CN107507998A - Nonaqueous electrolytic solution secondary battery anti-over-charging method - Google Patents
Nonaqueous electrolytic solution secondary battery anti-over-charging method Download PDFInfo
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- CN107507998A CN107507998A CN201610412559.4A CN201610412559A CN107507998A CN 107507998 A CN107507998 A CN 107507998A CN 201610412559 A CN201610412559 A CN 201610412559A CN 107507998 A CN107507998 A CN 107507998A
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- electrolytic solution
- nonaqueous electrolytic
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- secondary battery
- charging method
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of method for nonaqueous electrolytic solution secondary battery anti-over-charging.Nonaqueous electrolytic solution secondary battery anti-over-charging method, including：Under normal battery operation, chemistry or electrochemical reaction do not occur for collector/lug, when battery overcharge to voltage>During 4.2V, with anti-over-charging compound chemistry or electrochemical reaction occur for collector/lug.The anti-over-charging method of the present invention, participate in chemistry in overcharge mainly by plus plate current-collecting body/positive pole ear or electrochemistry is put and should be achieved, the present invention effectively can lift overcharge safety performance under the conditions of high current overcharge.
Description
Technical field
The present invention relates to a kind of method for nonaqueous electrolytic solution secondary battery anti-over-charging.
Background technology
The electrolyte generally use carbonates mixed solvent of nonaqueous electrolytic solution secondary battery, as propene carbonate (PC),
Diethyl carbonate (DEC), ethylene carbonate (EC), dimethyl carbonate (DMC) or methyl ethyl carbonate (EMC)), electrolytic salt is
LiPF6Or NaPF6.The boiling point and flash-point of carbonate solvent are all relatively low, and lithium-ion battery electrolytes belong to flammable liquid model
Farmland；When battery (such as high charge-discharge magnification, overcharges, high in the machinery such as impact, acupuncture, extruding abuse or abnormal use state
Used under warm environment, inside and outside short circuit etc.) under, because electrolyte is inflammable, easily trigger the security incidents such as burning, blast.Carbonic acid
Ester solvent, or most organic solvents, its oxidizing potential are generally lower than 5V；When over-charging of battery, the voltage and temperature of battery
The quick rise of degree, if positive electrode is the materials such as cobalt acid lithium, lithium nickel manganese cobalt composite oxide, Li+It can be further backing out (deep
The de- lithium of degree), discharge oxygen and heat；When reach certain potentials (such as>When 4.6V), electrolyte by active oxygen oxidation Decomposition or
Person is catalytically decomposed and (also has catalytic action while the transition metal oxide of positive pole is to solvent oxidation).Meanwhile on negative pole
Lithium metal deposits (analysis lithium), and active lithium reacts with electrolyte, or Li dendrite pierces through barrier film and triggers internal short-circuit.Inside battery occurs
A variety of violent chemistry and electrochemical reaction, substantial amounts of heat is produced, with the accumulation of inside battery heat, battery temperature is with electricity
The rising of pressure and steeply rise, the boiling point of even up to some solvents, gas caused by electrolyte decomposition and low boiling point solvent
Steam, cause cell internal pressure is also rapid therewith to rise, air-blowing, battery case breakage, leakage, phenomena such as smoldering occur.
If Mars or large area negative pole are exposed to air, then cells burst can occur or even explode.Overcharge, especially to Soft Roll
For packed battery, once causing battery case damaged, security incident is difficult to avoid.
Some additives added in the electrolytic solution controlled using its oxidation-reduction potential or electropolymerization current potential the mistake of battery
Charging, is two kinds of safeguard measures being widely adopted at present.Redox couple (redox shuttle) protection mechanism is to be electrolysed
Suitable pi-electron conjugated compound (benzene derivative, such as toluene, tert-butyl benzene, di-tert-butyl etc.) shape is added in liquid
Into redox couple.When charging normal, this redox couple does not participate in any chemistry or electrochemical reaction, and when charging electricity
Pressure exceedes when charging normal blanking voltage of battery, and additive starts to aoxidize on positive pole, and oxidation product is diffused into negative pole and gone back
Original, reduzate are diffused into positive pole and are oxidized again, and whole process circulation is carried out, until the overcharge of battery terminates.Electropolymerization is anti-
Should protect mechanism be when over-charging of battery is to certain potentials, certain polymer monomer molecule of addition (aromatic compound, such as
Biphenyl, cyclohexyl benzene etc.) electric polymerization reaction (electric polymerization reaction typically occurs in 4~6V) occurs, avoid electrolyte when overcharging
It is oxidized, decomposes；And polymerizate is covered in electrode and membrane surface, increase lithium ion abjection/insertion difficulty, battery it is interior
Resistive is big, and cell voltage reaches higher limit in shorter time, overcharge is terminated as early as possible.
Makoto Ue exist《Lithium-Ion Batteries》Overcharge defence additive is summarized in one book, point
Redox couple and electropolymerization mechanism are not described, to haloalkoxybenzene derivative, haloalkyl benzene derivative and part
The molecular structure of hydroaromatic compound is contrasted with mechanism of action.Zhu Ya common vetch et al. is also in Master's thesis《Lithium-ion electric
The research of pond overcharge safety》In the defense mechanism and additive of overcharge are discussed in depth.Chinese patent
CN102005619A discloses a kind of technology for being used in mixed way redox couple and electropolymerization, and the redox shuttle additives should have
There are preferable cyclical stability, high steric effect；And its own does not occur polymerisation during protection is overcharged, while
Also do not reacted in the presence of electropolymerization monomer with electropolymerization monomer, in redox couple/electropolymerization additive package
During use, two kinds overcharge protection mechanism and independently orderly battery are protected, and improve the safe handling of battery
Performance.But most of documents only present low capacity soft-package battery (<Successful application on 1Ah), and above-mentioned document
Point out that redox couple and electropolymerization mechanism can not play effective work in overcharge under the conditions of high magnification (high current density)
With.
The content of the invention
The present invention researcher found during nonaqueous electrolytic solution secondary battery overcharge safety is studied, no matter
It is single use redox shuttle additives or electropolymerization additive or both is used in conjunction with, applied to Large Copacity Soft Roll electricity
Pond (>Overcharge safety can not be all effectively improved when 5Ah).High capacity cell is the main flow of current power battery, and therefore, having must
Find a kind of method that can effectively lift overcharge safety under the conditions of high current overcharge.In order to solve the above problems,
The invention provides a kind of nonaqueous electrolytic solution secondary battery anti-over-charging method, including nonaqueous electrolytic solution：Under normal battery operation,
Chemistry or electrochemical reaction do not occur for collector/lug；When battery overcharge to voltage>During 4.2V, collector/lug and anti-mistake
Fill compound and chemistry or electrochemical reaction occurs.
The method that the present invention uses is different from the redox couple and electropolymerization that generally use, in the inventive method, battery
In normal operation, collector/lug is not involved in chemical or electrochemical reaction, does not influence the normal discharge and recharge of battery；Work as battery
Cross (i.e. voltage when being charged to certain potentials>During 4.2V), chemistry occurs with anti-over-charging compound for collector/lug or electrochemistry is anti-
Should, suppress electrolyte solvent and be oxidized to decompose or be catalytically decomposed that (transition metal oxide of positive pole is to the same of solvent oxidation
When also there is catalytic action), i.e., protect electrolyte in a manner of " sacrifice " collector/lug, it is ensured that electric during overcharge
Pond safety.The present invention anti-over-charging method, mainly by collector/lug in overcharge with anti-over-charging compound
Learn or electrochemistry is put and should be achieved, the chemical or electrochemical reaction being related to, including collector/lug and certain in electrolyte
The reaction of electrolyte lithium salt, the reaction of collector/lug and certain additive in electrolyte, or collector/lug and electrode plates
In a certain material reaction etc., the present invention is not construed as limiting.The anti-over-charging method of present aspect, mainly by plus plate current-collecting body/just
Pole lug participates in chemical or electrochemical reaction in overcharge and is achieved.Concrete structure and title of the present invention to collector
Be not construed as limiting, it can be metal foil, such as aluminium foil, its function mainly by electric current caused by cell active materials collect with
Just larger current versus output is formed, therefore the battery component for playing similar effect can be classified as collector scope of the present invention.
The present invention is not construed as limiting to the concrete structure and title of lug, and it can be lug metal tape, and its main function is by both positive and negative polarity
The metallic conductor extracted, therefore the battery component for playing similar effect can be classified as the scope of lug of the present invention.
Preferably, under normal battery operation, chemistry or electrochemical reaction do not occur for collector/lug；When battery mistake
Charge to voltage>During 4.4V, with anti-over-charging compound chemistry or electrochemical reaction occur for collector/lug.It is preferably, described
Anti-over-charging compound has at least one structure as shown in formula 1, formula 2, formula 3, formula 4 and formula 5：
Formula 1：MN(CmF2m+1SO2)(CnF2n+1SO2)；
Formula 2：MNCxF2x(SO2)2；
Formula 3：L(CyF2y+1SO3)k；
Formula 4：L(CH(SO2CF3)2)k；
Formula 5：L(C(SO2CF3)3)k；
Wherein, m, n are respectively natural number, and x is positive integer and x ≠ 1, y are positive integer, and k takes 1~3 integer respectively；M is
Li or Na；L is selected from Li, Na, K, Ag, Cu, Zn, Rb, Cs, Mg or Al.Natural number of the present invention includes zero.
At least meet following condition as the especially great-capacity power battery anti-over-charging method of the secondary cell in the present invention：
(1) in normal battery operation voltage range, 4.2V, not more than 4.5V are usually no more than, this method does not start, and ensures electricity
Pond performance is normal；(2) during overcharge, typically in more than 4.2V, preferably more than 4.4V, collector/lug and anti-over-charging chemical combination
Chemical or electrochemical reaction occurs for thing, and the chemistry related to electrolyte solvent and electrochemical reaction are suppressed；(3) it is resistant to
Larger current density, to the secondary cell of more than 10Ah capacity, during 1C multiplying power overcharges, cell safety is (with reference to GB/T
31485—2015)。
Preferably, the anti-over-charging compound is electrolytic salt；The electrolytic salt has as shown in formula 1 and/or formula 2
Structure.
As one embodiment of the present invention, preferred technology of the collector/lug with electrolytic salt reaction of the present invention
Scheme.By adding certain electrolytic salt in the electrolytic solution, the electrolytic salt in the range of secondary cell normal working voltage with
Chemical or electrochemical reaction does not occur for collector/lug, or nor affects on battery normal operation even if reacting.Serve as
During charging, and more than some magnitude of voltage, electrolytic salt just reacts with collector/lug.Using electrolytic salt as LiN
(SO2CF3)2And collector is exemplified by aluminium, reaction mechanism may be as follows, but is not limited to following reactions：
N(SO2CF3)2 —Ion diffuses to electrode surface, N (SO from solution bulk2CF3)2 —Ion is adsorbed to anode collection
On the active site of body/lug, at crystal defect or mechanical damage.Adsorbed N (SO2CF3)2 -Ion is lived with collector/lug
Al at property site2O3React, the complex ion formed centered on N atoms, reaction equation is as follows：
N(SO2CF3)2 —+Al2O3→{Al[N(SO2CF3)2]x}(3+x)—+02+e—
The complex ion of generation is from the diffusion into the surface of electrode to electrolyte body, diaphragm Al203It is exposed after being dissolved
Al starts to be dissolved under high potential in the electrolytic solution, similar cell reaction：
Al→Al3+ electrode+e—
Al3+From Al collectors/lug surface to electrolyte bulk diffusion,
Al3+ electrode→Al3+ bulk
Al3+Ion is adsorbed to negative terminal surface, and is reduced into metallic aluminium.
Al3+ electrode+3e—→Alelectrode
Electrolytic salt reacts with positive pole aluminium collector/aluminium pole ears, and with the rise of voltage, reaction is more violent, and
And its reaction rate exceedes the reaction rate related to electrolyte solvent, electrolyte solvent is oxidized in overcharge whole process
Or be decomposed and be inhibited, until overcharge terminates, battery bulge unobvious, so that it is guaranteed that battery outer packing is not damaged, Du
Smolder absolutely, the even security incident such as blast of burning.Or as electrolytic salt and positive pole aluminium collector/aluminium pole ears reaction aggravate,
By-product deposition is excessively violent in collector/lug surface, or even due to reacting, and lug is connected the (class that breaks down with external circuit
Like " micro- open circuit "), collector is partially disengaged with electrode coating, causes cell contact resistance to increase considerably, according to U=IR, electricity
Pressure also significantly rises in the short time therewith, terminates overcharge.
Preferably, the electrolytic salt is selected from following at least one：
Preferably, the quality of the electrolytic salt is 0.5wt%~30.0wt% of nonaqueous electrolytic solution quality.As entering
One step is preferred, and the quality of the electrolytic salt is 1.0wt%~18.0wt% of nonaqueous electrolytic solution quality.As further excellent
Choosing, the quality of the electrolytic salt are 2.0wt~10.0wt% of nonaqueous electrolytic solution quality.Addition is very few, it is impossible to plays effect
Fruit, addition is excessive, can cause cost increase, and the wind for causing corrosion to collector/lug in normal discharge and recharge be present
Danger, influences the normal performance of secondary cell.
Preferably, the anti-over-charging compound is non-water electrolytic solution additive；The non-water electrolytic solution additive is
CF3SO3Li、CF3SO3Na、CF3SO3K、KN(SO2F)2、KN(SO2CF3)2、AgN(SO2F)2、AgN(SO2CF3)2、LiC
(SO2CF3)3、LiCH(SO2CF3)2、C2F5SO3Li and C4F9SO3At least one of Li.
Preferably, the quality of the non-water electrolytic solution additive for nonaqueous electrolytic solution quality 0.1wt%~
10.0wt%.As further preferred, the quality of the non-water electrolytic solution additive for nonaqueous electrolytic solution quality 0.2wt%~
2.0wt%.As it is another preferably, the quality of the non-water electrolytic solution additive for nonaqueous electrolytic solution quality 1.0wt%~
5.0wt%.
Preferably, the anti-over-charging compound is material in pole piece；Material includes containing LiN in the pole piece
(SO2C2F5)2Or LiN (SO2F)2Polymer dielectric.As further preferred, material includes polyoxyethylene in the pole piece
Alkene (PEO) and LiN (SO2F)2Compound and/or polyethylene glycol oxide (PEO) and LiN (SO2CF3)2Compound.In the present invention
Anti-over-charging compound can be used as electrolytic salt, electrolysis additive or pole piece in certain material exist, i.e., collector/lug can
To be reacted with least one of above-mentioned three kinds of anti-over-charging compounds.Material refers to the material included in pole piece in the pole piece
Material.
Preferably, the nonaqueous electrolytic solution also includes redox shuttle additives and/or electropolymerization additive；The oxygen
Change reduction and following at least one is selected to additive or electropolymerization additive：
Wherein, R is alkyl.
The anti-over-charging method of the present invention, can also be used in conjunction with redox shuttle additives and/or electropolymerization additive.
During using redox couple or electropolymerization additive, molecular structure, regulation oxidation electricity can be adjusted according to battery material system
Position or polymerization current potential play a role in particular voltage range, chemical or electrochemical related to collector/lug of the method
Reaction synergy is learned, at utmost improves overcharge safety.Also, a variety of methods use simultaneously, it can increase and overcharge tolerance
Electric current.
Preferably, the redox shuttle additives and/or electropolymerization additive quality are nonaqueous electrolytic solution quality
0wt%~10wt%.As further preferred, redox shuttle additives and/or electropolymerization the additive quality is non-aqueous
1.0wt%~8.0wt% of electrolyte quality.As still more preferably, the redox shuttle additives and/or electropolymerization
Additive quality is 2.0wt%~5.0wt% of nonaqueous electrolytic solution quality.
Preferably, the material of the collector/lug is aluminium.
Preferably, the nonaqueous electrolytic solution also includes flame-retardant additive；The flame-retardant additive is selected from phosphate, phosphono
At least one of amine, phosphite ester, fluorophosphate ester, fluorophosphite, ionic liquid and phosphonitrile.In order to further lift lithium
The safety of ion battery, flame-retardant electrolyte or the electrolyte that do not burn are used preferably while using anti-over-charging method.Work as electricity
Under pond overheat or overcharge condition, all kinds of reactions of inside battery occur simultaneously, positive active material release active oxygen, electrolyte quilt
Oxidation Decomposition, the reaction between positive pole high-valence state transition metal and electrolyte, negative pole lower valency metallic element and electrolyte
Between reaction etc..Organic electrolyte is all extremely incendive material, and electrolyte can be reduced by adding flame-retardant additive
The energy discharged during burning.The researcher of the present invention is had found by DSC method, and 10wt% resistance is added in conventional electrolyte
Fire agent, you can so that the energy that electrolyte discharges when pyrolysis occurs for high temperature reduces by more than 70%, carried for cell safety
For another guarantee.
Preferably, the flame-retardant additive is selected from phosphate, phosphonic amide, phosphite ester, fluorophosphate ester, cyclic phosphines nitrile
And at least one of fluorophosphite.
Preferably, the flame-retardant additive is selected from following at least one：
Wherein, X1, X2, X3, X4, X5, X6Separately represent halogen or ORx；The RxRepresent that hydrogen is substituted or hydrogen not by
Substituted saturation aromatic group or the RxRepresent that hydrogen is substituted or the unsubstituted saturated aliphatic groups of hydrogen.
Preferably, the quality of the flame-retardant additive is 0wt%~88.0wt% of nonaqueous electrolytic solution quality.The resistance
The quality for firing additive is 0wt%~50.0wt% of nonaqueous electrolytic solution quality.The quality of the flame-retardant additive is non-water power
Solve 0wt%~30.0wt% of liquid quality.
The positive electrode of secondary cell of the present invention can be selected from lithium nickel cobalt manganese oxide, sodium nickel cobalt manganese composite oxygen
Compound, sodium nickel/cobalt composite oxide, lithium nickel cobalt aluminium composite oxide, li-mn-ni compound oxide, olivine-type Lithium Phosphor Oxide,
At least one of lithium and cobalt oxides, sodium cobalt/cobalt oxide, lithium manganese oxide, sodium manganese oxide and lithium-rich manganese-based composite oxides.
The negative material of secondary cell of the present invention can be selected from graphite, carbonaceous mesophase spherules, agraphitic carbon, lithium titanyl chemical combination
Thing, silica-base material, tin-based material and transition metal oxide, lithium-transition metal composite oxide and sodium transition metal combined oxidation
At least one of thing.
The barrier film of secondary cell of the present invention can be selected from polyalkene diaphragm；Or the barrier film is selected from poly terephthalic acid second two
At least one of alcohol ester, Kynoar, aramid fiber and polyamide are the barrier film of base material；Or selected from high softening-point porous matrix material
The barrier film of upper coating polyolefin.
Heretofore described nonaqueous electrolytic solution secondary battery, profile can be that cylindrical type, square etc. are variously-shaped, and pole piece can
It can be also laminated with winding, need to design according to practical application.
Brief description of the drawings
Fig. 1：In embodiment 1 during the overcharge of 1C multiplying powers voltage and temperature with overcharge time change curve map；
Fig. 2：SEM photograph before and after plus plate current-collecting body and lug overcharge in embodiment 1；
Fig. 3：In embodiment 2 during the overcharge of 1C multiplying powers voltage and temperature with overcharge time change curve map；
Fig. 4：SEM photograph before and after the plus plate current-collecting body of embodiment 2 and lug overcharge；
Fig. 5：In comparative example 1 during overcharge voltage and temperature with overcharge time change curve map；
Fig. 6：SEM photograph before and after plus plate current-collecting body and lug overcharge in comparative example 1；
Fig. 7：Embodiment 1 and secondary cell 3C3D charge and discharge cycles curves in comparative example 1.
The flexible-packed battery of embodiment 1, embodiment 2 and comparative example 1 is carried out overcharging experiment by the present invention, and observation overcharges
The outward appearance of flexible-packed battery afterwards, when any method is not taken in discovery, the Large Copacity Soft Roll ternary battery of comparative example 1 is overcharging
Burnt when electric；When taking method in embodiment 1, embodiment 2, flexible-packed battery is that pico- flatulence, outer packing are intact,
Battery core quality does not change before and after overcharge, and anti-over-charging security is obviously improved.
From Fig. 1, Fig. 3 and Fig. 5, secondary cell exists than secondary cell in comparative example 1 in embodiment 1, embodiment 2
During overcharge, more than 8.4V can be increased to by voltage in shorter time, terminate overcharge ahead of time, i.e., during overcharge, fill
Enter less capacity/energy.Compares figure 1, Fig. 3 and Fig. 5, it is also found that secondary cell compares ratio in embodiment 1, embodiment 2
In overcharge, increasing extent of temperature substantially diminishes secondary cell in embodiment 1, at the end of overcharge, battery temperature still 50 DEG C with
Under, do not take the battery of " collector and lug " the anti-over-charging method temperature before the burning of battery thermal runaway will rise to 60 DEG C with
On.
From Fig. 2 (embodiment 1), Fig. 4 (embodiment 2) and Fig. 6 (contrast implements 1), during overcharge, anti-over-charging additive
Really there occurs chemical or electrochemical reaction with collector/lug.It can be found that positive pole ear, positive pole collection from Fig. 2, Fig. 4
Fluid corrodes after overcharge, and pit occurs in lug surface, and (anode pole piece is in nipping process for the small rut of collection liquid surface
In caused by) disappeared after overcharge, big pit occurs.In contrast, it can be found that positive pole ear, plus plate current-collecting body from Fig. 6
Have almost no change, illustrate before and after overcharge, under the premise of existing for no anti-over-charging additive, overcharge behavior can't
Cause the corrosion of positive pole ear, plus plate current-collecting body.Above-mentioned phenomenon explanation, can reach suppression by " sacrifice " collector/lug
Electrolyte solvent is oxidized the purpose decomposed or be catalytically decomposed, it can be ensured that the cell safety during overcharge.
The flexible-packed battery of comparative example 2 and comparative example 3 overcharges that rear bulge is serious, the outer packing cracking of battery,
Show that redox couple or electropolymerization anti-over-charging mechanism is used alone to be had very much in Large Copacity soft-package battery, the effect of performance
Limit.Although battery does not burn finally, bulge is serious, the outer packing cracking of battery, for a long time exposed to air, security incident
It is difficult to avoid that.If after multiple battery core connection in series-parallel after comprising modules, consequence during overcharge is hardly imaginable.
To further ensure that cell safety, the flexible-packed battery of embodiment 7 and embodiment 8 overcharge and tests and observes
Its visual condition, show that a variety of anti-over-charging means can be used in conjunction with." collector and lug " anti-over-charging method and redox
Mechanism is used in conjunction with, either " collector and lug " anti-over-charging method and electropolymerization mechanism be used in conjunction with or, three is common
Use.It is, of course, also possible to it is used in conjunction with other anti-over-charging means.
The flexible-packed battery of embodiment 9 overcharge and tests and observe its outward appearance, shows to add fire-retardant add in the electrolytic solution
Add agent, make electrolyte incombustible, reduce the reaction energy of electrolyte, be used in conjunction with anti-over-charging method, can further be carried
Rise cell safety.
Fig. 7 (embodiment 1) illustrates, under normal battery operation, collector/lug is not involved in chemistry or electrochemistry is anti-
Should, the normal discharge and recharge of battery is not influenceed, and cycle life, high rate performance are suitable with not using the battery of anti-over-charging method, and (contrast is real
Apply example 1).
Embodiment
Following specific embodiment expands detailed description to the present invention, but the present invention is not restricted to following implementation
Example.
TPO is used using stacking aluminum plastic film flexible-packed battery, design capacity 10Ah, barrier film in the embodiment of the present invention
Fusion drawn barrier film.
In order to absolutely prove that anti-over-charging method of the present invention is effective, in addition to using 10Ah high capacity cells, two
The positive electrode of primary cell uses high nickel content ternary material LiNi0.5Co0.2Mn0.3O2(NCM523), plus plate current-collecting body is aluminium
Paper tinsel, negative material uses carbon-based material, including graphite (Delanium, native graphite), carbonaceous mesophase spherules and agraphitic carbon are (firmly
Carbon, soft carbon) it is at least one, negative current collector is copper foil, and battery energy density is higher.
Embodiment 1
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) is then added thereto, and content is non-aqueous
The 2.0wt% of electrolyte gross mass.It is slowly added to electrolytic salt LiPF6And cooled down, it is the non-aqueous of 8.5wt% to form concentration
Electrolyte, then it is slow added into LiFSI (double fluorine sulfimide lithiums), content 5.0wt%.
Battery overcharge safety test
First by 1C multiplying powers by constant-current charging of battery to 4.2V, then 4.2V constant-voltage charges, cut-off current 0.2C.It will be filled with electricity
Lithium ion battery be connected with overcharging electric equipment, according to rated capacity setting electric current value on galvanostat, carry out 1C overcharges,
Changed with time by digital multimeter recording voltage.Overcharge test is carried out according to the established procedures of GB/T 31485-2015
And judge whether to pass through test.
Battery cycle life test condition
Under normal temperature condition, by the discharge and recharge in 2.50V~4.10V voltage ranges of above-mentioned flexible-packed battery, constant-current charge
Multiplying power is 3C, constant-current discharge multiplying power 3C, investigates its charge and discharge cycles stability.
Overcharge rear battery dissection and analysis
After overcharge terminates, battery is dissected, takes out positive pole ear and plus plate current-collecting body, after cleaning, SEM points of sample presentation
Analysis, and compareed with the lug before overcharge and collector, reference picture 1, Fig. 3；Cathode pole piece is taken out, scrapes inferior pole piece coating, sample presentation
Icp analysis Al constituent contents, analysis result show, Al elements are contained in negative pole coating.
Embodiment 2
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) is then added thereto, and content is non-aqueous
The 2.0wt% of electrolyte heavy amount.It is slowly added to electrolytic salt LiPF6And cooled down, it is the non-of 3.5wt% to form concentration
Water electrolysis liquid, then it is slow added into LiFSI (double fluorine sulfimide lithiums), content 10.0wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Embodiment 3
The electrolyte used：Prepare ethylene carbonate (EC) and methyl ethyl carbonate (EMC) non-water mixed solvent, volume ratio
3:7, film for additive vinylene carbonate (VC) and PS (1,3-PS), content difference are then added thereto
For the 1.5wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt LiPF6And cooled down, it is 9.5wt% to form concentration
Nonaqueous electrolytic solution, be then slow added into LiTFSI (double trifluorosulfonimide lithiums), content 4.0wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Embodiment 4
The electrolyte used：Prepare ethylene carbonate (EC) and methyl ethyl carbonate (EMC) non-water mixed solvent, volume ratio
3:7, film for additive vinylene carbonate (VC) and PS (1,3-PS), content difference are then added thereto
For the 1.5wt% of nonaqueous electrolytic solution gross mass.It is slowly added to LiFSI (double fluorine sulfimide lithiums) electrolytic salts and is cooled down,
Content is 13.5wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Embodiment 5
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) is then added thereto, and content is non-aqueous
The 2.0wt% of electrolyte gross mass.It is slowly added to electrolytic salt LiBF4And cooled down, it is the non-aqueous of 1.0wt% to form concentration
Electrolyte, then it is slow added into LiFSI (double fluorine sulfimide lithiums), content 20.0wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T31485-
2015 judge to pass through test.
Embodiment 6
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) is then added thereto, and content is non-aqueous
The 2.0wt% of electrolyte gross mass.It is slowly added to electrolytic salt LiPF6And cooled down, it is the non-of 12.5wt% to form concentration
Water electrolysis liquid, is then slow added into LiCF3SO3(trifluoromethyl sulfonic acid lithium), content 1.0wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T31485-
2015 judge to pass through test.
Embodiment 7
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) and electropolymerization monomer are then added thereto
Cyclohexyl benzene, content are respectively the 2.0wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt LiPF6And cooled down,
The nonaqueous electrolytic solution that concentration is 8.5wt% is formed, is then slow added into LiFSI (double fluorine sulfimide lithiums), content is
5.0wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T31485-
2015 judge to pass through test.
Embodiment 8
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) and methylbenzene are then added thereto, are contained
Amount is respectively the 2.0wt% and 3.0wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt LiPF6And cooled down, shape
Into the nonaqueous electrolytic solution that concentration is 10.5wt%, LiFSI (double fluorine sulfimide lithiums) is then slow added into, content is
3.0wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T31485-
2015 judge to pass through test.
Embodiment 9
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) and flame-retardant additive are then added thereto
The fluorine phosphine nitrile of phenoxy group five, content are respectively the 2.0wt% and 8.0wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt
LiPF6And cooled down, the nonaqueous electrolytic solution that concentration is 8.0wt% is formed, being then slow added into LiFSI, (double fluorine sulphonyl are sub-
Amine lithium), content 5.0wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T31485-
2015 judge to pass through test.
Embodiment 10
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) and flame-retardant additive are then added thereto
Three (trifluoroethyl) phosphates, content are respectively the 2.0wt% and 10.0wt% of nonaqueous electrolytic solution gross mass.It is slowly added to be electrolysed
Matter salt LiPF6And cooled down, the nonaqueous electrolytic solution that concentration is 7.0wt% is formed, is then slow added into LiFSI (double fluorine sulphurs
Imide li), content 5.0wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Embodiment 11
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, mass ratio 20.0:32.0:32.6, film for additive vinylene carbonate (VC) is then added thereto, is contained
Measure as the 1.8wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt LiPF6And cooled down, forming concentration is
12.0wt% nonaqueous electrolytic solution, then it is slow added into LiFSI (double fluorine sulfimide lithiums), content 1.6wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T31485-
2015 judge to pass through test.
Embodiment 12
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) and fluoro ethylene are then added thereto
Alkene ester (F-EC), content are respectively the 2.0wt% and 5.0wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt LiPF6
And cooled down, the nonaqueous electrolytic solution that concentration is 12.5wt% is formed, is then slow added into AgCF3SO3(trifluoromethane sulfonic acid
Silver), content 0.5wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Embodiment 13
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) and fluoro ethylene are then added thereto
Alkene ester (F-EC), content are respectively the 2.0wt% and 5.0wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt LiPF6
And cooled down, the nonaqueous electrolytic solution that concentration is 8.0wt% is formed, is then slow added into KFSI (double fluorine sulfimide potassium),
Content is 5.0wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Embodiment 14
The secondary cell used with embodiment 1, unlike, be mixed into during anode pole piece coating paste is prepared solid
Body polymer dielectric (PEO and double fluorine sulfimide lithium compounds), double fluorine sulfimide lithiums, which account for anode pole piece coating, (not to be included
Afflux weight) quality 2.5wt%.
The non-water mixed solvent of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) is prepared,
Volume ratio 1:1:1, film for additive vinylene carbonate (VC) is then added thereto, and content is nonaqueous electrolytic solution gross mass
2.0wt%.It is slowly added to electrolytic salt LiPF6And cooled down, form the nonaqueous electrolytic solution that concentration is 13.5wt%.Battery mistake
Charging safety test is with overcharging rear battery dissection and analysis step with embodiment 1.Judged to pass through survey according to GB/T 31485-2015
Examination.
Embodiment 15
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) and fluoro ethylene are then added thereto
Alkene ester (F-EC), content are respectively the 2.0wt% and 5.0wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt LiPF6
With LiFSI (double fluorine sulfimide lithiums) and cooled down (mol ratio 9:1) nonaqueous electrolytic solution that concentration is 12.5wt%, is formed,
Then AgFSI (double fluorine sulfimide silver), content 0.1wt% are slow added into.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Embodiment 16
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) and fluoro ethylene are then added thereto
Alkene ester (F-EC), content are respectively the 2.0wt% and 5.0wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt LiPF6
With LiFSI (double fluorine sulfimide lithiums) and cooled down (mol ratio 8:2) nonaqueous electrolytic solution that concentration is 12.5wt%, is formed,
Then it is slow added into CF3SO3Na (trifluoro sodium sulfonate), content 0.5wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Embodiment 17
The electrolyte used：The non-aqueous mixing for preparing ethylene carbonate (EC), diethyl carbonate (DEC) and sulfolane is molten
Agent, volume ratio 3:5:2, then add film for additive vinylene carbonate (VC) thereto and LiBOB, content are respectively non-aqueous
The 2.0wt% and 1.0wt% of electrolyte gross mass.It is slowly added to electrolytic salt LiPF6With NaFSI (double fluorine sulfimide sodium) simultaneously
Cooled down (mol ratio 7:3) nonaqueous electrolytic solution that concentration is 13.5wt%, is formed.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Embodiment 18
The electrolyte used：Prepare ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC)
Non- water mixed solvent, volume ratio 3:3:4, film for additive vinylene carbonate (VC) is then added thereto, and content is respectively
The 3.0wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt LiPF6With NaFSI (double fluorine sulfimide sodium) and be subject to
Cool down (mol ratio 8:2) nonaqueous electrolytic solution that concentration is 13.5wt%, is formed, is then slow added into CF3SO3K (three fluosulfonic acid
Sodium), content 0.1wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Embodiment 19
The electrolyte used：Prepare ethylene carbonate (EC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) and spy
The non-water mixed solvent of valeronitrile, volume ratio 3:3:3:1, film for additive vinylene carbonate (VC) and 1 are then added thereto,
4- butyl sultones, content are respectively the 1.5wt% and 1.5wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt
LiPF6With NaFSI (double fluorine sulfimide sodium) and cooled down (mol ratio 9:1) the non-water power that concentration is 13.5wt%, is formed
Liquid is solved, is then slow added into CF3SO3K (trifluoro sodium sulfonate), content 1.0wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Comparative example 1
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) is then added thereto, and content is non-aqueous
The 2.0wt% of electrolyte gross mass.It is slowly added to electrolytic salt LiPF6And cooled down, it is the non-of 13.5wt% to form concentration
Water electrolysis liquid.
Battery overcharge safety test, cycle life test are with overcharging rear battery dissection and analysis step with embodiment 1.According to
GB/T 31485-2015 judges not passing through test.
Comparative example 2
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) and electropolymerization monomer are then added thereto
Cyclohexyl benzene, content are respectively the 2.0wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt LiPF6And cooled down,
Form the nonaqueous electrolytic solution that concentration is 13.5wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Comparative example 3
The electrolyte used：Prepare ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC)
Non- water mixed solvent, volume ratio 1:1:1, film for additive vinylene carbonate (VC) and methylbenzene are then added thereto, are contained
Amount is respectively the 2.0wt% and 3.0wt% of nonaqueous electrolytic solution gross mass.It is slowly added to electrolytic salt LiPF6And cooled down, shape
Into the nonaqueous electrolytic solution that concentration is 13.5wt%.
Battery overcharge safety test is with overcharging rear battery dissection and analysis step with embodiment 1.According to GB/T 31485-
2015 judge to pass through test.
Claims (25)
1. nonaqueous electrolytic solution secondary battery anti-over-charging method, including nonaqueous electrolytic solution, it is characterised in that：In normal battery operation
Under, chemistry or electrochemical reaction do not occur for collector/lug；When battery overcharge to voltage>During 4.2V, collector/lug with
Chemistry or electrochemical reaction occur for anti-over-charging compound.
2. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 1, it is characterised in that：In normal battery operation
Under, chemistry or electrochemical reaction do not occur for collector/lug；When battery overcharge to voltage>During 4.4V, collector/lug with
Chemistry or electrochemical reaction occur for anti-over-charging compound.
3. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 1, it is characterised in that：The anti-over-charging compound
With at least one structure as shown in formula 1, formula 2, formula 3, formula 4 and formula 5：
Formula 1：MN(CmF2m+1SO2)(CnF2n+1SO2)；
Formula 2：MNCxF2x(SO2)2；
Formula 3：L(CyF2y+1SO3)k；
Formula 4：L(CH(SO2CF3)2)k；
Formula 5：L(C(SO2CF3)3)k；
Wherein, m, n are respectively natural number, and x is positive integer and x ≠ 1, y are positive integer, and k takes 1~3 integer respectively；M be Li or
Na；L is selected from Li, Na, K, Ag, Cu, Zn, Rb, Cs, Mg or Al.
4. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 3, it is characterised in that：The anti-over-charging compound
For electrolytic salt；The electrolytic salt has the structure as shown in formula 1 and/or formula 2.
5. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 4, it is characterised in that：The electrolytic salt is selected from
Following at least one：
6. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 4, it is characterised in that：The matter of the electrolytic salt
Measure as 0.5wt%~30.0wt% of nonaqueous electrolytic solution quality
7. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 6, it is characterised in that：The matter of the electrolytic salt
Measure as 1.0wt%~18.0wt% of nonaqueous electrolytic solution quality.
8. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 7, it is characterised in that：The matter of the electrolytic salt
Measure as 2.0wt~10.0wt% of nonaqueous electrolytic solution quality.
9. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 3, it is characterised in that：The anti-over-charging compound
For non-water electrolytic solution additive；The non-water electrolytic solution additive is CF3SO3Li、CF3SO3Na、CF3SO3K、KN(SO2F)2、KN
(SO2CF3)2、AgN(SO2F)2、AgN(SO2CF3)2、LiC(SO2CF3)3、LiCH(SO2CF3)2、C2F5SO3Li and C4F9SO3In Li
It is at least one.
10. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 9, it is characterised in that：The nonaqueous electrolytic solution
The quality of additive is 0.1wt%~10.0wt% of nonaqueous electrolytic solution quality.
11. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 10, it is characterised in that：The nonaqueous electrolytic solution
The quality of additive is 0.2wt%~2.0wt% of nonaqueous electrolytic solution quality.
12. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 10, it is characterised in that：The nonaqueous electrolytic solution
The quality of additive is 1.0wt%~5.0wt% of nonaqueous electrolytic solution quality.
13. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 3, it is characterised in that：The anti-over-charging chemical combination
Thing is material in pole piece；Material includes containing LiN (SO in the pole piece2C2F5)2Or LiN (SO2F)2Polymer dielectric.
14. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 13, it is characterised in that：Material in the pole piece
Including polyethylene glycol oxide (PEO) and LiN (SO2F)2Compound, and/or polyethylene glycol oxide (PEO) and LiN (SO2CF3)2Answer
Compound.
15. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 1, it is characterised in that：The nonaqueous electrolytic solution
Including redox shuttle additives and/or electropolymerization additive；Redox shuttle additives or the electropolymerization additive is selected from
Following at least one：
Wherein, R is alkyl.
16. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 15, it is characterised in that：The redox couple
Additive and/or 0wt%~10.0wt% that electropolymerization additive quality is nonaqueous electrolytic solution quality.
17. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 16, it is characterised in that：The redox couple
Additive and/or 1.0wt%~8.0wt% that electropolymerization additive quality is nonaqueous electrolytic solution quality.
18. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 17, it is characterised in that：The redox couple
Additive and/or 2.0wt%~5.0wt% that electropolymerization additive quality is nonaqueous electrolytic solution quality.
19. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 1, it is characterised in that：Collector/the lug
Material be aluminium.
20. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 1, it is characterised in that：The nonaqueous electrolytic solution
Including flame-retardant additive；The flame-retardant additive is selected from phosphate, phosphonic amide, phosphite ester, fluorophosphate ester, fluoro phosphorous acid
At least one of ester, ionic liquid and phosphonitrile.
21. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 20, it is characterised in that：The flame-retardant additive
Selected from least one of phosphate, phosphonic amide, phosphite ester, fluorophosphate ester, cyclic phosphines nitrile and fluorophosphite.
22. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 21, it is characterised in that：The flame-retardant additive
Selected from following at least one：
Wherein, X1, X2, X3, X4, X5, X6Separately represent halogen or ORx；The RxRepresent that hydrogen is substituted or hydrogen is unsubstituted
Saturation aromatic group or the RxRepresent that hydrogen is substituted or the unsubstituted saturated aliphatic groups of hydrogen.
23. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 20, it is characterised in that：The flame-retardant additive
Quality be nonaqueous electrolytic solution quality 0wt%~88.0wt%.
24. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 23, it is characterised in that：The flame-retardant additive
Quality be nonaqueous electrolytic solution quality 0wt%~50.0wt%.
25. nonaqueous electrolytic solution secondary battery anti-over-charging method as claimed in claim 24, it is characterised in that：The flame-retardant additive
Quality be nonaqueous electrolytic solution quality 0wt%~30.0wt%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108511801A (en) * | 2018-04-10 | 2018-09-07 | 山东海容电源材料股份有限公司 | A kind of high safety type lithium battery electrolytes |
| CN110998958A (en) * | 2018-02-12 | 2020-04-10 | 株式会社Lg化学 | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
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| CN102005561A (en) * | 2009-08-31 | 2011-04-06 | 三洋电机株式会社 | Positive electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same |
| CN104752767A (en) * | 2015-03-27 | 2015-07-01 | 山东海容电源材料有限公司 | Anti-overcharge lithium battery electrolyte solution |
| CN105449189A (en) * | 2014-09-18 | 2016-03-30 | 日立麦克赛尔株式会社 | Lithium secondary battery |
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| CN102005561A (en) * | 2009-08-31 | 2011-04-06 | 三洋电机株式会社 | Positive electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same |
| CN105449189A (en) * | 2014-09-18 | 2016-03-30 | 日立麦克赛尔株式会社 | Lithium secondary battery |
| CN104752767A (en) * | 2015-03-27 | 2015-07-01 | 山东海容电源材料有限公司 | Anti-overcharge lithium battery electrolyte solution |
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| CN110998958A (en) * | 2018-02-12 | 2020-04-10 | 株式会社Lg化学 | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| US11476500B2 (en) | 2018-02-12 | 2022-10-18 | Lg Energy Solution, Ltd. | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
| CN108511801A (en) * | 2018-04-10 | 2018-09-07 | 山东海容电源材料股份有限公司 | A kind of high safety type lithium battery electrolytes |
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