CN109904521A - Electrolyte and battery comprising same - Google Patents
Electrolyte and battery comprising same Download PDFInfo
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- CN109904521A CN109904521A CN201711293161.4A CN201711293161A CN109904521A CN 109904521 A CN109904521 A CN 109904521A CN 201711293161 A CN201711293161 A CN 201711293161A CN 109904521 A CN109904521 A CN 109904521A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application relates to the field of batteries, in particular to electrolyte and a battery containing the electrolyte. The electrolyte comprises an organic solvent, an electrolyte and an additive, wherein the additive contains a sulfonyl nitrogen-containing heterocyclic compound and a bissulfonyl imide salt; wherein, the nitrogen-containing heterocycle in the sulfonyl nitrogen-containing heterocyclic compound is at least one selected from pyrazole-containing ring, pyrroline ring, imidazole ring, pyrrolidine ring, piperidine ring and pyridine ring. The electrolyte can improve the property of the interface film of the anode and the cathode of the battery, effectively reduce the dissolution of transition metal elements in the anode material at the anode and the deposition of the transition metal elements at the cathode, inhibit the decomposition of the electrolyte at the anode and the cathode, and ensure the high-temperature storage performance and the high-temperature cycle performance of the battery under high voltage.
Description
Technical field
This application involves field of batteries more particularly to a kind of electrolyte and including the battery of the electrolyte.
Background technique
The electronic mobile devices such as laptop, mobile phone, handheld device, tablet computer are able to achieve more and more function
Can, the application technology of electric car, smart grid etc. also reaches its maturity.People to the lithium as its main drive energy from
The cruising ability of sub- battery requires also higher and higher.
Lithium ion battery has many advantages, such as high-energy density, long circulation life, environmental-friendly, memory-less effect, answers extensively
For fields such as digital product, electric car, space flight and aviation.With the development of science and technology and social progress, market is to lithium ion
The charge cutoff voltage of battery requires higher and higher.
But under the high voltage of 4.3V, conventional electrolysis liquid is oxidizable at positive interface, and negative electrode volume expansion effect causes
SEI film constantly ruptures recombination, these effects all can cause electrolyte constantly to decompose at positive and negative anodes interface, the decomposition of electrolyte itself
It can promote the deterioration of positive and negative anodes active material simultaneously, further influence the performance of lithium ion battery.
Summary of the invention
In consideration of it, the primary goal of the invention of the application is to propose a kind of electrolyte, after electrolyte is applied in battery,
The property that positive and negative anodes interfacial film can be improved improves battery cycle performance under high voltages and storage performance.
The second goal of the invention of the application is to propose a kind of battery using the electrolyte.
In order to complete the purpose of the application, the technical solution of use are as follows:
A kind of electrolyte, including organic solvent, electrolyte and additive contain sulphonyl nitrogen-containing heterocycle compound in additive
With double sulfimide salts, specifically, the optional self-contained pyrazole ring of nitrogen-containing heterocycle, pyrrolin ring in sulphonyl nitrogen-containing heterocycle compound,
At least one of imidazole ring, pyrrolidine ring, piperidine ring, pyridine ring.
The technical solution of the application at least has following beneficial effect:
When the application electrolyte sulphonyl nitrogen-containing heterocycle compound can positive electrode surface ring-opening polymerisation formed passivating film, but by
Also the biggish SEI film of impedance can be formed in cathode interface in sulphonyl nitrogen-containing heterocycle compound can hinder for lithium ion battery
Hinder lithium ion in the insertion and abjection of cathode, causes the loss of active lithium and battery capacity.The electrolyte of the application contains sulphonyl
Nitrogen heterocyclic and double sulfimide salts share, and preferentially stable height can be formed in negative terminal surface by sulphonyl nitrogen-containing heterocycle compound
The SEI film of ionic conductivity inhibits sulphonyl nitrogen-containing heterocycle compound to the adverse effect of cathode interface impedance, reduces the pole of battery
Change and improve discharge capacity, and the high-temperature storage performance and high temperature cyclic performance of battery can be significantly improved.
Specific embodiment
Combined with specific embodiments below, the application is further described.It should be understood that these embodiments are merely to illustrate the application
Rather than limitation scope of the present application.
It is nitrogenous containing sulphonyl in additive this application involves a kind of electrolyte, including organic solvent, electrolyte and additive
Heterocyclic compound and double sulfimide salts；Nitrogen-containing heterocycle in sulphonyl nitrogen-containing heterocycle compound is selected from containing pyrazole ring, pyrrolin
At least one of ring, imidazole ring, pyrrolidine ring, piperidine ring, pyridine ring.The sulphonyl nitrogen-containing heterocycle compound of the application electrolyte
In the N atom containing lone pair electrons be connected directly with S atom, since the cloud density of N atom drops in the electron attraction of sulfuryl
It is low.During battery high-temperature chemical conversion, sulphonyl nitrogen-containing heterocycle compound can form passivating film in positive electrode surface ring-opening polymerisation.But
Since sulphonyl nitrogen-containing heterocycle compound can also form the biggish SEI film of impedance, for lithium ion battery, meeting in cathode interface
It hinders lithium ion in the insertion and abjection of cathode, causes the loss of active lithium and battery capacity.The application passes through sharp study, will
Sulphonyl nitrogen-containing heterocycle compound and double sulfimide salts share, and double sulfimide salts can preferentially sulphonyl nitrogen-containing heterocycle compound born
Pole surface forms the SEI film of stable high ionic conductivity, inhibit sulphonyl nitrogen-containing heterocycle compound to cathode interface impedance not
Benefit influences, to significantly improve the high-temperature storage performance and high temperature cyclic performance of battery.
As a kind of improvement of the application electrolyte, sulphonyl nitrogen-containing heterocycle compound is selected from the compound as shown in Formulas I to Formula V
At least one of:
Wherein, R11、R12、R13、R21、R22、R23、R24、R31、R32、R33、R41、R42、R43、R44、R51、R52、R53、R54、R55Respectively
From independently selected from hydrogen atom, halogen atom, amino, sulfonic group, substituted or unsubstituted C1-C20It is alkyl, substituted or unsubstituted
C2-C20Alkenyl, substituted or unsubstituted C6-C26Aryl, substituted or unsubstituted C1-C20It is Sulfonylalkyl, substituted or unsubstituted
C2-C20Sulphonyl alkenyl, substituted or unsubstituted C6-C26Sulphonyl aryl；
R14、R25、R34、R45、R56It is independently selected from hydrogen atom, halogen atom, amino, sulfonic group, pyrrolinyl, pyrazoles
Base, pyrrolidinyl, imidazole radicals, pyridyl group, piperidyl, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20
Alkenyl, substituted or unsubstituted C6-C26Aryl, substituted or unsubstituted C1-C20Sulfonylalkyl, substituted or unsubstituted C2-C20
Sulphonyl alkenyl, substituted or unsubstituted C6-C26Sulphonyl aryl；
Substituent group is selected from halogen atom, amino or C1-C4Alkyl.
As a kind of improvement of the application electrolyte, sulphonyl nitrogen-containing heterocycle compound is selected from the chemical combination as shown in Formulas I A to Formula V A
At least one of object；
Wherein, R61、R62、R63、R64、R65、R66、R71、R72、R73、R74、R75、R76、R77、R78、R81、R82、R83、R84、R85、
R86、R91、R92、R93、R94、R95、R96、R97、R98、R101、R102、R103、R104、R105、R106、R107、R108、R109、R110It is respectively independent
Ground is selected from hydrogen atom, halogen atom, amino, sulfonic group, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkene
Base, substituted or unsubstituted C6-C26Aryl, substituted or unsubstituted C1-C20Sulfonylalkyl, substituted or unsubstituted C2-C20Sulphur
Acyl alkenyl, substituted or unsubstituted C6-C26Sulphonyl aryl；Substituent group is selected from halogen atom, amino or C1-C4Alkyl.
As a kind of improvement of the application electrolyte, sulphonyl nitrogen-containing heterocycle compound is selected from compound 1 into compound 5
It is at least one:
In addition to above-claimed compound, the sulphonyl nitrogen-containing heterocycle compound of the application is further selected from least one in following compound
Kind, however it is not limited to this:
As a kind of improvement of the application electrolyte, double sulfimide salts in the compound as shown in Formula IV at least one
Kind,
Wherein, R111、R112Independently selected from halogen, substituted or unsubstituted C1-C6Alkyl；Substituent group is selected from halogen.
It is further alternative, R111、R112It is independently selected from fluorine, C1-C6Fluoro-alkyl；Wherein, fluoro-alkyl includes portion
Divide the fluoro-alkyl replaced and the fluoro-alkyl replaced entirely.
As a kind of improvement of the application electrolyte, double sulfimide salts are selected from double fluorine sulfimide lithium LiFSI (LiN
(SO2F)2) and double trifluoromethanesulfonimide lithium LiTFSI (LiN (SO2CF3)2At least one of), the following institute of concrete structure formula
Show:
In addition to above-claimed compound, double sulfimide salts are further selected from following compound, however it is not limited to this:
As a kind of improvement of the application electrolyte, also contain cyclic sulfates in additive.Cyclic sulfates can be preferential
Sulphonyl nitrogen-containing heterocycle compound forms stable high ionic conductivity SEI film in negative terminal surface, to further suppress double sulphonyl
Adverse effect of the nitrogen-containing heterocycle compound to cathode interface impedance.
As a kind of improvement of the application electrolyte, cyclic sulfates have the structure as shown in Formula VII,
Wherein, R122Selected from substituted or unsubstituted C2~C6Alkylidene, substituted or unsubstituted C2~C6Alkenylene；Replace
Base is selected from halogen, C1~C3Alkyl, C2~C4Alkenyl.
As a kind of improvement of the application electrolyte, cyclic sulfates are selected from sulfuric acid vinyl ester, sulfuric acid acrylic ester and 4- first
At least one of base sulfuric acid vinyl ester, concrete structure formula is as follows:
In addition to above-claimed compound, cyclic sulfates compound is also selected from:
As a kind of improvement of the application electrolyte, additive further includes cyclic annular sultones, double bond containing cyclic carbonate
At least one of ester, fluorine-containing carbonic ester, boracic lithium salts, phosphorous lithium salts.
Wherein, cyclic annular sultones, double bond containing cyclic carbonate, fluorine-containing carbonic ester, boracic lithium salts, phosphorous lithium salts can close
The compound of following (a)~(e) is enumerated suitablely:
(a) cyclic annular sultones
Cyclic annular sultone compounds are selected from least one of compound as shown in formula N-1；
Wherein, R101Selected from substituted or unsubstituted C1~C6Alkylidene, substituted or unsubstituted C2~C6Alkenylene；Replace
Base is selected from halogen, C1~C3Alkyl, C2~C4Alkenyl.
Specifically, cyclic annular sultone compounds are selected from 1,3- propane sultone (referred to as PS), 1,3- propene sulfonic acid
At least one of lactone (referred to as PES), concrete structure formula is as follows；
Cyclic annular sultone compounds are also selected from:
(b) double bond containing cyclic carbonate
Double bond containing cyclic carbonate compound is selected from least one of compound as shown in formula N-2；
Wherein, R102The C replaced selected from alkenyl1~C6Alkylidene, substituted or unsubstituted C2~C6Alkenylene.
Double bond containing cyclic carbonate compound is selected from least one of following compound, and concrete structure formula is as follows:
(c) fluorine-containing carbonic ester
Fluorine-containing carbonate products are selected from least one of formula N-3 compound represented；
Wherein, R1041Selected from fluorine-substituted C1~C6Alkylidene, fluorine-substituted C2~C6Alkenylene.
Fluorine-containing carbonic ester specifically can be selected from fluorinated ethylene carbonate (FEC), fluoropropylene carbonate, three fluoro propylene carbonates
Ester.
(d) boracic lithium salts
Boracic lithium salts is selected from LiBF4、LiB(C2O4)2And LiBC2O4F2At least one of.
(e) phosphorous lithium salts
Phosphorous lithium salts is selected from least one of lithium metaphosphate, lithium phosphate, difluorophosphate and difluoro oxalate lithium phosphate.
In the above-mentioned general formula of the application:
Halogen can be selected from fluorine, chlorine, bromine.
The alkyl that carbon atom number is 1~20, alkyl can be chain-like alkyl, can also be naphthenic base, on the ring of naphthenic base
Hydrogen can be replaced by alkyl, in the alkyl the preferred lower limit value of carbon atom number be 2,3,4,5, preferred upper limit value be 3,4,5,
6,8,10,12,14,16,18.Preferably, select carbon atom number for 1~10 alkyl, it is further preferred that selection carbon atom number
For 1~6 chain-like alkyl, carbon atom number is 3~8 naphthenic base, it is further preferred that select carbon atom number for 1~4 chain
Shape alkyl, the naphthenic base that carbon atom number is 5~7.It as the example of alkyl, can specifically enumerate: methyl, ethyl, n-propyl, different
Propyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, 2- Methyl pentyl, 3- first
Base-amyl, 1,1,2- trimethyl-propyl, 3,3 ,-dimethyl-butyl, heptyl, 2- heptyl, 3- heptyl, 2- methylhexyl, 3- first
Base hexyl, different heptyl, octyl, nonyl, decyl.
The alkenyl that carbon atom number is 2~20 can be cyclic alkenyl radical, can also be chain alkenyl.In addition, in alkenyl double bond
Number preferably 1.The preferred lower limit value of carbon atom number is 3,4,5 in the alkenyl, and preferred upper limit value is 3,4,5,6,8,10,
12,14,16,18,.Preferably, select carbon atom number for 2~10 alkenyl, it is further preferred that selecting carbon atom number for 2~8
Alkenyl, it is further preferred that select carbon atom number for 2~6 alkenyl.As the example of alkenyl, can specifically enumerate: second
Alkenyl, allyl, isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base.
Carbon atom number be 6~26 aryl, such as phenyl, benzene alkyl, such as xenyl of the aryl at least containing a phenyl,
Condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and condensed-nuclei aromatics base can also be replaced alkyl or alkenyl.Preferably, it selects
Select carbon atom number be 6~16 aryl, it is further preferred that select carbon atom number for 6~14 aryl, still more preferably
Ground, select carbon atom number for 6~9 aryl.As the example of aryl, can specifically enumerate: phenyl, benzyl, xenyl, to first
Phenyl, o-tolyl, tolyl.
It as sulfonyl example is contained, can specifically enumerate: methyl sulphonyl, ethylsulfonyl, n-propyl sulfonyl, different
Sulfonyl propyl base, normal-butyl sulfonyl, iso-butylsulfonyl, tert. butylsulfonyl, n-pentyl sulfonyl, isopentyl sulfonyl,
Neopentyl sulfonyl, 2,3- dimethyl propyl sulfonyl, 1- ethyl propyl sulfonyl, n-hexyl sulfonyl, Cyclopentylsulfonyl,
Cyclohexylsulfonyl, suberyl sulfonyl, cyclooctyl sulfonyl, n-heptyl sulfonyl, n-octyl sulfonyl, suberyl sulphonyl
Base, cyclooctyl sulfonyl, acrylic sulfonyl, cyclobutenyl sulfonyl, pentenyl sulfonyl, hexenyl sulfonyl, heptenyl sulphur
Acyl group, octenyl sulfonyl, phenyl sulfonyl, 4- Methyl benzenesulfonyl base.
The alkyl that carbon atom number is 1~6, alkyl can be chain-like alkyl, can also be naphthenic base, on the ring of naphthenic base
Hydrogen can be replaced by alkyl.It as the example of alkyl, can specifically enumerate: methyl, ethyl, n-propyl, isopropyl, normal-butyl, different
Butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, cyclopropane, cyclobutane, pentamethylene, hexamethylene.
As a kind of improvement of the application electrolyte, the mass percentage of sulphonyl nitrogen-containing heterocycle compound in the electrolytic solution
For 0.01%-5%.If sulphonyl nitrogen-containing heterocycle compound content is excessive, fine and close and thick passivation can be formed in positive and negative pole surface
Film increases the interface impedance of positive and negative anodes, to deteriorate the cycle performance of battery to a certain extent；Sulphonyl nitrogen-containing heterocycle compound
Content is too small, then is not obviously improved to high-temperature behavior.
The upper limit of the mass percentage range of sulphonyl nitrogen-containing heterocycle compound in the electrolytic solution optionally from 5%, 4.5%,
4%, 3.5%, 3%, 2.5%, 2%, 1%, 0.8%, 0.7%, lower limit optionally from 0.01%, 0.05%, 0.1%, 0.3%,
0.5%, 0.6%.It is further preferred that the mass percentage of sulphonyl nitrogen-containing heterocycle compound in the electrolytic solution is
0.01%-3%.
As a kind of improvement of the application electrolyte, the mass percentage of double sulfimide salts in the electrolytic solution is
0.01%-5%.If double sulfimide salt contents are excessive, it will increase electrolysis fluid viscosity and reduce conductivity；If double sulphonyl are sub-
Amine salt content is too small, does not have positive effect to cathode film formation impedance is reduced.
Specifically, the upper limit of the mass percentage range of double sulfimide salts in the electrolytic solution optionally from 5%, 4.5%,
4%, 3.5%, 3%, 2.5%, 2%, 1%, 0.8%, 0.7%, lower limit optionally from 0.01%, 0.05%, 0.1%, 0.3%,
0.5%, 0.6%.It is further preferred that the mass percentage of double sulfimide salts in the electrolytic solution is 0.1%-3%.
As a kind of improvement of the application electrolyte, the mass percentage of cyclic sulfates in the electrolytic solution is
0.01%-5%.If cyclic sulfates content is excessive, it can be aoxidized in anode under high temperature and produce gas, to deteriorate to a certain extent
Battery performance；If cyclic sulfates content is too small, film forming efficiency is not high, and cycle performance of battery is not improved.
Specifically, the upper limit of the mass percentage range of cyclic sulfates in the electrolytic solution optionally from 5%, 4.5%,
4%, 3.5%, 3%, 2.5%, 2%, 1%, 0.8%, 0.7%, lower limit optionally from 0.01%, 0.05%, 0.1%, 0.3%,
0.5%, 0.6%.It is further preferred that the mass percentage of cyclic sulfates in the electrolytic solution is 0.1%-3%.
As electrolyte used herein, following lithium salts can be suitably enumerated.
(- 1 class of Li salt)
It can suitably enumerate selected from LiPF6、LiBF4、LiAsF6、LiSbF6、LiPF4(CF3)2、LiPF3(C2F5)3、
LiPF3(CF3)3、LiPF3(iso- C3F7)3And LiPF5(iso- C3F7) one of or two kinds or more " lewis acid and LiF's
Complex salt ", wherein it is preferred that LiPF6、LiBF4、LiAsF6, more preferable LiPF6、LiBF4。
(- 2 class of Li salt)
It can suitably enumerate selected from LiN (SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2、(CF2)2(SO2)2NLi
(ring-type), (CF2)3(SO2)2NLi (ring-type) and LiC (SO2CF3)3One of or two kinds or more " imines or methylation lithium
Salt ", wherein it is preferred that LiN (SO2F)2、LiN(SO2CF3)2Or LiN (SO2C2F5)2, more preferable LiN (SO2F)2Or LiN (SO2CF3)2。
(- 3 class of Li salt)
It can suitably enumerate selected from LiSO3F、LiCF3SO3、CH3SO4Li、C2H5SO4Li、C3H7SO4Li, trifluoro ((first
Sulphonyl) oxygroup) one of lithium borate (LiTFMSB) and five fluorine ((methylsulfonyl) oxygroup) lithium phosphate (LiPFMSP) or two kinds with
On " contain S (=O)2The lithium salts of O structure ", wherein more preferable LiSO3F、CH3SO4Li、C2H5SO4Li or LiTFMSB.
(- 4 class of Li salt)
It can suitably enumerate selected from LiPO2F2、Li2PO3F and LiClO4One of or two kinds or more " contain P=
The lithium salts of O or Cl=O structure ", wherein it is preferred that LiPO2F2、Li2PO3F.(- 5 class of Li salt)
It can suitably enumerate and be selected from bis- [oxalate-O, O '] lithium borates (LiBOB), difluoro [oxalate-O, O '] boron
One of bis- [oxalate-O, the O '] lithium phosphates (LiPFO) of sour lithium, difluoro and tetrafluoro [oxalate-O, O '] lithium phosphate or two kinds
Above " using the oxalates ligand as the lithium salts of anion ", wherein more preferable LiBOB, LiPFO.One in them can be mixed
Kind or two kinds or more use.
Wherein, it is preferably selected from LiPF6、LiPO2F2、Li2PO3F、LiBF4、LiSO3F, trifluoro ((methylsulfonyl) oxygroup) boron
Sour lithium (LiTFMSB), LiN (SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2, bis- [oxalate-O, O '] lithium borates
(LiBOB), one of bis- [oxalate-O, the O '] lithium phosphates (LiPFO) of difluoro and tetrafluoro [oxalate-O, O '] lithium phosphate or two
Kind or more, more preferably it is selected from LiPF6、LiBF4、LiSO3F, trifluoro ((methylsulfonyl) oxygroup) lithium borate (LiTFMSB),
LiPO2F2、LiN(SO2CF3)2、LiN(SO2F)2, bis- [oxalate-O, O '] lithium borates (LiBOB) and difluoro it is bis- [oxalate-O,
O '] one of lithium phosphate (LiPFO) or two kinds or more, further preferably LiPF6。
The concentration of lithium salts in the electrolytic solution is 0.5M-2M (M=molL-1), the preferably concentration of lithium salts in the electrolytic solution is
0.8M-1.2M。
In above-mentioned electrolyte, organic solvent is selected from at least one of carbonate products, carboxylate compound, wherein
Carbonate products can be linear carbonate, can also be cyclic carbonate.
It as the example of organic solvent, can enumerate: ethylene carbonate, propene carbonate, butylene, fluoro carbonic acid second
Enester, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- fourth
At least one of lactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl butyrate.
Organic solvent is also selected from methyl acrylate, dimethyl sulfite, diethyl sulfite, acid anhydrides, N- methyl
Pyrrolidones, N-METHYLFORMAMIDE, N- methylacetamide, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, methyl sulfide, tetrahydro
One or more of furans.
The electrolyte of the embodiment of the present application can for example be obtained by following methods: mix above-mentioned organic solvent, thereto
The additive sulphonyl nitrogen-containing heterocycle compound and pair sulfimide salt for adding electrolyte and the application, can also add cyclic annular sulfuric acid
Ester, and can also continue to add cyclic annular sultones, double bond containing cyclic carbonate, fluorine-containing carbonic ester, boracic lithium salts, phosphorous lithium salts
At least one of.
The another object of the application is to provide a kind of battery, including anode pole piece, cathode pole piece, be placed in anode pole piece and
Isolation film and electrolyte between cathode pole piece, wherein electrolyte is the electrolyte that the application first aspect proposes.It needs
Bright, the battery of the embodiment of the present application can be lithium ion battery, sodium-ion battery or Magnesium ion battery.
When the battery of the application is lithium ion battery, contain positive electrode active materials in positive plate.
Further alternative, positive electrode active materials are lithium nickel cobalt manganese ternary material；Wherein, the knot of lithium nickel cobalt manganese ternary material
Structure formula is LiNixCoyMnzO2, 0 < x < 1,0 < y < 1,0 < z < 1, x+y+z=1.
Further alternative, lithium nickel cobalt manganese ternary material is selected from LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、
LiNi0.6Co0.2Mn0.2O2And LiNi0.8Co0.1Mn0.1O2At least one of.
Wherein, further include binder and conductive agent in anode pole piece, will include positive electrode active materials, binder and conduction
The anode sizing agent of agent is coated on plus plate current-collecting body, obtains positive plate after anode sizing agent is dry.Likewise, will include cathode
The negative electrode slurry of active material, binder and conductive agent is coated on negative current collector, obtains cathode after negative electrode slurry is dry
Piece.
Preferably, negative electrode active material is carbon material and/or silicon materials.
In above-mentioned battery, the specific type of diaphragm is not exposed to specific limitation, can be used in existing battery
Any diaphragm material, such as polyethylene, polypropylene, Kynoar and their multilayer complex films, but it is not limited only to these.
Embodiment 1-25
(1) preparation of the positive plate of lithium ion battery
By positive electrode active materials nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2), conductive agent Super-P, bonding agent gather inclined two
Vinyl fluoride (PVDF) 96:2:2 in mass ratio, which is dissolved in being uniformly mixed in solvent N-methyl pyrilidone (NMP), is made anode sizing agent,
Solid content is 75wt.% in anode sizing agent.Anode sizing agent is uniformly coated in current collector aluminum foil later, coating weight is
0.0102g/cm2, it is cold-pressed after then being dried at 85 DEG C, trimming, cut-parts, slitting, is done under 85 DEG C of vacuum conditions later
The positive plate of lithium ion battery is made in dry 4h, soldering polar ear.
(2) preparation of the negative electrode tab of lithium ion battery
Negative electrode active material artificial graphite, conductive agent Super-P, thickener CMC, bonding agent butadiene-styrene rubber (SBR) are pressed
Mass ratio 96.4:1.5:0.5:1.6, which is dissolved in being uniformly mixed in solvent deionized water, is made negative electrode slurry, later that negative electrode slurry is equal
It is even to be coated on the tow sides of copper foil of affluxion body, coating weight 0.0071g/cm2, carried out after then being dried at 85 DEG C cold
Pressure, trimming, cut-parts, slitting, the cathode of lithium ion battery is made in dry 4h, soldering polar ear under 110 DEG C of vacuum conditions later
Piece.
(3) preparation of the electrolyte of lithium ion battery
In the glove box full of argon gas, by ethylene carbonate (EC), methyl ethyl carbonate (EMC) and diethyl carbonate
(DEC) with mass ratio EC:EMC:DEC=20:60:20 mixing, as non-aqueous organic solvent.Six are added into non-aqueous organic solvent
The concentration of lithium fluophosphate, lithium salts is 1.0mol/L, and additive is then added thereto, after mixing, the as described electrolyte.
(4) preparation of lithium ion battery
Using 16 μm of polyethylene films (PE) as isolation film.Positive plate obtained, isolation film, negative electrode tab are folded in order
It is good, it is in isolation film among positive/negative plate, winding obtains naked battery core, and naked battery core is placed in outer packing by soldering polar ear, will be upper
The electrolyte for stating preparation is injected into the battery core after drying, and encapsulation is stood, later with 0.02C constant-current charge to 3.3V, then with
0.1C constant-current charge completes the preparation of lithium ion battery to 3.6V, shaping, volume test.Soft bag lithium ionic cell obtained
Thickness 4.0mm, width 60mm, length 140mm.
In embodiment 1-25, the additive amount of used each additive is as shown in Table 1 and Table 2, wherein in table 1, table 2
In the additive amount of each additive obtained mass percent is calculated based on the gross mass of electrolyte.
Table 1
Note: the substance is not added in "-" expression.
Table 2
Comparative example 1-16
The additive of electrolyte in comparative example 1-16 is as shown in table 3, and the additive amount of each additive is based on electricity in table 3
The gross mass for solving liquid calculates obtained mass percent.
Table 3
Note: the substance is not added in "-" expression.
The battery being prepared in embodiment 1-25 and comparative example 1-16 carries out following tests:
(1) cycle performance of lithium ion battery tests (25 DEG C and 45 DEG C)
By lithium ion battery with 1C constant current charging to 4.3V, then it is with 4.3V constant voltage charging to electric current
Then 0.05C is discharged to 2.8V with 1C constant current, this is a charge and discharge cycles.With the capacity that discharges for the first time for 100%,
Calculate the capacity retention ratio after lithium ion battery recycles 500 times.Lithium ion battery recycle 500 times after capacity retention ratio (%)=
The discharge capacity of 500th circulation/capacity × 100% that discharges for the first time.
Test result is as follows shown in table 4.
(2) the storage gas generation property test of lithium ion battery
At 25 DEG C, 4.3V is first charged to battery with the constant current of 0.5C, further with 4.3V constant voltage charging
It is 0.05C to electric current, then battery is measured in deionized water to drainage the initial volume of battery, be then placed in battery
At 85 DEG C, every storage is taken out afterwards for 24 hours, stands 60min at room temperature, is deposited in 1 after being cooled to room temperature hour with drainage test
When volume after storage, cubical expansivity=(volume/initial volume -1 after storage) × 100%, cubical expansivity reach 30%
Number of days is denoted as the time for being resistant to 85 DEG C of production gas.
Test result is as follows shown in table 4.
(3) the battery capacity test of lithium ion battery
At 25 DEG C, lithium ion battery is discharged to 2.8V with 1C constant current for the first time, stood after ten minutes, with 1C perseverance
Constant-current charge is 0.05C with 4.3V constant voltage charging to electric current to 4.3V, then stands 30 minutes, then uses the constant electricity of 1C
Stream is discharged to 2.8V for the second time, takes secondary discharge capacity as the capacity of lithium ion battery.
Test result is as follows shown in table 4.
The performance test results of 4 lithium ion battery of table
By the test result of table 4, it can be seen that, compared with comparative example 1-11, the application contains sulphonyl nitrogen-containing heterocycle chemical combination simultaneously
The embodiment 1-4 of object and double sulfimide salts, the discharge capacity of lithium ion battery significantly improve, capacity retention ratio after circulation,
High temperature storage gas generation property also significantly improves.
According to the experimental data of embodiment 5-20 it is found that further adding cyclic sulfates, after the capacity of battery, circulation
Capacity retention ratio, high temperature storage gas generation property are further improved.
In embodiment 21 and 22, addition PS and VC can improve high-temperature storage performance, but since it is larger at membrane impedance, meeting
The cycle performance of slight deterioration lithium ion battery.In embodiment 23-25, sulphonyl nitrogen-containing heterocycle compound, double sulfimide salts
It is combined with cyclic sulfates, further adds FEC, LiBF4And difluorophosphate, the capacity after the capacity of battery, circulation are kept
Rate, high temperature storage gas generation property are further improved.
It is not for limiting claim, any this field skill although the application is disclosed as above with preferred embodiment
Art personnel without departing from the concept of this application, can make several possible variations and modification, therefore the application
Protection scope should be subject to the range that the claim of this application is defined.
Claims (13)
1. a kind of electrolyte, including organic solvent, electrolyte and additive, which is characterized in that contain sulphonyl in the additive
Nitrogen-containing heterocycle compound and double sulfimide salts；
Wherein, the nitrogen-containing heterocycle in the sulphonyl nitrogen-containing heterocycle compound is selected from containing pyrazole ring, pyrrolin ring, imidazole ring, pyrrole
Cough up at least one of alkane ring, piperidine ring, pyridine ring.
2. electrolyte according to claim 1, which is characterized in that the sulphonyl nitrogen-containing heterocycle compound is selected from such as Formulas I extremely
At least one of compound shown in Formula V:
Wherein, R11、R12、R13、R21、R22、R23、R24、R31、R32、R33、R41、R42、R43、R44、R51、R52、R53、R54、R55Respectively solely
On the spot it is selected from hydrogen atom, halogen atom, amino, sulfonic group, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20
Alkenyl, substituted or unsubstituted C6-C26Aryl, substituted or unsubstituted C1-C20Sulfonylalkyl, substituted or unsubstituted C2-C20
Sulphonyl alkenyl, substituted or unsubstituted C6-C26Sulphonyl aryl；
R14、R25、R34、R45、R56It is independently selected from hydrogen atom, halogen atom, amino, sulfonic group, pyrrolinyl, pyrazolyl, pyrrole
Cough up alkyl, imidazole radicals, pyridyl group, piperidyl, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl,
Substituted or unsubstituted C6-C26Aryl, substituted or unsubstituted C1-C20Sulfonylalkyl, substituted or unsubstituted C2-C20Sulphonyl alkene
Base, substituted or unsubstituted C6-C26Sulphonyl aryl；
Substituent group is selected from halogen atom, amino or C1-C4Alkyl.
3. electrolyte according to claim 2, which is characterized in that the sulphonyl nitrogen-containing heterocycle compound is selected from such as Formulas I A extremely
At least one of compound shown in Formula V A:
Wherein, R61、R62、R63、R64、R65、R66、R71、R72、R73、R74、R75、R76、R77、R78、R81、R82、R83、R84、R85、R86、
R91、R92、R93、R94、R95、R96、R97、R98、R101、R102、R103、R104、R105、R106、R107、R108、R109、R110Each independently
Selected from hydrogen atom, halogen atom, amino, sulfonic group, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkene
Base, substituted or unsubstituted C6-C26Aryl, substituted or unsubstituted C1-C20Sulfonylalkyl, substituted or unsubstituted C2-C20Sulphur
Acyl alkenyl, substituted or unsubstituted C6-C26Sulphonyl aryl；
Substituent group is selected from halogen atom, amino or C1-C4Alkyl.
4. electrolyte according to claim 1, which is characterized in that the sulphonyl nitrogen-containing heterocycle compound is selected from following chemical combination
At least one of object:
5. electrolyte according to claim 1, which is characterized in that double sulfimide salts are double sulfimide lithium salts,
Double sulfimide lithium salts are selected from least one of compound as shown in Formula IV:
Wherein, R111、R112It is each independently selected from halogen, substituted or unsubstituted C1-C6Alkyl；Substituent group is selected from halogen.
6. electrolyte according to claim 5, which is characterized in that double sulfimide lithium salts are selected from double fluorine sulfimides
At least one of lithium and double trifluoromethanesulfonimide lithiums.
7. electrolyte according to claim 1, which is characterized in that also contain cyclic sulfates in the additive；
Preferably, the cyclic sulfates are selected from such as at least one of Formula VII compound represented:
Wherein, R122Selected from substituted or unsubstituted C2~C6Alkylidene, substituted or unsubstituted C2~C6Alkenylene；Substituent group choosing
From halogen, C1~C3Alkyl, C2~C4Alkenyl.
8. electrolyte according to claim 7, which is characterized in that the cyclic sulfates are selected from sulfuric acid vinyl ester, sulfuric acid
At least one of acrylic ester and 4- methylsulfuric acid vinyl acetate.
9. electrolyte according to claim 1, which is characterized in that the sulphonyl nitrogen-containing heterocycle compound is in the electrolyte
In mass percentage be 0.01%-5%；Preferably, matter of the sulphonyl nitrogen-containing heterocycle compound in the electrolyte
Amount percentage composition is 0.01%-3%.
10. electrolyte according to claim 1, which is characterized in that double sulfimide salts are in the electrolyte
Mass percentage is 0.01%-5%, it is preferred that mass percentage of the double sulfimide salts in the electrolyte
For 0.1%-3%.
11. electrolyte according to claim 7, which is characterized in that matter of the cyclic sulfates in the electrolyte
Amount percentage composition is 0.01%-5%, it is preferred that mass percentage of the cyclic sulfates in the electrolyte be
0.1%-3%.
12. according to claim 1 to 11 described in any item electrolyte, which is characterized in that also containing ring-type in the additive
At least one of sultones, double bond containing cyclic carbonate, fluorine-containing carbonic ester, boracic lithium salts, phosphorous lithium salts.
13. a kind of battery, including anode pole piece, cathode pole piece, be placed between the anode pole piece and the cathode pole piece every
From film and electrolyte, which is characterized in that the electrolyte is the described in any item electrolyte of claim 1 to 12；
Preferably, positive electrode active materials are contained in the anode pole piece, the positive electrode active materials are selected from lithium nickel cobalt manganese ternary material
Material；The structural formula of the lithium nickel cobalt manganese ternary material is LiNixCoyMnzO2, wherein 0 < x < 1,0 < y < 1,0 < z < 1, x+y+z=1；
It is furthermore preferred that the lithium nickel cobalt manganese ternary material is selected from LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、
LiNi0.6Co0.2Mn0.2O2And LiNi0.8Co0.1Mn0.1O2At least one of.
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