method is as follows: at 25 DEG C, first charging to end of charge voltage for 4.4V, then to lithium ion battery with the constant current of 0.5C
It is 0.05C with 4.4V constant-voltage charge to electric current, tests the thickness of lithium ion battery and be denoted as h0；Lithium ion battery is put into later
60 DEG C of insulating box keeps the temperature 30 days, and every the thickness of 5 days test lithium ion batteries and is denoted as hn, n is high-temperature lithium ion battery
The number of days of storage.
Thickness swelling (%)=(h after high-temperature lithium ion battery storage n daysn-h0)/h0× 100%.
(2) the cycle performance test of lithium ion battery
The cycle performance of the lithium ion battery prepared in comparative example 1-5 and embodiment 1-11 is tested respectively, method
It is as follows: at 25 DEG C, after lithium ion battery is stood 30 minutes, to be with 0.5C multiplying power constant-current charge to end of charge voltage
Then 4.4V is 0.05C with 4.4V constant-voltage charge to electric current, and stand 5 minutes, then with 0.5C multiplying power constant-current discharge to 3.0V,
This is a charge and discharge cycles process, this discharge capacity is the discharge capacity for the first time of lithium ion battery, is carried out 200 times later
Charge and discharge cycles process.
Capacity retention ratio (%)=n-th circulation discharge capacity/discharge capacity for the first time after lithium ion battery n times circulation
× 100%.
The high-temperature storage performance test result of 2 lithium ion battery of table
The cycle performance test result of 3 lithium ion battery of table
It can be seen that from comparative example 1-3 test result and individually add tripropyl phosphoric acid cyclic anhydride or 1 in nonaqueous electrolytic solution,
4- dicyano -2- butylene, can slightly improve the high-temperature storage performance and cycle performance of lithium ion battery, but effect is unknown
It is aobvious, it still will appear flatulence problem after high-temperature lithium ion battery storage and after long-term circulation.Embodiment 1-11 is in nonaqueous electrolytic solution
In be added Isosorbide-5-Nitrae-dicyano -2- butylene and tripropyl phosphoric acid cyclic anhydride, the high-temperature storage performance and circulation of lithium ion battery simultaneously
Performance is all significantly improved.High level tripropyl phosphoric acid cyclic anhydride, comparative example is added in comparative example 4 in nonaqueous electrolytic solution
5 are added high level Isosorbide-5-Nitrae-dicyano -2- butylene, since the dinitrile compound and phosphoric acid cyclic anhydride of unsaturated bond are in positive electrode surface institute
It forms composite protection film to thicken, impedance increases, and high-temperature storage performance and cycle performance is caused to reduce instead.
It can be seen that the quality hundred when tripropyl phosphoric acid cyclic anhydride in nonaqueous electrolytic solution from the test result of embodiment 1-5
When point content reaches 3%, since it is thickeied in Low ESR passivating film that surface of positive electrode active material generates, impedance increases, lithium from
The Capacity fading of sub- battery is accelerated, but still is better than comparative example 1-3.Thus, tripropyl phosphoric acid cyclic anhydride is in nonaqueous electrolytic solution
Additive amount be preferably 0.2%~2%, further preferably 0.5%~1%.
It can be seen that from the test result of embodiment 6-11 when Isosorbide-5-Nitrae-matter of the dicyano -2- butylene in nonaqueous electrolytic solution
When amount percentage composition reaches 4%, since it is too strong with the complexing of the transition metal element formation in positive electrode active materials, and
Polymerization crosslinking degree is high, and the very thick lithium ion that is unfavorable for of the protective layer of formation passes through, and causes positive impedance to dramatically increase, lithium ion battery
Capacity fading accelerates, but still is better than comparative example 1-3.Thus, Isosorbide-5-Nitrae-quality of the dicyano -2- butylene in nonaqueous electrolytic solution
Score is preferably 0.2%~3%, and further preferably 0.5%~2%.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (11)
1. a kind of nonaqueous electrolytic solution, comprising:
Non-aqueous organic solvent；
Lithium salts；And
Additive；
It is characterized in that,
The additive includes:
Phosphoric acid cyclic anhydride compound；And
Dinitrile compound containing unsaturated bond；
Mass percentage of the phosphoric acid cyclic anhydride compound in nonaqueous electrolytic solution is 0.1%~3%；
Mass percentage of the dinitrile compound containing unsaturated bond in nonaqueous electrolytic solution is 0.1%~4%.
2. nonaqueous electrolytic solution according to claim 1, which is characterized in that the phosphoric acid cyclic anhydride compound is selected from a kind of or several
Kind has the compound of formula (I) structure,
In formula (I), R1、R2、R3Alkyl, carbon atom number that carbon atom number is 1~7 is each independently selected to be 6~15 and contain
The group of at least one phenyl ring.
3. nonaqueous electrolytic solution according to claim 2, which is characterized in that R1、R2、R3It is each independently selected from carbon atom number
Alkyl, phenyl for 1~3.
4. nonaqueous electrolytic solution according to claim 2, which is characterized in that R1、R2、R3It is identical.
5. according to nonaqueous electrolytic solution described in Claims 2 or 3 or 4, which is characterized in that the phosphoric acid cyclic anhydride compound is selected from three
One or more of propyl phosphoric acid cyclic anhydride, trimethyl phosphoric acid cyclic anhydride, triethyl group phosphoric acid cyclic anhydride and triphenyl phosphoric acid cyclic anhydride.
6. nonaqueous electrolytic solution according to claim 1, which is characterized in that the dinitrile compound choosing containing unsaturated bond
There are the compounds of formula (II) structure from one or more,
In formula (II), A1The alkylene for being 1~10 selected from carbon atom number, A2The alkylene for being 1~10 selected from carbon atom number, A3
The alkyl for being 1~10 selected from H or carbon atom number, A4The alkyl for being 1~10 selected from H or carbon atom number.
7. nonaqueous electrolytic solution according to claim 6, which is characterized in that
A1The alkylidene for being 1~5 selected from carbon atom number；
A2The alkylidene for being 1~5 selected from carbon atom number；
A3Selected from H, carbon atom number be 1~5 alkyl or carbon atom number be 6~10 aryl；
A4Selected from H, carbon atom number be 1~5 alkyl or carbon atom number be 6~10 aryl.
8. nonaqueous electrolytic solution according to claim 6, which is characterized in that the dinitrile compound tool containing unsaturated bond
There is symmetrical structure.
9. the nonaqueous electrolytic solution according to claim 6 or 8, which is characterized in that the dintrile chemical combination containing unsaturated bond
Object is in 1,4- dicyano -2- butylene, 1,6- dicyano -3- hexene and 1,4- dicyano -2,3- dimethyl -2- butylene
It is one or more of.
10. nonaqueous electrolytic solution according to claim 1, which is characterized in that
Mass percentage of the phosphoric acid cyclic anhydride compound in nonaqueous electrolytic solution is 0.5%~2%；
Mass percentage of the dinitrile compound containing unsaturated bond in nonaqueous electrolytic solution is 0.5%~2%.
11. 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 1-10.
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| WO2021261886A1 (en) * | 2020-06-22 | 2021-12-30 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| EP4040558A4 (en) * | 2020-02-21 | 2023-04-19 | LG Energy Solution, Ltd. | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
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| CN109428118B (en) * | 2017-08-23 | 2021-04-30 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and electrolyte thereof |
| CN109802176B (en) * | 2017-11-16 | 2022-04-22 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery containing electrolyte |
| CN111712961B (en) * | 2018-02-16 | 2023-09-22 | 大金工业株式会社 | Electrolyte, electrochemical device, lithium ion secondary battery and assembly |
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| CN109180729B (en) * | 2018-09-05 | 2021-04-27 | 九江天赐高新材料有限公司 | Preparation method of n-propyl phosphoric cyclic anhydride |
| CN109301326B (en) | 2018-09-21 | 2020-11-27 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device |
| CN109830749B (en) | 2019-01-25 | 2021-06-04 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device |
| US20220200051A1 (en) * | 2019-11-07 | 2022-06-23 | Lg Energy Solution, Ltd. | Non-Aqueous Electrolyte Solution for Lithium Secondary Battery and Lithium Secondary Battery Including the Same |
| US20220115695A1 (en) * | 2020-03-24 | 2022-04-14 | Ningde Amperex Technology Limited | Electrolyte and electrochemical device comprising the same |
| JP2023549806A (en) * | 2020-11-12 | 2023-11-29 | 寧徳新能源科技有限公司 | Electrolytes, electrochemical devices and electronic devices |
| CN112768772B (en) * | 2021-02-22 | 2023-08-08 | 九江天赐高新材料有限公司 | Nitrile ether electrolyte additive containing tetracyano, electrolyte and lithium ion battery |
| CN114552011A (en) * | 2022-02-23 | 2022-05-27 | 珠海市赛纬电子材料股份有限公司 | Electrolyte additive, non-aqueous electrolyte and lithium ion battery |
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| KR100326461B1 (en) * | 2000-01-21 | 2002-02-28 | 김순택 | A electrolyte for a lithium secondary battery |
| JP5935318B2 (en) * | 2011-12-26 | 2016-06-15 | ソニー株式会社 | Electrolyte for lithium ion secondary battery, lithium ion secondary battery, battery pack, electric vehicle, power storage system, electric tool and electronic device |
| CN105226321A (en) * | 2015-09-14 | 2016-01-06 | 宁德新能源科技有限公司 | Electrolyte and comprise the lithium ion battery of this electrolyte |
| CN105070947B (en) * | 2015-09-22 | 2017-07-14 | 宁德新能源科技有限公司 | Electrolyte and the lithium ion battery including the electrolyte |
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| EP4040558A4 (en) * | 2020-02-21 | 2023-04-19 | LG Energy Solution, Ltd. | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| WO2021261886A1 (en) * | 2020-06-22 | 2021-12-30 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
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