CN107086325B - A kind of electrolyte for spinel structure manganate lithium ion battery - Google Patents
A kind of electrolyte for spinel structure manganate lithium ion battery 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
A kind of electrolyte for spinel structure manganate lithium ion battery, the composition of the electrolyte are as follows: carbonats compound 40-70 mass parts, lithium salts 5-10 mass parts, ionic liquid 20-30 mass parts and additive 3-8 mass parts.It is not easily decomposed under electrolyte hot conditions provided by the invention, and poplar-Taylor effect of Manganic ion can be effectively inhibited and cause the deterioration of material crystal structure, the solubility and degree of dissociation of lithium salts are high, electronic conductivity can be improved and solid interface membrane impedance can be reduced, be conducive to the electrochemistry comprehensive performance for improving spinel structure manganate lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly, to a kind of spinel structure manganate lithium ion battery
Electrolyte.
Background technique
Today's society, energy crisis and environmental pollution common threats the survival and development of human society, the hair of new energy
It opens up extremely urgent.Lithium ion battery is a kind of novel secondary charge power supply, and except having, energy density is high, has extended cycle life, high
Outside the characteristics such as voltage, self discharge is small, operating temperature range is wide, memory-less effect, and there is safe and reliable and energy fast charging and discharging
The advantages that, it is widely used in the fields such as mobile communication, digital camera, laptop, and as lithium ion battery technology is sent out
The maturation of exhibition has a extensive future in energy storage and automotive field, thus becomes the hot spot of novel power supply technical research in recent years.Meanwhile
Since lithium ion battery is environmentally protective and free of contamination secondary power supply, meets the development in terms of countries nowadays energy environment protection and want
It asks, it has been more than lead-acid battery, nickel-metal hydride battery etc. that explosive growth, which is presented, in usage amount.
The advantages that spinel structure LiMn2O4 is resourceful, cost is relatively low, working voltage platform is high and small to environmental toxicity,
But its spinel structure manganate lithium ion battery related fields being prepared also have the following drawbacks: (1) in spinelle knot
It is injected after electrolyte in structure manganate lithium ion battery commercial process to monomer and needs to shelve infiltration 48 hours or more,
It just can guarantee the complete permeation electrode pole piece of the electrolyte for being injected into shell, time of penetration of the electrolyte in electrode plates is long, should
Link production economy is low；(2) cycle performance and poor high temperature stability of spinel structure manganate lithium ion battery influences
One of factor is that electrolyte functionality and stability are poor.For these disadvantages, each research structure and cell production companies have been done greatly
Quantity research work, but fail thoroughly to solve spinel structure manganate lithium ion battery problem above.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art especially solves existing spinel structure
The above two o'clock problem of manganate lithium ion battery, provide a kind of time of penetration it is shorter for spinel structure lithium manganate lithium ion
The electrolyte of battery.
The technical scheme adopted by the invention to solve the technical problem are as follows:
A kind of electrolyte for spinel structure manganate lithium ion battery specifically includes that lithium salts, carbonates chemical combination
Object, additive and ionic liquid；
Carbonats compound 40-70 mass parts；
Lithium salts 5-10 mass parts；
Ionic liquid 20-30 mass parts；
Additive 3-8 mass parts.
The lithium salts is lithium hexafluoro phosphate, LiBF4, lithium perchlorate, trifluoromethyl sulfonic acid lithium, lithium chloride, iodate
One or more of lithium, lithium aluminate, hexafluoroarsenate lithium, fluoro sulfimide lithium.
The carbonats compound is ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid
One or more of methyl ethyl ester, dibutyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, ethyl butyl carbonate, fluorine-containing carbonic ester.
The fluorine-containing carbonic ester, structure is as shown in formula (one) -1 or formula (one) -2:
Wherein, Rh is H or hydrocarbon chain group, and Rf is H (CF2CF2)n1CH2-、F(CF2CF2)n2CH2CH2Or
CF3CF2CF2O(CF(CF3)CF2O)n3CF(CF3)CH2,n1、n2For positive integer,n3For nonnegative integer.
Two Rf in formula (one) -1 can not be identical.
Shown in the anion chemical structure such as formula (two) of the ionic liquid:
The cation of the ionic liquid include quaternary ammonium ion, piperidines ion, pyrrolidinium ion, quaternary phosphine ion, pyrazolium ion,
One or more of imidazol ion, chemical structure is respectively as shown in formula (three):
Wherein, R1~R4And R18~R21Independently select carbon atom number for 1~8 alkyl or replace alkyl；R5、R6、
R12、R13、R26、R31Independently select carbon atom number for 1~6 alkyl；R7~R11、R14~R17、R22~R25、R27~R30
Independently select hydrogen atom, halogen atom or carbon atom number for 1~6 alkyl or replace alkyl.
The additive includes film for additive, stability additive and high temperature additive.
One or more of described film for additive, including vinylene carbonate, vinyl vinylene carbonate.
The stability additive, including hexamethyldisilazane, seven methyl disilazanes, triphenyl phosphite, phosphorous
One or more of sour trimethyl.
The high temperature additive, including ethylene sulfite, propylene sulfite, butylene sulfite, 1,3- propane
One or more of sultone, 1,4- butane sultone.
Embodiment according to the present invention provides a kind of preparation side of spinel structure manganate lithium ion battery electrolyte
Method, described method includes following steps:
Carbonats compound and ionic liquid are weighed, it, will in the environment of humidity is less than 8ppm, temperature is 25 ± 2 DEG C
Carbonats compound and ionic liquid stir evenly, and obtain non-aqueous organic solvent；
Lithium salts is weighed, lithium salts is added into the non-aqueous organic solvent, stirring to lithium salts is completely dissolved；
Additive is weighed, the additive is added into the non-aqueous organic solvent dissolved with lithium salts, stirring stands 18-
36h obtains spinel structure manganate lithium ion battery electrolyte.
From the above technical scheme, the present invention provides a kind of electrolyte of spinel structure manganate lithium ion battery
And preparation method, the composition of the electrolyte are as follows: carbonats compound 40-70 mass parts, lithium salts 5-10 mass parts, ionic liquid
Body 20-30 mass parts and additive 3-8 mass parts.The constituent of the additive are as follows: vinylene carbonate, vinyl carbon
One or both of sour vinylene；Hexamethyldisilazane, seven methyl disilazanes, triphenyl phosphite, phosphorous acid three
One or more of methyl esters；Ethylene sulfite, propylene sulfite, butylene sulfite, 1,3- propane sultone, 1,4-
One or more of butane sultone.The cation of the ionic liquid is quaternary ammonium ion, piperidines ion, pyrrolidinium ion, season
One or more of phosphonium ion, pyrazolium ion, imidazol ion；The organic solvent is one or more of carbonats compounds
Mixture.It is not easily decomposed under electrolyte hot conditions provided by the invention, and poplar-Thailand of Manganic ion can be effectively inhibited
It strangles effect and causes the deterioration of material crystal structure, the solubility and degree of dissociation of lithium salts are high, can improve electronic conductivity and can drop
Low solid interface membrane impedance is conducive to the electrochemistry comprehensive performance for improving spinel structure manganate lithium ion battery.
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.
For the specific embodiment of the electrolyte of spinel structure manganate lithium ion battery provided by the invention, please join
See following embodiment and comparative example:
Embodiment one:
Methyl ethyl carbonate, dibutyl carbonate, ionic liquid are taken respectively, are less than mechanical stirring mixing in 8ppm environment in humidity
Uniformly, solution temperature control is configured to electrolyte solvent at 25 ± 2 DEG C；Trifluoromethane sulfonic acid is added into electrolyte solvent again
Lithium continues to add vinylene carbonate, seven methyl disilazanes, Isosorbide-5-Nitrae-butane into electrolyte solvent after it is completely dissolved
After sultone is uniformly mixed, the electrolyte of the lithium ion battery of the present embodiment is obtained after standing 24 hours.
The electrolyte includes: 28 mass parts of methyl ethyl carbonate, 33 mass parts of dibutyl carbonate, the ionic liquid
23 mass parts, 9 mass parts of trifluoromethyl sulfonic acid lithium, 2 mass parts of vinylene carbonate, the seven methyl disilazane
2 mass parts, 3 mass parts of Isosorbide-5-Nitrae-butane sultone.
It is worth noting that: carbonats compound includes methyl ethyl carbonate and dibutyl carbonate, therefore the carbonic ester
61 mass parts of class compound.
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 spinel structure lithium manganate lithium ion
In battery, preparing monomer capacity is 20.0AH aluminum hull square battery, according to GB T31484-2015, GB T31485-2015 standard
Carry out battery performance test；
It is as shown in table 1 to obtain test result:
Table 1
It learns, is compounded using the electrolyte of embodiment one into spinel structure manganate lithium ion battery, system from table 1
Standby monomer capacity is 20.0AH aluminum hull square battery, and under the conditions of 25 DEG C, according to 0.5C multiplying power after 3000 circulations, capacity is protected
Holdup is 82.5%；Under the conditions of 50 DEG C, according to 0.5C multiplying power after 3000 circulations, capacity retention ratio 81.5%；75℃
Under the conditions of, according to 0.5C multiplying power after 3000 circulations, capacity retention ratio 81.0%.And the electrolyte shown in comparative example one
It compounds in spinel structure manganate lithium ion battery, preparing monomer capacity is 20.0AH aluminum hull square battery, 25 DEG C of conditions
Under, according to 0.5C multiplying power after 3000 circulations, capacity retention ratio 68.0%；Under the conditions of 50 DEG C, passed through according to 0.5C multiplying power
After crossing 3000 circulations, capacity retention ratio 61.5%；Under the conditions of 75 DEG C, according to 0.5C multiplying power after 3000 circulations, hold
Measuring conservation rate is 52.0%.It can be seen that using spinel structure LiMn2O4 lithium made of the electrolyte shown in the embodiment of the present application one from
Sub- battery, the capacity retention ratio still with higher after charge and discharge system multiple under different hot conditions circulation.Embodiment two:
Dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ionic liquid are taken respectively, are less than in 8ppm environment in humidity
Mechanical stirring is uniformly mixed, and solution temperature is controlled at 25 ± 2 DEG C, is configured to electrolyte solvent；It is added again into electrolyte solvent
Fluoro sulfimide lithium continues to add vinylene carbonate, seven methyl, two silicon amine into electrolyte solvent after it is completely dissolved
After alkane, ethylene sulfite are uniformly mixed, the electrolyte of the lithium ion battery of the present embodiment is obtained after standing 24 hours.
The electrolyte includes: 16 mass parts of dimethyl carbonate, 20 mass parts of diethyl carbonate, two fourth of carbonic acid
25 mass parts of ester, 23 mass parts of ionic liquid, 9 mass parts of fluoro sulfimide lithium, vinyl carbonic acid Asia second
2 mass parts of enester, 2 mass parts of hexamethyldisilazane, 3 mass parts of ethylene sulfite.
It is worth noting that: carbonats compound includes dimethyl carbonate, diethyl carbonate and dibutyl carbonate, therefore
61 mass parts of carbonats compound.
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 one and the electrolyte of comparative example one are compounded to spinel structure lithium manganate lithium ion
In battery, preparing monomer capacity is 20.0AH aluminum hull square battery, according to GB T31484-2015, GB T31485-2015 standard
Carry out battery performance test；
It is as shown in table 2 to obtain test result:
Table 2
It learns, is compounded using the electrolyte of embodiment two into spinel structure manganate lithium ion battery, system from table 2
Standby monomer capacity is 20.0AH aluminum hull square battery, and under the conditions of 25 DEG C, according to 0.5C multiplying power after 3000 circulations, capacity is protected
Holdup is 84.0%；Under the conditions of 50 DEG C, according to 0.5C multiplying power after 3000 circulations, capacity retention ratio 82.5%；75℃
Under the conditions of, according to 0.5C multiplying power after 3000 circulations, capacity retention ratio 81.5%.And the electrolyte shown in comparative example two
It compounds in spinel structure manganate lithium ion battery, preparing monomer capacity is 20.0AH aluminum hull square battery, 25 DEG C of conditions
Under, according to 0.5C multiplying power after 3000 circulations, capacity retention ratio 72.0%；Under the conditions of 50 DEG C, passed through according to 0.5C multiplying power
After crossing 3000 circulations, capacity retention ratio 67.0%；Under the conditions of 75 DEG C, according to 0.5C multiplying power after 3000 circulations, hold
Measuring conservation rate is 58.0%.It can be seen that using spinel structure LiMn2O4 lithium made of the electrolyte shown in the embodiment of the present application two
Ion battery, the capacity retention ratio still with higher after charge and discharge system multiple under different hot conditions circulation.
Embodiment three:
Dibutyl carbonate, ethyl butyl carbonate, fluorine-containing carbonic ester, ionic liquid are taken respectively, are less than in 8ppm environment in humidity
Mechanical stirring is uniformly mixed, and solution temperature is controlled at 25 ± 2 DEG C, is configured to electrolyte solvent；It is added again into electrolyte solvent
Lithium hexafluoro phosphate continues to add vinylene carbonate, Trimethyl phosphite, Asia into electrolyte solvent after it is completely dissolved
After sulfuric acid acrylic ester is uniformly mixed, the electrolyte of the lithium ion battery of the present embodiment is obtained after standing 24 hours.
The electrolyte includes: 15 mass parts of dibutyl carbonate, 20 mass parts of ethyl butyl carbonate, the fluorine-containing carbonic acid
26 mass parts of ester, 23 mass parts of ionic liquid, 9 mass parts of lithium hexafluoro phosphate, 2 mass of vinylene carbonate
Part, 2 mass parts of Trimethyl phosphite, 3 mass parts of propylene sulfite.
It is worth noting that: carbonats compound includes dibutyl carbonate, ethyl butyl carbonate and fluorine-containing carbonic ester, therefore
61 mass parts of carbonats compound.
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 is respectively as follows: 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 one.
The electrolyte of above-described embodiment three and the electrolyte of comparative example three are compounded to spinel structure lithium manganate lithium ion
In battery, preparing monomer capacity is 20.0AH aluminum hull square battery, according to GB T31484-2015, GB T31485-2015 standard
Carry out battery performance test；
It is as shown in table 3 to obtain test result:
Table 3
It learns, is compounded using the electrolyte of embodiment three into spinel structure manganate lithium ion battery, system from table 3
Standby monomer capacity is 20.0AH aluminum hull square battery, and under the conditions of 25 DEG C, according to 0.5C multiplying power after 3000 circulations, capacity is protected
Holdup is 86.5%；Under the conditions of 50 DEG C, according to 0.5C multiplying power after 3000 circulations, capacity retention ratio 84.0%；75℃
Under the conditions of, according to 0.5C multiplying power after 3000 circulations, capacity retention ratio 83.5%.And the electrolyte shown in comparative example three
It compounds in spinel structure manganate lithium ion battery, preparing monomer capacity is 20.0AH aluminum hull square battery, 25 DEG C of conditions
Under, according to 0.5C multiplying power after 3000 circulations, capacity retention ratio 73.0%；Under the conditions of 50 DEG C, passed through according to 0.5C multiplying power
After crossing 3000 circulations, capacity retention ratio 70.5%；Under the conditions of 75 DEG C, according to 0.5C multiplying power after 3000 circulations, hold
Measuring conservation rate is 65.5%.It can be seen that using spinel structure LiMn2O4 lithium made of the electrolyte shown in the embodiment of the present application three
Ion battery, the capacity retention ratio still with higher after charge and discharge system multiple under different hot conditions circulation.
Example IV:
Dibutyl carbonate, ethyl butyl carbonate, fluorine-containing carbonic ester, ionic liquid are taken respectively, are less than in 8ppm environment in humidity
Mechanical stirring is uniformly mixed, and solution temperature is controlled at 25 ± 2 DEG C, is configured to electrolyte solvent；It is added again into electrolyte solvent
Lithium hexafluoro phosphate continues to add vinylene carbonate, Trimethyl phosphite, Asia into electrolyte solvent after it is completely dissolved
After sulfuric acid acrylic ester is uniformly mixed, the electrolyte of the lithium ion battery of the present embodiment is obtained after standing 24 hours.
The electrolyte includes: 15 mass parts of dibutyl carbonate, 20 mass parts of ethyl butyl carbonate, the fluorine-containing carbonic acid
26 mass parts of ester, 28 mass parts of ionic liquid, 9 mass parts of lithium hexafluoro phosphate, 2 mass of vinylene carbonate
Part, 2 mass parts of Trimethyl phosphite, 3 mass parts of propylene sulfite.
It is worth noting that: carbonats compound includes dibutyl carbonate, ethyl butyl carbonate and fluorine-containing carbonic ester, therefore
61 mass parts of carbonats compound.
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 embodiment three are compounded to spinel structure lithium manganate lithium ion
In battery, preparing monomer capacity is 20.0AH aluminum hull square battery, according to GB T31484-2015, GB T31485-2015 standard
Carry out battery performance test；
It is as shown in table 4 to obtain test result:
Table 4
It learns, is compounded using the electrolyte of embodiment three into spinel structure manganate lithium ion battery, system from table 4
Standby monomer capacity is 20.0AH aluminum hull square battery, and under the conditions of 25 DEG C, according to 0.5C multiplying power after 3000 circulations, capacity is protected
Holdup is 86.5%；Under the conditions of 50 DEG C, according to 0.5C multiplying power after 3000 circulations, capacity retention ratio 84.0%；75℃
Under the conditions of, according to 0.5C multiplying power after 3000 circulations, capacity retention ratio 83.5%.And the electrolyte shown in example IV
It compounds in spinel structure manganate lithium ion battery, preparing monomer capacity is 20.0AH aluminum hull square battery, 25 DEG C of conditions
Under, according to 0.5C multiplying power after 3000 circulations, capacity retention ratio 90.0%；Under the conditions of 50 DEG C, passed through according to 0.5C multiplying power
After crossing 3000 circulations, capacity retention ratio 88.0%；Under the conditions of 75 DEG C, according to 0.5C multiplying power after 3000 circulations, hold
Measuring conservation rate is 87.0%.It can be seen that after electrolyte intermediate ion liquid quality point increases, spinelle knot made of the electrolyte that shows
Structure manganate lithium ion battery, capacity retention ratio is higher after charge and discharge system multiple under different hot conditions 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 aluminum hull square batteries with different electrolytes in 20.0AH aluminum hull square battery, wherein
After injecting electrolyte, record it is required shelve time of penetration, the results are shown in Table 5:
Table 5
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 13h to the time of penetration of electrolyte provided by embodiment three, especially the electrolyte that provides of embodiment three
Time of penetration it is most short, only 8h；And the time of penetration of comparative example one to comparative example three is all larger than 30h, especially comparative example one
The time of penetration of the electrolyte of offer is up to 38h.
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 quality point increases, when electrolyte shelving in electrode plates is impregnated with
Between can be further effectively reduced.Thus to infer, for electrolyte intermediate ion liquid in reasonable range, quality point is higher,
It is better to the wellability of electrode plates.
The application shows a kind of preparation method of spinel structure manganate lithium ion battery electrolyte, the method packet
It includes:
S101 weighs organic solvent and ionic liquid, in the environment of humidity is less than 8ppm, temperature is 25 ± 2 DEG C, by institute
It states organic solvent and the ionic liquid stirs evenly, obtain non-aqueous organic solvent；
S102 weighs lithium salts, and the lithium salts is slowly added into the non-aqueous organic solvent, stirs completely molten to lithium salts
Solution；
S103 weighs additive, and the additive is slowly added into the non-aqueous organic solvent dissolved with lithium salts, stirring,
18-36h is stood, spinel structure manganate lithium ion battery electrolyte is obtained.
From the above technical scheme, the embodiment of the present application shows a kind of spinel structure manganate lithium ion battery electrolysis
Liquid and preparation method: the electrolyte includes: carbonats compound 40-70 mass parts, lithium salts 5-10 mass parts, ionic liquid
20-30 mass parts and additive 3-8 mass parts.The application passes through the type of optimization electrolyte contained substance and every kind of substance
Mass fraction, from the parameters such as control adjustment electrolyte system viscosity, moisture content, acidity value, compatibility and conductivity with using
The variation of environment and micro variation.Electrolyte is to the wellability of spinel structure manganate lithium ion battery positive and negative anodes pole piece and simultaneous
Capacitive increases.Using spinel structure manganate lithium ion battery made of the electrolyte shown in the embodiment of the present application 25 DEG C,
Under the conditions of 50 DEG C, 75 DEG C, capacity retention ratio is above 80.0% after recycling 3000 times respectively according to 0.5C charge and discharge system, can
See, different high temperature items are passed through using spinel structure manganate lithium ion battery made of the electrolyte shown in the embodiment of the present application
Capacity retention ratio still with higher after charge and discharge system circulation under part.Meanwhile the application selects ionic liquid as electrolyte
Component part, and play and act synergistically with the additive in electrolyte, be not easily decomposed under hot conditions, and can effectively inhibit
Poplar-Taylor effect of Manganic ion and the deterioration for causing material crystal structure, the solubility and degree of dissociation of lithium salts are high, can improve
Electronic conductivity simultaneously can reduce solid interface membrane impedance, be conducive to the electrochemistry for improving spinel structure manganate lithium ion battery
Comprehensive performance.
Those skilled in the art after considering the specification and implementing the invention disclosed here, will readily occur to of the invention its
Its embodiment.This application is intended to cover any variations, uses, or adaptations of the invention, these modifications, purposes or
Person's adaptive change follows general principle of the invention and including the undocumented common knowledge in the art of the present invention
Or conventional techniques.The description and examples are only to be considered as illustrative, and true scope and spirit of the invention are by following
Claim is pointed out.
It should be understood that the invention is not limited to being described above, and can carry out without departing from the scope
Various modifications and change.The scope of the present invention is limited only by the attached claims.
Claims (6)
1. a kind of electrolyte for spinel structure manganate lithium ion battery, which is characterized in that the electrolyte mainly wraps
It includes: lithium salts, carbonats compound, additive and ionic liquid；
Carbonats compound 40-70 mass parts；
Lithium salts 5-10 mass parts；
Ionic liquid 20-30 mass parts；
Additive 3-8 mass parts；
The additive includes film for additive, stability additive and high temperature additive；
One or more of described film for additive, including vinylene carbonate, vinyl vinylene carbonate；
The stability additive, including hexamethyldisilazane, seven methyl disilazanes, triphenyl phosphite, phosphorous acid three
One or more of methyl esters；
In the high temperature additive, including ethylene sulfite, propylene sulfite, butylene sulfite, 1,3- propane sulphur
One or more of ester, 1,4- butane sultone；
Shown in the anion chemical structure such as formula (two) of the ionic liquid:
2. the electrolyte of spinel structure manganate lithium ion battery according to claim 1, it is characterised in that: described
Lithium salts is lithium hexafluoro phosphate, LiBF4, lithium perchlorate, trifluoromethyl sulfonic acid lithium, lithium chloride, lithium iodide, lithium aluminate, hexafluoro
One or more of arsenic acid lithium, fluoro sulfimide lithium.
3. the electrolyte of spinel structure manganate lithium ion battery according to claim 1 or 2, it is characterised in that: institute
The carbonats compound stated is ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbon
One or more of dibutyl phthalate, methyl propyl carbonate, ethyl propyl carbonic acid ester, ethyl butyl carbonate, fluorine-containing carbonic ester.
4. the electrolyte of spinel structure manganate lithium ion battery according to claim 3, it is characterised in that: described to contain
Fluorine carbonic ester, structure is as shown in formula (one) -1 or formula (one) -2:
Wherein, Rh is H or hydrocarbon chain group, Rf are H (CF2CF2)n1CH2-、F(CF2CF2)n2CH2CH2Or CF3CF2CF2O(CF
(CF3)CF2O)n3CF(CF3)CH2, n1, n2 are positive integer, and n3 is nonnegative integer.
5. the electrolyte of spinel structure manganate lithium ion battery according to claim 1 or 2, it is characterised in that: institute
State ionic liquid cation include quaternary ammonium ion, piperidines ion, pyrrolidinium ion, quaternary phosphine ion, pyrazolium ion, in imidazol ion
One or more, shown in chemical structure such as formula (three):
Wherein, R1~R4And R18~R21Independently select carbon atom number for 1~8 alkyl or replace alkyl；R5、R6、R12、
R13、R26、R31Independently select carbon atom number for 1~6 alkyl；R7~R11、R14~R17、R22~R25、R27~R30Respectively
It is independent select hydrogen atom, halogen atom or carbon atom number for 1~6 alkyl or replace alkyl.
6. a kind of side for the electrolyte for preparing the spinel structure manganate lithium ion battery as described in one of claim 1-5
Method, which is characterized in that described method includes following steps:
Carbonats compound and ionic liquid are weighed, it, will be described in the environment of humidity is less than 8ppm, temperature is 25 ± 2 DEG C
Carbonats compound and the ionic liquid stir evenly, and obtain non-aqueous organic solvent；
Lithium salts is weighed, the lithium salts is added into the non-aqueous organic solvent, stirring to lithium salts is completely dissolved；
Additive is weighed, the additive is added into the non-aqueous organic solvent dissolved with lithium salts, stirring stands 18-36h,
Obtain spinel structure manganate lithium ion battery electrolyte.
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