CN110416610A - A kind of high power electrolyte and the lithium ion battery containing the electrolyte - Google Patents
A kind of high power electrolyte and the lithium ion battery containing the electrolyte Download PDFInfo
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- CN110416610A CN110416610A CN201910606487.0A CN201910606487A CN110416610A CN 110416610 A CN110416610 A CN 110416610A CN 201910606487 A CN201910606487 A CN 201910606487A CN 110416610 A CN110416610 A CN 110416610A
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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
- 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 invention discloses a kind of high power electrolyte and contain the lithium ion battery of the electrolyte, it includes lithium salts electrolyte, organic solvent and film for additive, the high power electrolyte also contains ion liquid addictive, and the ion liquid addictive is bis- (fluorine sulphonyl) the imines salt compounds of nano silica-imidazole radicals.By the synergistic effect of organic matter and inorganic matter, the solvation of lithium ion is improved, and combine film for additive to form a film in negative terminal surface to reduce impedance, it will be apparent that improve cyclical stability and safety of the lithium ion battery under high rate charge-discharge.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of high power electrolyte and lithium containing the electrolyte from
Sub- battery.
Background technique
In recent years, lithium ion battery has presented good in the fields such as aerospace, number 3C, electric car, energy storage
Application prospect, in order to meet the raising of consumption electronic product power consumption and the demand of electric car course continuation mileage, lithium ion battery face
Face two significant challenges, first is that higher energy density, first is that faster charge rate.Higher energy density means material
Ultimate attainment application and design and the compression for manufacturing surplus, and charge rate then means bigger charging current, higher faster
Ohm heat release.Both the serious security performance for affecting lithium ion battery, especially faster charge rate will increase
Lithium ion negative electrode material surface precipitation, generate Li dendrite pierce through diaphragm, seriously affect lithium ion battery cycle life and
Safety.
The carrier of battery intermediate ion transmission as the electrolyte of one of the big critical material of lithium ion battery four, generally by
The raw materials such as organic solvent, electrolyte lithium salt, the necessary additive of high-purity, prepare under certain condition, by a certain percentage and
At.For safety problem caused by the charging of current high power, the method that the prior art is taken is to be added in the electrolytic solution largely
Film for additive, form a film repeatedly after each circulation, to achieve the effect that inhibit negative electrode material surface analysis lithium, but due to
The SEI film generated repeatedly can generate sour gas in battery charge and discharge process, and then corrode the SEI film generated, or even destroy
The structure of material seriously affects the security performance generation of lithium ion battery.
Summary of the invention
In view of this, novel ionic liquid is added in the electrolytic solution and adds the present invention provides a kind of high power electrolyte
Add bis- (fluorine sulphonyl) the imines salt compounds of agent i.e. nano silica-imidazole radicals, the anion in electrolyte can be captured, mentioned
The solvation of high-lithium ion, promote lithium ion in the electrolytic solution migration formed and particle flux, in combination with film forming
Additive forms a film in negative terminal surface reduces impedance, inhibits the Li dendrite of negative terminal surface to generate, to solve lithium branch under high power
The SEI film that safety problem caused by crystalline substance puncture diaphragm and film for additive generate repeatedly generates what sour gas corrosion generated
The problem of SEI film.
To achieve the goals above, the high power electrolyte in the present invention, including lithium salts electrolyte, organic solvent and film forming
Additive, the high power electrolyte also contain ion liquid addictive, and the ion liquid addictive is nano silica-
Bis- (fluorine sulphonyl) the imines salt compounds of imidazole radicals, structural formula are as follows:
Wherein, R is the group that carbon atom number is 1~6, and the group is straight chained alkyl, fluoro-alkyl or itrile group.
Further, in the high power electrolyte, the mass fraction of the ion liquid addictive is 0.1~5%.
The present invention adds the ion liquid addictive of this organic and inorganic combination in the electrolytic solution, thus realize organic matter with it is inorganic
The synergistic effect of object though having certain effect when the additive amount of ion liquid addictive is too low, but effect is unobvious, and is worked as and is added
Electrolyte viscosity may then be will increase when dosage is excessively high to influence battery performance, therefore, inventor is to ionic liquid
The additive amount of additive has carried out preferably, and discovery accounts for the 0.1~5% of high power electrolyte quality score when ion liquid addictive
When electrolyte property obtained it is best.
Further, the ion liquid addictive the preparation method comprises the following steps:
S1, (3- chloropropyl) trimethoxy silane and glyoxaline compound are dissolved in n,N-Dimethylformamide, In
It is stirred to react in 80-90 DEG C 40-50 hours under protective atmosphere, obtains the first product using extraction, removal solvent, wherein institute
Stating protective atmosphere is inert gas or nitrogen；Inert gas in this step refers to seven kinds of gases of 0 race on the periodic table of elements,
It is used equally in technical solution of the present invention, but considers the factor of cost, in some embodiments of the invention preferential choosing
Use nitrogen.In addition, the extraction in the present invention generally uses organic solvent to carry out, drying, rotary evaporation etc. is can be used in removal solvent,
It is the conventional means that those skilled in the art know, does not do specific restriction here, in some embodiments of the invention,
The extraction uses ether, and the effect in order to guarantee extraction, can repeated multiple times extraction as needed；And solvent is removed, In
It is carried out, is operated fairly simple using Rotary Evaporators in some embodiments of the present invention.
S2, first product is slowly dropped in silica glue, the silica glue excess 1.5-2.0
Times, after being quickly stirred to react 10-15 hours at 80-90 DEG C, temperature is improved to 100-120 DEG C of evaporation and removes water, using
Purifying obtains the second product；Purifying generally comprises washing, separation, drying etc. in this step, belongs to those skilled in the art's
Conventional means, therefore do not limit specifically here, in some embodiments of the invention, in order to improve the efficiency of purifying, it is
After being eluted repeatedly using ethyl alcohol, centrifuge separation, the solvent for being finally freeze-dried to remove trace obtains the second product.
S3, will be bis- (fluorine sulphonyl) imines lithium salts, second product dissolution solution is respectively prepared in deionized water, will be double
(fluorine sulphonyl) imines lithium salt solution is slowly dropped in the second reaction mixture, the rapid generating negative ions exchange reaction of the two, stirring
It stands after 2-4 hours, purifies again, obtain the ion liquid addictive.Purifying in this step is equally art technology
The conventional means that personnel know, it is in some embodiments of the invention, product centrifuge separation, the dry removal after standing is water-soluble
Agent, then again disperses product to remove part byproduct of reaction in acetone again, is finally freeze-dried the water for removing trace again
Obtain ion liquid addictive.
It is specific that the reaction mechanism is as follows:
The preparation method of ion liquid addictive through the invention, the yield of final product is up to 85% or more, purity
95% or more.
Further, in step S1, mole of (3- chloropropyl) trimethoxy silane and the glyoxaline compound
Than for (1.05~1.2): 1, the glyoxaline compound is alkyl imidazole, fluoro-alkyl imidazoles or itrile group imidazoles.In order to make miaow
Azole compounds fully reacting, conducive to the purification of product, inventor is to (3- chloropropyl) trimethoxy silane and imidazoles chemical combination
The ratio of object has carried out preferably.According to the difference of the R of final product, raw material also can be different, when glyoxaline compound is alkyl miaow
When azoles, the first obtained product is 1- alkyl -3- (3- chloropropyl) trimethoxy silane imidazoles chloride salt ions liquid, and final product is
Bis- (fluorine sulphonyl) the imines ionic liquids of Nano particles of silicon dioxide -1- alkyl -3- (3- chloropropyl) trimethoxy silane miaow；When
When glyoxaline compound is fluoro-alkyl imidazoles, the first obtained product is 1- fluoro-alkyl -3- (3- chloropropyl) trimethoxy
Silane imidazoles chloride salt ions liquid, final product are Nano particles of silicon dioxide -1- fluoro-alkyl -3- (3- chloropropyl) trimethoxy
Bis- (fluorine sulphonyl) the imines ionic liquids of silane miaow；When glyoxaline compound is itrile group imidazoles, the first obtained product is 1-
Itrile group -3- (3- chloropropyl) trimethoxy silane imidazoles chloride salt ions liquid, final product are Nano particles of silicon dioxide -1- nitrile
Bis- (fluorine sulphonyl) the imines ionic liquids of base -3- (3- chloropropyl) trimethoxy silane miaow, the mechanism of reaction be it is the same, because
This, is no longer described in detail.
Further, in step S2, it is by dioxide/silica gel that the mass fraction of the silica glue, which is 1-5%,
Cream dilutes to obtain with deionized water, and the silica latex is the titanium dioxide of mass fraction 20-30%, particle diameter 5-10nm
Silicon aqueous emulsion.The partial size of silica also has a certain impact to the performance of electrolyte in latex, when the partial size mistake of silica
The low additive molecule that easily causes is reunited, excessively high, is unfavorable for dispersion in the electrolytic solution, so that the effect promoting of electrolyte is not
Obviously, in order to guarantee the best performance of electrolyte, inventor carries out the particle diameter of silica and the mass fraction of glue
Preferably.
Further, in step S3, the molar ratio of bis- (fluorine sulphonyl) imines lithium salts and second product (1.05~
1.2):1.Herein in preferred range, react more abundant, and purity and yield are relatively high.
Further, in the electrolyte, the mass fraction of the lithium salts electrolyte is 12-15%, and the film forming adds
The mass fraction for adding agent is 0.1~5%.In electrolyte system of the invention, lithium salts electrolyte and film for additive are normal
Rule addition, in order to enable the best performance of electrolyte, inventor carries out the additive amount of lithium salts electrolyte and film for additive
It is preferred that.
Preferably, the lithium salts electrolyte includes lithium hexafluoro phosphate, di-oxalate lithium borate, bis- (fluoroform sulphonyl) imines
At least one of lithium, bis- (fluorine sulphonyl) imine lithiums, difluorine oxalic acid boracic acid lithium, difluorophosphate, LiBF4.It is understood that
, the lithium salts electrolyte that can be used in the present invention is including but not limited to above-mentioned, lithium salts electrolysis as known to those skilled in the art
Matter is used equally in the present invention.And the battery performance as made of fluorine-containing lithium salts is good, has without explosion danger, strong applicability, and also
There is the processing work of waste battery relatively easy, the advantages of to eco-friendly, therefore, fluorine-containing lithium is preferably used in the present invention
Salt is as lithium salts electrolyte, wherein most prominent with lithium hexafluoro phosphate advantage, therefore, hexafluorophosphoric acid is most preferably used in the present invention
Lithium.
Further, the organic solvent include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate,
Ethylene carbonate, methyl ethyl carbonate enester, propene carbonate, butylene, tetrahydrofuran, N,N-dimethylformamide, N- first
At least one of base -2-Pyrrolidone；
The film for additive includes vinylene carbonate, sulfuric acid vinyl ester, fluorinated ethylene carbonate, sulfurous acid propylene
At least one of ester, vinylethylene carbonate, cyclohexyl benzene.
It is understood that the organic solvent that can be used in the present invention, film for additive are including but not limited to above-mentioned, ability
Organic solvent that field technique personnel know, film for additive are used equally in the present invention, and that illustrates in the present invention is several for invention
People carries out preferred, so that electrolyte property obtained is more excellent.
It is another object of the present invention to provide a kind of lithium ion batteries, contain above-mentioned high power electrolyte.It incite somebody to action this
High power electrolyte in invention is in lithium ion battery, lithium ion battery obtained to have in high power charging
High safety and good cycle life.The state of the art is prepared as due to lithium ion battery, here
No longer it is described in detail.
Compared with prior art, the invention has the following advantages:
The present invention is combined nano silica with ionic liquid by cleverly MOLECULE DESIGN, to realize organic
The synergistic effect of object and inorganic matter.Wherein, nano silica is conducive to dispersion of the additive in electrolyte organic solvent, miaow
Azoles cation can be effectively combined the anion in electrolyte, be equivalent to anion " catcher ", improve the molten of lithium ion
Agentization effect promotes lithium ion to form uniform particle flux during migration, and combines film for additive in cathode table
Face film forming reduces impedance, and the Li dendrite of negative terminal surface is inhibited to generate.The ion liquid addictive in the present invention can be effective simultaneously
Inhibit electrolyte under high power charge and discharge further to react with film for additive, to reduce the generation of sour gas, protects SEI
Film is not by electrolytic corrosion, it will be apparent that improves cyclical stability and peace of the lithium ion battery under high power, high rate charge-discharge
Quan Xing.
Specific embodiment
To facilitate the understanding of the present invention, below in conjunction with specific embodiments to invention is more fully described.But
It is that the invention can be realized in many different forms, however it is not limited to embodiments described herein.On the contrary, providing
The purpose of these embodiments is to make to make the present disclosure more fully understandable.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
Comparative example 1
The preparation of electrolyte:
In the glove box (moisture < 1ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate EC, dimethyl carbonate
DMC, methyl ethyl carbonate EMC are uniformly mixed with 30:60:10 mass ratio, are slow added into the LiPF that mass fraction is 14%6, stir
It mixes to it and is completely dissolved, the film for additive of mass fraction 1% is then added, obtains electrolyte.
The 1 specific preparation method of intermediate ion liquid additive of embodiment is the (addictive preparation method in other embodiments
Identical as 1 process of embodiment, only raw material and product are different due to the difference of R, therefore, are no longer described in detail):
The alkyl imidazole of molar ratio 1.2:1 and (3- chloropropyl) trimethoxy silane are dissolved in N,N-dimethylformamide
In, and be stirred to react at 85 DEG C under nitrogen protection 48 hours, then reaction solution is extracted repeatedly with ether, rotary evaporation
Instrument removes solvent and obtains 1- alkyl -3- (3- chloropropyl) trimethoxy silane imidazoles chloride salt ions liquid.
It dilutes silica latex (25% mass fraction aqueous emulsion, particle diameter 5nm) to obtain 2% matter with deionized water
Measure the silica glue of score.1- alkyl -3- (3- chloropropyl) trimethoxy silane imidazoles chloride salt ions liquid is slowly dripped
It is added in silica glue, silica glue is 1.5 times excessive, is quickly stirred to react at 85 DEG C 12 hours, then will be warm
Degree improves to 110 DEG C of evaporations and removes water, then the obtained ionic liquid chloride solution containing Nano particles of silicon dioxide uses second
Alcohol elutes repeatedly, is centrifugated, be freeze-dried the solvent for removing trace after obtain the ionic liquid containing Nano particles of silicon dioxide
Body villaumite.
Again by bis- (fluorine sulphonyl) imines lithium salts of molar ratio 1.2:1 and ionic liquid chlorine containing Nano particles of silicon dioxide
Salt dissolution solution is respectively prepared in deionized water, will be bis- (fluorine sulphonyl) imines lithium salt solution be slowly dropped to ionic liquid chlorine
In salt-Nano particles of silicon dioxide solution, and persistently stir to get bis- (fluorine sulphonyl) inferior amine salts of Nano particles of silicon dioxide-from
Sub- liquid, reaction stand after 2 hours, are centrifugated, dry and remove aqueous solvent.Then product is dispersed again to remove in acetone
Chloride ion-Nano particles of silicon dioxide by-product that part reaction generates, the water that finally freeze-drying removes trace obtain yield
87%, Nano particles of silicon dioxide -1- alkyl -3- (3- chloropropyl) trimethoxy silane miaow of purity 99.5% is bis- (fluorine sulphonyl)
Imines ionic liquid.
Embodiment 1
In the glove box (moisture < 1ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate EC, dimethyl carbonate
DMC, methyl ethyl carbonate EMC are uniformly mixed with 30:60:10 mass ratio, are slow added into the LiPF that mass fraction is 14%6, stir
It mixes to it and is completely dissolved, the film for additive of mass fraction 1% and the aforementioned nanometer two obtained of mass fraction 1% is then added
Silica-ion liquid compound 1 obtains high power electrolyte.
Wherein, the structural formula of compound 1 are as follows:
Embodiment 2
In the present embodiment in high power electrolyte, only ion liquid addictive is different from embodiment 1, is mass fraction
1% nano silica-ion liquid compound 2, remaining component, additive amount and preparation method are same as Example 1.
Wherein, the structural formula of compound 2 are as follows:
Embodiment 3
In the present embodiment in high power electrolyte, only ion liquid addictive is different from embodiment 1, is mass fraction
1% nano silica-ion liquid compound 3, remaining component, additive amount and preparation method are same as Example 1.
Wherein, the structural formula of compound 3 are as follows:
Embodiment 4
In the present embodiment in high power electrolyte, only ion liquid addictive is different from embodiment 1, is mass fraction
1% nano silica-ion liquid compound 4, remaining component, additive amount and preparation method are same as Example 1.
Wherein, the structural formula of compound 4 are as follows:
Embodiment 5
In the present embodiment in high power electrolyte, only ion liquid addictive is different from embodiment 1, is mass fraction
1% nano silica-ion liquid compound 5, remaining component, additive amount and preparation method are same as Example 1.
Wherein, the structural formula of compound 5 are as follows:
Embodiment 6
In the present embodiment in high power electrolyte, only ion liquid addictive is different from embodiment 1, is mass fraction
1% nano silica-ion liquid compound 6, remaining component, additive amount and preparation method are same as Example 1.
Wherein, the structural formula of compound 6 are as follows:
Embodiment 7
In the present embodiment in high power electrolyte, only ion liquid addictive is different from embodiment 1, is mass fraction
1% nano silica-ion liquid compound 7, remaining component, additive amount and preparation method are same as Example 1.
Wherein, the structural formula of compound 7 are as follows:
Embodiment 8
In the present embodiment in high power electrolyte, only ion liquid addictive is different from embodiment 1, is mass fraction
1% nano silica-ion liquid compound 8, remaining component, additive amount and preparation method are same as Example 1.
Wherein, the structural formula of compound 8 are as follows:
Embodiment 9
In the present embodiment in high power electrolyte, only ion liquid addictive is different from embodiment 1, is mass fraction
0.1% nano silica-ion liquid compound 4, remaining component, additive amount and preparation method are same as Example 1.
Wherein, the structural formula of compound 4 are as follows:
Embodiment 10
In the present embodiment in high power electrolyte, only ion liquid addictive is different from embodiment 1, is mass fraction
5% nano silica-ion liquid compound 7, remaining component, additive amount and preparation method are same as Example 1.
Wherein, the structural formula of compound 7 are as follows:
Lithium ion battery is respectively prepared in electrolyte in comparative example 1 and Examples 1 to 10, specific preparation process is as follows:
The preparation of positive plate: by active material nickle cobalt lithium manganate (NCM811), the super conductive carbon of conductive agent (SP), binder
Kynoar (PVDF) 97.5:1:1.5 in mass ratio is thoroughly mixed in n-methyl-2-pyrrolidone dicyandiamide solution
After even, slurry is coated on collector Al foil, obtains positive plate, compacted density 3.3g/ through cutting, cross cutting, roll-in
cm3；
The preparation of negative electrode tab: by active material artificial graphite, the super conductive carbon of conductive agent (SP), binder butadiene-styrene rubber
(SBR), thickener sodium carboxymethylcellulose (CMC) 95:1:2:2 in mass ratio is sufficiently stirred mixed in deionized water solvent system
After closing uniformly, slurry is coated on collector Cu foil, negative electrode tab is obtained after cutting, roll-in, cross cutting, compacted density is
1.6g/cm3；
Polypropylene (PP) basement membrane that diaphragm used is 12 μm coats the nano oxidized aluminized coating of 4um.
Technique after positive plate, diaphragm, negative electrode tab are stacked gradually according to laminated batteries obtains naked battery core, then by naked electricity
Core is placed in pre-packaged in aluminum plastic film, encapsulates again after injecting the electrolyte of preparation, obtains soft pack cell.
By above-mentioned lithium ion battery 1C constant volume at normal temperature, with 2C/2C, 5C/5C charge and discharge cycles 100 under room temperature
Week, voltage range are that 3.0~4.2V tests its coulombic efficiency, 2C capacity retention ratio and 5C capacity retention ratio for the first time.It then will be electric
After high temperature storage 7 days, the internal resistance of battery before and after high temperature storage is tested using internal resistance instrument at 55 DEG C for pond, (wherein R1For the internal resistance for recycling preceding battery, R2For the internal resistance of battery after circulation), internal resistance change rate is compared,
Concrete outcome is as shown in table 1.
1 electric performance test result of table
| Number | Coulombic efficiency/% for the first time | 2C capacity retention ratio/% | 5C capacity retention ratio/% | Internal resistance growth rate/% |
| Comparative example 1 | 78.2 | 90.8 | 85.7 | 20.3 |
| Embodiment 1 | 81.3 | 95.7 | 91.1 | 10.2 |
| Embodiment 2 | 83.4 | 96.1 | 90.8 | 11.7 |
| Embodiment 3 | 80.8 | 95.2 | 90.6 | 10.5 |
| Embodiment 4 | 81.1 | 94.8 | 91.0 | 12.3 |
| Embodiment 5 | 81.6 | 94.4 | 90.2 | 11.8 |
| Embodiment 6 | 82.5 | 95.1 | 89.5 | 10.6 |
| Embodiment 7 | 79.1 | 94.2 | 89.8 | 14.7 |
| Embodiment 8 | 82.6 | 93.6 | 89.1 | 15.6 |
| Embodiment 9 | 80.6 | 92.8 | 88.5 | 14.6 |
| Embodiment 10 | 81.2 | 94.8 | 90.3 | 13.4 |
The test result comparison of above-described embodiment 1~10 and comparative example 1, which can be seen that, joined provided by the invention receive
Rice silica-ion liquid addictive all has obviously the high rate charge-discharge and high-temperature storage performance of lithium ion battery
It improves, illustrates that electrolyte provided by the invention is a kind of lithium-ion battery electrolytes that excellent high power is stable.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of high power electrolyte comprising lithium salts electrolyte, organic solvent and film for additive, which is characterized in that described
High power electrolyte also contains ion liquid addictive, and the ion liquid addictive is the bis- (fluorine of nano silica-imidazole radicals
Sulphonyl) imines salt compound, structural formula are as follows:
Wherein, R is the group that carbon atom number is 1~6, and the group is straight chained alkyl, fluoro-alkyl or itrile group.
2. high power electrolyte as described in claim 1, which is characterized in that in the high power electrolyte, the ion
The mass fraction of liquid additive is 0.1~5%.
3. high power electrolyte as described in claim 1, which is characterized in that the preparation method of the ion liquid addictive
Are as follows:
S1, (3- chloropropyl) trimethoxy silane and glyoxaline compound are dissolved in n,N-Dimethylformamide, are being protected
It is stirred to react in 80-90 DEG C 40-50 hours under atmosphere, obtains the first product using extraction, removal solvent, wherein the guarantor
Protecting atmosphere is inert gas or nitrogen；
S2, first product is slowly dropped in silica glue, 1.5-2.0 times of excess of the silica glue,
After being quickly stirred to react 10-15 hours at 80-90 DEG C, temperature is improved to 100-120 DEG C of evaporation and removes water, using purifying
Obtain the second product；
S3, will be bis- (fluorine sulphonyl) imines lithium salts, second product dissolution solution is respectively prepared in deionized water, by bis- (fluorine
Sulphonyl) imines lithium salt solution is slowly dropped in the second reaction mixture, stirring is stood after 2-4 hour, is purified again, obtain described in
Ion liquid addictive.
4. high power electrolyte as claimed in claim 3, which is characterized in that in step S1, (3- chloropropyl) trimethoxy
The molar ratio of base silane and the glyoxaline compound is (1.05~1.2): 1, the glyoxaline compound is alkyl imidazole, fluorine
Substituted alkyl imidazoles or itrile group imidazoles.
5. high power electrolyte as claimed in claim 3, which is characterized in that in step S2, the matter of the silica glue
Amount score is 1-5%, is that silica latex is spent ionized water to dilute to obtain, and the silica latex is mass fraction
The silica aqueous emulsion of 20-30%, particle diameter 5-10nm.
6. high power electrolyte as claimed in claim 3, which is characterized in that in step S3, bis- (fluorine sulphonyl) imine lithiums
The molar ratio (1.05~1.2) of salt and second product: 1.
7. high power electrolyte as described in claim 1, which is characterized in that in the electrolyte, the lithium salts electrolyte
Mass fraction be 12-15%, the mass fraction of the film for additive is 0.1~5%.
8. high power electrolyte as described in claim 1, which is characterized in that the lithium salts electrolyte include lithium hexafluoro phosphate,
Di-oxalate lithium borate, bis- (fluoroform sulphonyl) imine lithiums, bis- (fluorine sulphonyl) imine lithiums, difluorine oxalic acid boracic acid lithium, difluorophosphoric acid
At least one of lithium, LiBF4.
9. high power electrolyte as described in claim 1, which is characterized in that the organic solvent includes dimethyl carbonate, carbon
Diethyl phthalate, methyl ethyl carbonate, methyl propyl carbonate, ethylene carbonate, methyl ethyl carbonate enester, propene carbonate, butylene,
At least one of tetrahydrofuran, N,N-dimethylformamide, n-methyl-2-pyrrolidone；
The film for additive includes vinylene carbonate, sulfuric acid vinyl ester, fluorinated ethylene carbonate, propylene sulfite, carbon
At least one of sour vinylethylene, cyclohexyl benzene.
10. a kind of lithium ion battery, which is characterized in that contain high power electrolyte as described in any one of claims 1 to 9.
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| CN113381067A (en) * | 2020-03-10 | 2021-09-10 | 荣盛盟固利新能源科技有限公司 | High-safety electrolyte of high-energy-density soft package battery and high-energy-density soft package battery |
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| JP2008130229A (en) * | 2006-11-16 | 2008-06-05 | National Institute Of Advanced Industrial & Technology | Lithium secondary battery |
| CN103765663A (en) * | 2011-07-11 | 2014-04-30 | 康奈尔大学 | Ionic-liquid nanoscale ionic material (IL-NIM) compositions, methods and applications |
| CN109070049A (en) * | 2016-03-04 | 2018-12-21 | 康奈尔大学 | Stable room temperature sodium-sulfur battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008130229A (en) * | 2006-11-16 | 2008-06-05 | National Institute Of Advanced Industrial & Technology | Lithium secondary battery |
| CN103765663A (en) * | 2011-07-11 | 2014-04-30 | 康奈尔大学 | Ionic-liquid nanoscale ionic material (IL-NIM) compositions, methods and applications |
| CN109070049A (en) * | 2016-03-04 | 2018-12-21 | 康奈尔大学 | Stable room temperature sodium-sulfur battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113381067A (en) * | 2020-03-10 | 2021-09-10 | 荣盛盟固利新能源科技有限公司 | High-safety electrolyte of high-energy-density soft package battery and high-energy-density soft package battery |
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