CN107293791A - A kind of tertiary cathode material lithium-ion battery electrolytes and the lithium ion battery comprising the electrolyte - Google Patents
A kind of tertiary cathode material lithium-ion battery electrolytes and the lithium ion battery comprising the electrolyte Download PDFInfo
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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
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- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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
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Abstract
The present invention provides a kind of tertiary cathode material lithium-ion battery electrolytes and the lithium ion battery comprising the electrolyte, is related to technical field of lithium ion.Tertiary cathode material lithium-ion battery electrolytes of the present invention are made up of organic solvent, Non-aqueous Organic Solvents, lithium salts, additive, wherein, the percentage that each component accounts for lithium-ion battery electrolytes gross mass is respectively：Organic solvent 15% 25%, lithium salts 17% 23%, additive 1% 4%, surplus is Non-aqueous Organic Solvents.The present invention uses organic solvent, Non-aqueous Organic Solvents as dicyandiamide solution, the dicyandiamide solution is high to lithium salts solubility, viscosity is low, coordinate the effect of low temperature additive simultaneously, electrolyte is realized while the chemical properties such as capacity, internal resistance are taken into account, also so that tertiary cathode material battery has circulating battery time lengthening under excellent cycle performance, cryogenic conditions.
Description
Technical field
The present invention relates to technical field of lithium ion, it is related to a kind of tertiary cathode material lithium-ion battery electrolytes and bag
Lithium ion battery containing the electrolyte.
Background technology
With the lifting demand of lithium ion battery specific energy density, high voltage low with cost, the three of high gram volume performance
First positive electrode is applied more and more extensively in lithium ion battery especially power lithium-ion battery, but tertiary cathode material is inhaled
It is aqueous strong, especially under high voltages and under higher nickel content, conventional electrolysis liquid decomposable process is significantly speeded up, has caused gas
Swollen serious, cycle performance is poor, therefore exploitation can be effectively improved the function electrolyte of ternary material cycle performance of battery and compel
The eyebrows and eyelashes.
At present, the correlative study for improving ternary material cycle performance of battery is a lot, still, ternary battery electrolyte still not into
It is ripe, while normal temperature performance is improved, high temperature safety can not be taken into account.On the other hand, commercial lithium-ion batteries are dominate
The LiPF in lithium salts market6Have the shortcomings that obvious：Heat endurance is poor, and slow thermal decomposition occurs at 80 DEG C；To trace water
Divide sensitivity, corrosive HF gases can be generated by meeting water.Therefore LiPF is found6Replacement lithium salts, be always lithium ion in recent years
One of emphasis and focus of Lithium Salts for battery application research.
In the prior art, mainly evaluated and tested by the screening to electrolyte solvent system and special function additive, optimization
Electrolyte prescription is constituted, and lifts cycle performance of battery.Although electrolyte prescription can effectively lift tertiary cathode in the prior art
The cycle performance of material lithium ion battery still still differs greatly from practical application request, and current electrolyte is all difficult
Take into account the balance of other chemical properties such as capacity, internal resistance.
Therefore also need to further optimize electrolyte, realize the lifting of battery combination property.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of tertiary cathode material lithium-ion battery electrolytes and includes the electricity
Solve the lithium ion battery of liquid.
To realize object above, the present invention is achieved by the following technical programs：
A kind of tertiary cathode material lithium-ion battery electrolytes, the tertiary cathode material lithium-ion battery electrolytes are by having
Machine solvent, Non-aqueous Organic Solvents, lithium salts, additive composition, wherein, each component accounts for the hundred of lithium-ion battery electrolytes gross mass
Point ratio is respectively：Organic solvent 15%-25%, lithium salts 17%-23%, additive 1%-4%, surplus are non-aqueous organic molten
Agent, the organic solvent is mixed by ethylene carbonate, methyl ethyl carbonate alkene ester, dimethyl carbonate, and the additive is by low temperature
Additive, film for additive, cyclic anhydride compound composition, the low temperature additive is triethanolamine, tetraethyl tetrafluoro boric acid
One kind in ammonium.
It is preferred that, the organic solvent is mixed by the raw material of following percentage by weight：Ethylene carbonate 20%-
30%th, diethyl carbonate 30%-40%, methyl ethyl carbonate 30%-40%, propene carbonate 5%-10%.
It is preferred that, the Non-aqueous Organic Solvents be diethyl carbonate, propene carbonate, methyl propyl carbonate, dioxy cycloalkanes,
At least one of diethyl diethylene glycol diethyl ether, gamma-butyrolacton.
It is preferred that, the lithium salts is lithium hexafluoro phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, double fluorine sulfimides
At least one of lithium, LiBF4, double trifluoromethanesulfonimide lithiums.
It is preferred that, the additive is by low temperature additive, film for additive, cyclic anhydride compound according to following percentage
Composition：Low temperature additive 30%-50%, film for additive 20%-40%, cyclic anhydride compound 15%-35%.
It is preferred that, the film for additive be fluorinated ethylene carbonate, difluorinated ethylene carbonate, vinylene carbonate,
At least one of ethylene sulfite, propylene sulfite；Vinylene carbonate easily forms stabilization on graphite cathode surface
SEI films, with excellent high temperature performance and anti-inflatable performance, can effectively lift battery capacity and cycle performance；Fluoro
Ethylene carbonate, difluorinated ethylene carbonate ester advantageously form fine and close SEI films, reduce impedance, improve the low-temperature circulating of electrolyte
Performance；The sulphur such as ethylene sulfite, propylene sulfite system additive has outstanding high-temperature behavior, for tertiary cathode material
Can suppress during battery metal ion it is molten and adsorb in negative terminal surface so that significant increase battery high-temperature cycle performance.
It is preferred that, the cyclic anhydride compound is succinic anhydride, maleic anhydride, 2- methyl succinics acid anhydrides, 2,3- diformazans
At least one of base succinic anhydride.
It is preferred that, the concentration of described lithium salts is 0.5-1.6mol/L.
A kind of lithium ion battery, including positive pole, negative pole, barrier film, in addition to tertiary cathode material lithium of the present invention from
Sub- battery electrolyte, the active material of the positive pole includes lithium manganate having spinel structure and tertiary cathode material, the spinel-type
The chemical formula of LiMn2O4 is LiMn2O4.
It is preferred that, the active material of the positive pole also includes adhesive, conductive agent and solvent；The barrier film is that polypropylene is micro-
At least one of pore membrane, polyethene microporous membrane, composite membrane, paper barrier film.
The present invention provides a kind of tertiary cathode material lithium-ion battery electrolytes and the lithium ion battery comprising the electrolyte,
Advantage is compared with prior art：
The present invention uses organic solvent, Non-aqueous Organic Solvents as dicyandiamide solution, and the dicyandiamide solution is to lithium salts solubility
Height, viscosity is low, while coordinating the effect of low temperature additive, realizes electrolyte and is taking into account the chemical properties such as capacity, internal resistance
Meanwhile, also cause tertiary cathode material battery that there is circulating battery time lengthening under excellent cycle performance, cryogenic conditions；
Tertiary cathode material lithium-ion battery electrolytes of the present invention, the electrolysis liquid energy makes tertiary cathode material lithium ion battery
Not only stable cycle performance at normal temperatures, moreover it is possible to suppress tertiary cathode material lithium ion battery aging, inflatable under the high temperature conditions
Phenomenon, and the internal resistance of tertiary cathode material lithium ion battery is diminished, use organic solvent, Non-aqueous Organic Solvents and lithium salts
With reference to electrolysis liquid energy meet ternary material system lithium ion battery discharge and recharge and security needs so that tertiary cathode material battery
There is excellent discharge and recharge and security performance at ambient and elevated temperatures；
Tertiary cathode material lithium-ion battery electrolytes of the present invention are different using additive, additive by low temperature additive,
Synergy between film for additive, cyclic anhydride compound composition, three class additives can take into account battery high-temperature simultaneously
Energy and cryogenic property.In film for additive, vinylene carbonate easily forms stable SEI films on graphite cathode surface, has
Excellent high temperature performance and anti-inflatable performance, can effectively lift battery capacity and cycle performance；Fluoro ethylene carbonate, difluoro
Fine and close SEI films are advantageously formed for ethylene carbonate ester, reduce impedance, the low-temperature circulating performance of electrolyte is improved；Sulfurous acid second
The sulphur such as alkene ester, propylene sulfite system additive has outstanding high-temperature behavior, can press down during for tertiary cathode material battery
Metal ion processed is molten and adsorbs in negative terminal surface, so that significant increase battery high-temperature cycle performance；Low temperature additive is three ethanol
Amine, tetraethyl ammonium tetrafluoroborate, such additive can coordinate the solvation radius for reducing lithium ion with lithium ion, make lithium salts
Solvation degree increase, so as to improve the low-temperature conductivity of electrolyte；
Tertiary cathode material lithium ion battery point electrolyte of the present invention has preferable resistance to oxidation, high-low temperature resistant and Special safety
Property, Non-aqueous Organic Solvents used in the present invention have higher decomposition electric potential, have preferably heat steady under high temperature, high pressure
Qualitative and electrochemical stability, so that stable electrochemical environment is provided for the electrical property of tertiary cathode material lithium ion battery,
Ensure that battery has preferable cycle life；There is higher electrical conductivity simultaneously, the high magnification and power characteristic of battery is can guarantee that,
Also there is higher security, the security performance of electrokinetic cell can be greatly improved.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, with reference to embodiment to the present invention
Technical scheme in embodiment is clearly and completely described, it is clear that described embodiment is that a part of the invention is implemented
Example, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creativeness
The every other embodiment obtained under the premise of work, belongs to the scope of protection of the invention.
Embodiment 1：
In the present embodiment, the preparation of tertiary cathode material lithium-ion battery electrolytes：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, by ethylene carbonate
Ester 20%, diethyl carbonate 30%, methyl ethyl carbonate 40%, propene carbonate 10% are mixed, and are stirred, and obtain organic molten
Agent, takes and accounts for the percentage of lithium-ion battery electrolytes gross mass to be slowly added to account for lithium ion battery battery in 15% organic solvent
The percentage for solving liquid gross mass is 17%, and concentration is 0.5mol/L lithium hexafluoro phosphate, accounts for the total matter of lithium-ion battery electrolytes
The percentage of amount is 67% diethyl carbonate, and it is 1% to be slow added into and account for the percentage of lithium-ion battery electrolytes gross mass
Additive, stirring be completely dissolved to it, obtain the tertiary cathode material lithium-ion battery electrolytes of embodiment 1.
Wherein additive is made up of low temperature additive, film for additive, cyclic anhydride compound according to following percentage：It is low
Warm additive 50%, film for additive 20%, cyclic anhydride compound 30%；And low temperature additive is triethanolamine；Film forming adds
Plus agent is fluorinated ethylene carbonate, vinylene carbonate, ethylene sulfite are mixed；Cyclic anhydride compound is butanedioic acid
Acid anhydride.
The preparation of lithium ion battery：
By positive active material LiMn2O4, nickle cobalt lithium manganate, conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF)
In mass ratio 25：70：3：After 2 are thoroughly mixed uniformly in 1-METHYLPYRROLIDONE dicyandiamide solution, it is coated on Al paper tinsels and dries
Dry, cold pressing, obtains anode pole piece, and its compacted density is 3.55g/cm3；
By negative electrode active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickener carbon Methyl cellulose
After plain sodium (CMC) is thoroughly mixed uniformly according to mass ratio 94: 3: 2: 1 in deionized water solvent system, Cu paper tinsels are coated on
Upper drying, cold pressing, obtain cathode pole piece, and its compacted density is 1.65g/cm3；
Using polyethene microporous membrane (PE) be basement membrane (12 μm) and the nano oxidized aluminized coating of coating on base films (2 μm) as every
Film；
Anode pole piece, barrier film, cathode pole piece are folded in order, barrier film is in the work for playing isolation in the middle of positive/negative plate
With, and winding obtains naked battery core.Naked battery core is placed in outer packing, inject prepare electrolyte and it is encapsulated, shelve, be melted into,
The processes such as aging, secondary encapsulation, partial volume, obtain tertiary cathode material lithium ion battery.
Embodiment 2：
In the present embodiment, the preparation of tertiary cathode material lithium-ion battery electrolytes：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, by ethylene carbonate
Ester 30%, diethyl carbonate 35%, methyl ethyl carbonate 30%, propene carbonate 5% are mixed, and are stirred, are obtained organic solvent,
Take and account for the percentage of lithium-ion battery electrolytes gross mass to be slowly added to account for lithium ion battery electrolysis in 25% organic solvent
The percentage of liquid gross mass is 23%, and concentration is 1.6mol/L double fluorine sulfimide lithiums, accounts for lithium-ion battery electrolytes total
The percentage of quality is 48% diethyl diethylene glycol diethyl ether, is slow added into and accounts for the percentage of lithium-ion battery electrolytes gross mass and be
4% additive, stirring is completely dissolved to it, obtains the tertiary cathode material lithium-ion battery electrolytes of embodiment 1.
Wherein additive is made up of low temperature additive, film for additive, cyclic anhydride compound according to following percentage：It is low
Warm additive 50%, film for additive 30%, cyclic anhydride compound 20%；And low temperature additive is triethanolamine, tetraethyl
Ammonium tetrafluoroborate is according to quality 1:1 mixes；Film for additive is fluorinated ethylene carbonate, vinylene carbonate, sulfurous acid
Vinyl acetate, propylene sulfite are mixed；Cyclic anhydride compound is succinic anhydride, maleic anhydride, 2- methylsuccinic acids
Acid anhydride, 2,3- dimethyl succinic anhydrides are mixed.
The preparation of lithium ion battery：
By positive active material LiMn2O4, nickle cobalt lithium manganate, conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF)
In mass ratio 25：70：3：After 2 are thoroughly mixed uniformly in 1-METHYLPYRROLIDONE dicyandiamide solution, it is coated on Al paper tinsels and dries
Dry, cold pressing, obtains anode pole piece, and its compacted density is 3.55g/cm3；
By negative electrode active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickener carbon Methyl cellulose
After plain sodium (CMC) is thoroughly mixed uniformly according to mass ratio 94: 3: 2: 1 in deionized water solvent system, Cu paper tinsels are coated on
Upper drying, cold pressing, obtain cathode pole piece, and its compacted density is 1.65g/cm3；
Using microporous polypropylene membrane as basement membrane (12 μm) and it is used as barrier film in the nano oxidized aluminized coating of coating on base films (2 μm)；
Anode pole piece, barrier film, cathode pole piece are folded in order, barrier film is in the work for playing isolation in the middle of positive/negative plate
With, and winding obtains naked battery core.Naked battery core is placed in outer packing, inject prepare electrolyte and it is encapsulated, shelve, be melted into,
The processes such as aging, secondary encapsulation, partial volume, obtain tertiary cathode material lithium ion battery.
Embodiment 3：
In the present embodiment, the preparation of tertiary cathode material lithium-ion battery electrolytes：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, by ethylene carbonate
Ester 25%, diethyl carbonate 35%, methyl ethyl carbonate 35%, propene carbonate 5% are mixed, and are stirred, are obtained organic solvent,
Take and account for the percentage of lithium-ion battery electrolytes gross mass to be slowly added to account for lithium ion battery electrolysis in 20% organic solvent
The percentage of liquid gross mass is 20%, and concentration is 1.1mol/L lithium salts, accounts for the percentage of lithium-ion battery electrolytes gross mass
Than the Non-aqueous Organic Solvents for 58%, it is slow added into and accounts for the percentage of lithium-ion battery electrolytes gross mass and add for 2%
Plus agent, stir and be completely dissolved to it, obtain the tertiary cathode material lithium-ion battery electrolytes of embodiment 1.
Wherein lithium salts is by lithium hexafluoro phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, double fluorine sulfimide lithiums, tetrafluoro
Lithium borate, double trifluoromethanesulfonimide lithiums are mixed, and lithium hexafluoro phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium,
Double fluorine sulfimide lithiums, LiBF4, double trifluoromethanesulfonimide lithiums account for lithium-ion battery electrolytes gross mass respectively
Percentage is 6%, 2.5%, 1.2%, 2.3%, 5%, 3%；Non-aqueous Organic Solvents by diethyl carbonate, propene carbonate,
Methyl propyl carbonate, dioxy cycloalkanes, diethyl diethylene glycol diethyl ether, gamma-butyrolacton are mixed, and diethyl carbonate, propene carbonate, carbon
Sour first propyl ester, dioxy cycloalkanes, diethyl diethylene glycol diethyl ether, gamma-butyrolacton account for the percentage of lithium-ion battery electrolytes gross mass respectively
For 10%, 8%, 12%, 10%, 12%, 6%；Additive is pressed by low temperature additive, film for additive, cyclic anhydride compound
According to following percentage composition：Low temperature additive 30%, film for additive 40%, cyclic anhydride compound 30%；And low temperature is added
Agent is tetraethyl ammonium tetrafluoroborate；Film for additive is difluorinated ethylene carbonate, vinylene carbonate, ethylene sulfite are mixed
Conjunction is formed；Cyclic anhydride compound is succinic anhydride, maleic anhydride, 2- methyl succinic acid anhydrides are mixed.
The preparation of lithium ion battery：
By positive active material LiMn2O4, nickle cobalt lithium manganate, conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF)
In mass ratio 25：70：3：After 2 are thoroughly mixed uniformly in 1-METHYLPYRROLIDONE dicyandiamide solution, it is coated on Al paper tinsels and dries
Dry, cold pressing, obtains anode pole piece, and its compacted density is 3.55g/cm3；
By negative electrode active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickener carbon Methyl cellulose
After plain sodium (CMC) is thoroughly mixed uniformly according to mass ratio 94: 3: 2: 1 in deionized water solvent system, Cu paper tinsels are coated on
Upper drying, cold pressing, obtain cathode pole piece, and its compacted density is 1.65g/cm3；
Using paper barrier film as basement membrane (12 μm) and it is used as barrier film in the nano oxidized aluminized coating of coating on base films (2 μm)；
Anode pole piece, barrier film, cathode pole piece are folded in order, barrier film is in the work for playing isolation in the middle of positive/negative plate
With, and winding obtains naked battery core.Naked battery core is placed in outer packing, inject prepare electrolyte and it is encapsulated, shelve, be melted into,
The processes such as aging, secondary encapsulation, partial volume, obtain tertiary cathode material lithium ion battery.
Embodiment 4：
In the present embodiment, the preparation of tertiary cathode material lithium-ion battery electrolytes：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, by ethylene carbonate
Ester 27%, diethyl carbonate 33%, methyl ethyl carbonate 33%, propene carbonate 7% are mixed, and are stirred, are obtained organic solvent,
Take and account for the percentage of lithium-ion battery electrolytes gross mass to be slowly added to account for lithium ion battery electrolysis in 16% organic solvent
The percentage of liquid gross mass is 18%, and concentration is 0.8mol/L LiBF4, accounts for lithium-ion battery electrolytes gross mass
Percentage be 64% gamma-butyrolacton, be slow added into and account for the percentage of lithium-ion battery electrolytes gross mass and add for 2%
Plus agent, stir and be completely dissolved to it, obtain the tertiary cathode material lithium-ion battery electrolytes of embodiment 1.
Wherein additive is made up of low temperature additive, film for additive, cyclic anhydride compound according to following percentage：It is low
Warm additive 45%, film for additive 20%, cyclic anhydride compound 35%；And low temperature additive is tetraethyl tetrafluoro boric acid
Ammonium；Film for additive is fluorinated ethylene carbonate；Cyclic anhydride compound is maleic anhydride.
The preparation be the same as Example 1 of lithium ion battery.
Embodiment 5：
In the present embodiment, the preparation of tertiary cathode material lithium-ion battery electrolytes：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, by ethylene carbonate
Ester 28%, diethyl carbonate 32%, methyl ethyl carbonate 34%, propene carbonate 6% are mixed, and are stirred, are obtained organic solvent,
Take and account for the percentage of lithium-ion battery electrolytes gross mass to be slowly added to account for lithium ion battery electrolysis in 22% organic solvent
The percentage of liquid gross mass is 21%, and concentration is 1.4mol/L difluorine oxalic acid boracic acid lithium, accounts for lithium-ion battery electrolytes total
The percentage of quality is 55% propene carbonate, is slow added into and accounts for the percentage of lithium-ion battery electrolytes gross mass and be
2% maleic anhydride, stirring is completely dissolved to it, obtains the tertiary cathode material lithium-ion battery electrolytes of embodiment 1.
Wherein additive is made up of low temperature additive, film for additive, cyclic anhydride compound according to following percentage：It is low
Warm additive 50%, film for additive 35%, cyclic anhydride compound 15%；And low temperature additive is triethanolamine；Film forming adds
Plus agent is difluorinated ethylene carbonate, vinylene carbonate, ethylene sulfite are mixed；Cyclic anhydride compound is 2- first
Base succinic anhydride.
The preparation be the same as Example 1 of lithium ion battery.
Comparative example 1：
In this comparative example, the preparation of tertiary cathode material lithium-ion battery electrolytes：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, by carbonic acid diethyl
Ester 55%, methyl ethyl carbonate 45% is mixed, and is stirred, is obtained organic solvent, is taken and is accounted for lithium-ion battery electrolytes gross mass
The percentage for being slowly added to account for lithium-ion battery electrolytes gross mass in the organic solvent that percentage is 25% is 23%, and concentration
For 1.6mol/L double fluorine sulfimide lithiums, the percentage for accounting for lithium-ion battery electrolytes gross mass is 48% diethanol two
Ether, it is 4% ethylene sulfite to be slow added into and account for the percentage of lithium-ion battery electrolytes gross mass, is stirred complete to its
Fully dissolved, obtains the tertiary cathode material lithium-ion battery electrolytes of embodiment 1.
The preparation be the same as Example 1 of lithium ion battery.
Comparative example 2：
In this comparative example, the preparation of tertiary cathode material lithium-ion battery electrolytes：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, by carbonic acid diethyl
Ester 55%, methyl ethyl carbonate 45% is mixed, and is stirred, is obtained organic solvent, is taken and is accounted for lithium-ion battery electrolytes gross mass
The percentage for being slowly added to account for lithium-ion battery electrolytes gross mass in the organic solvent that percentage is 25% is 23%, and concentration
For 1.6mol/L double fluorine sulfimide lithiums, the percentage for accounting for lithium-ion battery electrolytes gross mass is 48% diethanol two
Ether, it is 4% tetraethyl ammonium tetrafluoroborate to be slow added into and account for the percentage of lithium-ion battery electrolytes gross mass, and stirring is extremely
It is completely dissolved, and obtains the tertiary cathode material lithium-ion battery electrolytes of embodiment 1.
The preparation be the same as Example 1 of lithium ion battery.
Lithium ion battery prepared by above-described embodiment 1-5 lithium ion batteries prepared and comparative example 1-2 is respectively at -20 DEG C
With 55 DEG C under the conditions of carry out 1C loop tests, until carry out 200 weeks circulation after end, the battery after circulation is maintained at full electricity
State, all test process set voltage range to be 3.0-4.2V.Record respectively and calculate all test batteries before being circulated
Capability retention, internal resistance growth, thickness swelling afterwards, test result are as shown in table 1 below：
The different lithium-ion battery electrolytes Capacity fading curve maps of table 1
Lithium-ion electric can be obviously improved by the electrolyte that it can be seen from -20 DEG C of loop-around datas prepared by the present invention of table 1
The cycle performance of pond under cryogenic, electrolyte shows that electrolyte prepared by the present invention can be with bright in 55 DEG C of loop-around data results
The high temperature cyclic performance of aobvious lifting lithium ion battery.In summary, it is electrolysed using tertiary cathode material lithium ion battery of the present invention
Battery prepared by liquid, the battery can obtain preferable high temperature and low-temperature circulating performance simultaneously, in addition in cyclic process battery
Resistance rises and aerogenesis swelling is also significantly improved, and realizes the lifting of battery combination property.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these modification or
Replace, the essence of appropriate technical solution is departed from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a kind of tertiary cathode material lithium-ion battery electrolytes, it is characterised in that the tertiary cathode material lithium ion battery
Electrolyte is made up of organic solvent, Non-aqueous Organic Solvents, lithium salts, additive, wherein, each component accounts for lithium-ion battery electrolytes
The percentage of gross mass is respectively：Organic solvent 15%-25%, lithium salts 17%-23%, additive 1%-4%, surplus are non-aqueous
Property organic solvent, the organic solvent is mixed by ethylene carbonate, methyl ethyl carbonate alkene ester, dimethyl carbonate, the addition
Agent is made up of low temperature additive, film for additive, cyclic anhydride compound, and the low temperature additive is triethanolamine, tetraethyl
One kind in ammonium tetrafluoroborate.
2. tertiary cathode material lithium-ion battery electrolytes according to claim 1, it is characterised in that the organic solvent
Mixed by the raw material of following percentage by weight：Ethylene carbonate 20%-30%, diethyl carbonate 30%-40%, carbonic acid first
Ethyl ester 30%-40%, propene carbonate 5%-10%.
3. tertiary cathode material lithium-ion battery electrolytes according to claim 1, it is characterised in that：Described non-aqueous have
Machine solvent is in diethyl carbonate, propene carbonate, methyl propyl carbonate, dioxy cycloalkanes, diethyl diethylene glycol diethyl ether, gamma-butyrolacton
It is at least one.
4. tertiary cathode material lithium-ion battery electrolytes according to claim 1, it is characterised in that：The lithium salts is six
Lithium fluophosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, double fluorine sulfimide lithiums, LiBF4, double fluoroform sulphonyl
At least one of imine lithium.
5. tertiary cathode material lithium-ion battery electrolytes according to claim 1, it is characterised in that the additive by
Low temperature additive, film for additive, cyclic anhydride compound are constituted according to following percentage：Low temperature additive 30%-50%, into
Film additive 20%-40%, cyclic anhydride compound 15%-35%.
6. tertiary cathode material lithium-ion battery electrolytes according to claim 1 or 5, it is characterised in that：The film forming
Additive is fluorinated ethylene carbonate, difluorinated ethylene carbonate, vinylene carbonate, ethylene sulfite, sulfurous acid propylene
At least one of ester.
7. tertiary cathode material lithium-ion battery electrolytes according to claim 1, it is characterised in that：The cyclic acid anhydride
Compound is at least one of succinic anhydride, maleic anhydride, 2- methyl succinics acid anhydrides, 2,3- dimethyl succinic anhydrides.
8. the tertiary cathode material lithium-ion battery electrolytes according to claim 1 or 4, it is characterised in that：Described lithium
The concentration of salt is 0.5-1.6mol/L.
9. a kind of lithium ion battery, including positive pole, negative pole, barrier film, it is characterised in that also including claim 1-8 any one
Described tertiary cathode material lithium-ion battery electrolytes, the active material of the positive pole includes lithium manganate having spinel structure and ternary
Positive electrode, the chemical formula of the lithium manganate having spinel structure is LiMn2O4。
10. tertiary cathode material lithium ion battery according to claim 9, it is characterised in that：The active material of the positive pole
Material also includes adhesive, conductive agent and solvent；The barrier film is microporous polypropylene membrane, polyethene microporous membrane, composite membrane, paper barrier film
At least one of.
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Application publication date: 20171024 |