CN107293784A - Electrolyte and lithium ion battery - Google Patents
Electrolyte and lithium ion battery Download PDFInfo
- Publication number
- CN107293784A CN107293784A CN201610223303.9A CN201610223303A CN107293784A CN 107293784 A CN107293784 A CN 107293784A CN 201610223303 A CN201610223303 A CN 201610223303A CN 107293784 A CN107293784 A CN 107293784A
- Authority
- CN
- China
- Prior art keywords
- silane
- electrolyte
- silylation
- base
- carbon number
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of electrolyte and lithium ion battery.The electrolyte includes lithium salts, organic solvent and additive.The additive includes：Silane phosphate compound and/or silane boric acid ester compound；Fluorocarbon surfactant；And anti-overcharge additive.After the electrolyte is applied in lithium ion battery, high-temperature storage performance, high temperature cyclic performance, over-charging and the high rate performance of lithium ion battery can be improved simultaneously.
Description
Technical field
The present invention relates to field of lithium, more particularly to a kind of electrolyte and lithium ion battery.
Background technology
In the information age developed rapidly, to the demands of the electronic products such as mobile phone, notebook, camera by
Year increase.Lithium ion battery as electronic product working power, with energy density is high, memoryless effect
, the features such as operating voltage is high, it just should progressively replace traditional Ni-Cd, MH-Ni battery.However as
The expansion of electronics market demand and power, the development of energy storage device, people want to lithium ion battery
Continuous improvement is asked, exploitation is with high-energy-density and meets the lithium ion battery of fast charging and discharging as when business
It is anxious.At present, effective method is to improve the voltage of electrode material, compacted density and the suitable electricity of selection
Solve liquid.
At present, the wide variety of electrolyte of lithium ion battery include using lithium hexafluoro phosphate as electric conducting lithium salt and with
Cyclic carbonate and the mixture of linear carbonate are organic solvent, however above-mentioned electrolyte still suffer from it is many
Deficiency, particularly under high voltages, the poor-performing of lithium ion battery, such as high temperature cyclic performance, height
Warm storage performance and high rate performance are poor.
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 electrolyte is applied in lithium ion battery, the high temperature of lithium ion battery can be improved simultaneously
Storage performance, high temperature cyclic performance, over-charging and high rate performance.
In order to achieve the above object, in one aspect of the invention, the invention provides a kind of electrolyte, its
Including lithium salts, organic solvent and additive.The additive includes：Silane phosphate compound and/
Or silane boric acid ester compound；Fluorocarbon surfactant；And anti-overcharge additive.
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：
In the electrolyte of the present invention, silane phosphate compound and/or silane boric acid ester compound not only press down
The excessive film forming of electrolyte processed, reduction cathode interface impedance, can also suppress oxygen of the electrolyte in positive electrode surface
Change reaction.Fluorocarbon surfactant can reduce the surface tension of electrolyte, improve wetting property.Silane
Phosphate compound and/or silane boric acid ester compound, fluorocarbon surfactant and anti-overcharge additive group
High-temperature storage performance, high temperature cyclic performance, the overcharging property of lithium ion battery can be improved simultaneously after closing use
Energy and high rate performance.
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 lithium salts, organic solvent and additive.It is described to add
Plus agent includes：Silane phosphate compound and/or silane boric acid ester compound；Fluorocarbon surfactant；With
And anti-overcharge additive.
In electrolyte described according to a first aspect of the present invention, the silane phosphate compound is selected from down
State the one or more in the compound shown in Formulas I；
One or more of the silane boric acid ester compound in the compound shown in following formula II；
Wherein, R11、R12、R13、R21、R22、R23、R31、R32、R33、R41、R42、R43、
R51、R52、R53、R61、R62、R63Be each independently selected from carbon number be 1~20 alkyl,
Alkylene that alkoxy that carbon number is 1~20, carbon number are 2~20, carbon number are 2~20
Alkynes base, carbon number for 6~20 aryl in one kind, alkyl, alkoxy, alkylene,
Alkynes base, aryl can be replaced by the one or more in F, Cl, Br.
In electrolyte described according to a first aspect of the present invention, it is preferable that R11、R12、R13、R21、
R22、R23、R31、R32、R33、R41、R42、R43、R51、R52、R53、R61、R62、R63Respectively
The alkoxy for being 1~10 from the alkyl, carbon number that are 1~10 independently selected from carbon number, carbon are former
The virtue that alkynes base that alkylene that subnumber is 2~10, carbon number are 2~10, carbon number are 6~20
One kind in base, alkyl, alkoxy, alkylene, alkynes base, aryl can be by F, Cl, Br
One or more substitution.
In electrolyte described according to a first aspect of the present invention, in R11、R12、R13、R21、R22、
R23、R31、R32、R33、R41、R42、R43、R51、R52、R53、R61、R62、R63In, alkane
The specific species of base is not exposed to specific limitation, can be selected according to the actual requirements, for example chain alkane
Alkyl and cyclic alkane base.Wherein chain alkyl includes linear paraffin base and branched alkane alkyl again.
In addition, on cyclic alkane base substituent can not can also be contained with substituted base.In the alkyl,
The preferred lower limit of carbon number can be 1,3,5 in alkyl, and carbon number is preferred in alkyl
Higher limit can be 3,5,6,7,8,10,12,16.
In electrolyte described according to a first aspect of the present invention, it is preferable that R11、R12、R13、R21、
R22、R23、R31、R32、R33、R41、R42、R43、R51、R52、R53、R61、R62、R63Respectively
The cyclic alkane for being 3~8 from the chain alkyl or carbon number that are 1~6 independently selected from carbon number
Base, the ring-type that the chain alkyl or carbon number for being 1~4 still more preferably for carbon number are 5~7
Alkyl.
Specifically, carbon number may be selected from methyl, ethyl, n-propyl, isopropyl for 1~20 alkyl
Base, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, cyclobutyl, n-pentyl, isopentyl,
Tertiary pentyl, newly defend base, cyclopenta, 2,2- dimethyl propyls, 1- ethyl propyls, 1- methyl butyls, 2-
Methyl butyl, n-hexyl, isohesyl, 2- hexyls, 3- hexyls, cyclohexyl, 2- methyl amyls, 3- methyl
Amyl group, 1,1,2- thmethylpropyls, 3,3- dimethylbutyls, n-heptyl, 2- heptyl, 3- heptyl, 2- first
Base hexyl, 3- methylhexyls, 4- methylhexyls, different heptyl, suberyl, n-octyl, cyclooctyl, nonyl
Base, decyl, hendecane alkyl, dodecane alkyl, tridecane alkyl, tetradecane alkyl, pentadecane
In base, hexadecane alkyl, heptadecane alkyl, octadecane alkyl, nonadecane alkyl, eicosane alkyl
It is a kind of.Above-mentioned alkyl can be replaced by the one or more in F, Cl, Br.
In electrolyte described according to a first aspect of the present invention, in R11、R12、R13、R21、R22、
R23、R31、R32、R33、R41、R42、R43、R51、R52、R53、R61、R62、R63In, alcoxyl
The specific species of base is not exposed to specific limitation, can be selected according to the actual requirements, for example chain alkane
Epoxide and cyclic alkoxy.Wherein chain alkoxy includes unbranched alkoxy and branched alkoxy again.
In addition, on cyclic alkoxy substituent can not can also be contained with substituted base.In the alkoxy,
The preferred lower limit of carbon number can be 1,3,5, the preferred higher limit of carbon number can for 3,5,
6、7、8、10、12、16。
In electrolyte described according to a first aspect of the present invention, it is preferable that R11、R12、R13、R21、
R22、R23、R31、R32、R33、R41、R42、R43、R51、R52、R53、R61、R62、R63Respectively
The ring-type alcoxyl for being 3~8 from the chain alkoxy or carbon number that are 1~6 independently selected from carbon number
Base, the ring-type that the chain alkoxy or carbon number for being 1~4 still more preferably for carbon number are 5~7
Alkoxy.
Specifically, the alkoxy that carbon number is 1~20 may be selected from the alkane that above-mentioned carbon number is 1~20
Base is by one kind in the compound of oxo.Preferably, carbon number is selected from methoxy for 1~20 alkoxy
Base, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, isobutyl
One kind in epoxide.Above-mentioned alkoxy can be replaced by the one or more in F, Cl, Br.
In electrolyte described according to a first aspect of the present invention, in R11、R12、R13、R21、R22、
R23、R31、R32、R33、R41、R42、R43、R51、R52、R53、R61、R62、R63In, alkene
Base, the specific species of alkynes base are not particularly limited, and can be selected according to the actual requirements.Alkene
In base in unsaturated bond (i.e. double bond), alkynes base unsaturated bond (i.e. three keys) number and unsaturation
The position of key is not particularly limited, and can be selected according to the actual requirements.Preferably, double bond, three
The number of key can be 1,2,3 or 4.It is double when double bond, the number of three keys are 1
Key, three key mappings are in the end of alkylene, alkynes base, i.e., positioned at alkylene, the remote silicon atom of alkynes base
Position.For example, when carbon number is more than or equal to 3 in alkylene, alkynes base, if double bond, three keys
Number be 1, then double bond, three keys can not be connected with silicon.In alkylene, alkynes base, alkene
Base, the preferred lower limit of the carbon number of alkynes base can be 3,5, alkylene, the carbon atom of alkynes base
Several preferred higher limits can be 3,5,6,7,8,10,12,16.
In electrolyte described according to a first aspect of the present invention, it is preferable that R11、R12、R13、R21、
R22、R23、R31、R32、R33、R41、R42、R43、R51、R52、R53、R61、R62、R63Respectively
The alkynyl for being 2~10 from the alkenyl, carbon number that are 2~10 independently selected from carbon number, it is further excellent
The alkynyl that alkenyl that selection of land is 2~6 selected from carbon number, carbon number are 2~6, still more preferably
The alkynyl that alkenyl that ground is 2~5 selected from carbon number, carbon number are 2~5.Above-mentioned alkylene, alkynes
Alkyl can be replaced by the one or more in F, Cl, Br.
Specifically, carbon number for 2~20 alkylene be selected from vinyl, pi-allyl, isopropenyl,
1- cyclobutenyls, 2- cyclobutenyls, 2- methyl -2- acrylic, 1- methyl -2- acrylic, 2- methylpropenyls,
One kind in pentenyl, 1- hexenyls, 3,3- dimethyl -1- cyclobutenyls, heptenyl, octenyl.It is above-mentioned
Alkylene can be replaced by the one or more in F, Cl, Br.Carbon number is 2~20 alkynes base
Selected from acetenyl, 1- propinyls, 2-propynyl, 1- butynyls, 2- butynyls, 3- butynyls, 3- methyl
- 1- propinyls, 2- methyl -3- propinyls, pentynyl, 1- hexin bases, 3- methyl isophthalic acids-butynyl, 3,3- bis-
One kind in methyl isophthalic acid-butynyl, heptynyl, octynyl.Above-mentioned alkynes base can be by F, Cl, Br
One or more of substitutions.
In electrolyte described according to a first aspect of the present invention, the silane phosphate compound is selected from three
(trimethylsilyl) phosphate, three (triethyl silyl) phosphates, three (three n-propyl silylation) phosphoric acid
Ester, three (tri isopropyl silane base) phosphates, three (three normal-butyl silylation) phosphates, three (triisobutyls
Silylation) phosphate, three (tri-tert silylation) phosphates, three (trimethoxy silane base) phosphates,
Three (triethoxysilicane alkyl) phosphates, three (three positive propoxy silylation) phosphates, three (three isopropoxies
Silylation) phosphate, three (three n-butoxy silane bases) phosphates, three (three sec-butoxy silane bases) phosphoric acid
Ester, three (three tert-butoxy silane bases) phosphates, three (trifluoromethyl silylation) phosphates, three (triethylenes
Base silane base) phosphate, the one or more in three (three acetenyl silylation) phosphates.
In electrolyte described according to a first aspect of the present invention, the silane boric acid ester compound is selected from three
(trimethylsilyl) borate, three (triethyl silyl) borates, three (three n-propyl silylation) boric acid
Ester, three (tri isopropyl silane base) borates, three (three normal-butyl silylation) borates, three (tri-terts
Silylation) borate, three (triisobutyl silylation) borates, three (trimethoxy silane base) borates,
Three (triethoxysilicane alkyl) borates, three (three positive propoxy silylation) borates, three (three isopropoxies
Silylation) borate, three (three n-butoxy silane bases) borates, three (three sec-butoxy silane bases) boric acid
Ester, three (three tert-butoxy silane bases) borates, three (trifluoromethyl silylation) borates, three (triethylenes
Base silane base) borate, the one or more in three (three acetenyl silylation) borates.
In electrolyte described according to a first aspect of the present invention, the fluorocarbon surfactant is selected from following
The one or more in compound shown in formula III；
C2F5(CF2CF2)xCH2CH2O(CH2CH2O)yH formula IIIs
Wherein, x is the integer in 1~30, and y is the integer in 1~30.Preferably, x is in 2~20
Integer；Y is the integer in 2~20.
In electrolyte described according to a first aspect of the present invention, the anti-overcharge additive be selected from biphenyl,
One or more in cyclohexyl benzene,toluene,xylene, fluorobenzene, tert-butyl benzene, tert-amyl benzene.
In electrolyte described according to a first aspect of the present invention, the silane phosphate compound and/or silicon
The content of alkane boric acid ester compound is the 0.5%~10% of the gross weight of the electrolyte.Specifically：Work as electricity
When silane phosphate compound is only included in solution liquid not including silane boric acid ester compound, silane Phosphation
The content of compound is the 0.5~10% of the gross weight of electrolyte；When only including silane acid esterification in electrolyte
When compound does not include silane phosphate compound, the content of silane boric acid ester compound is the gross weight of electrolyte
The 0.5~10% of amount；When in electrolyte simultaneously including silane phosphate compound and silane boric acid ester compound
When, the total content of the two is the 0.5~10% of the gross weight of electrolyte.It has been investigated that, if silane phosphoric acid
The too high levels of ester compounds and/or silane boric acid ester compound, when electrolyte is applied in lithium ion battery
Afterwards, the high temperature cyclic performance and high-temperature storage performance of lithium ion battery can not be significantly improved,
Conversely it can also deteriorate high rate performance.Preferably, the silane phosphate compound and/or silane acid esterification
The content of compound is the 1~5% of the gross weight of the electrolyte.
In electrolyte described according to a first aspect of the present invention, the content of the fluorocarbon surfactant is
The 0.01%~1% of the gross weight of the electrolyte.Preferably, the content of the fluorocarbon surfactant is
The 0.05%~0.1% of the gross weight of the electrolyte.
In electrolyte described according to a first aspect of the present invention, the content of the anti-overcharge additive is institute
State the 0.5%~15% of the gross weight of electrolyte.Preferably, the content of the anti-overcharge additive is described
The 1%~5% of the gross weight of electrolyte.When too high levels, the viscosity of electrolyte can increase, Er Qiehui
Deteriorate high-temperature storage performance.
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 and 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
Ethyl (EC), propylene carbonate (PC), butylene carbonate, pentylene, fluoro carbonic acid
Ethyl, dimethyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, methyl ethyl carbonate, 1,4-
One kind in butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl 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 LiPF6、LiBF4、
LiN(SO2F)2(being abbreviated as LiFSI), LiN (CF3SO2)2(being abbreviated as LiTFSI), LiClO4、LiAsF6、
LiB(C2O4)2(being abbreviated as LiBOB), LiBF2C2O4One kind or several in (being abbreviated as LiDFOB)
Kind.
In electrolyte described according to a first aspect of the present invention, the content of the lithium salts is the electrolyte
Gross weight 6.2%~25%.Preferably, the content of the lithium salts is the gross weight of the electrolyte
6.25%~18.8%.It is further preferred that the content of the lithium salts is the gross weight of the electrolyte
10%~15%.
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.
According to a second aspect of the present invention described lithium ion battery include positive plate, negative plate, barrier film with
And electrolyte.
In lithium ion battery described according to a second aspect of the present invention, the positive plate includes anode collection
Body and the positive-active pulp layer on the plus plate current-collecting body, wherein, the positive-active pulp layer
Including positive electrode active materials.The positive electrode active materials are selected from cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2)、
LiFePO4 (the LiFePO of olivine-type4), the LiMPO of olivine-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, one or more of the M in Co, Ni, Fe, Mn, V；A, B are selected independently of one another
From one kind in Co, Al, Mn, and A and B are differed；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 Co, Ni, Fe, Mn
In one kind, and A ', B ', C differ.
In lithium ion battery described according to a second aspect of the present invention, the negative plate includes negative pole currect collecting
Body and the negative electrode active pulp layer on the negative current collector.The negative electrode active pulp layer includes negative
Pole active material.The negative active core-shell material can be selected from lithium metal.The negative active core-shell material can also
Selected from relative to Li/Li+The material of lithium can be embedded in during the electrode potential ＜ 2V of equilibrium potential.Specifically,
The negative active core-shell material be selected from native graphite, Delanium, the micro- carbon ball of interphase (referred to as MCMB),
Hard carbon, soft carbon, silicon, silico-carbo compound, Li-Sn alloys, Li-Sn-O alloys, Sn, SnO, SnO2、
The lithiumation TiO of spinel structure2-Li4Ti5O12, one or more in Li-Al alloys.
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments are merely to illustrate
The application rather than limitation scope of the present application.
In the following embodiments, reagent, material and the instrument used as without special explanation,
It is commercially available.
For convenience of description, the additive used in the following embodiments writes a Chinese character in simplified form as follows：
A1：Three (trimethylsilyl) phosphates
A2：Three (trimethylsilyl) borates
B1：C2F5(CF2CF2)2CH2CH2O(CH2CH2O)2H
B2：C2F5(CF2CF2)4CH2CH2O(CH2CH2O)10H
C1：Biphenyl；
C2：Tert-butyl benzene
(1) prepared by positive plate
By positive electrode active materials cobalt acid lithium (LiCoO2), binding agent (Kynoar), conductive agent (second
Acetylene black) compare 98 according to weight:1:1 is mixed, and is added 1-METHYLPYRROLIDONE (NMP), is stirred in vacuum
The lower stirring of machine effect is mixed to system into transparent and homogeneous shape, anode sizing agent is obtained；Anode sizing agent is uniformly coated
In thickness on 12 μm of aluminium foil；Aluminium foil is transferred to 120 DEG C of oven drying 1h after room temperature is dried,
Then positive plate is obtained by cold pressing, cutting.
(2) prepared by negative plate
By negative active core-shell material graphite, thickener sodium carboxymethylcellulose (CMC), binding agent butylbenzene rubber
Glue compares 98 according to weight:1:1 is mixed, and adds deionized water, is born under de-airing mixer effect
Pole slurry；Cathode size is coated uniformly on the copper foil that thickness is 8 μm；By copper foil after room temperature is dried
120 DEG C of oven drying 1h are transferred to, then negative plate are obtained by cold pressing, cutting.
(3) prepared by electrolyte
Organic solvent is to contain ethylene carbonate (EC), propylene carbonate (PC) and diethyl carbonate
(DEC) mixed liquor, wherein, EC, PC and DEC volume ratio are 1:1:1.In water content<10ppm
Argon gas atmosphere glove box in, will fully dry lithium salts LiPF6It is dissolved in organic solvent, Ran Hou
Additive is added in organic solvent, is well mixed, electrolyte is obtained.Wherein, LiPF6Content for electricity
Solve the 12.5% of the gross weight of liquid.The specific species and content such as table of used additive in electrolyte
Shown in 1.In table 1, the content of additive calculates obtained weight hundred for the gross weight based on electrolyte
Fraction.
(4) preparation of barrier film
From the polypropylene barrier film of 16 μ m-thicks (model A273 is provided by Celgard companies).
(5) preparation of lithium ion battery
Positive plate, barrier film, negative plate are folded in order, barrier film is between positive and negative plate
Play a part of isolation, then winding obtains naked battery core；Naked battery core is placed in outer packing paper tinsel, will be above-mentioned
The electrolyte prepared is injected into dried naked battery core, by Vacuum Package, standing, chemical conversion, whole
The processes such as shape, obtain lithium ion battery.
The embodiment 1-10 of table 1 and comparative example 1-7 additive and content
Note："-" represents not add.
Next the performance test of explanation lithium ion battery.
Test one, the high temperature cyclic performance test of lithium ion battery
At 45 DEG C, by lithium ion battery with 1C constant-current charges to 4.45V, then constant-voltage charge is to electricity
Flow for 0.05C, then with 1C constant-current discharges to 3.0V, now to circulate first, enter according to above-mentioned condition
300 cycle charge-discharges of row, calculate the capability retention after lithium ion battery is circulated 300 times.
Capability retention=(lithium ion battery circulation 300 times after the circulation 300 times of 45 DEG C of lithium ion battery
Discharge capacity after discharge capacity afterwards/circulation first) × 100%.
Test two, the high-temperature storage performance test of lithium ion battery
At 60 DEG C, by lithium ion battery with 0.5C constant-current charges to 4.45V, then constant-voltage charge is to electric current
For 0.05C, now test the thickness of lithium ion battery and be designated as h0；Lithium ion battery is put into 60 afterwards
DEG C insulating box, storage takes out after 30 days, and test now the thickness of lithium ion battery and is designated as h1。
Thickness swelling=[(h after the storage 30 days of 60 DEG C of lithium ion battery1-h0)/h0] × 100%.
Test three, the high rate performance test of lithium ion battery
At 25 DEG C, by lithium ion battery with 1C (nominal capacity) constant-current charge to 4.45V, then with perseverance
Pressure 4.45V charge to electric current≤0.05C, shelve after 5min, using 0.2C constant-current discharges to by voltage as
3V, is now designated as D by actual discharge capacity0；Then with 1C constant-current charges to 4.45V, then with constant pressure
4.45V charges to electric current≤0.05C, is finally discharged to using 5C by voltage as 3V, the reality of record now
Border discharge capacity D1。
The high rate performance of lithium ion battery=[(D1-D0)/D0] × 100%.
Test four, the over-charging test of lithium ion battery
At 25 DEG C, by lithium ion battery with 3C (nominal capacity) constant-current charges to 7.5V, then constant pressure
Whether 5h, 10 lithium ion batteries of every group of test are on fire on lithium ion battery.
The embodiment 1-10 of table 2 and comparative example 1-7 the performance test results
From the correlated results in table 2 it is known that only adding silane phosphate compound in comparative example 2,
The high temperature cyclic performance and high-temperature storage performance of lithium ion battery are obviously improved, but forthright again
Can be poor；Fluorocarbon surfactant is only added in comparative example 3, the high rate performance of lithium ion battery is obtained
Very big improvement, but high-temperature storage performance and high temperature cyclic performance deteriorate.Only added in comparative example 4 anti-
Overcharging additive, can improve over-charging, but deteriorate high rate performance, high temperature cyclic performance and high temperature
Storage performance.
Comparative example 5 only adds silane phosphate compound and fluorocarbon surfactant, can improve high gentle
Performance is stored up, but high rate performance and high temperature cyclic performance are undesirable, can not meet over-charging.Contrast
Example 6 only adds fluorocarbon surfactant and anti-overcharge additive, although high rate performance and over-charging are obtained
Improve, but be due to anti-overcharge additive at high temperature can on positive pole oxidation Decomposition so as to deteriorating high temperature
Cycle performance and high-temperature storage performance.Comparative example 7 only adds silane phosphate compound and anti-overcharge addition
Agent, film forming of the silane phosphate on positive pole can stop that oxidation of the anti-overcharge additive on positive pole is anti-
Should, so that improve high temperature cyclic performance, high-temperature storage performance and over-charging, but its both positive and negative polarity hinders
Anti- increase is so as to cause dynamic performance (i.e. high rate performance) poor.
To sum up, because the film forming of silane phosphate compound can stop anti-overcharge additive on positive pole
Side reaction, improves high temperature cyclic performance and high-temperature storage performance, and fluorocarbon surfactant can reduce electricity
The surface tension of liquid is solved, improves deterioration of the silane phosphate compound to high rate performance, on the basis of the two
It is upper to add after anti-overcharge additive, in addition to over-charging is improved, can also further improve high rate performance,
High temperature cyclic performance, while not bringing the obvious deterioration of high-temperature storage performance.Therefore three kinds are added simultaneously to add
Plus agent, high rate performance, high temperature cyclic performance, high-temperature storage performance and the over-charging of lithium ion battery
Improved.
Claims (10)
1. a kind of electrolyte, including lithium salts, organic solvent and additive, it is characterised in that described to add
Plus agent includes：
Silane phosphate compound and/or silane boric acid ester compound；
Fluorocarbon surfactant；And
Anti-overcharge additive.
2. electrolyte according to claim 1, it is characterised in that
One or more of the silane phosphate compound in the compound shown in following formula I；
One or more of the silane boric acid ester compound in the compound shown in following formula II；
Wherein,
R11、R12、R13、R21、R22、R23、R31、R32、R33、R41、R42、R43、R51、R52、
R53、R61、R62、R63Being each independently selected from alkyl, carbon number that carbon number is 1~20 is
Alkynes base that alkylene that 1~20 alkoxy, carbon number are 2~20, carbon number are 2~20, carbon
Atomicity is one kind in 6~20 aryl, alkyl, alkoxy, alkylene, alkynes base, aryl
It can be replaced by the one or more in F, Cl, Br.
3. electrolyte according to claim 2, it is characterised in that R11、R12、R13、R21、R22、
R23、R31、R32、R33、R41、R42、R43、R51、R52、R53、R61、R62、R63It is each independent
Ground is selected from the alkyl that carbon number is 1~10, the alkoxy that carbon number is 1~10, carbon number
One in the aryl that alkynes base that 2~10 alkylene, carbon number are 2~10, carbon number are 6~20
Kind, alkyl, alkoxy, alkylene, alkynes base, aryl can be by one kind in F, Cl, Br or several
Plant substitution.
4. electrolyte according to claim 3, it is characterised in that
The silane phosphate compound is selected from three (trimethylsilyl) phosphates, three (triethyl silyls)
Phosphate, three (three n-propyl silylation) phosphates, three (tri isopropyl silane base) phosphates, three (three just
Butylsilane base) phosphate, three (triisobutyl silylation) phosphates, three (tri-tert silylation) phosphoric acid
Ester, three (trimethoxy silane base) phosphates, three (triethoxysilicane alkyl) phosphates, three (three positive third oxygen
Base silane base) phosphate, three (three isopropoxy silylation) phosphates, three (three n-butoxy silane bases) phosphorus
Acid esters, three (three sec-butoxy silane bases) phosphates, three (three tert-butoxy silane bases) phosphates, three (three
Methyl fluoride silylation) phosphate, three (trivinyl silylation) phosphates, three (three acetenyl silylation) phosphorus
One or more in acid esters；
The silane boric acid ester compound is selected from three (trimethylsilyl) borates, three (triethyl silyls)
Borate, three (three n-propyl silylation) borates, three (tri isopropyl silane base) borates, three (three just
Butylsilane base) borate, three (tri-tert silylation) borates, three (triisobutyl silylation) boric acid
Ester, three (trimethoxy silane base) borates, three (triethoxysilicane alkyl) borates, three (three positive third oxygen
Base silane base) borate, three (three isopropoxy silylation) borates, three (three n-butoxy silane bases) boron
Acid esters, three (three sec-butoxy silane bases) borates, three (three tert-butoxy silane bases) borates, three (three
Methyl fluoride silylation) borate, three (trivinyl silylation) borates, three (three acetenyl silylation) boron
One or more in acid esters.
5. electrolyte according to claim 1, it is characterised in that the fluorocarbon surfactant choosing
One or more from the compound shown in following formula III；
C2F5(CF2CF2)xCH2CH2O(CH2CH2O)yH formula IIIs
Wherein, x is the integer in the integer in 1~30, preferably 2~20；Y is the integer in 1~30,
Integer in preferably 2~20.
6. electrolyte according to claim 1, it is characterised in that the anti-overcharge additive is selected from
Biphenyl, cyclohexyl benzene,toluene,xylene, fluorobenzene, tert-butyl benzene, one kind in tert-amyl benzene or several
Kind.
7. electrolyte according to claim 1, it is characterised in that the silane phosphate compound
And/or the content of silane boric acid ester compound is the 0.5%~10% of the gross weight of the electrolyte, is preferably
1%~5%.
8. electrolyte according to claim 1, it is characterised in that the fluorocarbon surfactant
Content is the 0.01%~1% of the gross weight of the electrolyte, preferably 0.05%~0.1%.
9. electrolyte according to claim 1, it is characterised in that the anti-overcharge additive contains
Measure 0.5%~15% of the gross weight for the electrolyte, preferably 1%~5%.
10. a kind of lithium ion battery, it is characterised in that including according to any one of claim 1-9
Electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610223303.9A CN107293784A (en) | 2016-04-12 | 2016-04-12 | Electrolyte and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610223303.9A CN107293784A (en) | 2016-04-12 | 2016-04-12 | Electrolyte and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107293784A true CN107293784A (en) | 2017-10-24 |
Family
ID=60095645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610223303.9A Pending CN107293784A (en) | 2016-04-12 | 2016-04-12 | Electrolyte and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107293784A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108365264A (en) * | 2018-01-17 | 2018-08-03 | 湖南博信新能源科技有限公司 | A kind of lithium battery tertiary electrolyte |
| CN108511802A (en) * | 2018-06-04 | 2018-09-07 | 东莞市杉杉电池材料有限公司 | A kind of lithium-ion-power cell Overcharge prevention electrolyte and lithium-ion-power cell |
| US20190036161A1 (en) * | 2017-07-27 | 2019-01-31 | Contemporary Amperex Technology Co., Limited | Electrolyte and electrochemical energy storage device |
| CN110247115A (en) * | 2019-06-19 | 2019-09-17 | 宁德新能源科技有限公司 | Electrolyte, electrochemical appliance and electronic device comprising the electrolyte |
| CN110611121A (en) * | 2019-09-10 | 2019-12-24 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery containing same |
| CN110854435A (en) * | 2019-11-22 | 2020-02-28 | 湖南新敏雅新能源科技有限公司 | Lithium battery electrolyte and lithium battery |
| CN111987359A (en) * | 2019-11-27 | 2020-11-24 | 中节能万润股份有限公司 | Novel lithium ion battery electrolyte additive and application thereof |
| CN112531212A (en) * | 2020-12-09 | 2021-03-19 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte with high-temperature characteristic and low impedance, application thereof and lithium ion battery |
| WO2022141010A1 (en) | 2020-12-29 | 2022-07-07 | 远景动力技术(江苏)有限公司 | Sulfate compound, nonaqueous electrolyte containing same, and power storage device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101771167A (en) * | 2010-02-05 | 2010-07-07 | 九江天赐高新材料有限公司 | High-capacity lithium-ion electrolyte, battery and preparation method of battery |
| CN101777668A (en) * | 2010-02-05 | 2010-07-14 | 九江天赐高新材料有限公司 | Electrolyte for lithium manganese battery |
| CN105047995A (en) * | 2015-09-22 | 2015-11-11 | 宁德新能源科技有限公司 | Electrolyte, lithium ion battery comprising same and preparation method of lithium ion battery |
| CN105261788A (en) * | 2015-09-22 | 2016-01-20 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery including same |
| CN105355968A (en) * | 2015-11-24 | 2016-02-24 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery inducing same |
-
2016
- 2016-04-12 CN CN201610223303.9A patent/CN107293784A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101771167A (en) * | 2010-02-05 | 2010-07-07 | 九江天赐高新材料有限公司 | High-capacity lithium-ion electrolyte, battery and preparation method of battery |
| CN101777668A (en) * | 2010-02-05 | 2010-07-14 | 九江天赐高新材料有限公司 | Electrolyte for lithium manganese battery |
| CN105047995A (en) * | 2015-09-22 | 2015-11-11 | 宁德新能源科技有限公司 | Electrolyte, lithium ion battery comprising same and preparation method of lithium ion battery |
| CN105261788A (en) * | 2015-09-22 | 2016-01-20 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery including same |
| CN105355968A (en) * | 2015-11-24 | 2016-02-24 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery inducing same |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10763546B2 (en) * | 2017-07-27 | 2020-09-01 | Contemporary Amperex Technology Co., Limited | Electrolyte and electrochemical energy storage device |
| US20190036161A1 (en) * | 2017-07-27 | 2019-01-31 | Contemporary Amperex Technology Co., Limited | Electrolyte and electrochemical energy storage device |
| CN108365264A (en) * | 2018-01-17 | 2018-08-03 | 湖南博信新能源科技有限公司 | A kind of lithium battery tertiary electrolyte |
| CN108511802A (en) * | 2018-06-04 | 2018-09-07 | 东莞市杉杉电池材料有限公司 | A kind of lithium-ion-power cell Overcharge prevention electrolyte and lithium-ion-power cell |
| CN110247115A (en) * | 2019-06-19 | 2019-09-17 | 宁德新能源科技有限公司 | Electrolyte, electrochemical appliance and electronic device comprising the electrolyte |
| CN110611121A (en) * | 2019-09-10 | 2019-12-24 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery containing same |
| WO2021047500A1 (en) * | 2019-09-10 | 2021-03-18 | 宁德时代新能源科技股份有限公司 | Electrolyte, and lithium ion battery, battery module, battery pack and device comprising same |
| CN110611121B (en) * | 2019-09-10 | 2021-06-22 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery containing same |
| US11942600B2 (en) | 2019-09-10 | 2024-03-26 | Contemporary Amperex Technology Co., Limited | Electrolyte, lithium-ion battery comprising electrolyte, battery module, battery pack and device |
| CN110854435A (en) * | 2019-11-22 | 2020-02-28 | 湖南新敏雅新能源科技有限公司 | Lithium battery electrolyte and lithium battery |
| CN111987359A (en) * | 2019-11-27 | 2020-11-24 | 中节能万润股份有限公司 | Novel lithium ion battery electrolyte additive and application thereof |
| CN112531212A (en) * | 2020-12-09 | 2021-03-19 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte with high-temperature characteristic and low impedance, application thereof and lithium ion battery |
| WO2022141010A1 (en) | 2020-12-29 | 2022-07-07 | 远景动力技术(江苏)有限公司 | Sulfate compound, nonaqueous electrolyte containing same, and power storage device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105261788B (en) | Electrolyte and the lithium ion battery including the electrolyte | |
| CN105047995B (en) | Lithium ion battery of electrolyte including the electrolyte and preparation method thereof | |
| CN107293784A (en) | Electrolyte and lithium ion battery | |
| CN102113164B (en) | Non-aqueous electrolytic solution, lithium secondary battery and method for producing same, and mixed non-aqueous electrolytic solution | |
| CN108123172B (en) | Electrolyte and secondary lithium battery | |
| CN108242567A (en) | Electrolyte solution and secondary battery | |
| CN108242556B (en) | Electrolyte solution and secondary battery | |
| CN105047994B (en) | Electrolyte and the lithium ion battery including the electrolyte | |
| CN107293782B (en) | Non-aqueous electrolyte and lithium ion battery | |
| CN108242557B (en) | Electrolyte solution and secondary battery | |
| CN109888384B (en) | Electrolyte and battery containing the same | |
| CN105514489A (en) | Electrolyte and lithium ion battery containing electrolyte | |
| CN105655640A (en) | Non-aqueous electrolyte and lithium-ion battery containing same | |
| CN108630989A (en) | Electrolyte and lithium ion battery | |
| CN107293776A (en) | Electrolyte and lithium ion battery | |
| CN108242566A (en) | Electrolyte solution and secondary battery | |
| WO2018120793A1 (en) | Electrolyte and secondary battery | |
| CN110808412A (en) | Electrolyte and lithium ion battery | |
| CN107403950A (en) | Electrolyte and lithium ion battery | |
| CN110808411B (en) | Electrolyte and lithium ion battery | |
| CN105186036B (en) | Electrolyte and the lithium ion battery including the electrolyte | |
| CN105375065A (en) | Electrolyte and lithium ion battery containing same | |
| CN109309249A (en) | Electrolyte and electrochemical energy storage device | |
| CN107403956A (en) | Electrolyte and lithium ion battery | |
| CN108878975A (en) | Electrolyte and secondary battery including the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171024 |