CN109411813A - Electrolyte and electrochemical energy storage device - Google Patents
Electrolyte and electrochemical energy storage device Download PDFInfo
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- CN109411813A CN109411813A CN201710706665.8A CN201710706665A CN109411813A CN 109411813 A CN109411813 A CN 109411813A CN 201710706665 A CN201710706665 A CN 201710706665A CN 109411813 A CN109411813 A CN 109411813A
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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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- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The application provides an electrolyte and an electrochemical energy storage device. The electrolyte includes an electrolyte salt and an additive. The additive comprises phosphate ester quaternary ammonium salt and cyclic sulfate ester. The synergistic effect of the two can enable the surfaces of the anode and the cathode of the electrochemical energy storage device to generate a layer of compact, uniform and stable passive film, especially a low-impedance and compact solid electrolyte interface film can be formed on the surface of the cathode, so that the contact between the anode and the cathode and the electrolyte can be reduced, the continuous oxidation and reduction reactions of the electrolyte on the surfaces of the anode and the cathode can be avoided, the decomposition of the electrolyte and the increase of the internal resistance of the electrochemical energy storage device can be further weakened, and the electrochemical energy storage device still has better high-temperature cycle performance and lower direct current resistance under high-pressure, solid and thick coating.
Description
Technical field
This application involves energy storage device field more particularly to a kind of electrolyte and electrochemical energy storage device.
Background technique
In recent years, being on the rise with the problems such as global environment deteriorates and energy shortage, relative to traditional ni-mh, nickel
Cadmium and lead-acid battery, using the lithium ion battery of nonaqueous electrolytic solution due to higher specific energy density, better cyclicity
Energy, broader operating temperature and more friendly environment compatibility, thus use demand has obtained the growth of explosion type, especially exists
It is even more to occupy the master of application in high-end consumer electronic devices field exigent to energy density and electric transporting vehicle field
Lead status.
In order to meet people to energy density increasingly higher demands, at high-pressure solid and the positive and negative anodes pole piece of thick coating
Science and engineering skill has become industry for promoting the general policies of lithium ion battery energy density.But, the problem of bringing therewith be,
Nonaqueous electrolytic solution is difficult the gap on the positive and negative anodes pole piece of complete wetting high-pressure solid and thick coating between each active material particle, single
The dynamic performance that the raising of the coating weight of active material on the collector of position will lead to lithium ion battery deteriorates seriously, thus
Cause lithium ion battery to will appear very big ohmic polarization (especially in low temperature environment) in charge and discharge, finally make lithium from
The properties of sub- battery sharply deteriorate, such as can seriously affect the mobility of lithium ion, so that lithium ion battery occurs
Phenomena such as high rate performance is poor, poor performance at low temperatures.
Therefore, now it is urgent to provide a kind of electrolyte, after being applied to it in lithium ion battery of high-pressure solid thickness coating, according to
The old performance that can be improved lithium ion battery.
Summary of the invention
In view of the problems in the background art, the purpose of the present invention is to provide a kind of electrolyte and electrochemical energy storage to fill
It sets, the electrochemical energy storage device is planted in the painting of high-pressure solid thickness still has preferable high temperature cyclic performance and lower direct current
Resistance.
In order to achieve the above object, in one aspect of the invention, the present invention provides a kind of electrolyte comprising electrolyte
Salt and additive.The additive includes phosphoric acid ester quat and cyclic sulfates.
In another aspect of this invention, the present invention provides a kind of electrochemical energy storage devices comprising the application is on the one hand
The electrolyte.
Compared with the existing technology, the invention has the benefit that
The electrolysis additive of the application includes phosphoric acid ester quat and cyclic sulfates, and the two synergistic effect can make
The positive and negative pole surface of electrochemical energy storage device generates one layer of densification, uniform and stable passivating film, especially in negative terminal surface
It is capable of forming the solid electrolyte interface film of Low ESR and densification, contact of the positive and negative electrode with electrolyte can be reduced, to avoid electricity
Lasting oxidation and reduction reaction occur on positive and negative electrode surface for solution liquid, and then reduce decomposition and the electrochemical energy storage of electrolyte
The internal resistance of device rises, and planting electrochemical energy storage device still in the painting of high-pressure solid thickness has preferable high temperature cyclic performance and lower
D.C. resistance.
Specific embodiment
The following detailed description of electrolyte according to the present invention and electrochemical energy storage device.
Illustrate electrolyte according to a first aspect of the present invention first.
Electrolyte according to the application first aspect includes electrolytic salt and additive.The additive includes phosphate
Quaternary ammonium salt and cyclic sulfates.
In the electrolyte according to the application first aspect, the phosphoric acid ester quat is selected from chemical combination shown in formula 1
One or more of object；In formula 1, R11、R12It is each independently selected from the alkyl of substituted or unsubstituted C1~C6, replaces
Or one of monocyclic aryl of unsubstituted C6~C16；R13One in alkylidene selected from substituted or unsubstituted C1~C12
Kind；R14One of alkyl selected from substituted or unsubstituted C1~C6；R15Alkylene selected from substituted or unsubstituted C1~C3
One of base；In R11、R12、R13、R14、R15In, substituent group is selected from one or more of the alkyl of C1~C3, halogen.
In formula 1,Indicate anion,Selected from F-、[PF6]-、[AsF6]-、[BF4]-、[NO3]-、[ClO4]-、 One of.
In the electrolyte according to the application first aspect, the cyclic sulfates are to contain-O-SO2- O- group
Cyclic compound, it is preferable that-the O-SO2- O- group is located on the ring of cyclic compound.Specifically, the cyclic annular sulfuric acid
Ester can be one of five-membered cyclic compound, six-membered cyclic compound, seven-membered compounds, their, octatomic ring shape compound.It is excellent
Selection of land can be one of five-membered cyclic compound, six-membered cyclic compound, octatomic ring shape compound.It is further preferred that can
For one of five-membered cyclic compound, six-membered cyclic compound.Wherein, there are several atoms on ring, which just claims " several members
Ring ".Specifically, the cyclic sulfates can be selected from one or more of formula 2,3 compound represented of formula；In formula 2, n 1
Integer in~3, R21、R22、R23、R24It is each independently selected from H, F, Cl, Br, I, cyano, carboxyl, sulfonic group, C1~C20
One of alkyl or alkyl halide alkyl, the unsaturated alkyl of C2~C20 or halogenated unsaturated alkyl；In formula 3, m be 0~
Integer in 3, R31、R32、R33、R34It is each independently selected from the alkane of H, F, Cl, Br, I, cyano, carboxyl, sulfonic group, C1~C20
One of alkyl or alkyl halide alkyl, the unsaturated alkyl of C2~C20 or halogenated unsaturated alkyl.
In the electrolyte according to the application first aspect, the electrolyte can be liquid electrolyte, solid-state polymerization
Object electrolyte or gel polymer electrolytes.Due to liquid electrolyte and solid polymer electrolyte, gel polymer electrolytes
The mechanism of action it is similar, therefore in this application only with liquid electrolyte citing be illustrated.
In the electrolyte according to the application first aspect, the phosphoric acid ester quat and cyclic sulfates collaboration are made
With the positive and negative pole surface of electrochemical energy storage device can be made to generate one layer of densification, uniform and stable passivating film, especially exist
Negative terminal surface is capable of forming the solid electrolyte interface film (SEI film) of Low ESR and densification, can reduce positive and negative electrode and electrolyte
Contact to avoid electrolyte that lasting oxidation and reduction reaction occur on positive and negative electrode surface, and then reduces point of electrolyte
The internal resistance of solution and electrochemical energy storage device rises, and electrochemical energy storage device is made to have preferable high temperature cyclic performance and lower straight
Leakage resistance.The reason is that electrochemical energy storage device is in chemical conversion, positive and negative electrode surface can form one layer of passivating film, work as electrolysis
When containing phosphoric acid ester quat in liquid, with special cationic structural, i.e., by the cyclic quaternary head of tape unit positive charge
It is formed with functional phosphate tail portion by intermediate organic carbon chain link.Since phosphate tail portion is in hydrophily, and it is cyclic annular
Quaternary ammonium head is then in lipophilic, this surface for advantageously reducing electrolyte in oleophylic and hydrophilic amphiphilic structure respectively end to end
Tension, it is each between enabling electrolyte quickly and uniformly to penetrate into positive and negative electrode on piece porous electrode active material particle
Interstitial site.And the internal electric field that the cyclic quaternary head of tape unit positive charge can be formed when electrochemical energy storage device is melted into
Under effect, entire cation is driven actively to be broken close to cathode by preferential reduction decomposition, and release functional phosphate
Tail portion, for establishing one layer mainly by alkylphosphonic XOP (=O) (OR) in negative terminal surface2Material compositions such as (X represent metal)
SEI film, due to alkylphosphonic intrinsic ionic conductivity with higher, and have very high thermal stability, so by
This SEI film formed has the features such as internal structure is fine and close, and impedance is low, dense uniform and high temperature performance are excellent, is very suitable to
The electrode slice design of high-pressure solid and thick coating, so that can reach improves electrochemical energy storage device high temperature cyclic performance and D.C. resistance
Purpose；Cyclic sulfates can then form a film in positive electrode surface, and the passivating film formed can be to avoid between electrolyte and anode
Oxidation reaction, to further improve the high temperature cyclic performance of electrochemical energy storage device.Therefore, when being added phosphorus simultaneously in electrolyte
When ester quat and cyclic sulfates, under the synergistic effect of the two, electrochemical energy storage device has preferable high gentle
Cycle performance at cycle performance, especially 40 DEG C~60 DEG C, simultaneous electrochemical energy storage device is planted in the painting of high-pressure solid thickness still to be had
There is lower DC impedance.
In the electrolyte according to the application first aspect, in formula 1, it is preferable that R11Selected from substituted or unsubstituted
C1~C6 alkyl or one of halogenated alkyl, R12One of alkylidene selected from substituted or unsubstituted C1~C12,
R13One of alkyl or halogenated alkyl selected from substituted or unsubstituted C1~C6, R14Selected from substituted or unsubstituted C1~
One of alkylidene of C2.
In the electrolyte according to the application first aspect, in formula 1, the cationic base of the phosphoric acid ester quat
Group can be selected from
One of.
In the electrolyte according to the application first aspect, specifically, the phosphoric acid ester quat can be selected from following
One or more of compound, but the application is not limited only to this；
Compound 1-1,Compound 1-2,Compound 1-3,Compound 1-4,Compound 1-5,Compound 1-6,Compound 1-7,Compound 1-8.
In the electrolyte according to the application first aspect, in formula 2, it is preferable that n is the integer in 1~2.
In the electrolyte according to the application first aspect, in formula 2, R21、R22、R23、R24Can be different,
It can also identical or R21、R22、R23、R24In it is both any identical, or be R21、R22、R23、R24In appoint
The three that anticipates is identical.
In the electrolyte according to the application first aspect, in formula 2, when n chooses 2 or more integer, except company
It is connected to substituent R21、R22Carbon atom outside, the type of the substituent group on remaining carbon atom position can be identical, can also be with
It is entirely different, or be that more than two substituent groups are identical, it is not exposed to the limitation of specific label.For example, being removed when n is 2
It is connected with substituent R21、R22Carbon atom outside, four substituent groups on remaining two carbon atoms can be identical, can also be with
It is entirely different, or be that any the two in four substituent groups or more is identical.
In the electrolyte according to the application first aspect, in formula 3, it is preferable that m is the integer in 0~1.
In the electrolyte according to the application first aspect, in formula 3, R31、R23、R33、R34Can be different,
It can also identical or R31、R23、R33、R34In it is both any identical, or be R31、R23、R33、R34In appoint
The three that anticipates is identical.
In the electrolyte according to the application first aspect, in formula 3, when m chooses 2 or more integer, except company
It is connected to substituent R31、R32Carbon atom outside, the type of the substituent group on remaining carbon atom can be identical, can also be complete
Difference, or be that more than two substituent groups are identical, it is not exposed to the limitation of specific label.For example, when m is 2, except connection
Substituted base R31、R32Carbon atom outside, four substituent groups on remaining two carbon atoms can be identical, can also be complete
Difference, or be that any the two in four substituent groups or more is identical.
In the electrolyte according to the application first aspect, in formula 2, formula 3, the alkyl of C1~C20 it is specific
Type is not particularly limited, such as chain alkyl, cyclic alkane base.Wherein, chain alkyl includes straight chain again
Alkyl and branched alkane alkyl.Preferably, the alkyl of C1~C20 selects linear paraffin base.It is further preferred that selection C1~
The alkyl of C10, it is further preferred that the alkyl of selection C1~C5 still further preferably selects the alkane of C1~C3
Base.Specifically, C1~C20 alkyl can be selected from methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, Zhong Ding
Base, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopenta, n-hexyl, isohesyl, cyclohexyl, heptyl, suberyl, octyl,
Cyclooctyl, nonyl, decyl, hendecane alkyl, dodecane alkyl, tridecane alkyl, tetradecane alkyl, pentadecane alkyl, 16
One of alkyl, heptadecane alkyl, octadecane alkyl, nonadecane alkyl, eicosane alkyl.
In the electrolyte according to the application first aspect, in formula 2, formula 3, in the alkyl halide alkyl of C1~C20
The number of halogen atom and its position are not particularly limited, can be according to actual needs on the alkyl to above-mentioned C1~C20
Part hydrogen atom or whole hydrogen atom replaced.For example, the number of the halogen atom on the alkyl of C1~C20 can be
1,2,3 or 4.Preferably, halogen atom is selected from one or both of F, Cl.When the number of halogen atom is 2
When above, the type of halogen atom can be identical, can also be entirely different, or is that part is identical.Preferably, C1~C20
Alkyl halide alkyl can be selected from
One of.
In the electrolyte according to the application first aspect, in formula 2, formula 3, the unsaturated alkyl of C2~C20
Specific type is not particularly limited, and can be selected according to actual needs.Preferably, chain unsaturated alkyl is selected.Into
One step preferably, selects alkenyl, alkynyl.The position of the number of unsaturated bond and unsaturated bond is not in the unsaturated alkyl
There is special limitation, can be selected according to the actual situation.For example, the number of unsaturated bond can be 1,2,3 or 4.
Preferably, unsaturated bond is located at the end of unsaturated alkyl, wherein the end is to be connected far from unsaturated alkyl with ring
Position.For example, unsaturated bond is located at the end of the unsaturated alkyl, works as unsaturation when the number of unsaturated bond is 1
When the carbon atom number of alkyl is more than or equal to 3, the carbon atom on unsaturated bond is not connected with ring.Preferably, select C2~C10's
Unsaturated alkyl, it is further preferred that the unsaturated alkyl of selection C2~C5, it is further preferred that selection C2~C3 is not
Saturated hydrocarbyl.Specifically, the unsaturated alkyl can be-CH=CH2、-CH2- CH=CH2、-CH2CH2CH=CH2、-
CH2CH2CH2CH=CH2、-C≡CH、-CH2-C≡CH、-CH2CH2-C≡CH、-CH2CH2CH2C ≡ CH ,-CH=CH-CH=CH2
One of.
In the electrolyte according to the application first aspect, in formula 2, formula 3, the halogenated unsaturated hydrocarbons of C2~C20
In base, the number of halogen atom and its position are not particularly limited, can be unsaturated to above-mentioned C2~C20 according to actual needs
Part hydrogen atom or whole hydrogen atoms on alkyl are replaced.For example, the number of halogen atom can be 1,2,3 or 4
It is a.Preferably, one or both of halogen atom F, Cl.When the number of halogen atom is 2 or more, halogen atom
Type can be identical, can also be entirely different, or is that part is identical.Preferably, the halogenated unsaturated alkyl of C2~C20 can
Selected from-C ≡ C-X ,-CH2—C≡C—X、—CH2CH2—C≡C—X、—CH2CH2CH2—C≡C—X、 In
It is a kind of, wherein one of X F, Cl, Br, I.
In the electrolyte according to the application first aspect, in formula 2, formula 3, it is preferable that R21、R22、R23、R24、
R31、R32、R33、R34It is each independently the insatiable hunger selected from H, F, Cl, C1~C10 alkyl or alkyl halide alkyl, C2~C10
With one of alkyl or halogenated unsaturated alkyl, wherein halogen atom is selected from F or Cl.It is further preferred that R21、R22、R23、
R24、R31、R32、R33、R34It is each independently the unsaturated hydrocarbons selected from H, C1~C5 alkyl or alkyl halide alkyl, C2~C5
One of base or halogenated unsaturated alkyl, wherein halogen atom is selected from F or Cl.It is further preferred that R21、R22、R23、
R24、R31、R32、R33、R34It is each independently selected from one of H, C1~C3 alkyl, the unsaturated alkyl of C2~C3,
Still further preferably, R21、R22、R23、R24、R31、R32、R33、R34Be each independently selected from H, C1~C3 alkyl, C2~
One of the alkenyl of C3, alkynyl of C2~C3.
In the electrolyte according to the application first aspect, specifically, the cyclic sulfates can be selected from followingization
Close one or more of object；
Compound 2-1,Compound 2-2,Compound 2-3,Compound 2-4,Compound 2-5,Compound 2-6,Compound 2-7,Compound 2-8,Compound 2-9,Compound 2-10,Compound 2-11,Compound 2-12,Compound 2-13,Compound 2-14,Compound 2-15,Compound 2-16,Compound 2-17,Compound 2-18,Compound 2-19,Compound 2-20,Compound 2-21,Compound 2-22,Compound 2-23,Compound 2-24,Compound 2-25,Compound 2-26,Compound 2-27,Compound 2-28,Compound 2-29,Compound 2-30,Compound 2-31,Compound 2-32,Compound 2-33,Compound 2-34,Compound 2-35,Compound 2-36,Compound 2-37,Compound 2-38,Compound 2-39,Compound 2-40.
In the electrolyte according to the application first aspect, the content of phosphoric acid ester quat is too small, soaks to electrolyte
The promotion of lubricant nature and unobvious in the film-formation result of negative terminal surface；And content is excessive, it will the viscosity of electrolyte is caused significantly to increase
Summing it up ionic conductivity significantly reduces, and then sharply deteriorates every dynamic performance of electrochemical energy storage device.Preferably, described
The content of phosphoric acid ester quat is the 0.01%~10% of the electrolyte gross mass.
In the electrolyte according to the application first aspect, the content of cyclic sulfates is not limited specifically, can
Selected according to actual needs, it is preferable that the content of the cyclic sulfates be the electrolyte gross mass 0.01%~
3%.
In the electrolyte according to the application first aspect, the electrolyte further includes non-aqueous organic solvent, described
The type of non-aqueous organic solvent is not particularly limited, as long as meeting without active hydrogen and being polarity.Specifically, described non-aqueous
Organic solvent can be selected from ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, carbonic acid first third
Ester, gamma-butyrolacton, δ-valerolactone, methyl formate, Ethyl formate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate,
Methyl butyrate, butyl formate, propyl propionate, ethyl butyrate, butyl acetate, methyl valerate, amyl formate, dimethyl suflfate, sulphur
Sour methyl ethyl ester, dithyl sulfate, tetrahydrofuran, 1,3- dioxolanes, 1,3- dioxane, dimethoxymethane, diethoxy
Methane, 1,2- dimethoxy-ethane, 1,2- diethoxyethane, sulfolane, penta sulfone of ring, dimethyl sulfone, the first and second sulfones, diethyl sulfone, ring
One or more of fourth sulfoxide, penta sulfoxide of ring, dimethyl sulfoxide, the first and second sulfoxides, ethyl-sulfoxide.It is examined from practical with commercialization angle
Consider, it is preferable that the non-aqueous organic solvent is selected from the mixture of carbonic ester or carbonic ester and carboxylate.
In the electrolyte according to the application first aspect, the concentration of the electrolytic salt is not limited specifically,
It can be selected according to actual needs, if the concentration of electrolytic salt is too low, the ionic conductivity of corresponding electrolyte is too low, if
Electrolytic salinity is excessively high, then the viscosity of corresponding electrolyte rises, and the ionic conductivity that this also results in electrolyte is too low.It is excellent
The concentration of selection of land, the electrolytic salt is 0.05mol/L~2.5mol/L, it is further preferred that the concentration of the electrolytic salt
For 0.9mol/L~2mol/L, it is further preferred that the concentration of the electrolytic salt is 0.7mol/L~1.5mol/L.
Secondly illustrate the electrochemical energy storage device described according to a second aspect of the present invention.
It include positive plate, negative electrode tab and according to the application according to electrochemical energy storage device described in the application second aspect
Electrolyte described in first aspect.The positive plate includes plus plate current-collecting body and is set on plus plate current-collecting body and lives including anode
The anode active material layer of property material.The negative electrode tab includes negative current collector and is set on negative current collector and including cathode
The anode active material layer of active material.
It should be noted that the electrochemical energy storage device can for lithium ion battery, sodium-ion battery, Zinc ion battery or
Supercapacitor.In embodiments herein, the embodiment that electrochemical energy storage device is lithium ion battery, but this Shen are only shown
It please be without being limited thereto.
In lithium ion battery, the type of the positive electrode active materials is not limited specifically, can according to actual needs into
Row selection, it is preferable that positive electrode active materials can be selected from LiFePO4、LiCoO2、LiNiO2、LiMn2O4、LiCo1-aMaO2(0 < a <
1)、LiNi1-bMbO2(0 < b < 1), LiMn2-cMcO4(0 < c < 2), LiNixCoyMnzM1-x-y-zO2One or more of,
In, M is selected from one or more of Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V, Ti, and 0≤y≤1, and 0
≤ x≤1,0≤z≤1, x+y+z≤1.Preferably, the positive electrode active materials are selected from LiCoO2, cobalt nickel lithium manganate ternary material,
LiFePO4、LiMnO2One or more of, wherein cobalt nickel lithium manganate ternary material specifically can be selected from LiNi1/3Co1/3Mn1/ 3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.25Mn0.25O2In one
Kind is several.
In lithium ion battery, the type of the negative electrode active material is not limited specifically, can according to actual needs into
Row selection, it is preferable that the negative electrode active material be selected from lithium metal, natural graphite, artificial graphite, the micro- carbon ball of interphase, hard carbon,
Soft carbon, silicon, silico-carbo compound, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO2, spinel structure lithiumation TiO2-
Li4Ti5O12, one or more of Li-Al alloy.
In lithium ion battery, the electrolytic salt can be selected from lithium salts, and the type of the lithium salts does not limit specifically, can
It is selected according to actual needs, as long as suitable lithium ion conductivity can be provided, specifically, the lithium salts be can be selected from
LiPF6、LiBF4、LiClO4、LiAsF6、LiSbF6、LiBOB、LiDFOB、LiFSI、LiN(SO2CF3)2LiTFSI、LiPO2F2、
LiPF2(C2O4)2、LiPF4(C2O4).Consider from practical with commercialization angle, it is preferable that the lithium salts is selected from LiPF6。
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.The case where electrochemical energy storage device is lithium ion battery, but this Shen are only shown in embodiment
It please be without being limited thereto.
In the following embodiments, reagent, material and the instrument used such as not special explanation, it is commercially available to obtain
?.
In embodiment and comparative example, used phosphoric acid ester quat can be prepared as follows:
The synthesis of compound 1-1:
First step reaction:
Second step reaction:
Third step reaction:
Four-step reaction:
Operating procedure:
Ethylene bromohyrin (3g, 24mmol) is added in the twoport flask containing anhydrous acetonitrile (80mL), 0 DEG C is cooled to, adds
Enter piperidines (2.04g, 24mmol) and potassium carbonate (13g, 96mmol), temperature rising reflux 8 hours.It is cooled to room temperature and carries out vacuum mistake
Filter removes organic solvent with Rotary Evaporators.Residue is purified into (chloroform: methanol=10:1) through flash chromatography silicagel column
Obtain colorless oil (0.9g, yield 30%).Wherein, the Structural Identification data of the compound are1H-NMR(400MHz,
CDCl3): δ=3.55 (dd, J=13.1,5.4Hz, 2H)；δ=2.48-2.27 (m, 6H)；δ=1.58-1.46 (m, 4H)；δ=
1.38(t,2H)。
Above compound (6.45g, 50mmol) and triethylamine (12.6g, 2.5eq) are dissolved in methylene chloride 50mL,
It is slowly added dropwise at -20 DEG C into the methylene chloride containing solutions of dimethyl phosphoryl chlorine (2.1mL) (40mL).It is small to be warmed to room temperature stirring 5
When, it is cooled to 0 DEG C of filtering, filtrate removes organic solvent through Rotary Evaporators.Residue is carried out through flash chromatography silicagel column
Purifying (chloroform: methanol=10:1) obtains brown oil liquid (7.1g, yield 60%).Wherein, the Structural Identification of the compound
Data are 1H-NMR (400MHz, CDCl3): δ=4.19-4.08 (m, 2H)；δ=3.76 (s, 3H)；δ=3.73 (s, 3H)；δ=
2.61 (t, J=6.0Hz, 2H), δ=2.42 (t, 4H), δ=1.55 (dt, J=11.1,5.6Hz, 4H)；δ=1.40 (dd, J=
10.8,5.9Hz,2H)。
Above compound (2.37g, 10mmol) is dissolved in anhydrous ether (30mL), excessive iodomethane is added, stirs
It mixes overnight, obtains salt iodide, obtain 3.4g substance, yield 90% by filtration and recrystallization.Wherein, the structure of the compound
Appraising datum is1H-NMR(400MHz,D2O): δ=4.49 (t, 2H)；δ=3.75 (s, 3H)；δ=3.72 (s, 3H)；δ=3.68
(t, J=3.0Hz, 2H)；δ=3.34 (t, J=5.4Hz, 4H)；δ=3.05 (s, 3H)；δ=1.80 (dt, 4H)；δ=1.62-
1.52(dd,2H)。
The compound (1g, 2.635mmol) that upper step obtains is added in anhydrous propanone (10mL), be slow added into containing
KPF6The acetone soln of (1.9g, 10.5mmol).Lower 40 DEG C of nitrogen protection are stirred 30 hours.It is removed using Rotary Evaporators organic
Solvent in methylene chloride by residue dissolution is filtered to remove insoluble matter, methylene chloride is removed in vacuum, solid product is through acetic acid
Ethyl ester and ether elute to obtain compound 1 (0.1g, yield 10%).
Compound 11H-NMR and19F-NMR nuclear-magnetism appraising datum:
1H-NMR(400MHz,CDCl3): δ=4.55 (dd, J=9.0,6.9Hz, 2H)；δ=4.07-4.02 (m, 2H)；δ
=3.83 (s, 3H)；δ=3.81 (s, 3H)；δ=3.71-3.63 (m, 4H)；δ=3.35 (s, 3H)；δ=1.96 (dd, J=
11.3,5.7Hz,4H)；δ=1.83-1.73 (m, 2H).
19F-NMR(376MHz,CDCl3)；δ=- 70.57；δ=- 72.46.
The synthesis of remaining compound is similar with compound 1, it is only necessary to feed change (such as change reaction substrate salt etc.) and it is anti-
Parameter is answered, this is no longer going to repeat them.
Lithium ion battery in embodiment 1-19 and comparative example 1-5 is prepared by the following method:
(1) preparation of positive plate
By positive electrode active materials LiNi0.5Co0.2Mn0.3O2, conductive agent Super P, binder polyvinylidene fluoride (PVDF)
It is sufficiently mixed in N-Methyl pyrrolidone (NMP) and anode sizing agent is made, wherein the solid content in anode sizing agent is
77wt%, LiNi0.5Co0.2Mn0.3O2, Super P and PVDF mass ratio be 97:1.4:1.6.By anode sizing agent even spread
On the plus plate current-collecting body aluminium foil with a thickness of 12 μm；It is cold-pressed after being dried at 85 DEG C；Then trimming, cut-parts, slitting are carried out
Afterwards, 4h is dried under 85 DEG C of vacuum condition, positive plate is made, wherein the coating weight 270mg/ of anode sizing agent
1540.25mm2。
(2) preparation of negative electrode tab
By negative electrode active material graphite, conductive agent Super P, thickener sodium carboxymethylcellulose (CMC), bonding agent butylbenzene
Rubber (SBR) is uniformly mixed in deionized water, and negative electrode slurry is made.Wherein, the solid content in negative electrode slurry is 54wt%,
Graphite, Super P, CMC and SBR mass ratio be 96.4:1.5:0.5:1.6.Negative electrode slurry is uniformly coated on a thickness of 8 μm
Negative current collector copper foil on, and dried at 85 DEG C；Then after carrying out trimming, cut-parts, slitting, under 120 DEG C of vacuum conditions
12h is dried, negative electrode tab is made, wherein the coating weight 165mg/1540.25mm of negative electrode slurry2。
(3) preparation of electrolyte
In mass ratio it is EC by ethylene carbonate, diethyl carbonate and methyl ethyl carbonate in the glove box full of argon gas:
DEC:EMC=3:2:5 is mixed, and is then slowly added to the lithium hexafluoro phosphate that concentration is 1.0mol/L to mixed solution, finally
Additive phosphoric acid ester quat, cyclic sulfates is added, obtains electrolyte after mixing evenly.Used phosphate in electrolyte
The specific type and content of quaternary ammonium salt and cyclic sulfates are as shown in table 1.In table 1, phosphoric acid ester quat, cyclic annular sulfuric acid contain
Amount is the mass percent that the gross mass based on electrolyte is calculated.
(4) preparation of isolation film
Using 12 μm of polyethylene films (PE) as isolation film.
(5) preparation of lithium ion battery
Positive plate, isolation film, negative electrode tab are folded in order, are in isolation film among positive/negative plate, winding obtains naked
Battery core；Soldering polar ear；Naked battery core is placed in outer packing, the electrolyte of above-mentioned preparation is injected into the lithium ion battery after drying
In, encapsulation, stand, chemical conversion (0.02C constant-current charge to 3.3V, then with 0.1C constant-current charge to 3.6V), shaping, volume test,
Complete the preparation of lithium ion battery.
The parameter of table 1 embodiment 1-19 and comparative example 1-5
The test process of lithium ion battery will be illustrated next.
(1) the cycle performance test of lithium ion battery
At 45 DEG C, by lithium ion battery with 1C constant-current charge to 4.3V, then it is with 4.3V constant-voltage charge to electric current
0.05C, then with 1C constant-current discharge to 2.8V, this is a charge and discharge cycles, this discharge capacity is lithium ion battery
Lithium ion battery, is carried out 200 cycle charging/discharge tests by discharge capacity for the first time according to the method described above, and detection obtains the 200th
The discharge capacity of secondary circulation.
45 DEG C of lithium ion battery circulation 200 times after capacity retention ratio (%)=200th time circulation discharge capacity/for the first time
Discharge capacity × 100%.
(2) the D.C. resistance test of lithium ion battery
By lithium ion battery with 1C constant-current discharge to 2.8V, 5 minutes are stood；Then 4.3V is charged to completely with 1C constant current, later
With 4.3V constant-voltage charge to 0.05C, 5 minutes are stood, then with 1C constant-current discharge to 2.8V, discharge electricity amount at this time is lithium ion
The actual discharge capacity of battery；Then lithium ion battery is completely charged to 4.3V with 1C constant current, later with 4.3V constant pressure to 0.05C,
Then with 4C constant-current discharge 30s, the voltage value of lithium ion battery at this time is read, and is denoted as U1。
D.C. resistance (DCR)=4.3V-U under lithium ion battery 100%SOC1/I1。
Lithium ion battery is completely similarly charged to 4.3V with 1C constant current, then with 0.5C constant-current discharge 1 hour, by lithium ion
Battery adjusts to 50%SOC and reads the voltage value of lithium ion battery at this time then with 4C constant-current discharge 30S, and is denoted as U2。
D.C. resistance (DCR)=4.3V-U under lithium ion battery 50%SOC2/I2。
The performance test results of table 2 embodiment 1-19 and comparative example 1-5
From the Correlative data analysis of table 2 it is found that in comparative example 1-3, phosphoric acid ester quat and ring are not added in comparative example 1
Shape sulfuric ester, high-temperature lithium ion battery cycle performance is poor, while the D.C. resistance (DCR) of lithium ion battery is larger.Work as electrolysis
When adding any in the two in liquid (comparative example 2,3), lithium can be certain from the high temperature cyclic performance of battery and D.C. resistance
Improved in degree, but still is not able to satisfy the painting of high-pressure solid thickness and plants to high-temperature lithium ion battery cycle performance and high power performance
Requirement.
The analysis in embodiment 1-10 is it is found that although the type of phosphoric acid ester quat and cyclic sulfates is variant,
Can in uniform, the fine and close and low impedance passivating film of positive and negative anodes Surface Creation of lithium ion battery, the lithium for being coated with high-pressure solid thickness from
Sub- battery has preferable high temperature cyclic performance and lower D.C. resistance.Especially when in electrolyte contain phosphoric acid ester quat
When, on the one hand, in lithium ion battery chemical conversion, it can be directed to migrate to cathode, generate resistance on cathode prior to non-aqueous organic solvent
Resist low and fine and close SEI film, when being combined with cyclic sulfates, mutual synergistic effect, which can improve, generates passivating film
Impedance reduces the DCR of lithium ion battery；On the other hand since phosphoric acid ester quat has both hydrophily and lipophilicity, so that electrolysis
Liquid can infiltrate rapidly to the inside of high-pressure solid thickness coating pole piece, so that the SEI film generated is more uniform, therefore lithium can be improved
The capacity retention ratio of the high temperature circulation of ion battery and the D.C. resistance for reducing lithium ion battery, to promote lithium ion battery
Discharge power.
The analysis in embodiment 11-19 and comparative example 4-5 is it is found that a small amount of phosphoric acid ester quat and cyclic sulfates is combined
When can effectively improve the film forming situation of lithium ion battery, make the preferable high temperature cyclic performance that has of lithium ion battery, and
Reduce the DC impedance of lithium ion battery, if but phosphoric acid ester quat content it is excessive (comparative example 4), effect is not proportional
Improvement.Equally, as the content of cyclic sulfates gradually increases, the high temperature cyclic performance and D.C. resistance of lithium ion battery
Can be improved, if but cyclic sulfates content it is excessive (comparative example 5), the improvement of lithium ion battery is subtracted
Weak, this may be excessive with additive, and the dynamics of electrolyte is deteriorated and forms a film blocked up related.
In conclusion the electrolyte containing phosphoric acid ester quat and cyclic sulfates to be applied to the lithium of high-pressure solid thickness coating
Ion battery can be respectively formed one layer of passivating film in positive and negative pole surface due to the synergistic effect of the two, especially can be in negative terminal surface
One layer is established mainly by alkyl phosphoric acid lithium LiOP (=O) (OR)2Etc. material compositions SEI film, SEI membrane impedance generated it is low and
It is more fine and close, therefore the high temperature cyclic performance and D.C. resistance of lithium ion battery can be obviously improved.
The announcement of book according to the above description, the application those skilled in the art can also carry out above embodiment
Change and modification appropriate.Therefore, the application is not limited to specific embodiment disclosed and described above, to the application's
Some modifications and changes should also be as falling into the protection scope of claims hereof.
Claims (10)
1. a kind of electrolyte, comprising:
Electrolytic salt；And
Additive,
It is characterized in that,
The additive includes phosphoric acid ester quat and cyclic sulfates.
2. electrolyte according to claim 1, which is characterized in that the phosphoric acid ester quat is selected from 1 compound represented of formula
One or more of；
In formula 1, R11、R12Be each independently selected from the alkyl of substituted or unsubstituted C1~C6, substituted or unsubstituted C6~
One of monocyclic aryl of C16, R13One of alkylidene selected from substituted or unsubstituted C1~C12, R14Selected from substitution
Or one of alkyl of unsubstituted C1~C6, R15One of alkylidene selected from substituted or unsubstituted C1~C3；
In R11、R12、R13、R14、R15In, substituent group is selected from one or more of the alkyl of C1~C3, halogen；
Indicate anion,Selected from F-、[PF6]-、[AsF6]-、[BF4]-、[NO3]-、[ClO4]-、
One of.
3. electrolyte according to claim 2, which is characterized in that the cation group of the phosphoric acid ester quat is selected from
One of.
4. electrolyte according to claim 3, which is characterized in that the phosphoric acid ester quat is in following compounds
It is one or more of；
5. electrolyte according to claim 1, which is characterized in that the cyclic sulfates, which are selected from shown in formula 2, formula 3, to be changed
Close one or more of object；
In formula 2, n is the integer in 1~3, R21、R22、R23、R24Be each independently selected from H, F, Cl, Br, I, cyano, carboxyl,
Sulfonic group, the alkyl of C1~C20 or alkyl halide alkyl, the unsaturated alkyl of C2~C20 or in halogenated unsaturated alkyl one
Kind；
In formula 3, m is the integer in 0~3, R31、R32、R33、R34Be each independently selected from H, F, Cl, Br, I, cyano, carboxyl,
Sulfonic group, the alkyl of C1~C20 or alkyl halide alkyl, the unsaturated alkyl of C2~C20 or in halogenated unsaturated alkyl one
Kind.
6. electrolyte according to claim 5, which is characterized in that the cyclic sulfates in following compounds one
Kind is several；
7. electrolyte according to claim 1, which is characterized in that
The content of the phosphoric acid ester quat is the 0.01%~10% of the electrolyte gross mass；
The content of the cyclic sulfates is the 0.01%~3% of the electrolyte gross mass.
8. electrolyte according to claim 1, which is characterized in that the electrolyte is liquid electrolyte, solid polymer
Electrolyte or gel polymer electrolytes.
9. electrolyte according to claim 1, which is characterized in that the concentration of the electrolytic salt be 0.05mol/L~
2.5mol/L。
10. a kind of electrochemical energy storage device characterized by comprising
Positive plate including plus plate current-collecting body and is set on plus plate current-collecting body and the positive electrode active materials including positive electrode active materials
Layer；
Negative electrode tab including negative current collector and is set on negative current collector and the negative electrode active material including negative electrode active material
Layer；And electrolyte according to claim 1 to 9.
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| US20170040638A1 (en) * | 2015-08-04 | 2017-02-09 | Battelle Energy Alliance, Llc. | Phosphoranimine compounds, electrolyte solutions including a phosphoranimine compound, and energy storage devices including same |
| CN109476688A (en) * | 2016-04-01 | 2019-03-15 | 诺姆斯技术公司 | Modified ionic liquid comprising phosphorus |
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| US20170040638A1 (en) * | 2015-08-04 | 2017-02-09 | Battelle Energy Alliance, Llc. | Phosphoranimine compounds, electrolyte solutions including a phosphoranimine compound, and energy storage devices including same |
| CN105845981A (en) * | 2016-03-30 | 2016-08-10 | 宁德新能源科技有限公司 | Non-aqueous electrolyte and lithium-ion battery employing same |
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