CN107507998B - Overcharge-resistant method for non-aqueous electrolyte secondary battery - Google Patents
Overcharge-resistant method for non-aqueous electrolyte secondary battery Download PDFInfo
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- CN107507998B CN107507998B CN201610412559.4A CN201610412559A CN107507998B CN 107507998 B CN107507998 B CN 107507998B CN 201610412559 A CN201610412559 A CN 201610412559A CN 107507998 B CN107507998 B CN 107507998B
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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 method for preventing overcharge of a nonaqueous electrolyte secondary battery. A method of anti-overcharge for a nonaqueous electrolyte secondary battery, comprising: the current collector/tab does not chemically or electrochemically react under normal operation of the cell, and chemically or electrochemically reacts with the anti-overcharge compound when the cell is overcharged to a voltage > 4.2V. The overcharge resisting method is realized mainly by the participation of the positive current collector/the positive pole tab in chemical or electrochemical discharge during overcharge, and can effectively improve the overcharge safety performance under the condition of large-current overcharge.
Description
Technical Field
The present invention relates to a method for preventing overcharge of a nonaqueous electrolyte secondary battery.
Background
The electrolyte of the non-aqueous electrolyte secondary battery generally employs a carbonate-based mixed solvent such as Propylene Carbonate (PC), diethyl carbonate (DEC), Ethylene Carbonate (EC), dimethyl carbonate (DMC) or Ethyl Methyl Carbonate (EMC), and the electrolyte salt is LiPF6Or NaPF6. The boiling point and the flash point of the carbonate solvent are lower, and the lithium ion battery electrolyte belongs to the category of flammable liquid; when the battery is in mechanical abuse such as impact, needling, extrusion and the like or in an abnormal use state (such as high charge-discharge rate, overcharge, use in a high-temperature environment, internal and external short circuit and the like), safety accidents such as combustion, explosion and the like are easily caused due to the flammability of the electrolyte. Carbonate solvents, or most organic solvents, generally have an oxidation potential of less than 5V; when the battery is overcharged, the voltage and temperature of the battery are rapidly increased, and if the anode material is lithium cobaltate, lithium nickel manganese cobalt composite oxide and the like, Li+Further de-lithiation (deep de-lithiation) and release of oxygen and heat; when a certain potential is reached (e.g. by>4.6V), the electrolyte is oxidatively decomposed by active oxygen or catalytically decomposed (the transition metal oxide of the positive electrode has a catalytic action on the solvent while oxidizing). At the same time, metallic lithium deposits (lithium precipitation) on the negative electrode, active lithium reacts with the electrolyte, or lithium dendrites pierce the separator to initiate internal short circuits. A plurality of violent chemical and electrochemical reactions occur inside the battery, a large amount of heat is generated, the temperature of the battery rises sharply along with the rise of voltage along with the accumulation of heat inside the battery, even the boiling point of some solvents is reached,the internal pressure of the battery also rises rapidly due to the gas generated by the decomposition of the electrolyte and the steam of the low-boiling point solvent, and phenomena such as air blowing, battery shell damage, liquid leakage, smoke generation and the like occur. If there is a spark or a large area of the negative electrode is exposed to air, battery ignition or even explosion may occur. Overcharge, particularly for soft pack batteries, is difficult to avoid if the battery case is damaged.
The addition of certain additives to the electrolyte to control the overcharge of the cell by virtue of its redox potential or electropolymerization potential is two protective measures that are currently widely adopted. The redox couple (redox couple) protection mechanism is the addition of a suitable pi-electron conjugated compound (an alkylbenzene derivative, such as toluene, t-butyl benzene, di-t-butyl benzene, etc.) to the electrolyte to form a redox couple. During normal charging, the redox couple does not participate in any chemical or electrochemical reaction, and when the charging voltage exceeds the normal charge cut-off voltage of the battery, the additive begins to oxidize on the positive electrode, the oxidation product diffuses to the negative electrode to be reduced, the reduction product diffuses to the positive electrode again to be oxidized, and the whole process is cycled until the overcharge of the battery is finished. The protection mechanism of the electropolymerization reaction is that when the battery is overcharged to a certain potential, certain polymer monomer molecules (aromatic compounds such as biphenyl and cyclohexylbenzene) added undergo electropolymerization reaction (generally, electropolymerization reaction occurs at 4-6V), so that the electrolyte is prevented from being oxidized and decomposed during overcharging; and the polymerization product covers the surfaces of the electrode and the diaphragm, so that the difficulty in lithium ion extraction/insertion is increased, the internal resistance of the battery is increased, and the voltage of the battery reaches an upper limit value in a shorter time, so that the overcharge is stopped as soon as possible.
Makoto Ue reviewed overcharge protection additives in Lithium-Ion Batteries, which introduced redox couple and electropolymerization mechanisms, respectively, compared molecular structures and mechanisms of action for haloalkoxybenzene derivatives, haloalkylbenzene derivatives, and partially hydrogenated aromatic compounds. Zhu ya Osmunda et al also made an intensive study on the overcharge protection mechanism and additives in Master 'study on lithium ion battery overcharge safety'. Chinese patent CN102005619A discloses a technique of using redox couple and electropolymerization in a mixed way, and the redox couple additive has better circulation stability and high steric effect; and the overcharge protection process does not generate polymerization reaction per se, and simultaneously does not react with the electropolymerization monomer under the condition that the electropolymerization monomer exists, and in the use process of the redox couple/electropolymerization mixed additive, the two overcharge protection mechanisms are independent and orderly to protect the battery, so that the safety use performance of the battery is improved. However, most of the documents show only successful application to small capacity pouch batteries (<1Ah), and the above documents also indicate that redox couple and electropolymerization mechanism do not exert effective action when overcharged under high rate (large current density) conditions.
Disclosure of Invention
In the process of researching the overcharge safety of the non-aqueous electrolyte secondary battery, the researchers of the invention find that whether the redox shuttle additive or the electropolymerization additive is used alone or the redox shuttle additive and the electropolymerization additive are used together, the overcharge safety can not be effectively improved when the redox shuttle additive is applied to a high-capacity soft package battery (>5 Ah). High-capacity batteries are the mainstream of current power batteries, and therefore, a method for effectively improving overcharge safety under the condition of high-current overcharge needs to be found. In order to solve the above problems, the present invention provides a method for preventing overcharge of a nonaqueous electrolyte secondary battery, comprising: under the normal work of the battery, the current collector/the electrode lug does not generate chemical or electrochemical reaction; when the cell is overcharged to a voltage >4.2V, the current collector/tab chemically or electrochemically reacts with the anti-overcharge compound.
The method adopted by the invention is different from the commonly used redox couple and electropolymerization, in the method, the current collector/tab does not participate in chemical or electrochemical reaction under the normal work of the battery, and the normal charge and discharge of the battery are not influenced; when the battery is overcharged to a certain potential (namely, when the voltage is greater than 4.2V), the current collector/tab and the overcharge-resisting compound generate chemical or electrochemical reaction, and the electrolyte solvent is inhibited from being oxidized and decomposed or catalytically decomposed (the transition metal oxide of the positive electrode has catalytic action while oxidizing the solvent), namely, the electrolyte is protected in a mode of 'sacrificing' the current collector/tab, and the safety of the battery in the overcharge process is ensured. The overcharge resisting method of the present invention is realized mainly through chemical or electrochemical reaction of the current collector/tab and overcharge resisting compound during overcharge, and the related chemical or electrochemical reaction includes the reaction of the current collector/tab and some electrolyte lithium salt in electrolyte, the reaction of the current collector/tab and some additive in electrolyte, the reaction of the current collector/tab and some material in electrode sheet, etc. the present invention is not limited. The anti-overcharge method of this aspect is achieved primarily by the positive current collector/positive tab participating in a chemical or electrochemical reaction upon overcharge. The invention is not limited to the specific structure and name of the current collector, and the current collector can be a metal foil, such as an aluminum foil, the function of the current collector is mainly to collect the current generated by the active materials of the battery so as to form larger current output, and therefore, the battery components with similar functions can be classified as the current collector of the invention. The invention does not limit the specific structure and name of the pole ear, and the pole ear metal band can be used as a metal conductor for leading out the positive pole and the negative pole, so that the battery components with similar functions can be classified as the pole ear of the invention.
Preferably, the current collector/tab does not undergo chemical or electrochemical reactions under normal operation of the battery; when the cell is overcharged to a voltage >4.4V, the current collector/tab chemically or electrochemically reacts with the anti-overcharge compound. Preferably, the anti-overcharge compound has at least one structure represented by formula 1, formula 2, formula 3, formula 4, and formula 5:
formula 1: MN (C)mF2m+1SO2)(CnF2n+1SO2)；
Formula 2: MNCxF2x(SO2)2；
Formula 3: l (C)yF2y+1SO3)k；
Formula 4: l (CH (SO)2CF3)2)k；
Formula 5: l (C (SO)2CF3)3)k；
Wherein m and n are natural numbers respectively, x is a positive integer and x is not equal to 1, y is a positive integer, and k is an integer of 1-3 respectively; m is Li or Na; l is selected from Li, Na, K, Ag, Cu, Zn, Rb, Cs, Mg or Al. The natural number of the present invention includes zero.
The anti-overcharge method of the secondary battery, especially the large-capacity power battery, at least meets the following conditions: (1) in the normal working voltage range of the battery, the voltage is generally not more than 4.2V, and the highest voltage is not more than 4.5V, the method is not started, and the normal performance of the battery is ensured; (2) upon overcharge, generally 4.2V or more, preferably 4.4V or more, the current collector/tab chemically or electrochemically reacts with the overcharge-resisting compound, while chemical and electrochemical reactions with the electrolyte solvent are suppressed; (3) the lithium ion secondary battery can resist large current density, and is safe when overcharged at a rate of 1C for a secondary battery with the capacity of more than 10Ah (refer to GB/T31485-2015).
Preferably, the overcharge resistance compound is an electrolyte salt; the electrolyte salt has a structure as shown in formula 1 and/or formula 2.
The invention preferably adopts the technical scheme that the current collector/tab reacts with the electrolyte salt as one embodiment of the invention. By adding certain electrolyte salt into the electrolyte, the electrolyte salt does not react with the current collector/electrode lug chemically or electrochemically within the normal working voltage range of the secondary battery, or even if the reaction occurs, the normal operation of the battery is not influenced. The electrolyte salt reacts with the current collector/tab when overcharged, and above a certain voltage value. Taking electrolyte salt as LiN (SO)2CF3)2And the current collector is aluminum, the reaction mechanism may be as follows, but is not limited to the following reaction:
N(SO2CF3)2 —diffusion of ions from the bulk of the solution to the electrode surface, N (SO)2CF3)2 —The ions are adsorbed onto active sites of the positive current collector/tab, such as crystal defects or mechanical damage. Adsorbed N (SO)2CF3)2 -Active site Al of ion and current collector/electrode ear2O3Reacting to form complex ion with N atom as centerThe reaction formula is as follows:
N(SO2CF3)2 —+Al2O3→{Al[N(SO2CF3)2]x}(3+x)—+02+e—
the generated complex ions are diffused to the electrolyte body from the surface of the electrode to protect the Al film 203After being dissolved, bare Al starts to be dissolved in the electrolyte at a high potential, similar to the electrolytic reaction:
Al→Al3+ electrode+e—
Al3+diffusing from the surface of the Al current collector/electrode lug to the electrolyte body,
Al3+ electrode→Al3+ bulk
Al3+the ions are adsorbed to the surface of the negative electrode and reduced to metallic aluminum.
Al3+ electrode+3e—→Alelectrode
The electrolyte salt reacts with the positive aluminum current collector/aluminum tab, the reaction is more violent along with the rise of voltage, the reaction rate exceeds the reaction rate related to the electrolyte solvent, the electrolyte solvent is oxidized or decomposed in the whole process of overcharge to be inhibited until the overcharge is finished, and the battery bulge is not obvious, so that the external package of the battery is not damaged, and the safety accidents of smoke, combustion, even explosion and the like are avoided. Or, as the reaction between the electrolyte salt and the positive aluminum current collector/aluminum tab is intensified, the by-product is deposited on the surface of the current collector/tab, even if the reaction is too violent, the tab is connected with an external circuit to cause a fault (similar to a 'micro-open circuit'), the current collector is partially separated from the electrode coating, so that the contact resistance of the battery is greatly increased, and the voltage is greatly increased in a short time according to U-IR, so that the overcharge is stopped.
Preferably, the electrolyte salt is selected from at least one of:
preferably, the mass of the electrolyte salt is 0.5 wt% to 30.0 wt% of the mass of the nonaqueous electrolytic solution. More preferably, the mass of the electrolyte salt is 1.0 wt% to 18.0 wt% of the mass of the nonaqueous electrolytic solution. More preferably, the mass of the electrolyte salt is 2.0 to 10.0 wt% of the mass of the nonaqueous electrolytic solution. The addition amount is too small to exert the effect, the addition amount is too large, the cost is increased, and the risk of corrosion to the current collector/tab during normal charge and discharge exists, so that the normal performance of the secondary battery is influenced.
Preferably, the overcharge-resistant compound is a nonaqueous electrolyte additive; the non-aqueous electrolyte 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 mass of the nonaqueous electrolyte additive is 0.1 wt% to 10.0 wt% of the mass of the nonaqueous electrolyte. More preferably, the mass of the nonaqueous electrolyte additive is 0.2 to 2.0 wt% of the mass of the nonaqueous electrolyte. Preferably, the mass of the nonaqueous electrolyte additive is 1.0 wt% to 5.0 wt% of the mass of the nonaqueous electrolyte.
Preferably, the anti-overcharge compound is a material in the pole piece; the material in the pole piece comprises LiN (SO)2C2F5)2Or LiN (SO)2F)2The polymer electrolyte of (1). Preferably, the materials in the pole piece include polyethylene oxide (PEO) and LiN (SO)2F)2And/or polyethylene oxide (PEO) and LiN (SO)2CF3)2The complex of (1). The overcharge-resisting compound in the present invention can be added as an electrolyte salt or an electrolytic solutionThe presence of a material in the agent or pole piece, i.e., the current collector/tab, may react with at least one of the three overcharge-resistant compounds described above. The material in the pole piece refers to the material contained in the pole piece.
Preferably, the nonaqueous electrolytic solution further comprises a redox couple additive and/or an electropolymerization additive; the redox shuttle additive or electropolymerization additive is selected from at least one of:
wherein R is a hydrocarbyl group.
The anti-overcharge method of the present invention may also be used in conjunction with a redox shuttle additive and/or an electropolymerization additive. When the redox couple or the electropolymerization additive is used, the molecular structure can be adjusted according to a battery material system, the oxidation potential or the polymerization potential can be adjusted to play a role in a specific voltage range, and the method is cooperated with the chemical or electrochemical reaction related to a current collector/electrode lug to improve the overcharge safety to the maximum extent. And, multiple methods are used simultaneously, can increase the overcharge withstand current.
Preferably, the mass of the redox shuttle additive and/or the electropolymerization additive is 0 wt% to 10 wt% of the mass of the nonaqueous electrolytic solution. More preferably, the redox shuttle additive and/or electropolymerization additive accounts for 1.0-8.0 wt% of the mass of the nonaqueous electrolyte. More preferably, the redox shuttle additive and/or electropolymerization additive accounts for 2.0-5.0 wt% of the nonaqueous electrolyte.
Preferably, the current collector/tab is made of aluminum.
Preferably, the nonaqueous electrolytic solution further comprises a flame retardant additive; the flame retardant additive is at least one selected from the group consisting of phosphate esters, phosphonamides, phosphite esters, fluorophosphate esters, fluorophosphite esters, ionic liquids, and phosphazenes. In order to further improve the safety of the lithium ion battery, it is preferable to use a flame-retardant electrolyte or a non-combustible electrolyte while using an anti-overcharge method. When the battery is overheated or overcharged, various reactions in the battery occur simultaneously, active oxygen is released from the positive active substance, the electrolyte is oxidized and decomposed, the high-valence transition metal element of the positive electrode reacts with the electrolyte, the low-valence metal element of the negative electrode reacts with the electrolyte, and the like. The organic electrolyte is extremely combustible, and the energy released by the electrolyte during combustion can be reduced by adding the flame retardant additive. According to the DSC method, researchers of the invention find that the energy released by the electrolyte during the thermal decomposition reaction at high temperature can be reduced by more than 70% by adding 10 wt% of flame retardant into the common electrolyte, so that another guarantee is provided for the safety of the battery.
Preferably, the flame retardant additive is at least one selected from the group consisting of phosphate esters, phosphonamides, phosphite esters, fluorophosphate esters, cyclic phosphazenes, and fluorophosphite esters.
Preferably, the flame retardant additive is selected from at least one of:
wherein, X1，X2，X3，X4，X5，X6Each independently represents halogen OR ORx(ii) a The R isxRepresents a saturated aromatic group in which hydrogen is substituted or unsubstituted or said RxRepresents a saturated aliphatic group in which hydrogen is substituted or unsubstituted.
Preferably, the mass of the flame retardant additive is 0 wt% to 88.0 wt% of the mass of the nonaqueous electrolyte. The mass of the flame retardant additive is 0-50.0 wt% of the mass of the nonaqueous electrolyte. The mass of the flame retardant additive is 0-30.0 wt% of the mass of the nonaqueous electrolyte.
The positive electrode material of the secondary battery of the present invention may be at least one selected from the group consisting of lithium nickel cobalt manganese composite oxide, sodium nickel cobalt composite oxide, lithium nickel cobalt aluminum composite oxide, lithium manganese nickel composite oxide, olivine-type lithium phosphorus oxide, lithium cobalt oxide, sodium cobalt oxide, lithium manganese oxide, sodium manganese oxide, and lithium manganese rich-based composite oxide.
The negative electrode material of the secondary battery can be at least one selected from graphite, mesocarbon microbeads, amorphous carbon, lithium titanium oxide, silicon-based materials, tin-based materials, transition metal oxides, lithium transition metal composite oxides and sodium transition metal composite oxides.
The separator of the secondary battery of the present invention may be selected from polyolefin separators; or the diaphragm is selected from at least one of polyethylene terephthalate, polyvinylidene fluoride, aramid fiber and polyamide as a base material; or a separator selected from a high softening point porous matrix material coated with polyolefin.
The shape of the non-aqueous electrolyte secondary battery can be various shapes such as cylindrical shape, square shape and the like, and the pole pieces can be wound or laminated and are designed according to the actual application requirement.
Drawings
FIG. 1: the 1C rate overcharge voltage and temperature change with overcharge time in example 1;
FIG. 2: SEM photographs before and after overcharge of the positive electrode current collector and the tab in example 1;
FIG. 3: the 1C rate overcharge voltage and temperature change with overcharge time in example 2;
FIG. 4: example 2 SEM photographs before and after overcharge of the positive electrode current collector and tab;
FIG. 5: comparative example 1 is a graph showing the change of voltage and temperature with overcharge time;
FIG. 6: SEM photographs before and after overcharge of the positive electrode current collector and the tab in comparative example 1;
FIG. 7: the charge and discharge cycle curves of the secondary battery 3C3D in example 1 and comparative example 1.
The invention carries out overcharge test on the soft package batteries of the embodiment 1, the embodiment 2 and the comparative embodiment 1, observes the appearance of the soft package battery after overcharge, and discovers that the high-capacity soft package ternary battery of the comparative embodiment 1 burns when overcharged when no method is adopted; when the method in the embodiment 1 and the embodiment 2 is adopted, the soft package battery is slightly inflated, the outer package is good, the quality of the battery core is not changed before and after overcharging, and the overcharge resistance safety is obviously improved.
As can be seen from fig. 1,3 and 5, the secondary batteries of examples 1 and 2 can increase in voltage to 8.4V or more in a shorter time than the secondary battery of comparative example 1 when overcharged, and the overcharge is terminated early, that is, less capacity/energy is charged during the overcharge. Referring to fig. 1,3 and 5, it can be seen that the temperature rise of the secondary batteries of examples 1 and 2 is significantly smaller than that of the secondary battery of comparative example 1 during overcharge, the battery temperature is still below 50 ℃ at the end of overcharge, and the temperature of the battery without the "collector and tab" anti-overcharge method is raised to above 60 ℃ before thermal runaway combustion.
As can be seen from fig. 2 (example 1), fig. 4 (example 2) and fig. 6 (comparative example 1), the overcharge inhibitor does chemically or electrochemically react with the current collector/tab during overcharge. As can be seen from fig. 2 and 4, the positive electrode tab and the positive electrode current collector are corroded after overcharging, pits appear on the tab surface, small pits (caused by the positive electrode sheet during rolling) on the current collector surface disappear after overcharging, and large pits appear. In contrast, it can be seen from fig. 6 that the positive electrode tab and the positive electrode current collector hardly change before and after overcharge, which indicates that the overcharge behavior does not cause corrosion of the positive electrode tab and the positive electrode current collector without the overcharge resistance additive. The above phenomena illustrate that the purpose of inhibiting the electrolyte solvent from being oxidatively decomposed or catalytically decomposed can be achieved by "sacrificing" the current collector/tab, and the safety of the battery during overcharge can be ensured.
The soft package batteries of comparative example 2 and comparative example 3 have serious bulging after overcharge, and the outer package of the batteries cracks, which shows that the redox couple or electropolymerization anti-overcharge mechanism is used for the high-capacity soft package battery alone, and the effect is very limited. Although the battery is not burnt at last, the bulge is serious, the outer package of the battery is cracked, the battery is exposed to air for a long time, and safety accidents are difficult to avoid. If a plurality of battery cells are connected in series and in parallel to form a module, the result of overcharge is unreasonable.
To further ensure the safety of the batteries, the soft pack batteries of examples 7 and 8 were subjected to an overcharge test and observed in appearance, indicating that various anti-overcharge means can be used in common. The current collector and tab anti-overcharge method and the redox couple mechanism are used together, or the current collector and tab anti-overcharge method and the electropolymerization mechanism are used together, or the current collector and the tab anti-overcharge method, the electropolymerization mechanism and the electropolymerization mechanism are used together. Of course, other means of anti-overcharge may also be used.
The overcharge test of the flexible package battery of example 9 was performed and the appearance thereof was observed, indicating that the addition of the flame retardant additive to the electrolyte made the electrolyte nonflammable, reducing the reaction energy of the electrolyte, and the use with the overcharge resistance method could further improve the battery safety.
Fig. 7 (example 1) illustrates that under normal operation of the battery, the current collectors/tabs do not participate in chemical or electrochemical reactions, normal charge and discharge of the battery is not affected, and the cycle life and rate performance are equivalent to those of the battery without the anti-overcharge method (comparative example 1).
Detailed Description
The following specific examples are intended to describe the present invention in detail, but the present invention is not limited to the following examples.
In the embodiment of the invention, the laminated aluminum-plastic film flexible package battery is adopted, the design capacity is 10Ah, and the diaphragm is a polyolefin melt-drawn diaphragm.
In order to fully illustrate the effectiveness of the overcharge resisting method of the present invention, in addition to the use of a 10Ah large-capacity battery, a ternary material LiNi with a high nickel content was used as a positive electrode material of a secondary battery0.5Co0.2Mn0.3O2(NCM523), the positive current collector is aluminum foil, the negative electrode material is carbon-based material comprising at least one of graphite (artificial graphite and natural graphite), mesocarbon microbeads and amorphous carbon (hard carbon and soft carbon), and the negative current collector is copper foil, so that the energy density of the battery is high.
Example 1
Electrolyte used: preparing a non-aqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1, and adding a film-forming agent to the mixed solventVinylene Carbonate (VC) as additive in 2.0 wt% of total weight of nonaqueous electrolyte. Slowly adding electrolyte salt LiPF6And cooled to form a nonaqueous electrolytic solution having a concentration of 8.5 wt%, and then LiFSI (lithium bis (fluorosulfonyl imide)) was slowly added in an amount of 5.0 wt%.
Battery overcharge safety test
The battery is charged to 4.2V by constant current according to 1C multiplying power, then charged by constant voltage of 4.2V, and the current is cut off by 0.2C. And connecting the fully charged lithium ion battery with overcharge equipment, setting a current value on a constant current instrument according to rated capacity, carrying out 1C overcharge, and recording the change of voltage along with time through a digital multimeter. And (3) carrying out overcharge test according to the specified program of GB/T31485-2015 and judging whether the test is passed or not.
Battery cycle life test conditions
Under the condition of normal temperature, the flexible package battery is charged and discharged in the voltage range of 2.50V-4.10V, the constant current charging rate is 3C, the constant current discharging rate is 3C, and the charge-discharge cycle stability of the flexible package battery is examined.
Post overcharge battery dissection analysis
After the overcharge is finished, dissecting the battery, taking out the positive electrode tab and the positive electrode current collector, cleaning, carrying out SEM analysis, and comparing with the tab and the current collector before the overcharge, and referring to fig. 1 and fig. 3; and taking out the negative pole piece, scraping the pole piece coating, and feeding a sample for ICP analysis of Al element content, wherein the analysis result shows that the negative pole coating contains Al element.
Example 2
Electrolyte used: a non-aqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) was prepared in a volume ratio of 1:1:1, and then a film-forming additive, Vinylene Carbonate (VC), was added thereto in an amount of 2.0 wt% based on the weight mass of the non-aqueous electrolyte. Slowly adding electrolyte salt LiPF6And cooled to form a nonaqueous electrolytic solution having a concentration of 3.5 wt%, and then LiFSI (lithium bis (fluorosulfonyl imide)) was slowly added thereto in an amount of 10.0 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 3
Electrolyte used: preparing a non-aqueous mixed solvent of Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 3:7, and then adding film-forming additives of Vinylene Carbonate (VC) and 1, 3-propane sultone (1,3-PS) into the non-aqueous mixed solvent, wherein the content of the Vinylene Carbonate (VC) and the 1, 3-propane sultone (1,3-PS) are respectively 1.5 wt% of the total mass of the non-aqueous electrolyte. Slowly adding electrolyte salt LiPF6And cooled to form a 9.5 wt% nonaqueous electrolytic solution, and then LiTFSI (lithium bistrifluorosulfonimide) was slowly added in an amount of 4.0 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 4
Electrolyte used: preparing a non-aqueous mixed solvent of Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 3:7, and then adding film-forming additives of Vinylene Carbonate (VC) and 1, 3-propane sultone (1,3-PS) into the non-aqueous mixed solvent, wherein the content of the Vinylene Carbonate (VC) and the 1, 3-propane sultone (1,3-PS) are respectively 1.5 wt% of the total mass of the non-aqueous electrolyte. LiFSI (lithium bis (fluorosulfonylimide)) electrolyte salt was slowly added and cooled to a content of 13.5 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 5
Electrolyte used: a nonaqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) was prepared in a volume ratio of 1:1:1, and then Vinylene Carbonate (VC), a film-forming additive, was added thereto in an amount of 2.0 wt% based on the total mass of the nonaqueous electrolytic solution. Slowly adding electrolyte salt LiBF4And cooled to form a non-aqueous electrolyte solution having a concentration of 1.0 wt%, and then LiFSI (lithium bis (fluorosulfonyl imide)) was slowly added thereto in an amount of 20.0 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 6
Electrolyte used: preparation of ethylene carbonate(EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1, and then a film-forming additive Vinylene Carbonate (VC) was added thereto in an amount of 2.0 wt% based on the total mass of the nonaqueous electrolytic solution. Slowly adding electrolyte salt LiPF6Cooling to form 12.5 wt% non-aqueous electrolyte, and slowly adding LiCF3SO3(lithium trifluoromethanesulfonate) in an amount of 1.0% by weight.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 7
Electrolyte used: preparing a non-aqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1, and then adding a film-forming additive of Vinylene Carbonate (VC) and an electropolymerization monomer of cyclohexylbenzene, wherein the contents of the Vinylene Carbonate (VC) and the electropolymerization monomer of cyclohexylbenzene are respectively 2.0 wt% of the total mass of the non-aqueous electrolyte. Slowly adding electrolyte salt LiPF6And cooled to form a nonaqueous electrolytic solution having a concentration of 8.5 wt%, and then LiFSI (lithium bis (fluorosulfonyl imide)) was slowly added in an amount of 5.0 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 8
Electrolyte used: a nonaqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) was prepared in a volume ratio of 1:1:1, and then Vinylene Carbonate (VC) and methylbenzene, which are film-forming additives, were added thereto in amounts of 2.0 wt% and 3.0 wt%, respectively, of the total mass of the nonaqueous electrolytic solution. Slowly adding electrolyte salt LiPF6And cooled to form a nonaqueous electrolytic solution having a concentration of 10.5 wt%, and then LiFSI (lithium bis (fluorosulfonyl imide)) was slowly added thereto in an amount of 3.0 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 9
Electrolyte used: fitting for mixingPreparing a non-aqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1, and then adding a film-forming additive of Vinylene Carbonate (VC) and a flame-retardant additive of phenoxy pentafluorophosphazene into the non-aqueous mixed solvent, wherein the contents of the Vinylene Carbonate (VC) and the flame-retardant additive of phenoxy pentafluorophosphazene are respectively 2.0 wt% and 8.0 wt% of the total mass of the non-aqueous electrolyte. Slowly adding electrolyte salt LiPF6And cooled to form a nonaqueous electrolytic solution having a concentration of 8.0 wt%, and then LiFSI (lithium bis (fluorosulfonyl imide)) was slowly added in an amount of 5.0 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 10
Electrolyte used: a nonaqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) was prepared in a volume ratio of 1:1:1, and then a film-forming additive, Vinylene Carbonate (VC) and a flame-retardant additive, tris (trifluoroethyl) phosphate, were added thereto in amounts of 2.0 wt% and 10.0 wt%, respectively, of the total mass of the nonaqueous electrolytic solution. Slowly adding electrolyte salt LiPF6And cooled to form a nonaqueous electrolytic solution having a concentration of 7.0 wt%, and then LiFSI (lithium bis (fluorosulfonyl imide)) was slowly added in an amount of 5.0 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 11
Electrolyte used: a nonaqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) was prepared in a mass ratio of 20.0:32.0:32.6, and then Vinylene Carbonate (VC), a film forming additive, was added thereto in an amount of 1.8 wt% based on the total mass of the nonaqueous electrolytic solution. Slowly adding electrolyte salt LiPF6And cooled to form a 12.0 wt% nonaqueous electrolytic solution, and then LiFSI (lithium bis (fluorosulfonyl) imide) was slowly added in an amount of 1.6 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 12
Electrolyte used: a nonaqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) was prepared in a volume ratio of 1:1:1, and then Vinylene Carbonate (VC) and fluoroethylene carbonate (F-EC), which are film forming additives, were added thereto in amounts of 2.0 wt% and 5.0 wt%, respectively, of the total mass of the nonaqueous electrolytic solution. Slowly adding electrolyte salt LiPF6Cooling to form 12.5 wt% nonaqueous electrolyte, and slowly adding AgCF3SO3(silver trifluoromethanesulfonate), content 0.5% by weight.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 13
Electrolyte used: a nonaqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) was prepared in a volume ratio of 1:1:1, and then Vinylene Carbonate (VC) and fluoroethylene carbonate (F-EC), which are film forming additives, were added thereto in amounts of 2.0 wt% and 5.0 wt%, respectively, of the total mass of the nonaqueous electrolytic solution. Slowly adding electrolyte salt LiPF6And cooled to form a nonaqueous electrolytic solution having a concentration of 8.0 wt%, followed by slowly adding KFSI (potassium bis-fluorosulfonylimide) in an amount of 5.0 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 14
The secondary battery used was the same as in example 1, except that a solid polymer electrolyte (a composite of PEO and lithium bis (fluorosulfonyl) imide) was mixed in the process of preparing the positive electrode sheet coating slurry, and the lithium bis (fluorosulfonyl) imide accounted for 2.5 wt% of the mass of the positive electrode sheet coating (excluding the mass of the current collector).
A nonaqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) was prepared in a volume ratio of 1:1:1, and then Vinylene Carbonate (VC), a film-forming additive, was added thereto in an amount of 2.0 wt% based on the total mass of the nonaqueous electrolytic solution. Slowly adding electrolyte salt LiPF6And cooled to formA nonaqueous electrolytic solution having a concentration of 13.5 wt%. The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 15
Electrolyte used: a nonaqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) was prepared in a volume ratio of 1:1:1, and then Vinylene Carbonate (VC) and fluoroethylene carbonate (F-EC), which are film forming additives, were added thereto in amounts of 2.0 wt% and 5.0 wt%, respectively, of the total mass of the nonaqueous electrolytic solution. Slowly adding electrolyte salt LiPF6And LiFSI (lithium bis (fluorosulfonyl) imide) and cooled (molar ratio 9:1) to form a 12.5 wt% nonaqueous electrolyte, and then AgFSI (silver bis (fluorosulfonyl) imide) was slowly added in an amount of 0.1 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 16
Electrolyte used: a nonaqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) was prepared in a volume ratio of 1:1:1, and then Vinylene Carbonate (VC) and fluoroethylene carbonate (F-EC), which are film forming additives, were added thereto in amounts of 2.0 wt% and 5.0 wt%, respectively, of the total mass of the nonaqueous electrolytic solution. Slowly adding electrolyte salt LiPF6And LiFSI (lithium bis (fluorosulfonyl) imide) and cooled (molar ratio 8:2) to form a 12.5 wt% nonaqueous electrolyte, and then slowly adding CF3SO3Na (sodium triflate) in an amount of 0.5 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 17
Electrolyte used: preparing a non-aqueous mixed solvent of Ethylene Carbonate (EC), diethyl carbonate (DEC) and sulfolane in a volume ratio of 3:5:2, and then adding film-forming additives of Vinylene Carbonate (VC) and LiBOB into the non-aqueous mixed solvent, wherein the content of the Vinylene Carbonate (VC) and the content of the LiBOB are respectively 2.0 wt% and 1.0 wt% of the total mass of the non-aqueous electrolyte. Slow addition electrolysisLiPF (sodium LiPF)6And NaFSI (sodium bis (fluorosulfonylimide)) and cooled (molar ratio 7:3) to form a 13.5 wt% strength nonaqueous electrolyte.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 18
Electrolyte used: a nonaqueous mixed solvent of Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) was prepared in a volume ratio of 3:3:4, and Vinylene Carbonate (VC), a film forming additive, was added thereto in an amount of 3.0 wt% based on the total mass of the nonaqueous electrolytic solution, respectively. Slowly adding electrolyte salt LiPF6And NaFSI (sodium bis (fluorosulfonyl) imide) and cooled (molar ratio 8:2) to form a 13.5 wt% nonaqueous electrolyte, and then slowly adding CF3SO3K (sodium trifluorosulfonate) in an amount of 0.1 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Example 19
Electrolyte used: preparing a nonaqueous mixed solvent of Ethylene Carbonate (EC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC) and pivalonitrile in a volume ratio of 3:3:3:1, and then adding film-forming additives of Vinylene Carbonate (VC) and 1, 4-butanesultone into the nonaqueous mixed solvent, wherein the content of the Vinylene Carbonate (VC) and the content of the 1.5 wt% and the 1.5 wt% of the total mass of the nonaqueous electrolyte respectively. Slowly adding electrolyte salt LiPF6And NaFSI (sodium bis (fluorosulfonylimide)) was cooled (molar ratio 9:1) to form a 13.5 wt% nonaqueous electrolyte, and then CF was slowly added3SO3K (sodium trifluorosulfonate) with the content of 1.0wt percent.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Comparative example 1
Electrolyte used: preparing a non-aqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1, and adding a film-forming additive to the mixed solventVinylene Carbonate (VC) as additive, the content of which is 2.0 wt% of the total mass of the nonaqueous electrolytic solution. Slowly adding electrolyte salt LiPF6And cooled to form a nonaqueous electrolytic solution having a concentration of 13.5 wt%.
The procedure for the overcharge safety test, cycle life test and the analysis of the battery after overcharge were the same as in example 1. The test was judged failed according to GB/T31485-2015.
Comparative example 2
Electrolyte used: preparing a non-aqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1, and then adding a film-forming additive of Vinylene Carbonate (VC) and an electropolymerization monomer of cyclohexylbenzene, wherein the contents of the Vinylene Carbonate (VC) and the electropolymerization monomer of cyclohexylbenzene are respectively 2.0 wt% of the total mass of the non-aqueous electrolyte. Slowly adding electrolyte salt LiPF6And cooled to form a nonaqueous electrolytic solution having a concentration of 13.5 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Comparative example 3
Electrolyte used: a nonaqueous mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) was prepared in a volume ratio of 1:1:1, and then Vinylene Carbonate (VC) and methylbenzene, which are film-forming additives, were added thereto in amounts of 2.0 wt% and 3.0 wt%, respectively, of the total mass of the nonaqueous electrolytic solution. Slowly adding electrolyte salt LiPF6And cooled to form a nonaqueous electrolytic solution having a concentration of 13.5 wt%.
The battery overcharge safety test and the analysis procedure for the battery anatomy after overcharge were the same as in example 1. The test is judged to be passed according to GB/T31485-2015.
Claims (23)
1. A method for preventing overcharge of a nonaqueous electrolyte secondary battery, comprising a nonaqueous electrolyte, characterized in that: under the normal work of the battery, the current collector/the electrode lug does not generate chemical or electrochemical reaction; when the battery is overcharged to a voltage >4.2V, the current collector/tab chemically or electrochemically reacts with the anti-overcharge compound; the anti-overcharge compound has at least one structure shown in formula 1, formula 2, formula 3, formula 4 and formula 5:
formula 1: MN (C)mF2m+1SO2)(CnF2n+1SO2)；
Formula 2: MNCxF2x(SO2)2；
Formula 3: l (C)yF2y+1SO3)k；
Formula 4: l (CH (SO)2CF3)2)k；
Formula 5: l (C (SO)2CF3)3)k；
Wherein m and n are natural numbers respectively, x is a positive integer and x is not equal to 1, y is a positive integer, and k is an integer of 1-3 respectively; m is Li or Na; l is selected from Li, Na, K, Ag, Cu, Zn, Rb, Cs, Mg or Al; the non-aqueous electrolyte comprises a redox shuttle additive and/or an electropolymerization additive; the redox shuttle additive or electropolymerization additive is selected from at least one of:
wherein R is a hydrocarbyl group.
2. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 1, wherein: under the normal work of the battery, the current collector/the electrode lug does not generate chemical or electrochemical reaction; when the cell is overcharged to a voltage >4.4V, the current collector/tab chemically or electrochemically reacts with the anti-overcharge compound.
3. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 1, wherein: the anti-overcharge compound is an electrolyte salt; the electrolyte salt has a structure as shown in formula 1 and/or formula 2.
4. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 3, wherein: the electrolyte salt is selected from at least one of:
5. the nonaqueous electrolyte secondary battery overcharge preventing method of claim 3, wherein: the mass of the electrolyte salt is 0.5 to 30.0 weight percent of the mass of the nonaqueous electrolyte.
6. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 5, wherein: the mass of the electrolyte salt is 1.0 to 18.0 weight percent of the mass of the nonaqueous electrolyte.
7. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 6, wherein: the mass of the electrolyte salt is 2.0 wt% to 10.0 wt% of the mass of the nonaqueous electrolyte.
8. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 1, wherein: the overcharge resisting compound is a nonaqueous electrolyte additive; the non-aqueous electrolyte 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.
9. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 8, wherein: the mass of the nonaqueous electrolyte additive is 0.1 to 10.0 weight percent of the mass of the nonaqueous electrolyte.
10. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 9, wherein: the mass of the nonaqueous electrolyte additive is 0.2 to 2.0 weight percent of the mass of the nonaqueous electrolyte.
11. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 9, wherein: the mass of the nonaqueous electrolyte additive is 1.0 to 5.0 weight percent of the mass of the nonaqueous electrolyte.
12. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 1, wherein: the anti-overcharging compound is a material in the pole piece; the material in the pole piece comprises LiN (SO)2C2F5)2Or LiN (SO)2F)2The polymer electrolyte of (1).
13. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 12, wherein: the materials in the pole piece comprise polyethylene oxide (PEO) and LiN (SO)2F)2And/or polyethylene oxide (PEO) and LiN (SO)2CF3)2The complex of (1).
14. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 1, wherein: the mass of the redox shuttle additive and/or the electropolymerization additive is 0-10.0 wt% of the mass of the nonaqueous electrolyte.
15. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 14, wherein: the mass of the redox shuttle additive and/or the electropolymerization additive is 1.0 to 8.0 weight percent of the mass of the nonaqueous electrolyte.
16. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 15, wherein: the mass of the redox shuttle additive and/or the electropolymerization additive is 2.0 to 5.0 weight percent of the mass of the nonaqueous electrolyte.
17. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 1, wherein: the current collector/tab is made of aluminum.
18. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 1, wherein: the non-aqueous electrolyte includes a flame retardant additive; the flame retardant additive is at least one selected from the group consisting of phosphate esters, phosphonamides, phosphite esters, fluorophosphate esters, fluorophosphite esters, ionic liquids, and phosphazenes.
19. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 18, wherein: the flame retardant additive is at least one selected from the group consisting of phosphate esters, phosphonamides, phosphite esters, fluorophosphate esters, cyclic phosphazenes and fluorophosphite esters.
20. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 19, wherein: the flame retardant additive is selected from at least one of:
wherein, X1，X2，X3，X4，X5，X6Each independently represents halogen OR ORx(ii) a The R isxRepresents a saturated aromatic group in which hydrogen is substituted or unsubstituted or said RxRepresents a saturated aliphatic group in which hydrogen is substituted or unsubstituted.
21. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 18, wherein: the mass of the flame retardant additive is 0-88.0 wt% of the mass of the nonaqueous electrolyte.
22. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 21, wherein: the mass of the flame retardant additive is 0-50.0 wt% of the mass of the nonaqueous electrolyte.
23. The nonaqueous electrolyte secondary battery overcharge preventing method of claim 22, wherein: the mass of the flame retardant additive is 0-30.0 wt% of the mass of the nonaqueous electrolyte.
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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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