CN109904515A - Lithium ion secondary battery - Google Patents
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Abstract
The invention discloses a lithium ion secondary battery, which comprises a positive pole piece, a negative pole piece, an isolating membrane and electrolyte, wherein a positive active substance of the positive pole piece contains LiNi(1‑x‑y)CoxMyO2Wherein M is Mn or Al, x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, and x + y is more than or equal to 0 and less than or equal to 0.5; the electrolyte includes: a lithium salt; a nonaqueous organic solvent containing a cyclic carbonate compound and a chain carbonate compound selected from compounds represented by formula 1Wherein in formula 1, R is1、R2Each independently selected from alkyl groups having 1 to 3 carbon atoms, and R1And R2Not being methyl at the same time; an additive comprising a cyclic sulfonate compound and a fluoroborate compound. The lithium ion secondary battery disclosed by the invention has good high-temperature performance and low-temperature performance at the same time.
Description
Technical field
The invention belongs to technical field of secondary batteries more particularly to a kind of lithium ion secondary batteries.
Background technique
Lithium ion secondary battery is due to having the characteristics that energy density is high, having extended cycle life, pollution-free, so that it is being consumed
It has broad application prospects on electron-like, power vehicle battery and accumulation power supply.
No matter in which application field, all to the cruising ability of lithium ion secondary battery, more stringent requirements are proposed by people.
In order to improve the energy density of lithium ion battery, it is to have that developing, which has the active material for anode of Li-ion secondary battery of height ratio capacity,
One of method of effect.Currently, tertiary cathode active material is compared to other positive active materials, since its theoretical specific capacity is high
Feature and the hot spot for becoming research.However in tertiary cathode material, nickel tenor is very high, in use, especially in height
In use, the significant deterioration of lithium ion secondary battery chemical property can be caused under temperature, cryogenic conditions.
Important component of the electrolyte as lithium ion secondary battery, to the high-temperature behavior of lithium ion secondary battery, low
Warm nature can have great influence.However, existing electrolyte cannot make lithium ion secondary battery while have both good high temperature
Performance and cryogenic property.
Summary of the invention
The present invention provides a kind of lithium ion secondary batteries, can have both good high-temperature behavior and cryogenic property simultaneously.
The present invention provides a kind of lithium ion secondary battery, the lithium ion secondary battery include: anode pole piece, cathode pole piece,
Isolation film and electrolyte, the positive active material of anode pole piece include LiNi(1-x-y)CoxMyO2, wherein M is Mn or Al, 0≤x
≤0.5,0≤y≤0.5,0≤x+y≤0.5；Electrolyte includes:
Lithium salts；
Non-aqueous organic solvent, it includes cyclic carbonate compound and linear carbonate compound, linear carbonate chemical combination
Object is selected from one or more of 1 compound represented of formula:
Wherein in formula 1, R1、R2It is each independently selected from the alkyl that carbon atom number is 1~3, and R1And R2It is not simultaneously first
Base；
Additive, it includes cyclic sulfonic acid ester compounds and fluoroboric ester compounds.
Lithium ion secondary battery provided by the invention, positive active material select ternary material, and electrolyte is selected specific
Non-aqueous organic solvent, and additive selects cyclic sulfonic acid ester compound and fluoroboric ester compounds simultaneously, on the one hand, Neng Gougai
Kind high temperature produces gas, improves the stability of positive active material, is effectively improved the high-temperature storage performance of lithium ion secondary battery, another
Aspect can be effectively reduced the low temperature direct impedance of lithium ion secondary battery, improve the low temperature dynamics of lithium ion secondary battery
Performance.Lithium ion secondary battery provided by the invention has both good high-temperature behavior and cryogenic property simultaneously, improves lithium ion
Adaptability of the secondary cell to adverse circumstances.
Specific embodiment
In order to be more clear goal of the invention of the invention, technical solution and advantageous effects, with reference to embodiments
The present invention will be described in further detail.It should be understood that embodiment described in this specification is just for the sake of explanation
The present invention is not intended to limit the present invention.
For simplicity, some numberical ranges are only expressly disclosed herein.However, any lower limit can be with any upper limit group
Close the range for being formed and being not known and recording；And any lower limit can form the range for being not known and recording with other lower values, together
Any upper limit of sample can combine the range to be formed and not yet explicitly be recorded with any other upper limit.In addition, recorded although being not known,
Each point or single number between endpoints of ranges are included within the scope of this.Thus, each point or single number can be used as certainly
The lower limit or the upper limit of body, which combine with any other point or single number or combine to be formed with other lower limits or the upper limit, not yet explicitly to be recorded
Range.
In description herein, it should be noted that unless otherwise indicated, " several " are meant that in " one or more "
Two or more, " more than ", " following " include this number.
Foregoing invention content of the invention is not intended to each disclosed embodiment or every kind of reality in the description present invention
Existing mode.Illustrative embodiments are more particularly exemplified described below.Many places in entire chapter application pass through a series of realities
It applies example and provides guidance, these embodiments can use in a variety of combinations.In various embodiments, it enumerates only as representativeness
Group should not be construed as exhaustion.
Lithium ion secondary battery
Embodiment of the present invention first aspect provides a kind of lithium ion secondary battery, which includes: just
Pole pole piece, cathode pole piece, isolation film and electrolyte, the positive active material of anode pole piece include LiNi(1-x-y)CoxMyO2,
In, M is Mn or Al, 0≤x≤0.5,0≤y≤0.5,0≤x+y≤0.5；Electrolyte includes:
Lithium salts；
Non-aqueous organic solvent includes cyclic carbonate compound and linear carbonate compound, linear carbonate compound
Selected from one or more of 1 compound represented of formula:
Wherein in formula 1, R1、R2It is each independently selected from the alkyl that carbon atom number is 1~3, and R1And R2It is not simultaneously first
Base；
Additive includes cyclic sulfonic acid ester compound and fluoroboric ester compounds.
In the electrolyte that embodiment of the present invention provides, contain more than one cyclic carbonate compound.As above-mentioned
One or both of cyclic carbonate compound, preferably ethylene carbonate (EC), propene carbonate (PC).
In the electrolyte that embodiment of the present invention provides, the general formula containing more than one is the linear carbonate chemical combination of formula 1
Object:
In formula 1, R1、R2It is each independently selected from the alkyl that carbon atom number is 1~3, and R1And R2It is not simultaneously methyl.
Work as R1And R2When being simultaneously methyl, linear carbonate compound shown in formula 1 is dimethyl carbonate (DMC), is sent out through further investigation
It is existing, the production gas of lithium ion secondary battery under the high temperature conditions can be dramatically increased when in non-aqueous organic solvent containing dimethyl carbonate
Amount, deteriorates its high-temperature behavior.
The linear carbonate compound that above-mentioned formula 1 indicates, such as methyl ethyl carbonate, diethyl carbonate, carbon can be enumerated
Sour dipropyl, diisopropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, ethylisopropyl base carbonic ester, isopropyl methyl carbonic acid
Ester.
As the linear carbonate compound that above-mentioned formula 1 indicates, preferably methyl ethyl carbonate (EMC), diethyl carbonate
One or both of (DEC).
Through further investigation find: the content of above-mentioned cyclic carbonate compound account for non-aqueous organic solvent total weight 15%~
40%, it, can be significant when weight percentage of the content of cyclic carbonate compound in non-aqueous organic solvent is higher than 40%
Influence the high-temperature behavior of lithium ion secondary battery；When weight hundred of the content in non-aqueous organic solvent of cyclic carbonate compound
When content being divided to be lower than 15%, the kinetics under the dynamic performance of lithium ion secondary battery, especially low temperature can be significantly affected
Energy.
In the electrolyte that embodiment of the present invention provides, containing more than one cyclic sulfonic acid ester compound, as preferred
, cyclic sulfonic acid ester compound is one or more of formula 2, the cyclic sulfonic acid ester Compound Compound of the expression of formula 3:
In formula 2, R3The alkylidene for being 3~8 selected from substituted or unsubstituted carbon atom number, the substituted substituent group choosing
From carbon atom number be 1~6 alkyl, one or more of F, Cl, Br, I, wherein be preferably F in F, Cl, Br, I.
The alkylidene for being 3~8 as above-mentioned carbon atom number, can be straight-chain alkyl-sub, or the Asia with branch
Alkyl.
As above-mentioned carbon atom number be 3~8 alkylidene, it is preferred that select carbon atom number for 3~7 alkylidene, it is more excellent
Choosing, select carbon atom number for 3~6 alkylidene, for example: propylidene, isopropylidene, butylidene, isobutylidene,
Sub- sec-butyl, pentylidene, hexylidene.
The alkyl for being 1~6 as above-mentioned carbon atom number, can be chain-like alkyl, or naphthenic base is located at naphthenic base
On hydrogen can be replaced by alkyl.
The alkyl for being 1~6 as above-mentioned carbon atom number, the preferred lower limit value of carbon atom number are 1,2,3, preferred upper limit value
Be 4,5,6, it is preferable that select carbon atom number for 1~3 chain-like alkyl.Reality as the alkyl that above-mentioned carbon atom number is 1~6
Example, for example, can enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl,
Neopentyl, hexyl, 2- Methyl pentyl, 3- Methyl pentyl, 1,1,2- trimethyl-propyl, 3,3- dimethyl-butyl.
As the cyclic sulfonic acid ester compound that above-mentioned formula 2, formula 3 indicate, in preferably following cyclic sulfonic acid ester compound
It is at least one:
In the electrolyte that embodiment of the present invention provides, the general formula containing more than one is that the fluoroboric of formula 4 is esterified conjunction
Object:
In formula 4, R4、R5、R6It is each independently selected from the alkyl, substitution that substituted or unsubstituted carbon atom number is 1~20
Or the aryl that unsubstituted carbon atom number is 6~16, and R4、R5、R6At least one of upper contain at least one fluorine atom.
The alkyl for being 1~20 as above-mentioned carbon atom number, can be chain-like alkyl, or cyclic alkyl, such as can
To enumerate methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, different
Amyl, neopentyl, cyclopenta, n-hexyl, isohesyl, cyclohexyl, heptyl, suberyl, octyl, cyclooctyl, nonyl, decyl, ten
One alkyl, dodecane alkyl, tridecane alkyl, tetradecane alkyl, pentadecane alkyl, hexadecane alkyl, heptadecane alkyl, ten
Eight alkyls, nonadecane alkyl, eicosane alkyl.
As above-mentioned carbon atom number be 6~16 aryl, such as can enumerate phenyl, benzyl, xenyl, to toluene
Base, o-tolyl, tolyl, to ethylbenzene, ethylbenzene, adjacent ethylbenzene, 3,5- xylyl, 2,6- 3,5-dimethylphenyl,
3,5- diethyl phenyl, 2,6- diethyl phenyl, 3,5- diisopropylbenzyl, 2,6- diisopropylbenzyl, bis- n-proplbenzene base of 3,5-, 2,
Bis- n-proplbenzene base of 6-, bis- n-butyl benzene base of 3,5-, bis- n-butyl benzene base of 2,6-, bis- isobutylphenyl of 3,5-, bis- isobutylphenyl of 2,6-, 3,5-
Two 2-methyl-2-phenylpropane bases, bis- 2-methyl-2-phenylpropane base of 2,6-, trityl, 1- naphthalene, 2- naphthalene.
It is understood that in formula 4, R4、R5、R6It may be the same or different.Preferably, R4、R5、R6Phase
Together.
As the fluoroboric ester compounds that above-mentioned formula 4 indicates, in preferably following fluoroboric ester compounds at least
It is a kind of:
Find through further investigation: the content by controlling above-mentioned cyclic sulfonic acid ester compound is electrolyte total weight
0.1%~5%, the content of above-mentioned fluoroboric ester compounds is the 0.05%~3% of electrolyte total weight, can improve high temperature
Gas is produced, the high-temperature storage performance of battery is improved, and can be effectively reduced the low temperature direct impedance of battery, to improve the height of battery
Warm nature energy and cryogenic property.
The content of above-mentioned cyclic sulfonic acid ester compound is preferably the 0.3%~3% of electrolyte total weight, further preferably
The 0.5%~2% of the total weight of electrolyte.
The content of above-mentioned fluoroboric ester compounds is preferably the 0.1%~1% of electrolyte total weight, further preferably
The 0.1%~0.5% of electrolyte total weight.
In the electrolyte that embodiment of the present invention provides, containing more than one lithium salts, the type selecting of lithium salts is not appointed
What is limited, and can be any known electrolyte lithium salt for electrolyte of lithium-ion secondary battery, such as can enumerate
LiPF6(lithium hexafluoro phosphate), LiBF4(LiBF4), LiClO4(lithium perchlorate), LiAsF6(hexafluoroarsenate lithium), LiFSI
(double fluorine sulfimide lithiums), LiTFSI (bis-trifluoromethylsulfoandimide lithium), LiTFS (trifluoromethanesulfonic acid lithium), LiDFOB (difluoro grass
Sour lithium borate), LiBOB (dioxalic acid lithium borate), LiPO2F2(difluorophosphate), LiDFOP (difluoro dioxalic acid lithium phosphate),
LiTFOP (tetrafluoro oxalic acid lithium phosphate).
As above-mentioned lithium salts, concentration in the electrolytic solution is 0.5mol/L~1.5mol/L, preferably 0.8mol/L~
1.2mol/L。
It optionally include other additives in the electrolyte that embodiment of the present invention provides, other additives are selected from carbonic acid
Vinylene (VC), vinylethylene carbonate (VEC), fluorinated ethylene carbonate (FEC), sulfuric acid vinyl ester (DTD), succinonitrile
(SN), adiponitrile (ADN), three (trimethyl silane) phosphates (TMSP), one in three (trimethyl silane) borates (TMSB)
Kind is several, and the content of other additives accounts for the 0.01%~5% of electrolyte total weight.
In the lithium ion secondary battery that embodiment of the present invention provides, anode pole piece includes plus plate current-collecting body and is formed in just
Positive electrode active material layer on the collector of pole, wherein positive electrode active material layer includes positive active material, binder and conduction
Agent；Cathode pole piece includes negative current collector and the negative electrode active material layer that is formed on negative current collector, wherein negative electrode active material
Matter layer includes negative electrode active material, binder and conductive agent；Isolation film is between anode pole piece and cathode pole piece.
As above-mentioned plus plate current-collecting body, negative current collector, negative electrode active material, binder, conductive agent and isolation film
Specific type is not limited specifically, be may each be any known raw material, can be selected according to demand.
In the lithium ion secondary battery that embodiment of the present invention provides, it is preferred that anode pole piece is using aluminium foil as anode collection
Body；Cathode pole piece is using copper foil as negative current collector；Negative electrode active material can be selected from lithium metal, natural graphite, artificial graphite, centre
Mutually micro- carbon ball (being abbreviated as MCMB), hard carbon, soft carbon, silicon, silico-carbo compound, SiO, Li-Sn alloy, Li-Sn-O alloy, Sn,
SnO、SnO2, spinel structure lithium titanate Li4Ti5O12, one or more of Li-Al alloy；The optional autohemagglutination of binder inclined two
One or more of vinyl fluoride (PVDF), polytetrafluoroethylene (PTFE) (PTFE), polyvinyl alcohol (PVA), butadiene-styrene rubber (SBR)；It is conductive
Agent can be selected from one or more of superconduction carbon, acetylene black, carbon nanotube, graphene and carbon nano-fiber；Isolation film can be selected from
Polyethylene, polypropylene, Kynoar and including above-mentioned polyethylene, polypropylene, Kynoar at least one multilayer it is multiple
Close film.
Lithium ion secondary battery provided by the invention, positive active material select ternary material, and electrolyte is selected specific
Non-aqueous organic solvent, and additive selects cyclic sulfonic acid ester compound and fluoroboric ester compounds simultaneously, on the one hand, Neng Gougai
Kind high temperature produces gas, improves the stability of positive active material, improves the high-temperature storage performance of lithium ion secondary battery, another party
Face can be effectively reduced the low temperature direct impedance of lithium ion secondary battery, improve the low temperature kinetics of lithium ion secondary battery
Energy.
Lithium ion secondary battery described above has both good high-temperature behavior and cryogenic property simultaneously, solves lithium ion
Secondary cell face the problem of chemical property deteriorates under the adverse circumstances of high temperature and low temperature, improve lithium ion two
Adaptability of the primary cell to adverse circumstances.
The preparation method of electrolyte
The second aspect of embodiment of the present invention provides a kind of preparation method of electrolyte, and this method is by lithium salts, includes
The non-aqueous organic solvent of cyclic carbonate compound and linear carbonate compound includes cyclic sulfonic acid ester compound and fluoro boron
The additive of ester compound is uniformly mixed, and is not particularly limited to the addition sequence of material, can be will be cyclic annular
Carbonate products and linear carbonate compound are mixed to get non-aqueous organic solvent, then by lithium salts, cyclic sulfonic acid ester compound,
Fluoroboric ester compounds, which are added in non-aqueous organic solvent, carries out uniformly mixed, obtained electrolyte；It is also possible to cyclic annular carbon
Ester compound and linear carbonate compound are mixed to get non-aqueous organic solvent, then lithium salts is dissolved in non-aqueous organic solvent
In, then cyclic sulfonic acid ester compound, fluoroboric ester compounds are added in non-aqueous organic solvent and carry out uniformly mixed, system
Obtain electrolyte.
It is above-mentioned be uniformly mixed, can by the way of any known mixed material, such as can enumerate mechanical stirring,
Ultrasonic agitation, airflow stirring.
Embodiment
Following embodiments more particularly describe present disclosure, these being only intended to illustrate property of embodiment are said
It is bright, because carrying out various modifications and changing in scope of the present disclosure is obvious for a person skilled in the art
's.Unless otherwise stated, all parts, percentage and the ratio reported in following embodiment are by weight meter, Er Qieshi
It is all commercially available or conventionally carry out synthesis acquisition to apply all reagents used in example, and can be used directly and
Without be further processed and embodiment used in instrument it is commercially available.
Embodiment 1-25, comparative example 1-11
Lithium ion secondary battery in embodiment 1-25 and comparative example 1-11 is prepared by the following method.
The preparation of lithium ion secondary battery
Anode pole piece preparation: positive active material, conductive agent conductive carbon black (Super P), binder are gathered into inclined difluoro second
Alkene (PVDF) is mixed according to mass ratio 97:1.4:1.6, and is added into solvent N-methyl pyrilidone (NMP), using true
Empty blender is stirred to system into transparent and homogeneous shape, obtains anode active material slurry, anode active material slurry is uniformly applied
It is overlying on plus plate current-collecting body aluminium foil and dries, then pass through cold pressing, trimming, cut-parts, slitting, obtain anode pole piece.
Cathode pole piece preparation: by negative electrode active material, conductive agent conductive carbon black (Super P), thickener carboxymethyl cellulose
Plain sodium (CMC), binder SBR emulsion (SBR) are mixed according to mass ratio 96.4:1.5:0.5:1.6, and are added extremely
In solvent deionized water, it is stirred until homogeneous system using de-airing mixer, negative electrode active material slurry is obtained, by negative electrode active material
Chylema material is coated uniformly on negative current collector copper foil and dries, and then passes through cold pressing, trimming, cut-parts, slitting, obtains cathode pole
Piece.
Film preparation is isolated: using polyethylene film (PE) as isolation film.
Electrolyte preparation: being mixed to get non-aqueous organic solvent for cyclic carbonate compound and linear carbonate compound,
Sufficiently dry lithium salts is dissolved in above-mentioned non-aqueous organic solvent, cyclic sulfonic acid ester is then added in non-aqueous organic solvent
Object and fluoroboric ester compounds are closed, other additives can also optionally be added, are uniformly mixed, electrolyte is obtained.Electrolyte
In component specific type and content it is as shown in table 1.In table 1, the content of cyclic sulfonic acid ester compound, fluoroboric ester
The content of compound is the weight percent that the total weight based on electrolyte is calculated.
Anode pole piece, isolation film, cathode pole piece are cascading, isolation film is made to be in anode pole piece and cathode pole piece
Between, be then wound into battery core and be fitted into Package casing, inject the electrolyte of above-mentioned preparation and sealing, later through standing,
The processes such as heat cold pressing, chemical conversion, obtain lithium ion secondary battery.
Lithium ion secondary battery parameter in embodiment 1-25 and comparative example 1-11 is as shown in table 1.
Table 1
Note: above-mentioned corresponding substance is not added in "/" expression in table 1；Lithium salt unit " M " is writing a Chinese character in simplified form for " mol/L ".
Part of detecting
The lithium ion secondary battery of Examples 1 to 25 and comparative example 1~11 is subjected to following tests respectively:
The high temperature storage volume expansion of lithium ion secondary battery is tested
At 25 DEG C, lithium ion secondary battery is stood into 30min first, is later 4.3V with 1C constant-current charge to voltage,
Then it is 0.05C with 4.3V constant-voltage charge to electric current, tests the volume of lithium ion secondary battery at this time and be denoted as V0；Then by lithium
Ion secondary battery is put into 80 DEG C of insulating box, and the volume of test lithium ion secondary battery is taken out after storage 10 days and is denoted as
V1.In this test, using the volume of drainage test lithium ion secondary battery.
80 DEG C of lithium ion secondary battery storage 10 days after cubical expansivity (%)=(V1-V0)/V0× 100%.
The low temperature direct impedance (DCR) of lithium ion secondary battery is tested
Under room temperature (25 DEG C), lithium ion secondary battery is stood into 30min first, is with 1C constant-current charge to voltage later
Then 4.3V is 0.05C with 4.3V constant-voltage charge to electric current, shelves 5min, with 1C constant-current discharge to blanking voltage 2.8V, record
Actual discharge capacity, and adjusted the state-of-charge (SOC) of lithium ion secondary battery to completely filling capacity with actual discharge capacity
20%, after the completion of adjustment, lithium ion secondary battery is placed in -25 DEG C of high-low temperature chamber, stands 2h, make lithium ion secondary battery
Temperature reaches -25 DEG C, tests the voltage of lithium ion secondary battery at this time and is denoted as U1, then with the multiplying power discharging 10s of 0.3C, survey
It tries the voltage after lithium ion secondary battery is discharged and is denoted as U2。
- 25 DEG C of lithium ion secondary battery of DCR=(U1-U2)/I, I indicate electric current.
Test result is as shown in table 2.
Table 2
It can be seen that cyclic sulfonic acid ester compound and fluoro boron from the test result of embodiment 1~11 and comparative example 1~7
The dosage of ester compound has a major impact the high temperature storage cubical expansivity of lithium ion secondary battery and low temperature direct impedance,
Beyond specific amount ranges, the high temperature storage cubical expansivity of lithium ion secondary battery, low temperature direct impedance correspondingly by
It influences.But it is required in relatively low or more secondary use demand for some, can equally improve lithium to a certain extent
The high-temperature storage performance and low temperature direct impedance of ion secondary battery.
From the test result of embodiment 4 and comparative example 11 it is found that electrolyte is with cyclic sulfonic acid ester compound and acid esterification
Object is closed as additive, has unfavorable shadow to the high temperature storage cubical expansivity and low temperature direct impedance of lithium ion secondary battery
It rings, especially significantly increases the low temperature direct impedance of lithium ion secondary battery, deteriorate the cryogenic property of lithium ion secondary battery.
From the test result of embodiment 9 and comparative example 8~9 it is found that cyclic carbonate compound in non-aqueous organic solvent
Content has a major impact the high temperature storage cubical expansivity of lithium ion secondary battery and low temperature direct impedance, uses beyond specific
Range is measured, the high temperature storage cubical expansivity of lithium ion secondary battery, low temperature direct impedance are correspondingly affected.From comparative example
10 and embodiment 9 test result it is found that when in non-aqueous organic solvent contain dimethyl carbonate (DMC) when, lithium ion secondary electricity
For cubical expansivity behind 80 DEG C of storages 10 days of pond up to 95.7%, the inhibiting effect which produces gas to high temperature is smaller.
It can be seen that lithium ion secondary battery provided in an embodiment of the present invention from the test result of Examples 1 to 25, pass through
Specific non-aqueous organic solvent is selected in electrolyte, and additive selects cyclic sulfonic acid ester compound and fluoroboric to be esterified simultaneously
Object is closed, so that the cubical expansivity after 80 DEG C of storages 10 days of lithium ion secondary battery is lower than 17.80%, and its -25 DEG C DCR
In 370.8m Ω hereinafter, lithium ion secondary battery has low high temperature storage cubical expansivity and low low temperature direct resistance simultaneously
It is anti-, i.e., the high-temperature storage performance and low temperature direct impedance of lithium ion secondary battery are improved simultaneously, so that lithium ion secondary
Battery has both good high-temperature behavior and cryogenic property simultaneously.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can readily occur in various equivalent modifications or replace
It changes, these modifications or substitutions should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with right
It is required that protection scope subject to.
Claims (10)
1. a kind of lithium ion secondary battery, comprising: anode pole piece, cathode pole piece, isolation film and electrolyte, which is characterized in that institute
The positive active material for stating anode pole piece includes LiNi(1-x-y)CoxMyO2, wherein M be Mn or Al, 0≤x≤0.5,0≤y≤
0.5,0≤x+y≤0.5；The electrolyte includes:
Lithium salts；
Non-aqueous organic solvent, the non-aqueous organic solvent includes cyclic carbonate compound and linear carbonate compound, described
Linear carbonate compound is selected from one or more of 1 compound represented of formula:
Wherein, in the formula 1, R1、R2It is each independently selected from the alkyl that carbon atom number is 1~3, and R1And R2It is not simultaneously first
Base；
Additive, the additive include cyclic sulfonic acid ester compound and fluoroboric ester compounds.
2. lithium ion secondary battery according to claim 1, which is characterized in that the cyclic carbonate compound is selected from carbon
One or both of vinyl acetate, propene carbonate.
3. lithium ion secondary battery according to claim 1, which is characterized in that the content of the cyclic carbonate compound
It is the 15%~40% of the non-aqueous organic solvent total weight.
4. lithium ion secondary battery according to claim 1, which is characterized in that the linear carbonate compound is selected from carbon
One or both of sour methyl ethyl ester, diethyl carbonate.
5. lithium ion secondary battery according to claim 1, which is characterized in that the cyclic sulfonic acid ester compound is selected from formula
2, one or more of 3 compound represented of formula:
Wherein, R3The alkylidene for being 3~8 selected from substituted or unsubstituted carbon atom number, the substituted substituent group are selected from carbon atom
Count one or more of the alkyl for 1~6, F, Cl, Br, I.
6. lithium ion secondary battery according to claim 5, which is characterized in that the cyclic sulfonic acid ester compound be selected from
One or more of lower compound:
7. lithium ion secondary battery according to claim 1, which is characterized in that the fluoroboric ester compounds are selected from formula
One or more of 4 compounds represented:
Wherein, in the formula 4, R4、R5、R6Be each independently selected from substituted or unsubstituted carbon atom number be 1~20 alkyl,
The aryl that substituted or unsubstituted carbon atom number is 6~16, and R4、R5、R6At least one of it is upper former containing at least one fluorine
Son.
8. lithium ion secondary battery according to claim 7, which is characterized in that the fluoroboric ester compounds be selected from
One or more of lower compound:
9. lithium ion secondary battery according to claim 1, which is characterized in that
The content of the cyclic sulfonic acid ester compound accounts for the 0.1%~5% of the electrolyte total weight；
The content of the fluoroboric ester compounds accounts for the 0.05%~3% of the electrolyte total weight.
10. lithium ion secondary battery according to claim 1, which is characterized in that the additive further comprises other
Additive, other additives are selected from vinylene carbonate, vinylethylene carbonate, fluorinated ethylene carbonate, sulfuric acid ethylene
One or more of ester, succinonitrile, adiponitrile, three (trimethyl silane) phosphates, three (trimethyl silane) borates, it is described
The content of other additives accounts for the 0.01%~5% of the electrolyte total weight.
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Application publication date: 20190618 |