CN106816628B - A kind of ternary material lithium-ion battery electrolytes - Google Patents
A kind of ternary material lithium-ion battery electrolytes Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
A kind of ternary material lithium-ion battery electrolytes, comprising: lithium salts, carbonats compound, additive and ionic liquid；Wherein, the mass fraction of lithium salts are as follows: 8.0%~13.0%, the mass fraction of carbonats compound are as follows: 50.0%~70.0%, the mass fraction of additive are as follows: 3.0%~7.0%, the mass fraction of ionic liquid are as follows: 20.0%~30.0%, the summation of the mass fraction of each substance is 100.0%.Ternary material lithium ion battery made of electrolyte using the present invention, under the conditions of 25 DEG C, capacity retention ratio is above 80.0% after recycling 4000 times, 2300 times, 1200 times respectively according to 1C, 2C, 3C charge and discharge system, as it can be seen that using ternary material lithium ion battery made of the electrolyte shown in the embodiment of the present application by multiple high power charging-discharging system circulation after capacity retention ratio still with higher.
Description
Technical field
This application involves energy technology field more particularly to a kind of ternary material lithium-ion battery electrolytes and preparation sides
Method.
Background technique
Lithium ion battery has that higher specific energy, higher specific power, higher voltage, self discharge be small, memoryless effect
It the outstanding advantages such as answers and environmentally protective, has become ideal battery system, become the first choice of mancarried electronic aid battery,
And it gradually has a wide range of applications in the fields such as new energy passenger car and special-purpose vehicle, energy storage, startup power supply.
Ternary material has many advantages, such as that gram volume is high, working voltage platform is high, at low cost and small to environmental toxicity, but it is made
There are several defects for standby process and performance of lithium ion battery, such as: (1) in ternary material lithium ion battery commercial process
After the middle injection electrolyte to monomer, needs to shelve infiltration 30 hours or more, just can guarantee that the electrolyte for being injected into shell is complete
Permeation electrode pole piece, time of penetration of the electrolyte in electrode plates is long, and the link production economy is low；(2) ternary material lithium
The safety of ion battery and high rate cyclic, service life are short.
Lithium ion battery during charge and discharge, lithium ion quickly from anode deviate from, into electrolyte, then pass through every
Film carries out embedding lithium into cathode, and the migration of a large amount of lithium ions requires electrolyte dynamic performance with higher, lithium ion is made to exist
There is smaller resistance to mass tranfer, it is therefore desirable to which electrolyte has better wellability, lower viscosity and more in mass transport process
Low lithium ion transport resistance.So solving above-mentioned subproblem existing for ternary material lithium ion battery, it is necessary to from electrolysis
Reasonable solution is found in terms of liquid.In order to achieve this, those skilled in the art generally use the high conductivity of low viscosity
Solvent is arranged in pairs or groups the technical solution of high lithium salt, although however, this technical solution can improve the dynamic performance of electrolyte,
But the high rate performance of battery can be made to be deteriorated, also it is unfavorable for the cycle life of battery.
Summary of the invention
This application provides a kind of ternary material lithium-ion battery electrolytes and preparation methods, to solve now to use existing electricity
Solve liquid ternary material lithium ion battery by multiple high power charging-discharging system circulation after capacity retention ratio it is lower, the battery longevity
Order short problem.
The application first aspect shows a kind of ternary material lithium-ion battery electrolytes, and the electrolyte includes: lithium salts, carbon
Acid esters compound, additive and ionic liquid；
The mass fraction of the lithium salts are as follows: 8.0%~13.0%；
The mass fraction of the carbonats compound are as follows: 50.0%~70.0%；
The mass fraction of the additive are as follows: 3.0%~7.0%；
The mass fraction of the ionic liquid are as follows: 20.0%~30.0%.
Further, the ternary material includes: LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.2Mn0.4O2、
LiNi0.5Co0.2Mn0.3O2One or more of.
Further, the lithium salts includes: one or both of lithium hexafluoro phosphate, LiBF4.
Further, the carbonats compound is ethylene carbonate, propene carbonate, dimethyl carbonate, carbonic acid diethyl
Ester, methyl ethyl carbonate, dibutyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, ethyl butyl carbonate, fluorine-containing carbonic ester one kind or
It is several.
Further, the structural formula of the fluorine-containing carbonic ester are as follows:
Wherein, Rh is H or alkyl；Rf is H (CF2CF2)n1CH2, F (CF2CF2)n2CH2CH2Or CF3CF2CF2O(CF
(CF3)CF2O)n3CF(CF3)CH2-；
Wherein, n1、n2For positive integer；n3For nonnegative integer.Two Rf in first structural formula can not be identical.
Further, the anion chemical structure of the ionic liquid are as follows:
Further, the cation of the ionic liquid include: quaternary ammonium ion, piperidines ion, pyrrolidinium ion, quaternary phosphine ion,
One or more of pyrazolium ion, imidazol ion；
Wherein, the structure of the quaternary ammonium ion are as follows:
The structure of the piperidines ion are as follows:
The structure of the pyrrolidinium ion are as follows:
The structure of the quaternary phosphine ion are as follows:
The structural formula of the pyrazolium ion are as follows:
The structural formula of the imidazol ion are as follows:
Wherein, R1~R4 and R18~R21 independently select carbon atom number for 1~8 alkyl or replace alkyl；
R5, R6, R12, R13, R26 and R31 independently select carbon atom number for 1~6 alkyl；
Selection hydrogen atom, halogen atom or the carbon of R7~R11, R14~R17, R22~R25, R27~R30 independently are former
The alkyl or replace alkyl that subnumber is 1~6.
Further, the additive includes: film for additive and stability additive.
Further, the film for additive includes: one of vinylene carbonate, vinyl vinylene carbonate or two
Kind.
Further, the stability additive includes: hexamethyldisilazane, seven methyl disilazanes, phosphorous triphenyl phosphate
One or more of ester.
The application second aspect shows a kind of preparation method of ternary material lithium-ion battery electrolytes, the method packet
It includes:
Carbonats compound and ionic liquid are weighed, is less than mechanical stirring in 5ppm environment in humidity and is uniformly mixed, obtain
To electrolyte solvent；
Lithium salts is added into the electrolyte solvent, at room temperature, the lithium salts is dissolved in stirring, and additive is then added and stirs
It mixes after being completely dissolved, stands 12h, obtain electrolyte.
The embodiment of the present application shows a kind of ternary material lithium-ion battery electrolytes and preparation method；The electrolyte packet
It includes: lithium salts, carbonats compound, additive and ionic liquid；Wherein, the mass fraction of lithium salts are as follows: 8.0%~13.0%,
The mass fraction of carbonats compound are as follows: 50.0%~70.0%, the mass fraction of additive are as follows: 3.0%~7.0%, from
The mass fraction of sub- liquid are as follows: 20.0%~30.0%, the summation of the mass fraction of each substance is 100.0%.
The application is by the type of optimization electrolyte contained substance and the mass fraction of every kind of substance, from control adjustment electrolysis
The micro variation with the variation of use environment of the parameters such as liquid system viscosity, moisture content, acidity value, compatibility and conductivity.It adopts
Ternary material lithium ion battery made of the electrolyte shown in the embodiment of the present application fills under the conditions of 25 DEG C according to 1C, 2C, 3C
Capacity retention ratio is above 80.0% after discharge system recycles 4000 times, 2300 times, 1200 times respectively, it is seen then that uses the application
Implement ternary material lithium ion battery made of the electrolyte exemplified still to have after multiple high power charging-discharging system circulation
There is higher capacity retention ratio.
Specific embodiment
The technical scheme in the embodiment of the invention is clearly and completely described below, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment one:
Ethylene carbonate, propene carbonate, ionic liquid are taken respectively, are less than mechanical stirring mixing in 5ppm environment in humidity
Uniformly, solution temperature control is configured to electrolyte solvent at 25 ± 1 DEG C；Lithium hexafluoro phosphate is added into electrolyte solvent again, to
After it is completely dissolved, continue to add into electrolyte solvent after vinylene carbonate, hexamethyldisilazane be uniformly mixed,
The electrolyte of the lithium ion battery of the present embodiment is obtained after standing 12 hours.
The mass fraction of the electrolyte ethylene carbonate is 30.0%, and the mass fraction of the propene carbonate is
35.0%, the mass fraction of the ionic liquid is 20.0%, and the mass fraction of the lithium hexafluoro phosphate is 10.0%, the carbon
The mass fraction of sour vinylene is 2.0%, and the mass fraction of the hexamethyldisilazane is 3.0%.
It is worth noting that: carbonats compound includes ethylene carbonate and propene carbonate, therefore the carbonic ester
The mass fraction of class compound is 65.0%.
Ionic liquid chemical structural formula in embodiment are as follows:
Wherein, R1 CH3CHFCH2, R2 CH3CH2, R3 BrCH2CH2, R4 CH3CH2CH2CH2CH2-。
Comparative example one:
The electrolyte of comparative example one, the electrolyte and embodiment of comparative example one are prepared under conditions of being the same as example 1
The component of one electrolyte is identical, only difference is that without addition ionic liquid in comparative example one.
The electrolyte of above-described embodiment one and the electrolyte of comparative example one are compounded to ternary material
LiNi0.5Co0.2Mn0.3O2In lithium ion battery, preparing monomer capacity is 20.0AH Soft Roll square battery, according to GB T31484-
2015, GB T31485-2015 standard carries out battery performance test；
It is as shown in table 1 to obtain test result:
Table 1
| Group | Embodiment one | Comparative example one |
| Rated capacity/AH | 20.0 | 20.0 |
| 1C recycles 4000 capacity/AH | 16.2 | 9.6 |
| 1C recycles 4000 capacity retention ratios | 81.0% | 48.0% |
| 2C recycles 2300 capacity/AH | 16.1 | 8.3 |
| 2C recycles 2300 capacity retention ratios | 80.5% | 41.5% |
| 3C recycles 1200 capacity/AH | 16.02 | 6.84 |
| 3C recycles 1200 capacity retention ratios | 80.1% | 34.2% |
It learns from table 1, is compounded using the electrolyte of embodiment one to ternary material LiNi0.5Co0.2Mn0.3O2Lithium ion
In battery, monomer capacity is prepared for 20.0AH Soft Roll square battery, under the conditions of 25 DEG C, according to 1C multiplying power by 4000 circulations
Afterwards, capacity retention ratio 81.0%；2C multiplying power is after 2300 circulations, capacity retention ratio 80.5%；3C multiplying power is passed through
After 1200 circulations, capacity retention ratio 80.1%.And the electrolyte shown in comparative example one is compounded to ternary material
LiNi0.5Co0.2Mn0.3O2In lithium ion battery, preparing monomer capacity is 20.0AH Soft Roll square battery, under the conditions of 25 DEG C, according to
1C multiplying power is after 4000 circulations, capacity retention ratio 48.0%；After 2300 circulations, capacity retention ratio is 2C multiplying power
41.5%；3C multiplying power is after 1200 circulations, capacity retention ratio 34.2%.It can be seen that using shown in the embodiment of the present application one
Ternary material LiNi made of electrolyte0.5Co0.2Mn0.3O2Lithium ion battery is followed by the multiple charge and discharge system of different high magnifications
Capacity retention ratio still with higher after ring.
Embodiment two:
Dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ionic liquid are taken respectively, are less than in 5ppm environment in humidity
Mechanical stirring is uniformly mixed, and solution temperature is controlled at 25 ± 1 DEG C, is configured to electrolyte solvent；It is added again into electrolyte solvent
Lithium hexafluoro phosphate continues to add vinyl vinylene carbonate, seven methyl, two silicon into electrolyte solvent after it is completely dissolved
After amine alkane is uniformly mixed, the electrolyte of the lithium ion battery of the present embodiment is obtained after standing 12 hours.
The mass fraction of the electrolyte dimethyl carbonate is 15.0%, and the mass fraction of the diethyl carbonate is
20.0%, the mass fraction of the dibutyl carbonate is 30.0%, and the mass fraction of the ionic liquid is 20.0%, described six
The mass fraction of lithium fluophosphate is 9.0%, and the mass fraction of the vinylene carbonate is 3.0%, the hmds
The mass fraction of alkane is 3.0%.
It is worth noting that: carbonats compound includes dimethyl carbonate, diethyl carbonate and dibutyl carbonate, therefore
The mass fraction of the carbonats compound is 65.0%.
Ionic liquid chemical structural formula in the present embodiment are as follows:
R12:CH3CH2, R13:CH3CH2, R14:CH3BrCH-, R15:CH3CH2CH2CH2CH2,
R16:BrCH2CH2, R17:CH3CH2CH2CH2CH2CH2-；
Comparative example two:
In the electrolyte for preparing comparative example two under the same conditions with embodiment two, the electrolyte and embodiment of comparative example two
The component of two electrolyte is identical, only difference is that without addition ionic liquid in comparative example two.
The electrolyte of above-described embodiment two and the electrolyte of comparative example two are compounded to ternary material
LiNi0.4Co0.2Mn0.4O2In lithium ion battery, preparing monomer capacity is 20.0AH Soft Roll square battery, according to GB T31484-
2015, GB T31485-2015 standard carries out battery performance test；
It is as shown in table 2 to obtain test result:
Table 2
It learns from table 2, is compounded using the electrolyte of embodiment two to ternary material LiNi0.4Co0.2Mn0.4O2Lithium ion
In battery, monomer capacity is prepared for 20.0AH Soft Roll square battery, under the conditions of 25 DEG C, according to 1C multiplying power by 4000 circulations
Afterwards, capacity retention ratio 83.0%；2C multiplying power is after 2300 circulations, capacity retention ratio 81.0%；3C multiplying power is passed through
After 1200 circulations, capacity retention ratio 80.3%.And the electrolyte shown in comparative example two is compounded to ternary material
LiNi0.4Co0.2Mn0.4O2In lithium ion battery, preparing monomer capacity is 20.0AH Soft Roll square battery, under the conditions of 25 DEG C, according to
1C multiplying power is after 4000 circulations, capacity retention ratio 56.0%；After 2300 circulations, capacity retention ratio is 2C multiplying power
48.5%；3C multiplying power is after 1200 circulations, capacity retention ratio 39.7%.It can be seen that using shown in the embodiment of the present application two
Ternary material LiNi made of electrolyte0.4Co0.2Mn0.4O2Lithium ion battery is followed by the multiple charge and discharge system of different high magnifications
Capacity retention ratio still with higher after ring.
Embodiment three:
Ethyl propyl carbonic acid ester, ethyl butyl carbonate, fluorine-containing carbonic ester, ionic liquid are taken respectively, are less than in 5ppm environment in humidity
Mechanical stirring is uniformly mixed, and solution temperature is controlled at 25 ± 1 DEG C, is configured to electrolyte solvent；It is added again into electrolyte solvent
LiBF4 continues to add vinylene carbonate, triphenyl phosphite stirring into electrolyte solvent after it is completely dissolved
After mixing, the electrolyte of the lithium ion battery of the present embodiment is obtained after standing 12 hours.
The mass fraction of the electrolyte ethyl propyl carbonic acid ester is 20.0%, and the mass fraction of the ethyl butyl carbonate is
21.0%, the mass fraction of the fluorine-containing carbonic ester is 22.0%, and the mass fraction of the ionic liquid is 20.0%, described four
The mass fraction of lithium fluoroborate is 12.0%, and the mass fraction of the vinylene carbonate is 2.5%, the triphenyl phosphite
Mass fraction be 2.5%.
It is worth noting that: carbonats compound includes ethyl propyl carbonic acid ester, ethyl butyl carbonate and fluorine-containing carbonic ester, therefore
The mass fraction of the carbonats compound is 63.0%.
Ionic liquid chemical structural formula in embodiment are as follows:
Wherein, R1 CH3CHFCH2, R2 CH3CH2, R3 BrCH2CH2, R4 CH3CH2CH2CH2CH2-。
Fluorine-containing carbonic ester chemical structural formula in the present embodiment are as follows:
Wherein Rf:H (CF2CF2)3CH2-、F(CF2CF2)5CH2CH2-；
Comparative example three:
In the electrolyte for preparing comparative example three under the same conditions with embodiment three, the electrolyte and embodiment of comparative example three
The component of three electrolyte is identical, only difference is that without addition ionic liquid in comparative example three.
The electrolyte of above-described embodiment three and the electrolyte of comparative example three are compounded to ternary material LiNi1/3Co1/3Mn1/ 3O2In lithium ion battery, preparing monomer capacity is 20.0AH Soft Roll square battery, according to GB T31484-2015, GB T31485-
2015 standards carry out battery performance test；
It is as shown in table 3 to obtain test result:
Table 3
| Group | Embodiment three | Comparative example three |
| Rated capacity/AH | 20.0 | 20.0 |
| 1C recycles 4000 capacity/AH | 16.8 | 12.3 |
| 1C recycles 4000 capacity retention ratios | 84.0% | 61.5% |
| 2C recycles 2300 capacity/AH | 16.6 | 10.4 |
| 2C recycles 2300 capacity retention ratios | 83.0% | 52.0% |
| 3C recycles 1200 capacity/AH | 16.3 | 8.7 |
| 3C recycles 1200 capacity retention ratios | 81.5% | 43.5% |
It learns from table 3, is compounded using the electrolyte of embodiment three to ternary material LiNi1/3Co1/3Mn1/3O2Lithium ion
In battery, monomer capacity is prepared for 20.0AH Soft Roll square battery, under the conditions of 25 DEG C, according to 1C multiplying power by 4000 circulations
Afterwards, capacity retention ratio 84.0%；2C multiplying power is after 2300 circulations, capacity retention ratio 83.0%；3C multiplying power is passed through
After 1200 circulations, capacity retention ratio 81.5%.And the electrolyte shown in comparative example three is compounded to ternary material LiNi1/ 3Co1/3Mn1/3O2In lithium ion battery, monomer capacity is prepared for 20.0AH Soft Roll square battery, under the conditions of 25 DEG C, according to 1C multiplying power
After 4000 circulations, capacity retention ratio 61.5%；After 2300 circulations, capacity retention ratio is 2C multiplying power
52.0%；3C multiplying power is after 1200 circulations, capacity retention ratio 43.5%.It can be seen that using shown in the embodiment of the present application three
Ternary material LiNi made of electrolyte1/3Co1/3Mn1/3O2Lithium ion battery is followed by the multiple charge and discharge system of different high magnifications
Capacity retention ratio still with higher after ring.
Example IV:
Ethyl propyl carbonic acid ester, ethyl butyl carbonate, fluorine-containing carbonic ester, ionic liquid are taken respectively, are less than in 5ppm environment in humidity
Mechanical stirring is uniformly mixed, and solution temperature is controlled at 25 ± 1 DEG C, is configured to electrolyte solvent；It is added again into electrolyte solvent
LiBF4 continues to add vinylene carbonate, triphenyl phosphite stirring into electrolyte solvent after it is completely dissolved
After mixing, the electrolyte of the lithium ion battery of the present embodiment is obtained after standing 12 hours.
The mass fraction of the electrolyte ethyl propyl carbonic acid ester is 13.0%, and the mass fraction of the ethyl butyl carbonate is
18.0%, the mass fraction of the fluorine-containing carbonic ester is 22.0%, and the mass fraction of the ionic liquid is 30.0%, described four
The mass fraction of lithium fluoroborate is 12.0%, and the mass fraction of the vinylene carbonate is 2.5%, the triphenyl phosphite
Mass fraction be 2.5%.
It is worth noting that: carbonats compound includes ethyl propyl carbonic acid ester, ethyl butyl carbonate and fluorine-containing carbonic ester, therefore
The mass fraction of the carbonats compound is 53.0%.
Ionic liquid chemical structural formula in embodiment are as follows:
Wherein, R1 CH3CHFCH2, R2 CH3CH2, R3 BrCH2CH2, R4 CH3CH2CH2CH2CH2-。
Fluorine-containing carbonic ester chemical structural formula in the present embodiment are as follows:
Wherein Rf:H (CF2CF2)3CH2-、F(CF2CF2)5CH2CH2-；
The electrolyte of above-described embodiment four and the electrolyte of example IV are compounded to ternary material LiNi1/3Co1/3Mn1/ 3O2In lithium ion battery, preparing monomer capacity is 20.0AH Soft Roll square battery, according to GB T31484-2015, GB T31485-
2015 standards carry out battery performance test；
It is as shown in table 4 to obtain test result:
Table 4
| Group | Embodiment three | Example IV |
| Rated capacity/AH | 20.0 | 20.0 |
| 1C recycles 4000 capacity/AH | 16.8 | 17.8 |
| 1C recycles 4000 capacity retention ratios | 84.0% | 89.0% |
| 2C recycles 2300 capacity/AH | 16.6 | 17.1 |
| 2C recycles 2300 capacity retention ratios | 83.0% | 85.5% |
| 3C recycles 1200 capacity/AH | 16.3 | 16.54 |
| 3C recycles 1200 capacity retention ratios | 81.5% | 82.7% |
It learns from table 4, is compounded using the electrolyte of embodiment three to ternary material LiNi1/3Co1/3Mn1/3O2Lithium ion
In battery, monomer capacity is prepared for 20.0AH Soft Roll square battery, under the conditions of 25 DEG C, according to 1C multiplying power by 4000 circulations
Afterwards, capacity retention ratio 84.0%；2C multiplying power is after 2300 circulations, capacity retention ratio 83.0%；3C multiplying power is passed through
After 1200 circulations, capacity retention ratio 81.5%.And use the electrolyte compounding of example IV to ternary material LiNi1/ 3Co1/3Mn1/3O2In lithium ion battery, monomer capacity is prepared for 20.0AH Soft Roll square battery, under the conditions of 25 DEG C, according to 1C multiplying power
After 4000 circulations, capacity retention ratio 89.0%；After 2300 circulations, capacity retention ratio is 2C multiplying power
85.5%；3C multiplying power is after 1200 circulations, capacity retention ratio 82.7%.It can be seen that electrolyte intermediate ion liquid quality percentage
After increasing, the electrolyte shown is compounded to ternary material LiNi1/3Co1/3Mn1/3O2Lithium ion battery, by different high magnifications
Capacity retention ratio is higher after multiple charge and discharge system circulation.
Seven kinds of electrolyte difference that above-described embodiment one to example IV and comparative example one are provided into comparative example three
Injecting monomer capacity is to obtain seven kinds of Soft Roll square batteries with different electrolytes in 20.0AH Soft Roll square battery, wherein
After injecting electrolyte, record it is required shelve time of penetration, the results are shown in Table 5:
Table 5
| Group | Embodiment one | Embodiment two | Embodiment three | Example IV | Comparative example one | Comparative example two | Comparative example three |
| Time of penetration/h | 8 | 7.5 | 6 | 5 | 37 | 35 | 32 |
As shown in Table 5, the electrolyte that the embodiment of the present invention one is provided to embodiment three is mentioned with comparative example one to comparative example three
The electrolyte of confession is compared, and the penetration period of shelving in electrode plates is effectively reduced, and illustrates the embodiment of the present invention one to reality
The constituent and mass fraction of applying the electrolyte of the offer of example three can be effectively improved the wellability of electrolyte.Wherein, embodiment
One is respectively less than and is equal to 8h to the time of penetration of electrolyte provided by embodiment three, especially embodiment three electrolyte that provides
Time of penetration is most short, only 6h；And the time of penetration of comparative example one to comparative example three is all larger than 30h, especially comparative example one mentions
The time of penetration of the electrolyte of confession is up to 37h.
It is worth noting that, the change of the mass fraction that the difference is that only ionic liquid of embodiment three, example IV
Change, it can be seen that in electrolyte system when ionic liquid mass percent increases, electrolyte shelves leaching in electrode plates
The saturating time can be further effectively reduced.Thus infer, electrolyte intermediate ion liquid is in reasonable range, quality percentage
It is better to the wellability of electrode plates than higher.
The application second aspect shows a kind of preparation method of ternary material lithium-ion battery electrolytes, the method packet
It includes:
S101 weighs carbonates chemical combination and ionic liquid respectively, and it is equal to be less than mechanical stirring mixing in 5ppm environment in humidity
It is even, obtain electrolyte solvent；
Lithium salts is added into the electrolyte solvent by S102, and at room temperature, the lithium salts is dissolved in stirring, and addition is then added
Agent after mixing evenly, stands 12h, obtains electrolyte.
From the above technical scheme, the embodiment of the present application shows a kind of ternary material lithium-ion battery electrolytes and preparation
Method: the electrolyte includes: lithium salts, carbonats compound, additive and ionic liquid；Wherein, the quality of the lithium salts
Score are as follows: 8.0%~13.0%, the mass fraction of the carbonats compound are as follows: 50.0%~70.0%, the additive
Mass fraction are as follows: 3.0%~7.0%, the mass fraction of the ionic liquid are as follows: 20.0%~30.0%, the matter of each substance
The summation for measuring score is 100.0%.The application passes through the type of optimization electrolyte contained substance and the mass fraction of every kind of substance,
From parameters such as control adjustment electrolyte system viscosity, moisture content, acidity value, compatibility and conductivity with the variation of use environment
And micro variation.Electrolyte increases the wellability and compatibility of ternary material lithium ion battery plus-negative plate pole piece.Using this Shen
It please implement ternary material lithium ion battery made of the electrolyte exemplified under the conditions of 25 DEG C, according to 1C, 2C, 3C charge and discharge system
Capacity retention ratio is above 80.0% after degree recycles 4000 times, 2300 times, 1200 times respectively, it is seen then that uses the embodiment of the present application
Ternary material lithium ion battery made of the electrolyte shown still has higher after multiple high power charging-discharging system circulation
Capacity retention ratio.Meanwhile the application selects component part of the ionic liquid as electrolyte, and with the additive in electrolyte
Synergistic effect is played, electrolyte quality quality, stability and functionality can be improved, can effectively improve ternary material lithium-ion electric
Contradiction between the safety and high rate performance and cycle life in pond.
Claims (7)
1. a kind of ternary material lithium-ion battery electrolytes, it is characterised in that: the electrolyte includes: lithium salts, carbonates
Close object, additive and ionic liquid；
The mass fraction of the lithium salts are as follows: 8.0%~13.0%；
The mass fraction of the carbonats compound are as follows: 50.0%~70.0%；
The mass fraction of the additive are as follows: 3.0%~7.0%；
The mass fraction of the ionic liquid are as follows: 20.0%~30.0%；
The additive includes: film for additive and stability additive；
The ternary material includes: LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.2Mn0.4O2、LiNi0.5Co0.2Mn0.3O2In one
Kind is several；
The stability additive include: one of hexamethyldisilazane, seven methyl disilazanes, triphenyl phosphite or
It is several；
The anion chemical structure of the ionic liquid are as follows:
2. ternary material lithium-ion battery electrolytes as described in claim 1, which is characterized in that the lithium salts includes: hexafluoro
One or both of lithium phosphate, LiBF4.
3. ternary material lithium-ion battery electrolytes as claimed in claim 1 or 2, which is characterized in that the film for additive
It include: one or both of vinylene carbonate, vinyl vinylene carbonate.
4. ternary material lithium-ion battery electrolytes as claimed in claim 1 or 2, which is characterized in that the carbonates
Closing object includes ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dibutyl carbonate, carbon
One or more of sour first propyl ester, ethyl propyl carbonic acid ester, ethyl butyl carbonate, fluorine-containing carbonic ester.
5. ternary material lithium-ion battery electrolytes as claimed in claim 4, which is characterized in that the knot of the fluorine-containing carbonic ester
Structure formula are as follows:
Wherein, Rh is H or alkyl；Rf is H (CF2CF2)n1CH2, F (CF2CF2)n2CH2CH2Or CF3CF2CF2O(CF(CF3)
CF2O)n3CF(CF3)CH2-；
Wherein, n1、n2For positive integer；n3For nonnegative integer.
6. ternary material lithium-ion battery electrolytes as claimed in claim 1 or 2, which is characterized in that the ionic liquid
Cation includes: one of quaternary ammonium ion, piperidines ion, pyrrolidinium ion, quaternary phosphine ion, pyrazolium ion, imidazol ion or several
Kind；
The wherein structure of the quaternary ammonium ion are as follows:
The structure of the piperidines ion are as follows:
The structure of the pyrrolidinium ion are as follows:
The structure of the quaternary phosphine ion are as follows:
The structural formula of the pyrazolium ion are as follows:
The structural formula of the imidazol ion are as follows:
Wherein, the alkyl or replace alkyl that the carbon atom number of R1~R4 and R18~R21 is 1~8；
R5, R6, R12, R13, R26 and R31 are respectively the alkyl that carbon atom number is 1~6；
R7~R11, R14~R17, R22~R25, R27~R30 are the alkyl that hydrogen atom, halogen atom or carbon atom number are 1~6
Or replace alkyl.
7. a kind of preparation method of ternary material lithium-ion battery electrolytes is suitable for as claimed in any one of claims 1 to 6
Electrolyte, which is characterized in that the described method includes:
Carbonates chemical combination and ionic liquid are weighed, is less than mechanical stirring in 5ppm environment in humidity and is uniformly mixed, be electrolysed
Matter solvent；Lithium salts is added into the electrolyte solvent, at room temperature, the lithium salts is dissolved in stirring, and additive is then added and stirs
It mixes after being completely dissolved, stands 12h, obtain electrolyte.
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| CN103641751A (en) * | 2011-05-20 | 2014-03-19 | 华中科技大学 | Alkali metal salts of binary or ternary fluorine-containing sulfimide and ionic liquid and applications thereof |
| CN103996874A (en) * | 2014-05-20 | 2014-08-20 | 珠海市赛纬电子材料有限公司 | Nonaqueous electrolyte of high-temperature safety lithium ion battery |
| CN105378871A (en) * | 2013-03-15 | 2016-03-02 | 伊赛欧尼克公司 | Methods of enhancing electrochemical double layer capacitor (EDLC) performance and EDLC devices formed therefrom |
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| CN102610859B (en) * | 2012-04-04 | 2014-03-05 | 山东鸿正电池材料科技有限公司 | Non-aqueous electrolyte for lithium manganate power battery |
| CN102593517B (en) * | 2012-04-09 | 2014-05-07 | 山东鸿正电池材料科技有限公司 | Non-aqueous electrolyte for lithium iron phosphate battery |
| CN103268956B (en) * | 2013-05-18 | 2015-10-21 | 山东鸿正电池材料科技有限公司 | A kind of nonaqueous electrolytic solution for high-voltage lithium ion batteries |
| CN103715458A (en) * | 2013-10-23 | 2014-04-09 | 江西优锂新材股份有限公司 | Preparation method of electrolyte used for lithium manganate power battery at high temperature |
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| CN103641751A (en) * | 2011-05-20 | 2014-03-19 | 华中科技大学 | Alkali metal salts of binary or ternary fluorine-containing sulfimide and ionic liquid and applications thereof |
| CN105378871A (en) * | 2013-03-15 | 2016-03-02 | 伊赛欧尼克公司 | Methods of enhancing electrochemical double layer capacitor (EDLC) performance and EDLC devices formed therefrom |
| CN103996874A (en) * | 2014-05-20 | 2014-08-20 | 珠海市赛纬电子材料有限公司 | Nonaqueous electrolyte of high-temperature safety lithium ion battery |
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