CN107293781A - Electrolyte and lithium ion battery - Google Patents
Electrolyte and lithium ion battery Download PDFInfo
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- CN107293781A CN107293781A CN201610221980.7A CN201610221980A CN107293781A CN 107293781 A CN107293781 A CN 107293781A CN 201610221980 A CN201610221980 A CN 201610221980A CN 107293781 A CN107293781 A CN 107293781A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
The present invention provides a kind of electrolyte and lithium ion battery.The electrolyte includes organic solvent, lithium salts and additive.The additive includes dinitrile compound and fluoroboric ester compounds with ehter bond.After the electrolyte is applied in lithium ion battery, it can effectively reduce DC internal resistance, the power-performance of improvement lithium ion battery and the analysis lithium situation of lithium ion battery, improve the normal temperature and high temperature cyclic performance of lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of electrolyte and lithium ion battery.
Background technology
Lithium ion battery has high-energy-density, high working voltage, long circulation life, environment-friendly, nothing
The advantages of memory effect, it is widely used in portable electric appts.With power battery core, accumulation power supply city
Developing rapidly for field, requires more next to the energy density of lithium ion battery, power-performance, cycle life etc.
It is higher.
Interface can occur between charge and discharge process, positive electrode active materials and negative active core-shell material and electrolyte
Reaction, forms CEI films and SEI films, this stratum boundary facial mask is to lithium ion battery respectively at both positive and negative polarity interface
Chemical property, security performance are most important.Using for example high ni-type ternary material of high performance electrode material
(NCM, NCA), high-voltage anode active material, Si-C composite material are current raising lithium-ion electrics
The effective way of pond energy density, still, all aligns the steady of cathode interface when high performance electrode material is applied
It is qualitative to have harmful effect.Nickel metal ion has under high catalytic activity, high voltage to the oxidation reaction of electrolyte
Electrolyte causes SEI films constantly to rupture restructuring in positive pole interfacial instability, silicon-carbon cathode Volumetric expansion,
These effects all can cause electrolyte constantly to be decomposed at both positive and negative polarity interface, and electrode surface impedance is continuously increased,
Active lithium is constantly consumed, and causes lithium ion battery ultimate failure.
Therefore, develop a property that can be effectively improved both positive and negative polarity interfacial film, improve both positive and negative polarity interfacial film
The electrolyte of stability is the key for solving this problem.
The content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of electrolyte and lithium from
Sub- battery, after the electrolyte is applied in lithium ion battery, can effectively reduce lithium ion battery
DC internal resistance (DCR), the power-performance for improving lithium ion battery and analysis lithium situation, improvement lithium-ion electric
The normal temperature and high temperature cyclic performance in pond.
In order to achieve the above object, in one aspect of the invention, the invention provides a kind of electrolyte, its
Including organic solvent, lithium salts and additive.The additive include with ehter bond dinitrile compound with
And fluoroboric ester compounds.
In another aspect of this invention, the invention provides a kind of lithium ion battery, it is included according to this hair
Electrolyte described in bright one side.
Relative to prior art, beneficial effects of the present invention are：
The present invention is esterified by adding dinitrile compound and fluoroboric with ehter bond in the electrolytic solution
Compound, the DCR that can effectively reduce lithium ion battery, the power-performance for improving lithium ion battery and analysis lithium
Situation, the normal temperature and high temperature cyclic performance for improving lithium ion battery.
Embodiment
The following detailed description of the electrolyte and lithium ion battery according to the present invention.
Illustrate electrolyte according to a first aspect of the present invention first.
Electrolyte according to a first aspect of the present invention includes organic solvent, lithium salts and additive.It is described to add
Plus agent includes dinitrile compound and fluoroboric ester compounds with ehter bond.
With the use of high pressure and high nickel positive active material, it is necessary to improve positive pole using suitable additive
The stability at interface, and the dinitrile compound with ehter bond can effectively stablize positive pole interface, raising lithium from
The high-temperature behavior of sub- battery, but the dinitrile compound and cathode interface with ehter bond are incompatible, in negative pole
Interface generation side effect, the impedance of increase cathode interface, the normal-temperature circulating performance of deterioration lithium ion battery,
Power-performance and analysis lithium.Fluoroboric ester compounds can be prior to organic solvent in negative terminal surface reduction point
Solution, improves the stability of SEI films, and suppresses the further reduction decomposition of organic solvent, while can press down
Fixture has side effect of the dinitrile compound in cathode interface of ehter bond, moreover, fluoroboric ester compounds are
Boryl anion receptor, can be with F-、O2-、O2 2-Deng anion binding, promote the inertia in SEI films
Component LiF, Li2O、Li2O2Deng the dissolving of inorganic salts, improve the composition of SEI films, effectively reduce negative pole
Interface impedance, the DCR for reducing lithium ion battery.Therefore, by dinitrile compound and fluoro with ehter bond
After boric acid ester compound is applied in combination, the dinitrile compound with ehter bond can effectively stablize positive pole circle
Face, meanwhile, fluoroboric ester compounds are reduced prior to the dinitrile compound with ehter bond in cathode interface
Film forming, suppresses side effect of the dinitrile compound with ehter bond in cathode interface, the SEI films resistance formed
Anti- small, stability is good, and structure is not easy to be destroyed in cyclic process, therefore can improve positive and negative simultaneously
Pole interface, reduces both positive and negative polarity interface impedance, improves the stability at both positive and negative polarity interface, reduces lithium ion battery
DCR, improve lithium ion battery power-performance and analysis lithium situation, improve lithium ion battery normal temperature and
High temperature cyclic performance.
In electrolyte described according to a first aspect of the present invention, the dinitrile compound with ehter bond
Structure is as shown in formula I：
Wherein, R1、R2、R3C1~C5 alkylidene or C2~C5 alkenylene are each independently selected from,
M is 1~5 integer.Preferably, R1、R3It is identical.Specifically, the dintrile chemical combination with ehter bond
Thing is selected from 3,5- dioxas-pimelic dinitrile, 1,4- bis- (cyanoethoxy) butane, ethylene glycol two (2- cyano ethyls)
Ether, 1,3- bis- (2- cyanoethoxies) propane, diethylene glycol two (2- cyano ethyls) ether, (2- of triethylene glycol two
Cyano ethyl) ether, 1,5- bis- (2- cyanoethoxies) pentane, one kind in ethylene glycol two (4- cyanobutyls) ether
Or it is several.The dinitrile compound with ehter bond is preferably ethylene glycol two (2- cyano ethyls) ether.
3,5- dioxas-pimelic dinitrile
1,4- bis- (cyanoethoxy) butane
Ethylene glycol two (2- cyano ethyls) ether
1,3- bis- (2- cyanoethoxies) propane
Diethylene glycol two (2- cyano ethyls) ether
Triethylene glycol two (2- cyano ethyls) ether
1,5- bis- (2- cyanoethoxies) pentane
Ethylene glycol two (4- cyanobutyls) ether
In electrolyte described according to a first aspect of the present invention, the structure of the fluoroboric ester compounds
As shown in Formula II：
Wherein, R11、R12、R13It is each independently selected from C1~C20 alkyl or C6~C16 virtue
Base, and R11、R12、R13In at least one on hydrogen atom by fluorine atom part replace or all replace.
Preferably, R11、R12、R13Three has hydrogen atom to be replaced or all replaced by fluorine atom part.For example,
R11、R12、R13In only R11On there is hydrogen atom to be replaced by fluorine atoms, R12、R13It is former in the absence of there is hydrogen
Son is replaced by fluorine atoms.Wherein alkyl can be chain alkyl, or cyclic alkane base.Wherein chain
Shape alkyl includes linear paraffin base and branched alkane alkyl again；In addition, can be with substituted on cyclic alkane base
Base, can also not contain substituent.Preferably, alkyl is selected from linear paraffin base.
In electrolyte described according to a first aspect of the present invention, C1~C20 alkyl be selected from methyl,
Ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, positive penta
Base, isopentyl, neopentyl, cyclopenta, n-hexyl, isohesyl, cyclohexyl, heptyl, suberyl,
Octyl group, cyclooctyl, nonyl, decyl, hendecane alkyl, dodecane alkyl, tridecane alkyl, 14
Alkyl, pentadecane alkyl, hexadecane alkyl, heptadecane alkyl, octadecane alkyl, nonadecane alkyl
Or the hydrogen atom on eicosane alkyl, and above-mentioned alkyl is replaced or all replaced by fluorine atom part.
C6~C16 aryl be selected from phenyl, benzyl, xenyl, p-methylphenyl, o-tolyl, a tolyl,
To ethylbenzene, an ethylbenzene, adjacent ethylbenzene, 3,5- xylyls, 2,6- 3,5-dimethylphenyls, 3,5- diethyls
Base phenyl, 2,6- diethyl phenyls, 3,5- diisopropylbenzyls, 2,6- diisopropylbenzyls, the n-proplbenzene bases of 3,5- bis-,
The n-proplbenzene bases of 2,6- bis-, the n-butyl benzene bases of 3,5- bis-, the n-butyl benzene bases of 2,6- bis-, the isobutylphenyls of 3,5- bis-, 2,6- bis-
Isobutylphenyl, the 2-methyl-2-phenylpropane bases of 3,5- bis-, the 2-methyl-2-phenylpropane bases of 2,6- bis-, trityl, 1- naphthyls or 2- naphthyls,
And the hydrogen atom on above-mentioned aryl is replaced or all replaced by fluorine atom part.
In electrolyte described according to a first aspect of the present invention, it is preferable that R11、R12、R13It is identical.
In electrolyte described according to a first aspect of the present invention, the fluoroboric ester compounds are selected from three
(2,2,2- trifluoroethyls) borate (TTFEB), three (fluoropropyls of 2,2,3,3- tetra-) borates (TTFPB),
One or more in three (hexafluoro isopropyl) borates (THFPB).
In electrolyte described according to a first aspect of the present invention, the dinitrile compound with ehter bond exists
Weight/mass percentage composition in electrolyte is 0.1%~3%.When the dinitrile compound with ehter bond in the electrolytic solution
Weight/mass percentage composition be less than 0.1% when, its positive electrode surface generate Low ESR passivating film reaction it is inadequate
Fully, improvement result is not obvious；When the quality percentage of the dinitrile compound with ehter bond in the electrolytic solution contains
When amount is higher than 3%, it thickeies in negative terminal surface film forming, impedance increase, is unfavorable for lithium ion battery on the contrary
Cycle performance.
In electrolyte described according to a first aspect of the present invention, the fluoroboric ester compounds are in electrolysis
Weight/mass percentage composition in liquid is 0.01%~5%.When the quality of fluoroboric ester compounds in the electrolytic solution
When percentage composition is less than 0.01%, modification of the fluoroboric ester compounds to negative pole SEI films be not obvious, no
Interface impedance and DCR can be effectively reduced, power-performance, cycle performance are not obviously improved；Work as fluoro
When the weight/mass percentage composition of boric acid ester compound in the electrolytic solution is higher than 5%, fluoroboric ester compounds meeting
Promote the decomposition of lithium salts, the PF of generation5The polymerisation of meeting catalytic electrolysis liquid, causes lithium ion battery
Cycle performance is deteriorated.
In electrolyte described according to a first aspect of the present invention, the specific species of the organic solvent can root
Selected according to actual demand, particularly, from non-aqueous organic solvent.The non-aqueous organic solvent can be with
For any kind, it can be selected according to the actual requirements.The non-aqueous organic solvent may include any kind
Carbonic ester, carboxylate, carbonic ester may include cyclic carbonate or linear carbonate.Described non-aqueous have
Machine solvent may also include the halogenated compound of carbonic ester.Specifically, the non-aqueous organic solvent is selected from carbonic acid
Vinyl acetate, propene carbonate, butylene, fluorinated ethylene carbonate, methyl ethyl carbonate, carbonic acid two
Methyl esters, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- butyrolactone,
One kind in methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate, ethyl butyrate
Or it is several.
In electrolyte described according to a first aspect of the present invention, the lithium salts is selected from lithium hexafluoro phosphate, double
Trifluoromethanesulfonimide lithium, lithium perchlorate, hexafluoroarsenate lithium, di-oxalate lithium borate, fluoroform sulphur
One or more in sour lithium.The lithium salts is preferably lithium hexafluoro phosphate.
In electrolyte described according to a first aspect of the present invention, the concentration of the lithium salts is
0.5M~1.5M, the concentration of the lithium salts is preferably 0.8M~1.2M.
Secondly lithium ion battery according to a second aspect of the present invention is illustrated, it is included according to first party of the present invention
Electrolyte described in face.
In lithium ion battery described according to a second aspect of the present invention, the lithium ion battery includes：Just
Pole collector and the positive pole diaphragm being coated on plus plate current-collecting body, negative current collector and it is coated on negative pole currect collecting
Cathode membrane, barrier film and above-mentioned electrolyte on body.The positive pole diaphragm include positive electrode active materials,
Binding agent and conductive agent.The cathode membrane includes negative active core-shell material, binding agent and conductive agent.
In lithium ion battery described according to a second aspect of the present invention, the positive electrode active materials may be selected from
Cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), the LiFePO4 (LiFePO of olivine-type4), olive
The LiMPO of stone-type4, spinel-type LiMn2O4, tertiary cathode material LiNixAyB(1-x-y)O2And
Li1-x’(A’y’B’z’C1-y’-z’)O2In one or more.Wherein, M is selected from Co, Ni, Fe, Mn, V
In one or more；A, B are each independently selected from one kind in Co, Al, Mn, and A and B
Differ；0<x<1,0<y<1 and x+y<1；0≤x’<1,0≤y '<1,0≤z '<1 and y '+z '<1；A’、
B ', C are each independently selected from the one or more in Co, Ni, Fe, Mn, and A ', B ', C are not
It is identical.
In lithium ion battery described according to a second aspect of the present invention, the negative active core-shell material can be selected
From lithium metal.The negative active core-shell material can also be selected from relative to Li/Li+The electrode potential of equilibrium potential
The material of lithium can be embedded in during ＜ 2V.Specifically, the negative active core-shell material is selected from native graphite, people
Make the micro- carbon ball of graphite, interphase (referred to as MCMB), hard carbon, soft carbon, silicon, silico-carbo compound,
Li-Sn alloys, Li-Sn-O alloys, Sn, SnO, SnO2, spinel structure lithiumation TiO2-Li4Ti5O12、
One or more in Li-Al alloys.
Technical scheme is further described with reference to embodiment, but is not limited to
This, it is every technical solution of the present invention to be modified or equivalent substitution, without departing from the technology of the present invention side
The spirit and scope of case, all should cover in protection scope of the present invention.
In following embodiments, comparative example, reagent, material and the instrument used be not such as special
Explanation, it is commercially available or synthesis obtain.
(1) preparation of electrolyte
By ethylene carbonate (EC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) with
Mass ratio EC:EMC:DEC=30:50:20 mixing, as non-aqueous organic solvent, to non-aqueous organic solvent
Middle addition additive, after being well mixed, lithium salts is added into non-aqueous organic solvent, the concentration of lithium salts is
1.1mol/L, as described electrolyte.
In embodiment 1-18 and comparative example 1-6, each used additive and its addition such as table 1
It is shown, wherein, the addition of each additive is obtained by the gross mass based on electrolyte is calculated in table 1
The mass percent arrived.
The parameter of the embodiment 1-18 of table 1 and comparative example 1-6 electrolyte
Note："-" is represented without any material.
(2) preparation of positive plate：
By positive electrode active materials LiNi0.8Co0.15Al0.05O2, conductive agent Super P, binding agent gather inclined difluoro
Ethene (PVDF) mixes in 1-METHYLPYRROLIDONE (NMP) and anode sizing agent is made.Anode sizing agent
Middle solids content is LiNi in 77wt%, solid constituent0.8Co0.15Al0.05O2, Super P and PVDF
Mass ratio is 97:1.4:1.6.Anode sizing agent is coated in current collector aluminum foil and dried at 85 DEG C laggard
Row cold pressing, then carries out after trimming, cut-parts, slitting, 4h is dried under 85 DEG C of vacuum condition, makes
Into positive plate.
(3) preparation of negative plate：
The graphite of negative active core-shell material and conductive agent Super P, thickener CMC, bonding agent fourth will be used as
Benzene rubber (SBR) is well mixed in deionized water, and cathode size is made.Solid contains in cathode size
Measure as 54wt%, graphite, Super P, CMC and SBR mass ratio are in solid constituent
96.4:1.5:0.5:1.6.Cathode size is coated on copper foil of affluxion body and dried at 85 DEG C, Ran Houjin
After row trimming, cut-parts, slitting, 12h is dried under 120 DEG C of vacuum conditions, negative plate is made.
(4) preparation of lithium ion battery：
Barrier film is used as using 16 μm of polyethylene films (PE).By obtained positive plate, barrier film,
Negative plate is folded in order, barrier film is in the middle of positive/negative plate, and winding obtains naked battery core, welds pole
Ear, naked battery core is placed in outer packing, and the electrolyte of above-mentioned preparation is injected into dried battery core,
Encapsulation, stand, chemical conversion (0.02C constant-current charges to 3.3V, then with 0.1C constant-current charges to 3.6V),
Shaping, volume test etc., complete lithium ion battery preparation (the thickness 4.0mm of soft bag lithium ionic cell,
Width 60mm, length 140mm).
Next the test process of lithium ion battery is illustrated.
(1) the cycle performance test of lithium ion battery
By lithium ion battery with 1C constant-current charges to 4.2V, then using 4.2V constant-voltage charges to electric current as
0.05C, then with 1C constant-current discharges to 2.8V, this is a charge and discharge cycles.With the appearance discharged first
Measure as 100%, calculate the capability retention after lithium ion battery is circulated 500 times.Lithium ion battery is circulated
Capability retention (%) after 500 times=discharge capacity of the 500th circulation/capacity discharged first
× 100%.Test is carried out at 25 DEG C and 45 DEG C respectively.
(2) the analysis lithium situation test of lithium ion battery
By lithium ion battery at -10 DEG C with 0.5C constant-current charges to 4.2V, then filled with 4.2V constant pressures
Electricity to electric current is 0.05C, then with 1C constant-current discharges to 2.8V, and this is a charge and discharge cycles.Follow
By lithium ion battery with 0.5C constant-current charges to 4.2V after ring 3 times.Lithium ion battery is taken apart in drying shed,
Observe the analysis lithium situation of negative terminal surface.
(3) DCR is tested at 25 DEG C of lithium ion battery
By lithium ion battery at 25 DEG C with 1C constant-current charges to 4.2V, then with 4.2V constant-voltage charges
It is 0.05C to electric current, then with 1C constant-current discharges 30min (regulation to 50%SOC), electric discharge
Preceding voltage, is designated as V0, then with 4C constant-current discharge 30s, the voltage after electric discharge is designated as V1。
DCR=(V of 25 DEG C of lithium ion batteries in 50%SOC1-V0)/4C。
(4) DCR is tested at -25 DEG C of lithium ion battery
By lithium ion battery at 25 DEG C with 1C constant-current charges to 4.2V, then with 4.2V constant-voltage charges
It is 0.05C to electric current, then with 1C constant-current discharges 30min (regulation to 50%SOC), adjusts temperature
To -25 DEG C, the voltage before electric discharge is designated as V0, then with 0.36C constant-current discharge 30s, test is put
Voltage after electricity, is designated as V1, then at -25 DEG C lithium ion battery in 50%SOC
DCR=(V1-V0)/0.36C。
The cycle performance test result of the embodiment 1-18 of table 2 and comparative example 1-6 lithium ion battery
| Battery is numbered | 25 DEG C circulation 500 times after appearance | 45 DEG C circulation 500 times after capacity |
| Embodiment 1 | 89.5% | 86.9% |
| Embodiment 2 | 93.6% | 87.2% |
| Embodiment 3 | 92.4% | 87.5% |
| Embodiment 4 | 91.5% | 86.5% |
| Embodiment 5 | 92.5% | 81.5% |
| Embodiment 6 | 93.1% | 86.5% |
| Embodiment 7 | 89.3% | 87.4% |
| Embodiment 8 | 92.5% | 85.4% |
| Embodiment 9 | 93.5% | 87.3% |
| Embodiment 10 | 92.1% | 86.2% |
| Embodiment 11 | 92.7% | 86.4% |
| Embodiment 12 | 92.9% | 86.8% |
| Embodiment 13 | 93.7% | 87.5% |
| Embodiment 14 | 92.9% | 87.4% |
| Embodiment 15 | 90.3% | 84.4% |
| Embodiment 16 | 93.3% | 87.7% |
| Embodiment 17 | 91.5% | 85.1% |
| Embodiment 18 | 92.2% | 85.9% |
| Comparative example 1 | 80.3% | 63.5% |
| Comparative example 2 | 89.8% | 66.5% |
| Comparative example 3 | 81.5% | 83.5% |
| Comparative example 4 | 75.5% | 82.7% |
| Comparative example 5 | 78.6% | 61.2% |
| Comparative example 6 | 67.5% | 55.4% |
The analysis lithium test of the lithium ion battery of table 3 and DCR test results
By table 2, table 3 test result it is known that being tested with comparative example 1-6 after obtained circulation
Capability retention, DCR are compared with analysis lithium situation, and embodiment 1-18 properties are obtained significantly
Lifting.Thus the dinitrile compound with ehter bond is used in combination with fluoroboric ester compounds, Ke Yitong
Shi Gaishan both positive and negative polarities interface, reduction both positive and negative polarity interface impedance, the stability for improving both positive and negative polarity interface, reduction
The DCR of lithium ion battery, the power-performance for improving lithium ion battery and analysis lithium situation, at the same improve lithium from
The normal temperature and high temperature cyclic performance of sub- battery.
Fluoroboric ester compounds are individually added into comparative example 2, because fluoroboric ester compounds can not have
The stable positive pole interface of effect, causes the high temperature cyclic performance of lithium ion battery to be deteriorated.
The dinitrile compound with ehter bond is individually added into comparative example 3, due to the dintrile chemical combination with ehter bond
Thing is incompatible with cathode interface, occurs the impedance that side effect increases cathode interface in cathode interface, deteriorates lithium
Normal-temperature circulating performance, power-performance and the analysis lithium situation of ion battery.
The content mistake of fluoroboric ester compounds and/or the dinitrile compound with ehter bond in comparative example 4-6
It is many, it is unfavorable for the improvement of the performance of lithium ion battery.
Claims (10)
1. a kind of electrolyte, including：
Organic solvent；
Lithium salts；And
Additive；
Characterized in that,
The additive includes：
Dinitrile compound with ehter bond；And
Fluoroboric ester compounds.
2. electrolyte according to claim 1, it is characterised in that two nitrilations with ehter bond
The structure of compound is as shown in formula I：
Wherein, R1、R2、R3C1~C5 alkylidene or C2~C5 alkenylene are each independently selected from,
M is 1~5 integer.
3. electrolyte according to claim 2, it is characterised in that two nitrilations with ehter bond
Compound is selected from 3,5- dioxas-pimelic dinitrile, 1,4- bis- (cyanoethoxy) butane, (the 2- cyano group second of ethylene glycol two
Base) ether, 1,3- bis- (2- cyanoethoxies) propane, diethylene glycol two (2- cyano ethyls) ether, triethylene glycol two
(2- cyano ethyls) ether, tetraethylene glycol two (2- cyano ethyls) ether, 1,4- bis- (2- cyanoethoxies) butane, 1,5-
One or more in two (2- cyanoethoxies) pentanes, ethylene glycol two (4- cyanobutyls) ether, preferably second
Glycol two (2- cyano ethyls) ether.
4. electrolyte according to claim 1, it is characterised in that the fluoroboric ester compounds
Structure as shown in Formula II：
Wherein, R11、R12、R13It is each independently selected from C1~C20 alkyl or C6~C16 virtue
Base, and R11、R12、R13In at least one on hydrogen atom by fluorine atom part replace or all replace,
Preferably, R11、R12、R13Three has hydrogen atom to be replaced or all replaced by fluorine atom part.
5. electrolyte according to claim 4, it is characterised in that
C1~C20 alkyl be selected from methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl,
It is isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, cyclopenta, n-hexyl, different
Hexyl, cyclohexyl, heptyl, suberyl, octyl group, cyclooctyl, nonyl, decyl, hendecane alkyl,
Dodecane alkyl, tridecane alkyl, tetradecane alkyl, pentadecane alkyl, hexadecane alkyl, heptadecane
Alkyl, octadecane alkyl, nonadecane alkyl or eicosane alkyl, and the hydrogen atom on alkyl is former by fluorine
Subdivision replaces or all substitutions；
C6~C16 aryl is selected from phenyl, benzyl, xenyl, p-methylphenyl, o-tolyl, a first
Phenyl, to ethylbenzene, an ethylbenzene, adjacent ethylbenzene, 3,5- xylyls, 2,6- 3,5-dimethylphenyls, 3,5-
Diethyl phenyl, 2,6- diethyl phenyls, 3,5- diisopropylbenzyls, 2,6- diisopropylbenzyls, 3,5- bis- positive third
Phenyl, the n-proplbenzene bases of 2,6- bis-, the n-butyl benzene bases of 3,5- bis-, the n-butyl benzene bases of 2,6- bis-, the isobutylphenyls of 3,5- bis-,
The isobutylphenyls of 2,6- bis-, the 2-methyl-2-phenylpropane bases of 3,5- bis-, the 2-methyl-2-phenylpropane bases of 2,6- bis-, trityl, 1- naphthyls or 2-
Hydrogen atom on naphthyl, and aryl is replaced or all replaced by fluorine atom part.
6. electrolyte according to claim 5, it is characterised in that the fluoroboric ester compounds
Selected from three (2,2,2- trifluoroethyls) borates, three (fluoropropyls of 2,2,3,3- tetra-) borates, three (hexafluoro isopropyls)
One or more in borate.
7. electrolyte according to claim 1, it is characterised in that two nitrilations with ehter bond
The weight/mass percentage composition of compound in the electrolytic solution is 0.1%~3%.
8. electrolyte according to claim 1, it is characterised in that the fluoroboric ester compounds
Weight/mass percentage composition in the electrolytic solution is 0.01%~5%.
9. electrolyte according to claim 1, it is characterised in that the organic solvent is selected from carbonic acid
Vinyl acetate, propene carbonate, butylene, fluorinated ethylene carbonate, methyl ethyl carbonate, carbonic acid two
Methyl esters, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- butyrolactone,
One kind in methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate, ethyl butyrate
Or it is several；The lithium salts is selected from lithium hexafluoro phosphate, double trifluoromethanesulfonimide lithiums, lithium perchlorate, six
One or more in fluorine arsenic acid lithium, di-oxalate lithium borate, trifluoromethayl sulfonic acid lithium, preferably hexafluoro phosphorus
Sour lithium.
10. a kind of lithium ion battery, it is characterised in that comprising according to any one of claim 1-9
Electrolyte.
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