CN105845984A - Lithium ion battery electrolyte and lithium ion battery using same - Google Patents
Lithium ion battery electrolyte and lithium ion battery using same Download PDFInfo
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- CN105845984A CN105845984A CN201610470747.2A CN201610470747A CN105845984A CN 105845984 A CN105845984 A CN 105845984A CN 201610470747 A CN201610470747 A CN 201610470747A CN 105845984 A CN105845984 A CN 105845984A
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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
- H01M10/05—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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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Abstract
The invention relates to the technical field of lithium ion batteries, in particular to lithium ion battery electrolyte and a lithium ion battery using same; the electrolyte is prepared from lithium salt, a non-aqueous organic solvent and an additive, wherein the additive is prepared from fluoroethylene carbonate, nitrile compounds and a compound with a structure as shown in formula I; R1, R2, R3, R4 and R5 in the formula I are separately selected from hydrogen, an amide group and alkyl or alkoxy with a carbon number being 1-3; R1, R2, R3, R4 and R5 at least contain one amide group. Compared with the prior art, the lithium ion battery electrolyte is excellent in wetting effect and excellent in fast charge performance under a high-voltage condition by virtue of a synergistic effect generated by the fluoroethylene carbonate, the nitrile compounds and an amide pyridine compound with a structure as shown in formula I; moreover, the lithium ion battery electrolyte has the comprehensive performance of a long cycle life and a low high-temperature storage expansion rate.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of high voltage and fill lithium soon
Ion battery electrolyte and use the lithium ion battery of this electrolyte.
Background technology
Since commercialization in 1991, lithium ion battery is big by its capacity density, work electricity
Pressure is high, manufacture process pollutes the advantages such as little, use process cleans is pollution-free, rapidly consumer
And power category terminal is widely used.From a lithium metal battery to cylinder, aluminum hull, Soft Roll etc.
Secondary chargeable lithium ion battery, lithium battery also presents more and more diversified product general layout, and
Highly customization, controlled shape, performance is wide in range the most gradually becomes a reality.
Although at the emerging consumer fields such as the mobile phone in recent years risen, panel computer, lithium ion battery
Great advantage has been manifested with its high capacity density and long circulation life, but along with relevant device function
Continuous variation, the continuous rising of electricity consumption module dissipation so that existing lithium ion battery is positive and negative
The drawback of pole material, conventional batteries design constantly manifests.In order to solve this problem, most in the industry
By promoting the charging upper limit voltage of positive terminal or increasing the compacted density of cathode membrane, to obtain
Obtain bigger volume energy density.Additionally, also have at the base not changing original battery charge frequency
On plinth, it is shortened by the required time of every time charging, to reach the purpose of quick charge.
Wherein, for filling lithium ion battery soon, the most multi-vendor is by using existing active substance,
Reduce both positive and negative polarity surface density or the method for compacted density simultaneously；Ye You manufacturer is to use kinetics
Performance more preferable both positive and negative polarity active substance, such as positive electrode and the bag of bulky grain low specific surface area
The schemes such as the Delanium covering soft carbon.But these methods bring cycle life to shorten undoubtedly, energy
Density reductions etc. negatively affect, it is therefore necessary to find rational solution from electrolyte end.
Electrolyte why so it is crucial that because battery is during quick charge, lithium ion
Quickly enter electrolyte from positive pole abjection, then pass through barrier film, enter negative pole and carry out embedding lithium, greatly
Amount lithium ion carries out fast transferring needs electrolyte to have higher dynamic performance, in mass transfer mistake
Journey has less resistance to mass tranfer, it is therefore desirable to electrolyte has preferable wellability, lower
Viscosity and lower lithium ion transport resistance.
But the existing electrolyte for lithium ion battery that fills soon, commonly used low viscosity high conductivity
The technical scheme of the solvent high lithium salt of collocation, and the program has the disadvantage that one is cost
Advantage is inconspicuous；Two is that produced battery high-temperature storage weak effect, cycle life are short.
In view of this, necessary the existing ion battery electrolyte that fills soon is optimized, makes
While it possesses rapid charging performance, also there is good high temperature storage and cycle performance.
Summary of the invention
An object of the present invention is: for filling electrolyte for lithium ion battery high temperature soon at present
Storage and the deficiency of cycle performance difference, and provide that one not only effect of impregnation is excellent, filling property soon
Can be excellent, and have the lithium ion battery battery of preferable cycle performance and high-temperature storage performance concurrently simultaneously
Solve liquid.
To achieve these goals, the present invention uses solution below:
A kind of lithium-ion battery electrolytes, including lithium salts, Non-aqueous Organic Solvents and additive,
Described additive includes fluorinated ethylene carbonate, nitrile compounds and has structure shown in formula I
Compound；
Wherein, the R in formula I1、R2、R3、R4、R5Separately selected from hydrogen, amide
Base, carbon number are alkyl or the alkoxyl of 1～3, and R1、R2、R3、R4、R5In extremely
Contain an amide groups less.
The present invention is by fluorinated ethylene carbonate, nitrile compounds and has structure shown in formula I
The synergism of compound so that use the battery of this electrolyte under high voltage is real not
Only effect of impregnation is excellent, electrochemical impedance is low, it is effective to fill soon, and possesses the circulation of excellence
And high-temperature storage performance.Wherein, during initial charge, fluorinated ethylene carbonate is at graphite
Negative terminal surface is reduced and forms thin and stable SEI film, by effective with graphite active site for solvent
Isolation, it is to avoid during battery uses, electrolyte is reduced, and fluorinated ethylene carbonate can also simultaneously
Promote the wetting capacity of electrolyte anticathode diaphragm；Nitrile compounds can with in positive active material
Transition metal atoms generation complexing formed one layer of positive pole passivating film, this passivating film is by solvent
It is effectively isolated with positive-active site, slows down electrolyte and decomposed by vigorous oxidation in cyclic process
And affect cycle life；Additionally, this passivating film can effectively contain that transition metal is in high temperature storage
Dissolution under environment, thus the high-temperature storage performance of electrolyte is effectively promoted；There is formula I
Shown in the pyridine compounds and their of structure, on the one hand its amide groups contained can whole by electrolyte
Body viscosity reduces, it is achieved the good infiltration of anticathode diaphragm, with reach excellent capacity play and
Rapid charging performance；On the other hand, its pyridine heterocycle contained can be with the transition in positive active material
Metallic element generation complexing, is passivated positive pole further, to protect electrolyte solvent not by oxygen
Change and decompose, thus obtain the cycle performance of excellence.
Preferably, described fluorinated ethylene carbonate weight/mass percentage composition in the electrolytic solution is
1%～8%；Described nitrile compounds weight/mass percentage composition in the electrolytic solution is 0.05%～5%；
The described compound with structure shown in formula I weight/mass percentage composition in the electrolytic solution is
0.01%～8%, preferably 0.5%～5%.
Preferably, described lithium salts is lithium hexafluoro phosphate, di-oxalate lithium borate, difluoro oxalate boric acid
In lithium, double fluorine sulfimide lithium, LiBF4 and double trifluoromethanesulfonimide lithium at least
A kind of；Described lithium salts weight/mass percentage composition in the electrolytic solution is 12%～20%.
Preferably, described Non-aqueous Organic Solvents is selected from ethylene carbonate, Allyl carbonate, carbon
Diethyl phthalate, Ethyl methyl carbonate, ethyl propionate, propyl propionate, methyl propyl carbonate, acetic acid second
Ester, propyl acetate, methyl acetate, methyl butyrate, ethyl n-butyrate., propyl butyrate, tetrahydrochysene furan
Mutter, one or more in dioxy cycloalkanes, gamma-butyrolacton；Described Non-aqueous Organic Solvents exists
Weight/mass percentage composition in electrolyte is 65%～85%.Above-mentioned Non-aqueous Organic Solvents has relatively
High decomposition electric potential, has preferable heat stability and electrochemically stable under high temperature, high voltage
Property, thus for 4.4V and above high voltage fill soon lithium ion battery electrical property provide stable
Electrochemical environment.
Preferably, described nitrile compounds be adiponitrile, succinonitrile, glutaronitrile, pimelic dinitrile,
2-methyl cellosolve acetate glutaronitrile and 1, at least one in 3,6-hexane three nitriles.Cited nitrile chemical combination
Thing can improve anode material for lithium-ion batteries stability under high voltages, and suppression electrolyte exists
Positive electrode surface oxidation Decomposition, improves high-temperature storage performance and the cyclicity of high-voltage lithium ion batteries
Energy.
Preferably, described in there is the compound of structure shown in formula I selected from 2,6-bis-pyridine diformazan
Amide (structural formula is as shown in formula I-1), 2-ascorbyl palmitate (structural formula is as shown in formula I-2),
(structural formula is such as Niacinamide (structural formula is as shown in formula I-3) and Isonicotinamide
Shown in formula I-4) in one or more.
The two of the purpose of the present invention are: fill high-temperature lithium ion battery storage effect soon for existing
The deficiency that difference, cycle life are short, and a kind of lithium ion battery using above-mentioned electrolyte is provided,
This lithium ion battery not only possesses circulation and the rapid charging performance of excellence, ensures good simultaneously
High temperature storage and cycle performance.
A kind of lithium ion battery using above-mentioned lithium-ion battery electrolytes to prepare, including positive pole pole
Sheet, cathode pole piece, the barrier film being arranged between described anode pole piece and described cathode pole piece, with
And electrolyte, described anode pole piece includes plus plate current-collecting body and is coated on anode collection surface
Positive pole diaphragm, described cathode pole piece includes negative current collector and be coated in negative pole currect collecting surface
On cathode membrane.
Wherein, described positive pole diaphragm includes positive active material, conductive agent and binding agent, and institute
State the compacted density >=4.0g/cm of positive pole diaphragm3。
Described cathode membrane includes negative electrode active material, conductive agent and binding agent, and described negative pole
Surface density >=the 80g/m of diaphragm2, compacted density >=1.55g/cm3。
The charge cutoff voltage of described lithium ion battery is 4.4～4.7V.
The present invention at least has the advantages that
1) one lithium-ion battery electrolytes of the present invention, including lithium salts, Non-aqueous Organic Solvents
And additive,
Described additive includes fluorinated ethylene carbonate, nitrile compounds and has structure shown in formula I
Amide pyridine compounds and their；Wherein, fluorinated ethylene carbonate forms SEI on graphite cathode surface
Film, it is ensured that cycle life, fluorinated ethylene carbonate can improve the wetting property of electrolyte simultaneously,
Reduce effective lithium transmission resistance (electrochemical impedance) in graphite layers, thus effectively promote electricity
The rapid charging performance in pond；Transition metal generation complexation in nitrile compounds, with positive active material
Effect, under suppression high temperature storage conditions, the dissolution of transition metal, assimilates in battery simultaneously
Micro-moisture, reduces phosphorus pentafluoride and the generation of flatulence, improves high-temperature behavior；There is formula I institute
Show the amide pyridine compounds and their of structure, on the one hand its pyridine heterocycle contained and positive electrode active material
Transition metal in matter occur coordination protect the not oxidized decomposition of solvent, lifting high temperature storage and
Cycle performance；On the other hand, its amide groups contained can reduce the viscosity of electrolyte, improves electricity
Solve the liquid infiltration to pole piece, and realize quickly embedding and deintercalation of lithium, promote rapid charging performance；
2) the Non-aqueous Organic Solvents system selected by the present invention, comprises ethylene carbonate, carbon
The solvent of the high-ks such as acid propylene ester, the beneficially dissolving of lithium salts, battery high-temperature and circulation
The lifting of performance；Additionally, comprise the solvent composition that viscosity is low and electrochemical window is wide, it is possible to no
Decomposed by the positive pole of high potential, and low viscosity disclosure satisfy that the electrolyte infiltration requirement to pole piece；
3) present invention is by adjusting fluorinated ethylene carbonate, nitrile compounds and having formula I
Cooperative effect produced by the proportioning of the amide pyridine compounds and their of shown structure so that using should
Lithium ion battery prepared by electrolyte, under 4.4V and above high voltage condition, not only infiltrates
Excellent effect, rapid charging performance are excellent, and have combine low with high temperature storage expansion that have extended cycle life concurrently
Close performance, have broad application prospects.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1～8 and comparative example 1～4 obtained by the circulation of lithium ion battery
Performance map.
Detailed description of the invention
Below in conjunction with detailed description of the invention and Figure of description to the present invention and beneficial effect thereof
It is described in further detail, but, the detailed description of the invention of the present invention is not limited thereto.
Embodiment 1
The preparation of electrolyte:
In the glove box (moisture ＜ 10ppm, oxygen content ＜ 1ppm) of full argon,
By ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate with
The quality of 25:10:30:10:25 than mix homogeneously and is stirred continuously, and is slowly added in mixed solvent
Mass fraction is the LiPF of 15%6, add fluorinated ethylene carbonate that mass fraction is 3%,
Mass fraction be 1% adiponitrile and mass fraction be the 2 of 0.5%, 6-bis-pyridine diformamide,
Stirring, to being completely dissolved, i.e. obtains the lithium-ion battery electrolytes of embodiment 1.
The preparation of lithium ion battery:
By positive active material cobalt acid lithium, conductive agent Super P, binding agent polyvinylidene fluoride
(PVDF) in mass ratio 95: 3: 2 fully stir in N-Methyl pyrrolidone dicyandiamide solution
After mixing mix homogeneously, it is coated on Al paper tinsel and dries, cold pressing, obtain anode pole piece, its compacting
Density is 4.0g/cm3。
By negative electrode active material graphite, conductive agent Super P, binding agent butadiene-styrene rubber (SBR),
Thickening agent carboxymethyl cellulose sodium (CMC) according to mass ratio 95: 2: 2: 1 go from
Sub-aqueous solvent is thoroughly mixed after uniformly, is coated on Cu paper tinsel and dries, cold pressing,
Obtaining cathode pole piece, its surface density is 80g/m2, its compacted density is 1.55g/cm3。
With PP-PE-PP film as basement membrane (12 μm) at the nano oxidized aluminized coating of coating on base films
(3 μm) is as barrier film.
Anode pole piece, barrier film, cathode pole piece are folded in order, makes barrier film be in positive/negative plate
The effect of isolation is played in centre, and winding obtains naked battery core.Naked battery core is placed in outer package,
Inject preparation electrolyte and encapsulated, shelve, be melted into, aging, secondary encapsulation, partial volume etc.
Operation, obtains the lithium ion battery that model is 504848.
Embodiment 2
The preparation of electrolyte as different from Example 1:
In the glove box (moisture ＜ 10ppm, oxygen content ＜ 1ppm) of full argon,
By ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate with
The quality of 25:10:30:10:25 than mix homogeneously and is stirred continuously, and is slowly added in mixed solvent
Mass fraction is the LiPF of 15%6, add fluorinated ethylene carbonate that mass fraction is 3%,
Mass fraction be 1% adiponitrile and mass fraction be the 2 of 3%, 6-bis-pyridine diformamide, stir
Mix to being completely dissolved, i.e. obtain the lithium-ion battery electrolytes of embodiment 2.
Remaining, with embodiment 1, repeats no more here.
Embodiment 3
The preparation of electrolyte as different from Example 1:
In the glove box (moisture ＜ 10ppm, oxygen content ＜ 1ppm) of full argon,
By ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate with
The quality of 25:10:30:10:25 than mix homogeneously and is stirred continuously, and is slowly added in mixed solvent
Mass fraction is the LiPF of 15%6, add fluorinated ethylene carbonate that mass fraction is 3%,
Mass fraction is the adiponitrile of 1% and 2-ascorbyl palmitate that mass fraction is 0.5%, and stirring is extremely
It is completely dissolved, i.e. obtains the lithium-ion battery electrolytes of embodiment 3.
Remaining, with embodiment 1, repeats no more here.
Embodiment 4
The preparation of electrolyte as different from Example 1:
In the glove box (moisture ＜ 10ppm, oxygen content ＜ 1ppm) of full argon,
By ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate with
The quality of 25:10:30:10:25 than mix homogeneously and is stirred continuously, and is slowly added in mixed solvent
Mass fraction is the LiPF of 15%6, add fluorinated ethylene carbonate that mass fraction is 3%,
Mass fraction is the adiponitrile of 1% and 2-ascorbyl palmitate that mass fraction is 3%, and stirring is to the completeest
CL, i.e. obtains the lithium-ion battery electrolytes of embodiment 4.
Remaining, with embodiment 1, repeats no more here.
Embodiment 5
The preparation of electrolyte as different from Example 1:
In the glove box (moisture ＜ 10ppm, oxygen content ＜ 1ppm) of full argon,
By ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate with
The quality of 25:10:30:10:25 than mix homogeneously and is stirred continuously, and is slowly added in mixed solvent
Mass fraction is the LiPF of 15%6, add fluorinated ethylene carbonate that mass fraction is 3%,
Mass fraction be 1% adiponitrile and mass fraction be the Niacinamide of 0.5%, stirring extremely
It is completely dissolved, i.e. obtains the lithium-ion battery electrolytes of embodiment 5.
Remaining, with embodiment 1, repeats no more here.
Embodiment 6
The preparation of electrolyte as different from Example 1:
In the glove box (moisture ＜ 10ppm, oxygen content ＜ 1ppm) of full argon,
By ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate with
The quality of 25:10:30:10:25 than mix homogeneously and is stirred continuously, and is slowly added in mixed solvent
Mass fraction is the LiPF of 15%6, add fluorinated ethylene carbonate that mass fraction is 3%,
Mass fraction be 1% adiponitrile and mass fraction be the Niacinamide of 3%, stirring is to the completeest
CL, i.e. obtains the lithium-ion battery electrolytes of embodiment 6.
Remaining, with embodiment 1, repeats no more here.
Embodiment 7
The preparation of electrolyte as different from Example 1:
In the glove box (moisture ＜ 10ppm, oxygen content ＜ 1ppm) of full argon,
By ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate with
The quality of 25:10:30:10:25 than mix homogeneously and is stirred continuously, and is slowly added in mixed solvent
Mass fraction is the LiPF of 15%6, add fluorinated ethylene carbonate that mass fraction is 3%,
Mass fraction be 1% adiponitrile and mass fraction be the Isonicotinamide of 0.5%, stirring extremely
It is completely dissolved, i.e. obtains the lithium-ion battery electrolytes of embodiment 7.
Remaining, with embodiment 1, repeats no more here.
Embodiment 8
The preparation of electrolyte as different from Example 1:
In the glove box (moisture ＜ 10ppm, oxygen content ＜ 1ppm) of full argon,
By ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate with
The quality of 25:10:30:10:25 than mix homogeneously and is stirred continuously, and is slowly added in mixed solvent
Mass fraction is the LiPF of 15%6, add fluorinated ethylene carbonate that mass fraction is 3%,
Mass fraction be 1% adiponitrile and mass fraction be the Isonicotinamide of 3%, stirring is to the completeest
CL, i.e. obtains the lithium-ion battery electrolytes of embodiment 8.
Remaining, with embodiment 1, repeats no more here.
Comparative example 1:
The preparation of electrolyte as different from Example 1:
In the glove box (moisture ＜ 10ppm, oxygen content ＜ 1ppm) of full argon,
By ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate with
The quality of 25:10:30:10:25 than mix homogeneously and is stirred continuously, and is slowly added in mixed solvent
Mass fraction is the LiPF of 15%6, add the fluorinated ethylene carbonate that mass fraction is 1%,
Stirring, to being completely dissolved, i.e. obtains the lithium-ion battery electrolytes of comparative example 1.
Remaining, with embodiment 1, repeats no more here.
Comparative example 2:
The preparation of electrolyte as different from Example 1:
In the glove box (moisture ＜ 10ppm, oxygen content ＜ 1ppm) of full argon,
By ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate with
The quality of 25:10:30:10:25 than mix homogeneously and is stirred continuously, and is slowly added in mixed solvent
Mass fraction is the LiPF of 15%6, add the fluorinated ethylene carbonate that mass fraction is 5%,
Stirring, to being completely dissolved, i.e. obtains the lithium-ion battery electrolytes of comparative example 2.
Remaining, with embodiment 1, repeats no more here.
Comparative example 3:
The preparation of electrolyte as different from Example 1:
In the glove box (moisture ＜ 10ppm, oxygen content ＜ 1ppm) of full argon,
By ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate with
The quality of 25:10:30:10:25 than mix homogeneously and is stirred continuously, and is slowly added in mixed solvent
Mass fraction is the LiPF of 15%6, add fluorinated ethylene carbonate that mass fraction is 3% and
Mass fraction is the adiponitrile of 1%, and stirring, to being completely dissolved, i.e. obtains the lithium ion of comparative example 3
Battery electrolyte.
Remaining, with embodiment 1, repeats no more here.
Comparative example 4:
The preparation of electrolyte as different from Example 1:
In the glove box (moisture ＜ 10ppm, oxygen content ＜ 1ppm) of full argon,
By ethylene carbonate, Allyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethyl acetate with
The quality of 25:10:30:10:25 than mix homogeneously and is stirred continuously, and is slowly added in mixed solvent
Mass fraction is the LiPF of 15%6, add fluorinated ethylene carbonate that mass fraction is 3% and
The adiponitrile of 3%, stirring, to being completely dissolved, i.e. obtains the lithium-ion battery electrolytes of comparative example 4.
Remaining, with embodiment 1, repeats no more here.
Respectively to lithium ion battery the filling property soon obtained by embodiment 1～8 and comparative example 1～4
Can test.Test result is as shown in table 1.
Table 1 embodiment 1～8 and comparative example 1～4 rapid charging performance test result in 25 ± 1 DEG C of environment
Note: constant current percentage of time refers to that the constant-current charge time accounts for the percentage ratio of total charging time；
Constant current volume percent refers to that constant-current charge amount accounts for the percentage ratio of total charge volume.
Additionally, for the advantage embodying the present invention further, respectively to embodiment 1～8 and contrast
Same batch battery obtained by example 1～4 carries out following performance test:
Room temperature 2C/1C loop test: by battery in 25 ± 1 DEG C of environment with 2C multiplying power constant current
Charging to 4.4V and limit voltage, then constant-potential charge is to cut-off current 0.05C, shelves 5min,
Carry out constant current electric discharge, discharge-rate 1C, discharge cut-off voltage 3.0V again；Finally follow
Ring test, cycle-index is set to more than 400 times.Test result is as shown in Figure 1.
85 DEG C of high temperature storage 6h tests: battery is limited with 0.2C multiplying power constant current charge to 4.4V
Voltage processed, then constant-potential charge is to cut-off current 0.02C, shelves 5min, then carries out 0.2C
Multiplying power constant-current discharge is to 3.0V blanking voltage, and recording this discharge capacity is initial discharge capacity,
And measure the cell thickness of original state, internal resistance；The battery of full power state is put into the baking of 85 DEG C
In case, store 6h with the steady temperatures of 85 ± 2 DEG C, after having stored, test battery high-temperature shape immediately
Thickness under state, cools down 2h under room temperature state, tests internal resistance, with 0.2C multiplying power constant-current discharge
Test residual capacity, the test of 0.2C multiplying power recover capacity；Calculate hot Thickness Measurement by Microwave expansion rate, internal resistance
Magnification, residual capacity percentage ratio, recovery volume percent.The related data of test gained is such as
Shown in table 2.
Table 2 embodiment 1～8 and the comparative example 1～4 storage performance test result at 85 DEG C
Below above-mentioned test result is carried out labor.
From the performance test results of comparative example 1 and comparative example 2 it is found that increase fluoro ethylene
The amount of alkene ester, is conducive to improving battery rapid charging performance.This is because: on the one hand fluoro ethylene
Alkene ester itself is a kind of carbonates organic compound, and its in slightly higher than room temperature environment in
Existing is liquid condition, when its dielectric constant reaches a timing, the ionization of lithium salts has been dissolved promotion
Effect, and electrolyte viscosity somewhat equalizes and can be conducive to its infiltration to pole piece；On the other hand,
Fluorinated ethylene carbonate contains F, and the electric charge that its strong electronegativity can dilute ethylene carbonate ring is close
Degree, forms more stable structure so that it is with gluing in the electrolyte in battery and pole piece diaphragm
The model ylid bloom action of knot agent reduces, and increases the electrolyte immersional wetting to pole piece further.Above
Both sides is combined with the electrochemical impedance beneficially reduced in electron transmission embedding pole piece, and subtracts
The mass transfer impedance that few electronics transmits in the electrolytic solution, thus shorten the charging interval of battery.But need
It should be noted that from the point of view of full power state 85 DEG C storage test result, fluorinated ethylene carbonate is not
Only it is not provided with profit help, increases cell expansion on the contrary, and internal resistance increases and charged holding
Same performance is not good enough.This is derived from the failure mechanism that lithium ion battery stores full power state 85 DEG C,
In electrolyte, existing many employing lithium hexafluoro phosphates are as main electrolyte, and lithium hexafluoro phosphate is at 85 DEG C
Through starting acutely decomposition, produce the material such as phosphorus pentafluoride and lithium fluoride, and phosphorus pentafluoride is a kind of
Strong lewis acid, this material is very easy to destroy battery in the battery and is formed when primary charging
SEI film, decompose produce the gas such as carbon dioxide and ethylene.So comparative example 1 and contrast occur
The best reason of example 2 high-temperature storage performance is: fluorinated ethylene carbonate is as a kind of ethylene carbonate
Esters organic compound, it has the effect forming SEI film, but its SEI formed equally
Film is the Organoalkyl lithium carbonate that rigidity is the strongest；And under full power state 85 DEG C storage environment, one
Aspect can be decomposed the most by force due to the rigidity of SEI film own；On the other hand lithium hexafluoro phosphate decomposes
The SEI film that this stability is the strongest is caused and greatly destroys and produce by phosphorus pentafluoride equally that produce
Gas.
And from the test result of comparative example 3 and comparative example 4 it can be seen that the height of comparative example 4 is gentle
Storage performance is substantially better than comparative example 3, but rapid charging performance, cycle performance are not as comparative example 3.From
The electrolyte that two comparative examples are injected is analyzed it can be seen that comparative example 4 is simply in comparative example 3
On the basis of add the adiponitrile of 2wt%.Nitrile contains carbon nitrogen three key and short of electricity as a class
The compound of son, it joins as additive can play in electrolyte and well deacidifies, removes
Water effect is especially the most notable 85 DEG C of full electricity storage effects.Because trace present in battery
Moisture, can make lithium hexafluoro phosphate decomposition reaction carry out to positive direction in 85 DEG C of storing processs, raw
More phosphorus pentafluoride is become to cause battery failure.And the nitrile compounds added, it is possible to will wherein
Micro-water content reduce, carrying out further of the reaction that effectively controls to lose efficacy.Additionally, due to nitrile
Compounds contains unsaturated bond, is easily coordinated with the transition metal in positive active material,
Effectively prevent transition metal dissolution from active material configuration, reduce metal and the electrolysis of dissolution
The probability of liquid solvent generation redox reaction.But, the highest temp effect of nitrile compounds shows
Write, but due to itself structure, on the one hand cause it to tend to interfere with battery initial charge
Form SEI film, and its poor compatibility with graphite cathode；On the other hand due to itself viscosity
Cause greatly battery mass transfer impedance rise obvious, so synthesis result causes filling soon and circulating of battery
Performance is had a greatly reduced quality.
And simple lithium hexafluoro phosphate being dissolved in ethylene carbonate, chain carboxylate, or
Adding the additive such as fluoro carbonic ester, nitrile compounds in electrolyte, this is the most on the market
The typical scenario of volume production electrolyte.Although finding performance most preferably to tie by the ratio adjusting each component
Chalaza, can reach good effect.But for filling lithium ion battery soon, by comparative example 1～4
Test result and above-mentioned analysis, it is seen that, conventional additive combined effect is limited, very
Difficulty is being filled soon and is being had further lifting on cycle performance.
Therefore the present invention introduces the pyridine compounds and their containing amide groups in embodiment 1～8,
Containing pyridine heterocycle in the structure of this compound, contain amide groups simultaneously and produce altogether with pyridine heterocycle
Yoke effect.Wherein, its amide groups contained can reduce the viscosity of electrolyte, improves electrolyte pair
The infiltration of pole piece, and realize quickly embedding and deintercalation of lithium, promote rapid charging performance；Additionally,
The unsaturated bond heterocycle that it contains easily is coordinated with the transition metal in positive active material, has
Effect prevents a large amount of dissolutions of transition metal；And by positive pole filming function, molten by electrolyte
Agent is effectively isolated with positive-active site so that high temperature storage and the cycle performance of battery are had
Effect promotes.And from circulation and the high temperature storage test result of embodiment 1～8 it can be seen that pyridine
Amide groups position in ring is the most notable the closer to nitrogen performance, this is because produced by this structure
Conjugation is the strongest.Analyze simultaneously and fill effect soon, be again based on conjugation and make 2,
6-bis-pyridine diformamide, 2-ascorbyl palmitate, Niacinamide, Isonicotinamide etc.
Amide pyridined additives has higher wellability to pole piece, effectively reduces the electrification of pole piece
Learning impedance, the most effective lithium is in the without hindrance transmission of graphite layers；Thus realize when shorter
Interior charging capacity is bigger, and big multiplying power charge efficiency is also obviously improved.
It is not difficult to judge that the addition of fluorinated ethylene carbonate makes battery first by above analysis
Charging process defines relatively stable SEI film to ensure cycle performance, and electricity can be improved
It is notable that the immersional wetting of pole piece is made battery fill effect soon by solution liquid；But fluorinated ethylene carbonate institute
The SEI film formed, under high temperature storage conditions, easily decomposes and produces the gas such as carbon dioxide and ethylene
Body causes battery flatulence.After introducing nitrile compounds, although fluorinated ethylene carbonate stores up at high temperature
The flatulence deposited is obtained effectively control, but simultaneously because nitrile compounds high viscosity and high impedance are special
Property, cause the electrochemical impedance of battery and mass transfer impedance all to become big, and during initial charge
The formation of battery SEI film can be hindered.Therefore, the present invention is at fluorinated ethylene carbonate and nitrile
In compound additive system, attempt adding amido pyridine class additive, find that effect is notable.
This is mostly derived from amido pyridine class additive and is on the one hand just having film forming function, the most anti-
The flatulence problem that only fluorinated ethylene carbonate causes under high-temperature storage；On the other hand it also has
Negative pole infiltration function, it is possible to reduce the electrochemical impedance of battery, promote rapid charging performance, thus have
Effect counteracts the defect introducing nitrile compounds.Therefore, the multiple additives of the present invention is mutually assisted
Together, it is complementary to one another, finally makes the combination property performance excellence of battery.
Comprehensive above analysis, the present invention passes through reasonable selection dicyandiamide solution and lithium salt, and
Rational allocation fluorinated ethylene carbonate and the ratio of adiponitrile, and introduce have positive pole passivation ability concurrently
And infiltrating amide pyridined additives so that 4.4V and above high voltage fill lithium-ion electric soon
It is comprehensive that pond has that short time charging high temperature storage expansion rate many, full electric is low, cycle performance is excellent
Performance.Under overall situation relative to the design of existing common batteries and common positive and negative pole material,
The present invention has broad application prospects in quick charging battery field.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also
Enough above-mentioned embodiment is changed and revises.Therefore, the invention is not limited in above-mentioned
Detailed description of the invention, every those skilled in the art are done any on the basis of the present invention
Conspicuously improved, replace or modification belong to protection scope of the present invention.Although additionally,
This specification employs some specific terms, but these terms is merely for convenience of description,
The present invention is not constituted any restriction.
Claims (10)
1. a lithium-ion battery electrolytes, including lithium salts, Non-aqueous Organic Solvents and additive,
It is characterized in that: described additive includes fluorinated ethylene carbonate, nitrile compounds and has formula
The compound of structure shown in I；
Wherein, the R in formula I1、R2、R3、R4、R5Separately selected from hydrogen, amide
Base, carbon number are alkyl or the alkoxyl of 1～3, and R1、R2、R3、R4、R5In extremely
Contain an amide groups less.
Lithium-ion battery electrolytes the most according to claim 1, it is characterised in that: described
Fluorinated ethylene carbonate weight/mass percentage composition in the electrolytic solution is 1%～8%；Described nitrile
Compound weight/mass percentage composition in the electrolytic solution is 0.05%～5%；Described have knot shown in formula I
The compound of structure weight/mass percentage composition in the electrolytic solution is 0.01%～8%.
Lithium-ion battery electrolytes the most according to claim 1, it is characterised in that: described
Lithium salts is lithium hexafluoro phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, double fluorine sulfimide
At least one in lithium, LiBF4 and double trifluoromethanesulfonimide lithium；Described lithium salts exists
Weight/mass percentage composition in electrolyte is 10%～20%.
Lithium-ion battery electrolytes the most according to claim 1, it is characterised in that: described
Non-aqueous Organic Solvents is selected from ethylene carbonate, Allyl carbonate, diethyl carbonate, carbonic acid first
Ethyl ester, propyl propionate, ethyl propionate, methyl propyl carbonate, oxolane, dioxy cycloalkanes, γ
-butyrolactone, ethyl acetate, propyl acetate, methyl acetate, methyl butyrate, ethyl n-butyrate.,
One or more in propyl butyrate；Described Non-aqueous Organic Solvents quality hundred in the electrolytic solution
Dividing content is 65%～85%.
Lithium-ion battery electrolytes the most according to claim 1, it is characterised in that: described
Nitrile compounds is adiponitrile, succinonitrile, glutaronitrile, pimelic dinitrile, 2-methyl cellosolve acetate glutaronitrile and 1,
At least one in 3,6-hexane three nitriles.
Lithium-ion battery electrolytes the most according to claim 1, it is characterised in that: described
There is the compound of structure shown in formula I selected from 2,6-bis-pyridine diformamide, 2-pyridinecarboxylic
One or more in amine, Niacinamide and Isonicotinamide.
7. a lithium ion battery, including anode pole piece, cathode pole piece, is arranged on described positive pole
Barrier film between pole piece and described cathode pole piece and electrolyte, described anode pole piece just includes
Pole collector and the positive pole diaphragm being coated on anode collection surface, described cathode pole piece includes
Negative current collector and the cathode membrane being coated on negative pole currect collecting surface, it is characterised in that: institute
Stating electrolyte is the lithium-ion battery electrolytes described in any one of claim 1～6.
Lithium ion battery the most according to claim 7, it is characterised in that: described cathode film
Sheet includes positive active material, conductive agent and binding agent, and the compacted density of described positive pole diaphragm
≥4.0g/cm3。
Lithium ion battery the most according to claim 7, it is characterised in that: described negative electrode film
Sheet includes negative electrode active material, conductive agent and binding agent, and the surface density of described cathode membrane >=
80g/m2, compacted density >=1.55g/cm3。
Lithium ion battery the most according to claim 7, it is characterised in that: described lithium from
The charge cutoff voltage of sub-battery is 4.4～4.7V.
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