CN109768319A - Non-aqueous electrolyte for lithium ion cell and the lithium ion battery for using the electrolyte - Google Patents
Non-aqueous electrolyte for lithium ion cell and the lithium ion battery for using the electrolyte Download PDFInfo
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Abstract
A kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery using the electrolyte, the nonaqueous electrolytic solution include being selected from 1 compound represented of structural formula, wherein R1、R2、R3、R4、R5、R6It is each independently selected from hydrogen, fluorine, cyano or the group containing 1-5 carbon atom；R is the group that carbon atom number is no more than 10, and contains 1 oxygen atom or 1 nitrogen-atoms in the R.Nonaqueous electrolytic solution of the invention can be improved the high-temperature storage and cycle performance of lithium ion battery.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of non-aqueous electrolyte for lithium ion cell and use should
The lithium ion battery of electrolyte.
Background technique
Lithium ion battery is because of the features such as its operating voltage is high, highly-safe, long-life, memory-less effect, in portable electric
Significant progress is achieved in sub- product scope.With the development of new-energy automobile, lithium ion battery is used dynamic in new-energy automobile
Power power-supply system has huge application prospect.
In non-aqueous electrolyte lithium ion battery, nonaqueous electrolytic solution is the key factor for influencing battery high temperature performance, special
Not, the additive in nonaqueous electrolytic solution is even more important to the performance of battery high temperature performance.In lithium ion battery initial charge
In the process, the lithium ion deintercalation in cell positive material comes out, and is embedded in Carbon anode by electrolyte.Due to its high response,
Electrolyte reacts on Carbon anode surface generates Li2CO3, the compounds such as LiO, LiOH should to form passivating film in negative terminal surface
Passivating film is known as solid electrolyte interfacial film (SEI).The SEI film formed in initial charge process, not only prevent electrolyte into
One step is decomposed on Carbon anode surface, and plays lithium ion tunneling, only lithium ion is allowed to pass through.Therefore, SEI film determines
The quality of performance of lithium ion battery.
In order to improve the properties of lithium ion battery, many scientific research persons by added into electrolyte different cathode at
The quality of film additive (such as vinylene carbonate, fluorinated ethylene carbonate, vinylethylene carbonate) Lai Gaishan SEI film, thus
Improve the properties of battery.For example, proposing in Japanese Unexamined Patent Publication 2000-123867 bulletin by adding in the electrolytic solution
Vinylene carbonate improves battery behavior.In negative terminal surface reduction point can occur for vinylene carbonate prior to solvent molecule
Solution reaction can form passivating film in negative terminal surface, prevent electrolyte from further decomposing in electrode surface, to improve following for battery
Ring performance.But after adding vinylene carbonate, battery is easy to produce gas in the process in high-temperature storage, and battery is caused to rouse
It is swollen.In addition, the passivation membrane impedance that vinylene carbonate is formed is larger, especially under cryogenic, it is easy to happen low temperature charging analysis
Lithium influences battery security.Fluorinated ethylene carbonate also can form passivating film in negative terminal surface, improve the cycle performance of battery,
And the passivating film impedance ratio formed is lower, can improve the low temperature performance of battery.But fluorinated ethylene carbonate is stored up in high temperature
It deposits and generates more gases, hence it is evident that reduce battery high-temperature storge quality.
Summary of the invention
The present invention provides a kind of non-aqueous electrolyte for lithium ion cell that can be improved battery high-temperature storage and cycle performance, into
One step provides the lithium ion battery including above-mentioned non-aqueous electrolyte for lithium ion cell.
According in a first aspect, providing a kind of non-aqueous electrolyte for lithium ion cell in a kind of embodiment, the lithium ion battery is non-
Water electrolysis liquid includes being selected from 1 compound represented of structural formula,
Wherein, R1、R2、R3、R4、R5、R6It is each independently selected from hydrogen, fluorine, cyano or the group containing 1-5 carbon atom；R is
Carbon atom number is no more than 10 groups, and contains 1 oxygen atom or 1 nitrogen-atoms in the R.
Further, on the basis of the electrolyte total weight, the content of 1 compound represented of structure above is
0.1%-10%.
Further, the above-mentioned group containing 1-5 carbon atom be selected from alkyl, halohydrocarbyl, oxygen-containing alkyl, hydrocarbyl silyl,
The oxygen-containing alkyl that the alkyl or cyano that cyano-containing replaces replace.
Further, above-mentioned R1、R2、R3、R4、R5、R6It is each independently selected from hydrogen, fluorine, cyano, methyl, ethyl, trimethyl
Siloxy, trifluoromethyl.
Further, above-mentioned R is selected from group shown in structural formula 2 or structural formula 3:
Structural formula 2:Wherein R7、R8It is each independently selected from the hydrocarbon that carbon atom number is 1-5
Base, m are the integer of 1-3；
Structural formula 3:Wherein R9、R10、R11Being each independently selected from carbon atom number is 1-5's
Alkyl.
Further, 1 compound represented of structure above is selected from following compound:
(compound 1),(compound 2),(compound 3),(compound 4),(compound 5),(compound 6),(compound 7).
Further, above-mentioned electrolyte further includes unsaturated cyclic carbonic ester, fluoric cyclic carbonate, in cyclic annular sulfonic acid
One or more of ester, cyclic sulfates.
Further, above-mentioned unsaturated cyclic carbonic ester includes vinylene carbonate, vinylethylene carbonate, mesomethylene carbon
At least one of vinyl acetate.
Further, above-mentioned fluoric cyclic carbonate includes fluorinated ethylene carbonate, trifluoromethyl ethylene carbonate, double fluorine
For at least one of ethylene carbonate.
Further, above-mentioned cyclic annular sultones includes 1,3-propane sultone, Isosorbide-5-Nitrae-butane sultone, acrylic -1,
At least one of 3- sultones.
Further, above-mentioned cyclic sulfates include at least one of sulfuric acid vinyl ester, 4- methylsulfuric acid vinyl acetate.
Further, above-mentioned electrolyte includes non-aqueous organic solvent and lithium salts.Above-mentioned non-aqueous organic solvent is cyclic carbonate
The mixture of ester and linear carbonate, above-mentioned cyclic carbonate is in ethylene carbonate, propene carbonate and butylene
One or more, above-mentioned linear carbonate be selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and carbonic acid first third
One or more of ester.
According to second aspect, provide a kind of lithium ion battery in a kind of embodiment, including anode, cathode and be placed in it is above-mentioned just
Diaphragm between pole and cathode further includes the non-aqueous electrolyte for lithium ion cell of first aspect.
Further, the active material of above-mentioned anode are as follows: LiNixCoyMnzL(1-x-y-z)O2、LiCox’L(1-x’)O2、LiNix”
L’y’Mn(2-x”-y’)O4、Liz’MPO4At least one of, wherein in L Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe at least
One kind, 0≤x≤1,0≤y≤1,0≤z≤1,0 < x+y+z≤1,0 < x '≤1,0.3≤x "≤0.6,0.01≤y '≤0.2,
L ' is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, Fe, 0.5≤z '≤1, in M Fe, Mn, Co at least
It is a kind of.
Contain 1 compound represented of structural formula in non-aqueous electrolyte for lithium ion cell of the invention, in initial charge process
In, reduction decomposition reaction can occur prior to solvent molecule for 1 compound represented of structural formula, and reaction product is in electrode surface
One layer of passivating film is formed, which is able to suppress solvent molecule and further decomposes.Since the passivating film of formation can effectively hinder
The only further decomposition of solvent molecule, lithium salts molecule causes the LiF ingredient of high impedance in passivating film less, is conducive to improve low
Warm nature energy, meanwhile, which is conducive to lithium ion and passes through, so as to be obviously improved the high-temperature storage and cyclicity of battery
Energy.
Specific embodiment
Below by specific embodiment, invention is further described in detail.
One of key of non-aqueous electrolyte for lithium ion cell of the invention is, containing 1 compound represented of structural formula,
In, R1、R2、R3、R4、R5、R6It is each independently selected from hydrogen, fluorine, cyano or the group containing 1-5 carbon atom；R be carbon atom number not
Group more than 10, and contain 1 oxygen atom or 1 nitrogen-atoms in the R.
R1、R2、R3、R4、R5、R6It is each independently selected from hydrogen, fluorine, cyano or the group containing 1-5 carbon atom, wherein contain
The alkyl or cyanogen that the group of 1-5 carbon atom can replace selected from alkyl, halohydrocarbyl, oxygen-containing alkyl, hydrocarbyl silyl, cyano-containing
The oxygen-containing alkyl that base replaces.
R in compound shown in structural formula 11、R2、R3、R4、R5、R6The example that can choose, it is typical but in non-limiting manner may be used
To include: hydrogen, fluorine, cyano, methyl, ethyl, trimethylsiloxy group, trifluoromethyl.
R in compound shown in structural formula 1 is the group that carbon atom number is no more than 10, and contains 1 oxygen atom or 1 in the R
A nitrogen-atoms, it is preferred that the R is selected from group shown in structural formula 2, structural formula 3:Its
Middle R7、R8It is each independently selected from the alkyl that carbon atom number is 1-5, m is the integer of 1-3；
Wherein R9、R10、R11It is each independently selected from the alkyl that carbon atom number is 1-5.
Illustrative compounds in compound shown in structure 1 are shown in table 1, but are not limited to this.
Table 1
Theoretically, adding compound shown in structural formula 1 is that can produce effect described in the invention (to take into account battery high-temperature storage
Deposit and recycle), it is possible to understand that, the effect generated when content is lower is on the weak side, the content of compound shown in structural formula 1 relative to
The gross mass of nonaqueous electrolytic solution is preferably 0.1% or more.In addition, comprehensively considering for electrolyte whole performance, more preferably
The content of compound shown in structural formula 1 is preferably 10% or less relative to the gross mass of nonaqueous electrolytic solution.Specifically, structural formula 1
The content of shown compound can for 0.1%, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%,
1.8%, 2%, 2.4%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9%, 10%.
Non-aqueous electrolyte for lithium ion cell of the invention can also add other additives, such as unsaturated cyclic carbonic acid
One or more of ester, fluoric cyclic carbonate, cyclic annular sultones, cyclic sulfates.These additives can be in electricity
Pole surface forms more stable SEI film, to improve the cycle performance of lithium ion battery.These additives can be according to ability
The general additive amount in domain adds, such as relative to electrolyte gross mass is 0.1%-10%, preferably 1%-5%, more preferable 3%-
5%.
Wherein, unsaturated cyclic carbonic ester can be vinylene carbonate (CAS:872-36-6), vinylethylene carbonate
(CAS:4427-96-7), at least one of mesomethylene carbon vinyl acetate (CAS:124222-05-5)；Fluoric cyclic carbonate
It can be fluorinated ethylene carbonate (CAS:114435-02-8), trifluoromethyl ethylene carbonate (CAS:167951-80-6), double
At least one of fluorinated ethylene carbonate (CAS:311810-76-1)；Cyclic annular sultones can be 1,3- propane sultone
(CAS:1120-71-4), 1,4- butane sultone (CAS:1633-83-6), acrylic -1,3- sultones (CAS:21806-
At least one of 61-1)；Cyclic sulfates can be sulfuric acid vinyl ester (CAS:1072-53-3), 4- methylsulfuric acid vinyl acetate
At least one of (CAS:5689-83-8).
It, can studies have shown that 1 compound represented of structural formula of the invention is used in combination with above-mentioned other additives
Obtain superior effect when being used alone than them, thus it is speculated that may be to have synergistic effect between them, i.e., shown in structural formula 1
Compound and other additives pass through the common improvement battery high-temperature storage of synergistic effect and cycle performance.
In embodiments of the invention, non-aqueous organic solvent and lithium salts are contained in nonaqueous electrolytic solution, it is above-mentioned non-aqueous organic
The content and specific substance of solvent and lithium salts can use routine, be not particularly limited in the present invention.
Wherein, non-aqueous organic solvent can be the mixture of cyclic carbonate and linear carbonate, and cyclic carbonate can be with
Selected from one or more of ethylene carbonate, propene carbonate and butylene, linear carbonate can be selected from carbon
One or more of dimethyl phthalate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate.Using high dielectric constant
The mixed liquor of cyclic carbonate organic solvent and the linear carbonate organic solvent of low viscosity is as lithium-ion battery electrolytes
Solvent, so that the mixed liquor of the organic solvent has high ionic conductivity, high dielectric constant and low viscosity simultaneously.
In a preferred embodiment of the invention, lithium salts can be selected from LiPF6、LiBF4Deng.
One embodiment of the invention provides a kind of lithium ion battery, including anode, cathode and be placed in above-mentioned anode with
Diaphragm between cathode further includes non-aqueous electrolyte for lithium ion cell of the invention.
In a preferred embodiment in accordance with this invention, positive active material are as follows: LiNixCoyMnzL(1-x-y-z)O2、
LiCox’L(1-x’)O2、LiNix”L’y’Mn(2-x”-y’)O4、Liz’MPO4At least one of, wherein L Al, Sr, Mg, Ti, Ca,
At least one of Zr, Zn, Si or Fe, 0≤x≤1,0≤y≤1,0≤z≤1,0 < x+y+z≤1,0 < x '≤1,0.3≤x "
≤ 0.6,0.01≤y '≤0.2, L ' it is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, Fe, 0.5≤z '≤1,
M is at least one of Fe, Mn, Co.
Below by way of specific embodiment, the present invention will be described in detail.It should be appreciated that these embodiments are only exemplary
, it does not constitute a limitation on the scope of protection of the present invention.
Embodiment 1
The preparation method of the present embodiment and the lithium ion battery of other embodiments, preparation, positive plate including electrolyte
Preparation, the preparation of negative plate, the preparation of battery core and the fluid injection of battery core and chemical conversion step；The present embodiment and the lithium of other embodiments from
The performance test of sub- battery includes that high temperature cyclic performance test and 60 DEG C of high-temperature storage performances are tested, specific as follows:
1) preparation of electrolyte
It is in mass ratio EC:DEC:EMC by ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC)
=1:1:1 is mixed, and lithium hexafluoro phosphate (LiPF is then added6) to molar concentration be 1mol/L.As shown in table 2, non-with this
The total weight of water electrolysis liquid is 100% meter, and 1% compound 1 based on electrolyte total weight is added and (is referred in embodiment
Compound 1, compound 2 ... refer to the compound for the reference numeral that table 1 is enumerated, below each example similarly).
2) preparation of positive plate
By the quality of 93:4:3 than blended anode active material lithium nickel cobalt manganese oxide (LiNi0.5Co0.2Mn0.3O2) or cobalt
Sour lithium (LiCoO2) (other embodiments), conductive carbon black Super-P and binder polyvinylidene fluoride (PVDF), then by them
It is dispersed in n-methyl-2-pyrrolidone (NMP), obtains anode sizing agent.Slurry is uniformly coated on the two sides of aluminium foil, is passed through
Drying, calendering and vacuum drying, and burn-on with supersonic welder and obtain positive plate after aluminum lead-out wire, the thickness of pole plate is in 120-
150μm。
3) preparation of negative plate
By mass ratio mixing negative electrode active material artificial graphite, the conductive carbon black Super-P, binder of 94:1:2.5:2.5
Butadiene-styrene rubber (SBR) and carboxymethyl cellulose (CMC), then disperse them in deionized water, obtain negative electrode slurry.It will slurry
Material is coated on the two sides of copper foil, is burn-on after nickel lead-out wire by drying, calendering and vacuum drying, and with supersonic welder
To negative plate, the thickness of pole plate is at 120-150 μm.
4) preparation of battery core
Placed between positive plate and negative plate with a thickness of 20 μm of three layers of isolation film, then by positive plate, negative plate and
The sandwich structure of isolation film composition is wound, then is put into aluminum foil sack after coiling body is flattened, and vacuum is dried at 85 DEG C
Roasting 28h, obtains battery core to be injected.
5) fluid injection and chemical conversion of battery core
In dew point control in -40 DEG C of glove boxes below, the electrolyte of above-mentioned preparation is injected in battery core, through vacuum seal
Dress, it is static for 24 hours.Then the conventional chemical conversion of initial charge: 0.05C constant-current charge 180min, 0.2C constant current is carried out according to the following steps
Charge to 3.95V, secondary vacuum sealing, then further with the electric current constant-current charge of 0.2C to 4.2V
(LiNi0.5Co0.2Mn0.3O2/ artificial graphite battery) or 4.4V (LiCoO2/ artificial graphite battery), normal temperature shelf is for 24 hours after r, with
The electric current constant-current discharge of 0.2C is to 3.0V.
6) high temperature cyclic performance is tested
At 45 DEG C, the battery after chemical conversion is charged to 4.2V (LiNi with 1C constant current constant voltage0.5Co0.2Mn0.3O2/ artificial graphite
Battery) or 4.4V (LiCoO2/ artificial graphite battery), it is 0.01C by electric current, then uses 1C constant-current discharge to 3.0V.So
After charge/discharge n times circulation, the conservation rate of capacity after n-th circulation is calculated, to assess its high temperature cyclic performance.
45 DEG C of 1C circulation n times capacity retention ratio calculation formula are as follows:
N-th circulation volume conservation rate (%)=(n-th cyclic discharge capacity/first time cyclic discharge capacity) ×
100%.
Embodiment 1 is as shown in table 2 in 45 DEG C of 1C 500 weeks capacity retention ratio test datas of circulation.
7) 60 DEG C of high-temperature storage performance tests
Battery after chemical conversion is charged to 4.2V (LiNi with 1C constant current constant voltage at normal temperature0.5Co0.2Mn0.3O2/ artificial graphite
Battery) or 4.4V (LiCoO2/ artificial graphite battery), it is 0.01C by electric current, then uses 1C constant-current discharge to 3.0V, measurement is electric
Pond initial discharge capacity, then with 1C constant-current constant-voltage charging to 4.2V (LiNi0.5Co0.2Mn0.3O2/ artificial graphite battery) or 4.4V
(LiCoO2/ artificial graphite battery), it is 0.01C by electric current, measures the original depth of battery, then stores battery at 60 DEG C
After N days, the thickness of battery is measured, then with 1C constant-current discharge to 3.0V, measure the holding capacity of battery, then filled with 1C constant current constant voltage
Electricity is to 4.2V (LiNi0.5Co0.2Mn0.3O2/ artificial graphite battery) or 4.4V (LiCoO2/ artificial graphite battery), be by electric current
0.01C, then with 1C constant-current discharge to 3.0V, measurement recovery capacity.Capacity retention ratio, capacity restoration rate, thickness swelling
Calculation formula is as follows:
Battery capacity conservation rate (%)=holding capacity/initial capacity × 100%；
Capacity resuming rate (%)=recovery capacity/initial capacity × 100%；
Cell thickness expansion rate (%)=(thickness-original depth after N days)/original depth × 100%.
Embodiment 1 is in 60 DEG C of storage 30 days capacity retention ratios, capacity restoration rate and thickness swelling test data such as 2 institutes of table
Show.
Embodiment 2
As shown in table 2, other than changing 1% compound 1 into 1% compound 2 in the preparation of electrolyte, Qi Tayu
Embodiment 1 is identical, and the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Embodiment 3
As shown in table 2, other other than changing 1% compound 1 into 0.1% compound 1 in the preparation of electrolyte
Same as Example 1, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Embodiment 4
As shown in table 2, other than changing 1% compound 1 into 2% compound 1 in the preparation of electrolyte, Qi Tayu
Embodiment 1 is identical, and the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Embodiment 5
As shown in table 2, other than changing 1% compound 1 into 3% compound 1 in the preparation of electrolyte, Qi Tayu
Embodiment 1 is identical, and the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Embodiment 6
As shown in table 2, other than changing 1% compound 1 into 5% compound 1 in the preparation of electrolyte, Qi Tayu
Embodiment 1 is identical, and the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Embodiment 7
As shown in table 2, other other than changing 1% compound 1 into 10% compound 1 in the preparation of electrolyte
Same as Example 1, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Embodiment 8
As shown in table 2, other than 1% vinylene carbonate is additionally added in the preparation of electrolyte, other and implementation
Example 1 is identical, and the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Embodiment 9
As shown in table 2, other than 1% fluorinated ethylene carbonate is additionally added in the preparation of electrolyte, it is other with it is real
Apply that example 1 is identical, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Embodiment 10
As shown in table 2, other than 1% 1,3-propane sultone is additionally added in the preparation of electrolyte, it is other with it is real
Apply that example 1 is identical, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Embodiment 11
As shown in table 2, other than 1% sulfuric acid vinyl ester is additionally added in the preparation of electrolyte, other and embodiment 1
Identical, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Comparative example 1
As shown in table 2, other same as Example 1 other than 1% compound 1 is not added in the preparation of electrolyte, it surveys
The data of the obtained high temperature cyclic performance of examination and high-temperature storage performance are shown in Table 2.
Comparative example 2
As shown in table 2, other than changing 1% compound 1 into 1% vinylene carbonate in the preparation of electrolyte,
Other same as Example 1, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Comparative example 3
As shown in table 2, in addition in the preparation of electrolyte by 1% compound 1 change into 1% fluorinated ethylene carbonate it
Outside, other same as Example 1, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Comparative example 4
As shown in table 2, in addition in the preparation of electrolyte by 1% compound 1 change into 1% 1,3-propane sultone it
Outside, other same as Example 1, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Comparative example 5
As shown in table 2, other than changing 1% compound 1 into 1% sulfuric acid vinyl ester in the preparation of electrolyte,
It is same as Example 1, and the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Comparative example 6
As shown in table 2, in addition to 1% compound 1 is changed into the preparation of electrolyte 1% LiN (SO2F)2Except, it is other
Same as Example 1, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 2.
Table 2
Embodiment 13
As shown in table 3, other than lithium nickel cobalt manganese oxide is replaced with cobalt acid lithium in the preparation of positive plate, it is other with it is real
Apply that example 1 is identical, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 3.
Embodiment 14
As shown in table 3, other than lithium nickel cobalt manganese oxide is replaced with cobalt acid lithium in the preparation of positive plate, it is other with it is real
Apply that example 2 is identical, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 3.
Embodiment 15
As shown in table 3, other than lithium nickel cobalt manganese oxide is replaced with cobalt acid lithium in the preparation of positive plate, it is other with it is real
Apply that example 3 is identical, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 3.
Comparative example 7
As shown in table 3, other than lithium nickel cobalt manganese oxide is replaced with cobalt acid lithium in the preparation of positive plate, it is other with than
Identical compared with example 1, the data of the high temperature cyclic performance and high-temperature storage performance tested are shown in Table 3.
Table 3
Can be seen that the case where no matter positive electrode is lithium nickel cobalt manganese oxide or cobalt acid lithium from the result of table 2 and table 3
Under, be added compound shown in structural formula 1 can be obviously improved lithium ion battery 45 DEG C of 1C recycle 300 weeks capacity retention ratios with
And capacity retention ratio, capacity restoration rate and the thickness swelling performance of the storage 14 days at 60 DEG C.
Use above specific case is illustrated the present invention, is merely used to help understand the present invention, not to limit
The system present invention.For those skilled in the art, according to the thought of the present invention, can also make several simple
It deduces, deform or replaces.
Claims (10)
1. a kind of non-aqueous electrolyte for lithium ion cell, which is characterized in that the non-aqueous electrolyte for lithium ion cell includes selected from knot
1 compound represented of structure formula,
Structural formula 1:
Wherein, R1、R2、R3、R4、R5、R6It is each independently selected from hydrogen, fluorine, cyano or the group containing 1-5 carbon atom；R is that carbon is former
Subnumber is no more than 10 groups, and contains 1 oxygen atom or 1 nitrogen-atoms in the R.
2. electrolyte according to claim 1, which is characterized in that on the basis of the electrolyte total weight, the structure
The content of 1 compound represented of formula is 0.1%-10%.
3. electrolyte according to claim 1, which is characterized in that the group containing 1-5 carbon atom is selected from alkyl, halogen
The oxygen-containing alkyl that the alkyl or cyano replaced for alkyl, oxygen-containing alkyl, hydrocarbyl silyl, cyano-containing replaces.
4. electrolyte according to claim 1, which is characterized in that the R1、R2、R3、R4、R5、R6It is each independently selected from
Hydrogen, fluorine, cyano, methyl, ethyl, trimethylsiloxy group, trifluoromethyl.
5. electrolyte according to claim 1, which is characterized in that the R is selected from base shown in structural formula 2 or structural formula 3
Group:
Structural formula 2:Wherein R7、R8It is each independently selected from the alkyl that carbon atom number is 1-5, m is
The integer of 1-3；
Structural formula 3:Wherein R9、R10、R11It is each independently selected from the alkyl that carbon atom number is 1-5.
6. electrolyte according to claim 1, which is characterized in that 1 compound represented of structural formula is selected from followingization
Close object:
7. electrolyte according to claim 1, which is characterized in that the electrolyte further include unsaturated cyclic carbonic ester,
One or more of fluoric cyclic carbonate, cyclic annular sultones, cyclic sulfates.
8. electrolyte according to claim 1, which is characterized in that the unsaturated cyclic carbonic ester includes vinylene carbonate
At least one of ester, vinylethylene carbonate, mesomethylene carbon vinyl acetate；
The fluoric cyclic carbonate includes fluorinated ethylene carbonate, trifluoromethyl ethylene carbonate, difluoroethylene carbonate
At least one of；
The ring-type sultones includes 1,3- propane sultone, 1,4- butane sultone, in acrylic -1,3- sultones
It is at least one；
The cyclic sulfates include at least one of sulfuric acid vinyl ester, 4- methylsulfuric acid vinyl acetate.
9. a kind of lithium ion battery, including anode, cathode and the diaphragm being placed between the positive electrode and negative electrode, which is characterized in that
It further include the described in any item non-aqueous electrolyte for lithium ion cell of claim 1 to 8.
10. lithium ion battery according to claim 9, which is characterized in that the active material of the anode are as follows:
LiNixCoyMnzL(1-x-y-z)O2、LiCox’L(1-x’)O2、LiNix”L’y’Mn(2-x”-y’)O4、Liz’MPO4At least one of, wherein
L is at least one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0≤x≤1,0≤y≤1,0≤z≤1,0 < x+y+z≤
1,0 < x '≤1,0.3≤x "≤0.6,0.01≤y '≤0.2, L ' be Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, Fe in extremely
Few one kind, 0.5≤z '≤1, at least one of M Fe, Mn, Co.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711099724.6A CN109768319B (en) | 2017-11-09 | 2017-11-09 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same |
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| JPH07165751A (en) * | 1993-03-31 | 1995-06-27 | Nippon Oil Co Ltd | Organic solvent and electrolytic solution |
| US20020102464A1 (en) * | 2000-12-06 | 2002-08-01 | Hiroshi Yoshida | Polymer gel electrolyte, secondary cell, and electrical double-layer capacitor |
| CN102964372A (en) * | 2012-09-24 | 2013-03-13 | 中国科学院广州能源研究所 | Halogenosilane functionalized carbonate electrolyte material, its preparation method and application in lithium-ion battery electrolyte solution |
| CN105789700A (en) * | 2016-03-29 | 2016-07-20 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery |
| US20160301101A1 (en) * | 2015-04-07 | 2016-10-13 | Seeo, Inc | Fluorinated alkali ion electrolytes with cyclic carbonate groups |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07165751A (en) * | 1993-03-31 | 1995-06-27 | Nippon Oil Co Ltd | Organic solvent and electrolytic solution |
| US20020102464A1 (en) * | 2000-12-06 | 2002-08-01 | Hiroshi Yoshida | Polymer gel electrolyte, secondary cell, and electrical double-layer capacitor |
| CN102964372A (en) * | 2012-09-24 | 2013-03-13 | 中国科学院广州能源研究所 | Halogenosilane functionalized carbonate electrolyte material, its preparation method and application in lithium-ion battery electrolyte solution |
| US20160301101A1 (en) * | 2015-04-07 | 2016-10-13 | Seeo, Inc | Fluorinated alkali ion electrolytes with cyclic carbonate groups |
| CN105789700A (en) * | 2016-03-29 | 2016-07-20 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery |
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