CN107293789B - A kind of lithium ion battery and its electrolyte that circulating effect is good - Google Patents
A kind of lithium ion battery and its electrolyte that circulating effect is good Download PDFInfo
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- CN107293789B CN107293789B CN201710609519.3A CN201710609519A CN107293789B CN 107293789 B CN107293789 B CN 107293789B CN 201710609519 A CN201710609519 A CN 201710609519A CN 107293789 B CN107293789 B CN 107293789B
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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
Abstract
A kind of lithium-ion battery electrolytes that circulating effect is good of the present invention, including organic solvent, lithium salts and additive；The additive includes monoisocyanates base alkoxysilane compound containing trialkylsilyl group in molecular structure and film forming compound；Invention additionally discloses a kind of good lithium ion batteries of circulating effect；The isocyanate alkoxysilane compound for including in electrolyte in the present invention is low in cost, it is readily synthesized, it can mutually act synergistically with film forming compound while as effective deicer, stable SEI film is capable of forming in electrode material surface, the structural stability for improving positive and negative pole material during charge and discharge cycles is good and avoid electrolyte in the decomposition of electrode surface, therefore can effectively promote cycle performance of the lithium ion battery under room temperature and hot conditions.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of circulating effect good lithium ion batteries and its electricity
Solve liquid.
Background technique
Lithium-ion battery electrolytes are mainly made of lithium salts, organic solvent and types of functionality additive, to lithium-ion electric
The properties such as capacity, internal resistance, circulation, multiplying power, the safety in pond all have a major impact.The solvent of electrolyte is generally by cyclic annular carbon
The combinations such as acid esters solvent such as EC, PC and linear carbonate class solvent such as DMC, DEC, EMC are formed, and have preferable electrochemistry steady
The features such as qualitative, higher dielectric constant, lower fusing point and higher flash-point and safety non-toxic.Electrolyte matter lithium salts
LiPF6Since solubility is big in carbonate-based solvent, conductivity is higher, preferable to graphite negative electrodes stability, is current quotient
The main lithium salts used with electrolyte, however LiPF6Thermal stability is poor and very sensitive to moisture, and meeting trace water can occur point
Solution, which generates, generates PF5, HF and LiF etc., to corrode collector, SEI film and electrode active material, so that battery performance declines rapidly
Subtract, cycle performance is poor.On the other hand, along with the promotion demand of lithium ion battery specific energy density, there is at low cost, high electricity
Pressure, tertiary cathode material such as nickle cobalt lithium manganate and nickel cobalt lithium aluminate that high gram volume plays etc. are especially dynamic in lithium ion battery
Using more and more extensive in power lithium ion battery, it is considered to be next-generation lithium ion battery mainstream positive electrode.However ternary is just
Pole material water imbibition is strong, especially under high voltages and under higher nickel content, has significantly speeded up conventional electrolysis liquid and had decomposed
Journey causes inflatable serious, and cycle performance is poor.In addition, silicon-based anode has gram volume hair more higher than commercialization graphite cathode
Therefore waving and analysing lithium risk and be greatly diminished is also the following Main way for improving lithium ion battery specific energy density, but by
The biggish volume expansion in charge and discharge process in silicon-based anode, so that conventional electrolyte is all difficult in silicon-based anode surface shape
At stable SEI film, cyclicity is poor.Therefore, new electrolysis additive compound is found in screening, improves the stabilization of electrolyte
Property and develop novel high specific energy positive and negative pole material enabled to realize that macrocyclic novel electrolyte is extremely urgent.
There are many correlative study for improving cycle performance of lithium ion battery at present, and main approach is by electrolyte solvent
The screening of system and special function additive is evaluated and tested, and optimization electrolyte prescription composition forms more stable SEI film, to be promoted
Cycle performance of battery.The patent of invention of Publication No. CN 105355970A reports a kind of tertiary cathode material lithium ion battery
Electrolyte is made of Non-aqueous Organic Solvents, lithium salts and additive, utilizes fluorinated ethylene carbonate, sulfurous organic compound and fluoro
Three kinds of additives of ether are used in conjunction with generated synergistic effect, so that tertiary cathode material battery has excellent cycle performance.
Publication No. CN 106129473A patent of invention provides a kind of silicon-based anode lithium ion battery that charge-discharge performance is excellent
Nonaqueous electrolytic solution.The electrolyte is by solvent, lithium salts, unsaturated siloxane class additive and fluoro sulfimide salt additive
Composition can integrate the high/low temperature and cycle performance for promoting silicon-based anode lithium ion battery.However there is presently no find to have
Effect takes into account positive and negative pole material characteristic, can effectively inhibit positive electrode digestion of metallic ion simultaneously and be formed on negative electrode material surface
Stablize the electrolysis additive of SEI film, therefore also need further to optimize the formula composition of electrolyte solvent or additive,
The stability of positive and negative pole material is promoted, realizes lithium ion battery especially high specific energy lithium-ion battery system comprehensive performance especially
The promotion of cycle performance.
Summary of the invention
The invention proposes a kind of circulating effect good lithium ion battery and its electrolyte, electrode material surface being capable of shape
At stable SEI film, the structural stability for improving positive and negative pole material during charge and discharge cycles is good and avoid electrolyte
In the decomposition of electrode surface, therefore it can effectively promote cycle performance of the lithium ion battery under room temperature and hot conditions.
A kind of good lithium-ion battery electrolytes of circulating effect proposed by the present invention, including organic solvent, lithium salts and addition
Agent；The additive includes monoisocyanates base alkoxysilane compound containing trialkylsilyl group in molecular structure and film forming compound.
Preferably, the monoisocyanates base alkoxysilane compound containing trialkylsilyl group in molecular structure in such as general formula I compound represented extremely
Few one kind:
Wherein:
R in general formula I1、R2It is independently selected from C1-20Alkyl, C3-20Naphthenic base, C2-20Alkenyl, C2-20Alkynyl, C3-20Ring
Alkenyl, C5-26Aryl and C5-26Heteroaryl is at least one；
It is further preferred that R1、R2In hydrogen moiety or all be substituted；
It is highly preferred that substituent group is selected from halogen and cyano is at least one；
R in general formula I3Selected from C1-20Alkylidene, C2-20Alkenyl, C2-20Alkynyl, sulfonic group, boronate and phosphorous acidic group are at least
It is a kind of；
It is further preferred that R3In hydrogen moiety or all be substituted；
It is highly preferred that substituent group is selected from halogen and cyano is at least one；
Preferably, R1、R2It is independently selected from C1-3Alkyl, C2-4Alkenyl, C2-4Alkynyl and C6Aryl is at least one；
Preferably, R3Selected from C1-3Alkylidene, C2-4Alkenyl, C2-4Alkynyl, C6Aryl, sulfonic group, boronate and phosphorous acidic group
It is at least one.
Preferably, the film forming compound includes vinylene carbonate base ester, vinyl ethylene carbonate, methyl Asia second
Ester, inorganic lithium salt, organic lithium salt, pyridine, furans, thiophene, sultones, sulfimide, phosphate, phosphite ester, nitrile, sulfone
At least one of class, amide, acid anhydrides；
Preferably, the hydrogen moiety in the film forming compound or all substituted；
It is further preferred that substituent group is selected from halogen, cyano, nitro, carboxyl and sulfonic group at least one；
Preferably, the film forming compound includes vinylene carbonate, acrylic acid sultones, ethyl sulfate, methane
Disulfonic acid dimethyl ester, three (trimethyl silane) phosphates, three (trimethyl silane) phosphates, dioxalic acid lithium borate and difluoro oxalate
At least one of lithium borate.
Preferably, the organic solvent includes organic carbonate, C1-10Alkyl ether, alkylene ether, cyclic ethers, carboxylate, sulfone,
At least one of nitrile, dintrile, ionic liquid；
Preferably, the organic solvent is selected from ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, carbon
Diethyl phthalate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, dimethyl ether, diethyl ether, adiponitrile, fourth
Dintrile, glutaronitrile, dimethyl sulfoxide, sulfolane, 1,4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate,
At least one of butyl propionate, ethyl butyrate；
Preferably, the hydrogen moiety in the organic solvent or all substituted；
It is further preferred that substituent group is selected from halogen, cyano at least one.
Preferably, the general formula of the lithium salts are as follows:
Li[F6-xP(CyF2y+1)x], wherein x is the integer of 0-6, and y is the integer of 1-20；
Li[B(R4)4], wherein R4It is selected from F, Cl, Br, I, C each, independently of the other1-4Alkyl, C2-4Alkenyl and C2-4Alkynyl；
Li[B(R5)2(OR6O)], wherein R5、R6Selected from C1-6Alkyl, C2-6Alkenyl and C2-6Alkynyl；
Li[B(OR6O)2], wherein (OR6O) derived from 1,2- glycol, 1,3- glycol, 1,2- dicarboxylic acids, 1,3- dicarboxylic acids,
1,2- hydroxycarboxylic acid or 1, the bivalent group of 3- hydroxycarboxylic acid, wherein the bivalent group is former via two oxygen atoms and center R
Son forms 5- or 6-membered ring；
And Li [X (CnF2n+1SO2) m] and salt at least one, wherein m and n are defined below: n be 1-20 integer；When
When X is oxygen or sulphur, m=1；When X is nitrogen or phosphorus, m=2；When X is carbon or silicon, m=3；
It is further preferred that the lithium salts is LiPF6、LiClO4、LiAsF6、LiBF4, tetrafluoro (oxalic acid) lithium phosphate, double grass
At least one of sour lithium borate, difluorine oxalic acid boracic acid lithium, double trifluoromethanesulfonimide lithiums, double fluorine sulfimide lithiums；
It is highly preferred that the lithium salts is LiPF6。
Preferably, using the total weight of electrolyte as matrix, the organic solvent mass concentration is 80-90%, the lithium salts
Mass concentration is 8-15%, and the isocyanate alkoxysilane compound quality concentration is 0.1-10%, described at membranization
Conjunction amount of substance concentration is 0.1-10%；
It is further preferred that the mass concentration of the organic solvent is 80-85%, the lithium salts mass concentration is 10-
14%, the isocyanate alkoxysilane compound quality concentration is 0.5-5%, and other film forming compound quality are dense
Degree is 0.5-5%.
A kind of good lithium ion battery of circulating effect that the present invention also proposes, including containing active material of cathode anode, contain
The cathode of active material of positive electrode, diaphragm and the good lithium-ion battery electrolytes of the circulating effect.
Preferably, the active material of cathode includes the material that can contain and discharge lithium ion；
It is further preferred that the active material of cathode is lithiated transition metal phosphate, tool with olivine structural
The lithium ion insertion transition metal oxide and the lithiated transition metal mixed oxide with spinel structure for having layer structure
At least one of.
Preferably, the active material of positive electrode includes the material that can contain and discharge lithium ion；
It is further preferred that the active material of positive electrode is carbonaceous material, titanium oxide, silicon, lithium, lithium alloy and being capable of shape
At at least one of the material of lithium alloy.
Preferably, the diaphragm is polyethylene, polypropylene, the one or more kinds of composite membranes for gathering inclined tetrafluoroethene.
In the good lithium ion battery of above-mentioned circulating effect, the specific lithium-ion membrane used is not limited by concrete type
System, can be all types diaphragm that existing lithium ion battery uses, including but not limited to polyethylene, polypropylene, gather inclined four
Vinyl fluoride and their composite membrane.
Compared with prior art, the beneficial effects of the present invention are:
(1) use monoisocyanates base alkoxysilane compound containing trialkylsilyl group in molecular structure as novel electrolysis additive in this programme,
Synthesis is simple, and low in cost, Side effect is small, is highly suitable as commercialization additive and uses；
(2) reactivity of isocyanate alkoxysilane compound is strong, may be used also while as film for additive
To remove micro-moisture reaction in electrolyte, avoid the generation of the acidic materials such as HF, hence it is evident that improve electrolysis as deicer
Liquid storage stability；
(3) monoisocyanates base alkoxysilane compound containing trialkylsilyl group in molecular structure be easy with other film for additive collective effects, by being crosslinked
Coupling can form stable SEI film in electrode surface, can be obviously improved the structural stability and electricity of positive and negative pole material
Pond cycle performance.
Specific embodiment
In following embodiments and comparative example, used reagent, material and instrument do not have specified otherwise such as,
Obtained by common mode, involved in reagent can be obtained by conventional synthesis process.
Embodiment 1
The preparation of electrolyte 1 and experimental cell 1
(1) preparation of electrolyte 1
In control moisture≤10ppm argon gas glove box, ethylene carbonate (EC) and methyl ethyl carbonate (EMC) are pressed
It is carried out according to mass ratio EC:EMC=3:7 uniformly mixed, lithium salts i.e. lithium hexafluoro phosphate is then slowly added to, after lithium salts is completely dissolved
The propyl isocyanate triethoxysilane that mass fraction is 0.5% and the vinylene carbonate that mass fraction is 1% is added, stirs
Electrolyte 1 is obtained after mixing uniformly, it is 14% that wherein lithium hexafluoro phosphate, which accounts for the mass concentration of entire electrolyte,.
(2) preparation of positive plate
Positive active material silicon based anode material, conductive agent acetylene black, binder are gathered into inclined tetrafluoroethene according to mass ratio
NMC811: acetylene black: polytetrafluoroethylene (PTFE)=95:2.5:2.5 is mixed, and N methyl pyrrolidone is added, mixing is sufficiently stirred,
It forms uniform anode sizing agent and is coated uniformly on 15 microns of thick aluminum foils, positive plate is obtained after drying.
(3) prepared by negative electrode tab
Negative electrode active material silicon based anode material, conductive agent acetylene black, binder butadiene-styrene rubber, thickening agent carboxymethyl is fine
Plain sodium is tieed up according to quality than silicon based anode material: acetylene black: butadiene-styrene rubber: thickener=95:2:2:1 is mixed, and addition is gone
Mixing is sufficiently stirred in ionized water, forms uniform negative electrode slurry and is coated uniformly on 8 microns thick copper foil, is born after drying
Pole piece.
(4) preparation of experimental cell 1
Dew point is controlled in -40 DEG C of dry environments below and makes the positive plate, diaphragm, step (3) of step (2) preparation
Standby negative electrode tab stacks in order, guarantees that diaphragm completely separates positive/negative plate, then pole piece coiling is fabricated to core, and uses
Band glue tab is encapsulated in fixed-size aluminum plastic film, forms soft-package battery to be injected, the electricity that will then prepare in step (1)
Solution liquid is injected into soft-package battery, and subsequent sealing, chemical conversion, aging, partial volume obtain the experimental cell 1 for test.
Embodiment 2
Prepare electrolyte 2 and experimental cell 2.
Be with 1 difference of embodiment: mass fraction is added after lithium salts is completely dissolved in electrolyte preparation process is
The vinylene carbonate that 1% propyl isocyanate trimethoxy silane and mass fraction is 1%.
Embodiment 3
Prepare electrolyte 3 and experimental cell 3.
Be with 1 difference of embodiment: mass fraction is added after lithium salts is completely dissolved in electrolyte preparation process is
The vinylene carbonate that 3% propyl isocyanate triethoxysilane and mass fraction is 1%.
Embodiment 4
Prepare electrolyte 4 and experimental cell 4.
Be with 1 difference of embodiment: mass fraction is added after lithium salts is completely dissolved in electrolyte preparation process is
The vinylene carbonate that 1% vinyl isocyanate trimethoxy silane and mass fraction is 1%.
Embodiment 5
Prepare electrolyte 5 and experimental cell 5.
Be with 1 difference of embodiment: mass fraction is added after lithium salts is completely dissolved in electrolyte preparation process is
The vinylene carbonate that 3% isocyanic acid sulphonic acid ester triethoxysilane and mass fraction is 1%.
Embodiment 6
Prepare electrolyte 6 and experimental cell 6.
Be with 1 difference of embodiment: mass fraction is added after lithium salts is completely dissolved in electrolyte preparation process is
The vinylene carbonate that 3% isocyanic acid phosphite ester triethoxysilane and mass fraction is 1%.
Embodiment 7
Prepare electrolyte 7 and experimental cell 7.
Be with 1 difference of embodiment: mass fraction is added after lithium salts is completely dissolved in electrolyte preparation process is
The vinylene carbonate that 3% isocyanic acid borate triethoxysilane and mass fraction is 1%.
Embodiment 8
Prepare electrolyte 8 and experimental cell 8.
Be with 1 difference of embodiment: mass fraction is added after lithium salts is completely dissolved in electrolyte preparation process is
The acrylic acid sultones that 1% propyl isocyanate triethoxysilane and mass fraction is 1%.
Embodiment 9
Prepare electrolyte 9 and experimental cell 9.
Be with 1 difference of embodiment: mass fraction is added after lithium salts is completely dissolved in electrolyte preparation process is
The difluorine oxalic acid boracic acid lithium that 1% propyl isocyanate triethoxysilane and mass fraction is 1%.
Embodiment 10
Prepare electrolyte 10 and experimental cell 10.
Be with 1 difference of embodiment: mass fraction is added after lithium salts is completely dissolved in electrolyte preparation process is
Three (trimethyl silane) borates that 1% propyl isocyanate triethoxysilane and mass fraction is 1%.
Comparative example 1
Prepare electrolyte 11 and experimental cell 11.
It is with 1 difference of embodiment: mass fraction is only added after lithium salts is completely dissolved in electrolyte preparation process
For 1% vinylene carbonate, it is added without propyl isocyanate triethoxysilane.
Comparative example 2
Prepare electrolyte 12 and experimental cell 12.
It is with 1 difference of embodiment: mass fraction is only added after lithium salts is completely dissolved in electrolyte preparation process
For 1% acrylic acid sultones, it is added without propyl isocyanate triethoxysilane.
Comparative example 3
Prepare electrolyte 13 and experimental cell 13.
It is with 1 difference of embodiment: mass fraction is only added after lithium salts is completely dissolved in electrolyte preparation process
For 1% difluorine oxalic acid boracic acid lithium, it is added without propyl isocyanate triethoxysilane.
Comparative example 4
Prepare electrolyte 14 and experimental cell 14.
It is with 1 difference of embodiment: mass fraction is only added after lithium salts is completely dissolved in electrolyte preparation process
For 1% propene sultone, it is added without propyl isocyanate triethoxysilane.
Comparative example 5
Prepare electrolyte 15 and experimental cell 15.
It is with 1 difference of embodiment: mass fraction is only added after lithium salts is completely dissolved in electrolyte preparation process
For 1% propyl isocyanate triethoxysilane, it is added without any other film for additive.
Comparative example 6
Prepare electrolyte 16 and experimental cell 16.
It is with 1 difference of embodiment: is added without any addition after lithium salts is completely dissolved in electrolyte preparation process
Agent substance.
The lithium salts of electrolyte, the composition of organic solvent and additive and the content of embodiment 1-10 and comparative example 1-6 referring to
Shown in the following table 1.
The composition and content of the lithium salts of 1 embodiment of table and comparative example electrolyte, organic solvent and additive
Test case 1: electrolyte and battery performance test
(1) the storage stability test of electrolyte
Resulting electrolyte in embodiment 1-10 and comparative example 1-6 is placed in 25 DEG C of constant temperature hutch of similarity condition
It is interior, 1 week is stood, records every kind of electrolyte before standing using karl fischer analysis moisture tester and acid-base titration detection respectively
The variation of moisture and acidity value afterwards, relevant correlation data is referring to table 2.
(2) 25 DEG C of charge and discharge cycles test of experimental cell
Experimental cell after partial volume is placed in 25 DEG C of insulating boxs and is connect with charge-discharge test instrument, first with 1C electric current constant current
For constant-voltage charge to 4.2V, setting cut-off current is 0.01C；Shelve after 10min again with 1C electric current constant-current discharge to 2.8V, so into
Row cyclic charging and discharging test records each discharge capacity, calculates separately the 50th week, 100 weeks and 200 weeks battery core capacity and protects
Holdup, relevant correlation data is referring to table 2, and wherein the N weeks capacity retention ratio (%) of lithium ion=the N weeks discharge capacity/head is all
Discharge capacity * 100%.
(3) 55 DEG C of charge and discharge cycles test of experimental cell
Experimental cell after partial volume is placed in 55 DEG C of insulating boxs and is connect with charge-discharge test instrument, first with 1C electric current constant current
For constant-voltage charge to 4.2V, setting cut-off current is 0.01C；Shelve after 10min again with 1C electric current constant-current discharge to 2.8V, so into
Row cyclic charging and discharging test records each discharge capacity, calculates separately the 50th week, 100 weeks and 200 weeks battery core capacity and protects
Holdup, relevant correlation data is referring to table 2, and wherein the N weeks capacity retention ratio (%) of lithium ion=the N weeks discharge capacity/head is all
Discharge capacity * 100%.
The detection and result of table 2 embodiment 1-10 and comparative example 1-6
It can be seen that from the battery 11-16 in the experimental cell 1-10 and comparative example 1-6 in embodiment 1-10 and work as electrolyte
It is stored under normal condition after a week, the moisture due to being added to monoisocyanates base alkoxyl silicone alkanes additive, in electrolyte
Content is substantially reduced on year-on-year basis, illustrates that the additive can play the role of deicer in electrolyte, and it is steady to be conducive to raising electrolyte
It is qualitative.In addition, storing after a week when under electrolyte normal condition, the acidity in electrolyte is significantly reduced, and general electrolytic liquid exists
Moisture and lithium hexafluoro phosphate reactant salt release HF during storage, can corrode positive and negative pole material structure, and the serious battery that reduces follows
Ring performance, and HF acid content in electrolyte can be reduced after being added to monoisocyanates base alkoxyl silicone alkanes additive.Comparison electricity
Capacity retention ratio of the pond 1-16 at 25 DEG C and 55 DEG C, we can see that being added to 1% monoisocyanates base alkoxyl silicone
Apparent cycle performance promotion effect is all shown than adding single additive or any additive being not added after alkane and film forming compound
Fruit, associated cyclic data ginseng are shown in Table 2, and instruction sheet isocyanate alkoxysilane can be with the organic film forming group of electrode surface
Split-phase interaction forms stable SEI film by synergistic effect, finally effectively improves the room temperature and high temperature circulation of battery
Energy.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (19)
1. a kind of good lithium-ion battery electrolytes of circulating effect, which is characterized in that including organic solvent, lithium salts and additive；
The additive includes monoisocyanates base alkoxysilane compound containing trialkylsilyl group in molecular structure and film forming compound；
The monoisocyanates base alkoxysilane compound containing trialkylsilyl group in molecular structure is as shown in the following general formula I:
Wherein:
R in general formula I1、R2、R3It is independently selected from C1-20Alkyl, C3-20Naphthenic base, C2-20Alkenyl, C2-20Alkynyl, C3-20Cyclenes
Base, C6-26Aryl and C6-26Heteroaryl is at least one；R in general formula I4Selected from C2-20Alkenyl, C2-20Alkynyl, sulfonic group, boronate and
Phosphorous acidic group is at least one；
On the basis of the total weight of electrolyte, the organic solvent mass concentration is 80-90%, and the lithium salts mass concentration is 8-
15%, the monoisocyanates base alkoxysilane compound containing trialkylsilyl group in molecular structure mass concentration is 0.1-10%, and the film forming compound quality is dense
Degree is 0.1-10%.
2. the good lithium-ion battery electrolytes of circulating effect according to claim 1, which is characterized in that R in general formula I1、R2、
R3In hydrogen moiety or all be substituted；Substituent group is selected from halogen and cyano is at least one.
3. the good lithium-ion battery electrolytes of circulating effect according to claim 1, which is characterized in that R in general formula I4In
Hydrogen moiety is all substituted；Substituent group is selected from halogen and cyano is at least one.
4. the good lithium-ion battery electrolytes of circulating effect according to claim 1 or 2, which is characterized in that R in general formula I1、
R2、R3It is independently selected from C1-3Alkyl, C2-4Alkenyl, C2-4Alkynyl and C6Aryl is at least one.
5. the good lithium-ion battery electrolytes of circulating effect according to claim 1 or 3, which is characterized in that R in general formula I4
Selected from C2-4Alkenyl, C2-4Alkynyl, sulfonic group, boronate and phosphorous acidic group are at least one.
6. the good lithium-ion battery electrolytes of circulating effect according to claim 1, which is characterized in that the film forming chemical combination
Object include vinylene carbonate base ester, vinyl ethylene carbonate, methyl ethyl, pyridine, furans, thiophene, sultones,
At least one of sulfimide, phosphate, phosphite ester, nitrile, sulfone class, amide, acid anhydrides.
7. the good lithium-ion battery electrolytes of circulating effect according to claim 6, which is characterized in that the film forming chemical combination
Hydrogen moiety or all substituted in object, it is at least one that substituent group is selected from halogen, cyano, nitro, carboxyl and sulfonic group.
8. the good lithium-ion battery electrolytes of circulating effect according to claim 6, which is characterized in that the film forming chemical combination
Object includes vinylene carbonate, acrylic acid sultones, ethyl sulfate, methane-disulfonic acid dimethyl ester, three (trimethyl silanes)
At least one of phosphate, dioxalic acid lithium borate and difluorine oxalic acid boracic acid lithium.
9. the good lithium-ion battery electrolytes of circulating effect according to claim 1, which is characterized in that the organic solvent
Including organic carbonate, C1-10At least one of alkyl ether, alkylene ether, cyclic ethers, carboxylate, sulfone, nitrile, ionic liquid.
10. the good lithium-ion battery electrolytes of circulating effect according to claim 1, which is characterized in that described organic molten
Agent is selected from ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbonic acid
Methyl ethyl ester, methyl propyl carbonate, ethyl propyl carbonic acid ester, dimethyl ether, diethyl ether, adiponitrile, succinonitrile, glutaronitrile, dimethyl sulfoxide, ring
Fourth sulfone, 1,4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, butyl propionate, in ethyl butyrate at least
It is a kind of.
11. the good lithium-ion battery electrolytes of circulating effect according to claim 9 or 10, which is characterized in that described to have
Hydrogen moiety or all substituted in solvent, it is at least one that substituent group is selected from halogen, cyano.
12. the good lithium-ion battery electrolytes of circulating effect according to claim 1, which is characterized in that the lithium salts
General formula are as follows:
Li[F6-xP(CyF2y+1)x], wherein x is the integer of 0-6, and y is the integer of 1-20；
Li[B(R4)4], wherein R4It is selected from F, Cl, Br, I, C each, independently of the other1-4Alkyl, C2-4Alkenyl and C2-4Alkynyl；
Li[B(R5)2(OR6O)], wherein R5、R6It is selected from C each, independently of the other1-6Alkyl, C2-6Alkenyl and C2-6Alkynyl；
Li[B(OR6O)2], wherein (OR6O 1,2- glycol, 1,3- glycol, 1,2- dicarboxylic acids, 1,3- dicarboxylic acids, 1,2-) are derived from
Hydroxycarboxylic acid or 1, the bivalent group of 3- hydroxycarboxylic acid, wherein the bivalent group is via two oxygen atoms and center R atom shape
At 5- or 6-membered ring；
And Li [X (CnF2n+1SO2) m] and salt at least one, wherein m and n are defined below: n be 1-20 integer；When X is oxygen
Or when sulphur, m=1；When X is nitrogen or phosphorus, m=2；When X is carbon or silicon, m=3.
13. the good lithium-ion battery electrolytes of circulating effect according to claim 1, which is characterized in that the lithium salts is
LiPF6、LiClO4、LiAsF6、LiBF4, tetrafluoro (oxalic acid) lithium phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, double trifluoros
At least one of sulfonyl methane imine lithium, double fluorine sulfimide lithiums.
14. the good lithium-ion battery electrolytes of circulating effect according to claim 13, which is characterized in that the lithium salts is
LiPF6。
15. the good lithium-ion battery electrolytes of circulating effect according to claim 1, which is characterized in that described organic molten
The mass concentration of agent is 80-85%, and the lithium salts mass concentration is 10-14%, the monoisocyanates base alkoxyl silicone alkanisation
Conjunction amount of substance concentration is 0.5-5%, and the film forming compound mass concentration is 0.5-5%.
16. a kind of good lithium ion battery of circulating effect, which is characterized in that including containing active material of cathode anode, contain anode
The cathode of active material, diaphragm and the good lithium ion battery battery of circulating effect described in any one of -15 according to claim 1
Solve liquid.
17. the good lithium ion battery of circulating effect according to claim 16, which is characterized in that the wherein cathode activity
Material is the lithiated transition metal phosphate with olivine structural, the insertion transiting metal oxidation of the lithium ion with layer structure
At least one of object and the lithiated transition metal mixed oxide with spinel structure.
18. the good lithium ion battery of circulating effect according to claim 16, which is characterized in that the wherein anode activity
Material is at least one of carbonaceous material, titanium oxide, silicon, lithium, lithium alloy and the material for being capable of forming lithium alloy.
19. the good lithium ion battery of the described in any item circulating effects of 6-18 according to claim 1, which is characterized in that it is described every
Film is polyethylene, polypropylene, the one or more kinds of composite membranes for gathering inclined tetrafluoroethene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101471455A (en) * | 2007-12-28 | 2009-07-01 | 张家港市国泰华荣化工新材料有限公司 | Additive for lithium ion battery non-aqueous electrolyte and non-aqueous electrolyte made by the same |
| CN103594730A (en) * | 2013-11-29 | 2014-02-19 | 张家港市国泰华荣化工新材料有限公司 | Electrolyte for lithium battery with silicon cathode and lithium battery with silicon cathode |
| CN104837850A (en) * | 2013-06-04 | 2015-08-12 | 塞勒创尼克斯公司 | Nitrile-substituted silanes and electrolyte compositions and electrochemical devices containing them |
-
2017
- 2017-07-25 CN CN201710609519.3A patent/CN107293789B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101471455A (en) * | 2007-12-28 | 2009-07-01 | 张家港市国泰华荣化工新材料有限公司 | Additive for lithium ion battery non-aqueous electrolyte and non-aqueous electrolyte made by the same |
| CN104837850A (en) * | 2013-06-04 | 2015-08-12 | 塞勒创尼克斯公司 | Nitrile-substituted silanes and electrolyte compositions and electrochemical devices containing them |
| CN103594730A (en) * | 2013-11-29 | 2014-02-19 | 张家港市国泰华荣化工新材料有限公司 | Electrolyte for lithium battery with silicon cathode and lithium battery with silicon cathode |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129595A (en) * | 2019-12-26 | 2020-05-08 | 杉杉新材料（衢州）有限公司 | High-voltage lithium ion battery non-aqueous electrolyte and lithium ion battery containing electrolyte |
| CN114039090A (en) * | 2021-10-29 | 2022-02-11 | 北京理工大学 | Lithium battery electrolyte and lithium battery |
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