CN109309247A - Electrolyte and electrochemical energy storage device - Google Patents
Electrolyte and electrochemical energy storage device Download PDFInfo
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- CN109309247A CN109309247A CN201710624394.1A CN201710624394A CN109309247A CN 109309247 A CN109309247 A CN 109309247A CN 201710624394 A CN201710624394 A CN 201710624394A CN 109309247 A CN109309247 A CN 109309247A
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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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M10/0569—Liquid materials characterised by the solvents
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/0042—Four or more solvents
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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
The application provides an electrolyte and an electrochemical energy storage device. The electrolyte includes an electrolyte salt, a non-aqueous organic solvent, and an additive. The non-aqueous organic solvent includes a carboxylic acid ester. The additive comprises sulfonate cyclic quaternary ammonium salt and cyclic sulfate. After the electrolyte is applied to the electrochemical energy storage device, the electrochemical energy storage device has better rate performance, high-temperature cycle performance, high-temperature storage performance and lower low-temperature direct-current resistance under the synergistic action of the electrolyte, the electrolyte and the electrochemical energy storage device.
Description
Technical field
This application involves energy storage device field more particularly to a kind of electrolyte and electrochemical energy storage device.
Background technique
As increasingly depleted and environmental pollution the pressure of fossil energy is increasing, there is an urgent need to a kind of new for automobile industry
The type energy provides driving for it, and lithium ion battery is due to having the characteristics that energy density height, memory-less effect, operating voltage are high de-
Grain husk and go out, become the preferred option of current new-energy automobile electrical source of power.Automobile industry requires power lithium-ion battery tool
There are long circulation life and long storage life, while power lithium-ion battery being required to be able to carry out the use need for meeting fast charging and discharging
It asks, however this is a very big challenge for traditional lithium ion battery.
Currently, widely applied electrolyte includes as the lithium hexafluoro phosphate of electric conducting lithium salt and as non-in lithium ion battery
The cyclic carbonate of aqueous organic solvent and the mixture of linear carbonate, can improve the electricity of lithium ion battery to a certain extent
Chemical property, however there are still many deficiencies for above-mentioned electrolyte, specifically under high voltages, the electrochemistry of lithium ion battery
Performance is still poor, for example, high temperature cyclic performance is poor, high-temperature storage performance difference and high rate performance difference etc..
Summary of the invention
In view of the problems in the background art, the application is designed to provide a kind of electrolyte and electrochemical energy storage dress
It sets, the electrochemical energy storage device has preferable high rate performance, high temperature cyclic performance, high-temperature storage performance and lower low
Warm D.C. resistance.
In order to achieve the above object, in the one side of the application, this application provides a kind of electrolyte comprising electrolyte
Salt, non-aqueous organic solvent and additive.The non-aqueous organic solvent includes carboxylate.The additive includes sulphonic acid ester ring-type
Quaternary ammonium salt and cyclic sulfates.
In the another aspect of the application, this application provides a kind of electrochemical energy storage devices comprising the application is on the one hand
Electrolyte.
Compared with the existing technology, the application has the beneficial effect that
The non-aqueous organic solvent of the electrolyte of the application includes carboxylate, while the electrolyte further includes additive sulfonic acid
Ester cyclic quaternary ammonium salts and cyclic sulfates, after the electrolyte is applied in electrochemical energy storage device, in the collaboration of three
Under effect, electrochemical energy storage device has preferable high rate performance, high temperature cyclic performance, high-temperature storage performance and lower low
Warm D.C. resistance.
Specific embodiment
The following detailed description of the electrolyte and electrochemical energy storage device according to the application.
Illustrate the electrolyte according to the application first aspect first.
Electrolyte according to the application first aspect includes electrolytic salt, non-aqueous organic solvent and additive.It is described non-
Aqueous organic solvent includes carboxylate.The additive includes sulphonic acid ester cyclic quaternary ammonium salts and cyclic sulfates.
In the electrolyte according to the application first aspect, the carboxylate can improve times of electrochemical energy storage device
Rate performance, but when carboxylate is applied to the electrochemical energy storage device of high voltage system, it is oxidized easily decomposition, so as to cause
Electrolyte is consumed, thus using carboxylate do the electrochemical energy storage device of non-aqueous organic solvent under high temperature environment in use,
Capacitance loss after electrochemical energy storage device repeatedly recycles is serious, and the high-temperature storage performance deterioration of electrochemical energy storage device is tight
Weight, the low temperature direct resistance of simultaneous electrochemical energy storage device can also be affected to a certain extent.And additive sulphonic acid ester is cyclic annular
Quaternary ammonium salt can preferentially form a film in negative terminal surface, and being formed by passivating film can inhibit side reaction between carboxylate and cathode, thus
The high temperature circulation of electrochemical energy storage device can be improved on the basis of significantly reducing the low temperature direct resistance of electrochemical energy storage device
Performance and high-temperature storage performance, cyclic sulfates can then form a film in positive electrode surface, and the passivating film formed can be to avoid carboxylate
Oxidation reaction between anode to further improve the high temperature cyclic performance of electrochemical energy storage device, but is individually added into ring
Shape sulfuric ester can significantly reduce the high rate performance of electrochemical energy storage device.Therefore, when the electrolyte simultaneously be added it is non-aqueous organic
When solvent carboxylate, additive sulphonic acid ester cyclic quaternary ammonium salts and cyclic sulfates, under the synergistic effect of above-mentioned substance, it can make
Electrochemical energy storage device has good high rate performance, high temperature cyclic performance, high-temperature storage performance and lower low temperature direct
Resistance meets its use demand in complex environment and high rate charge-discharge.
In the electrolyte according to the application first aspect, the carboxylate is in 1 compound represented of formula
It is one or more of；In formula 1, R11Selected from H, C1~and 10 alkyl, one of the halogenated alkyl of C1~10, R12Selected from C1~
One of 10 alkyl, halogenated alkyl of C1~10.
In formula 1, it can also be cyclic alkyl that the alkyl of C1~10, which can be chain-like alkyl,.Wherein, chain-like alkyl wraps again
Include straight chained alkyl and branched alkyl.In addition, on cyclic alkyl substituent group can not can also be contained with substituted base.In the C1
In~10 alkyl, the lower limit value of carbon atom number is preferably 1,2,3, the upper limit value of carbon atom number is preferably 4,5,6,7,8,
9,10.Preferably, R11、R12It is each independently selected from one of the chain-like alkyl of C1~6, cyclic alkyl of C3~8.Into one
It walks preferably, R11、R12It is each independently selected from one of the chain-like alkyl of C1~4, cyclic alkyl of C5~7.
In formula 1, specifically, the alkyl of C1~10 can be selected from methyl, ethyl, n-propyl, isopropyl, cyclopropyl,
Normal-butyl, isobutyl group, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, cyclopenta, 2,2 diformazans
Base propyl, 1- ethyl propyl, 1- methyl butyl, 2- methyl butyl, n-hexyl, isohesyl, 2- hexyl, 3- hexyl, cyclohexyl, 2-
Methyl amyl, 3- methyl amyl, 1,1,2- thmethylpropyl, 3,3- dimethylbutyl, n-heptyl, 2- heptyl, 3- heptyl, 2- first
One of base hexyl, 3- methylhexyl, 4- methylhexyl, different heptyl, suberyl, n-octyl, cyclooctyl, nonyl, decyl.
In formula 1, there is no special for the substitution number of halogen atom and its position of substitution in the halogenated alkyl of C1~10
Limitation, can be selected according to actual needs.Specifically, the number of halogen atom can be 1,2,3 or 4.When halogen original
Son number be 2 or more when, the type of halogen atom can be identical, can also be entirely different, can also part it is identical.The C1
~10 halogenated alkyl can be that chain halogenated alkyl is also cyclic haloalkyl.The chain halogenated alkyl includes straight chain halogen again
Substituted alkyl and branched haloalkyl.On the cyclic haloalkyl substituent group can not can also be contained with substituted base.Described
In the halogenated alkyl of C1~10, the lower limit value of carbon atom number is preferably 1,2,3, the upper limit value of carbon atom number is preferably 4,5,
6,7,8,9,10.Preferably, R11、R12It is each independently selected from the chain halogenated alkyl of C1~6, the cyclic haloalkyl of C3~8
One of.It is further preferred that R11、R12It is each independently selected from the chain halogenated alkyl of C1~4, the cyclic halo of C5~7
One of alkyl.
In formula 1, specifically, the halogenated alkyl of C1~10 is selected from chloromethyl, dichloromethyl, trichloromethyl, 1- chlorine
Ethyl, 1,2- Dichloroethyl, 2- chlorine n-propyl, the chloro- n-propyl of 2,2- bis-, 1- chloro isopropyl, a chlorine cyclopropyl, the positive fourth of 1- chlorine
Base, 2- chlorine isobutyl group, a chlorine cyclobutyl, 1- chlorine n-pentyl, 2- chlorine n-pentyl, 1- chlorine isopentyl, 2,2- dichloromethyl propyl, one
The chloro- 2,2- dimethyl propyl of chlorine cyclopenta, 3-, the chloro- 1- ethyl propyl of 1-, the chloro- 1- methyl butyl of 1-, 2- chloro-2-methyl butyl,
2- chlorine n-hexyl, a chlorine cyclohexyl, 2- chloromethyl amyl, the chloro- 3- methyl amyl of 3-, the chloro- 1,1,2- thmethylpropyl of 2-, 4-
One of chloro- 3,3- dimethylbutyl, 2- chlorine n-heptyl.In above-mentioned group, the Cl atom in halogenated alkyl can also quilt
F, the part one or more of Br, I replaces or all replaces.
In the electrolyte according to the application first aspect, the carboxylate can be selected from methyl formate, Ethyl formate,
Methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, third
Sour pentyl ester, isoamyl propionate, isopropyl acetoacetic ester, ethyl butyrate, ethyl isobutyrate, butyl butyrate, butyl isobutyrate, butyric acid penta
Ester, isoamyl butyrate, ethyl valerate, ethyl isovalerate, propyl valerate, propyl isovalerate and above compound are by halogen atom
One or more of part replace or one or more of the compound all replaced.Preferably, the carboxylate is selected from
Methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate and above-mentioned carboxylate by F, Cl, Br,
One or more of the substitution of the part one or more of I or the compound all replaced.
In the electrolyte according to the application first aspect, the sulphonic acid ester cyclic quaternary ammonium salts are selected from shown in formula 2
One or more of compound；In formula 2, R21Alkyl selected from-CN, substituted or unsubstituted C1~12 replaces or does not take
The alkenyl of C2~12 in generation, the alkynyl of substituted or unsubstituted C2~12, the alkoxy of substituted or unsubstituted C1~12, substitution
Or one of acyloxy of unsubstituted C1~12；R22Alkylidene selected from substituted or unsubstituted C1~12 replaces or not
The alkenylene of substituted C2~12, the alkynylene of substituted or unsubstituted C2~12, substituted or unsubstituted C1~12 alkylene
One of acyl group；R23The alkenyl of alkyl, substituted or unsubstituted C2~12 selected from substituted or unsubstituted C1~12 replaces
Or the alkynyl of unsubstituted C2~12, the alkoxy of substituted or unsubstituted C1~12, substituted or unsubstituted C1~12 acyl
One of oxygroup, the aryl of substituted or unsubstituted C6~22, heterocyclic base of substituted or unsubstituted C5~22；R24Selected from taking
The alkylidene of generation or unsubstituted C1~3；Substituent group is selected from one or more of-CN, halogen atom.
In formula 2,Indicate anion,Selected from F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、(FSO2)2N-、 One of.
In the electrolyte according to the application first aspect, the cation group of the sulphonic acid ester cyclic quaternary ammonium salts is selected
From
One of.
In the electrolyte according to the application first aspect, the sulphonic acid ester cyclic quaternary ammonium salts are selected from following compounds
One or more of；But the application is without being limited thereto；
In the electrolyte according to the application first aspect, the cyclic sulfates are selected from 3 compound represented of formula
One or more of；In formula 3, n is the integer in 1~3, R31、R32、R33、R34Be each independently selected from H, F, Cl, Br, I,
One of the alkyl or halogenated alkyl of C1~10, the alkoxy of C1~10 or halogenated alkoxy.
In the electrolyte according to the application first aspect, the cyclic sulfates in following compounds one
Kind is several；But the application is without being limited thereto；
In the electrolyte according to the application first aspect, the volume of the carboxylate is the non-aqueous organic solvent
The 5%~50% of total volume, it is unknown to the improvement of the high rate performance of electrochemical energy storage device if the content of carboxylate is very few
It is aobvious, if the content of carboxylate is excessive, more side reaction can occur with positive and negative electrode, thus can severe exacerbation electrochemical energy storage
The chemical property of device, especially high-temperature behavior.Preferably, the volume of the carboxylate is that the non-aqueous organic solvent is overall
Long-pending 10%~40%, it is further preferred that the volume of the carboxylate be the non-aqueous organic solvent total volume 20%~
35%.
In the electrolyte according to the application first aspect, the content of the sulphonic acid ester cyclic quaternary ammonium salts is the electricity
The 0.05%~10% of liquid gross mass is solved, the content of the cyclic sulfates is the 0.1%~5% of the electrolyte gross mass,
In the electrolyte of the application, the carboxylate, sulphonic acid ester cyclic quaternary ammonium salts and cyclic sulfates, which are used cooperatively, can reduce electricity
The interface impedance of chemical energy storage device positive and negative electrode makes electrochemical energy storage device have lower low temperature direct resistance, and changes simultaneously
High temperature cyclic performance, high-temperature storage performance and the high rate performance of kind electrochemical energy storage device, it is to be understood that the sulfonic acid
The variation of the dosage of ester cyclic quaternary ammonium salts and cyclic sulfates necessarily directly influences the performance of electrolyte, to influence to store up electrochemistry
The improvement of energy device chemical property, for example, if the content of sulphonic acid ester cyclic quaternary ammonium salts and/or cyclic sulfates is very few, shape
At passivation it is lepthymenia, be not enough to prevent electrolyte from lasting oxidation reaction and reduction reaction occurring on positive and negative electrode surface, therefore
It is also unobvious to the improvement of the chemical property of electrochemical energy storage device, if sulphonic acid ester cyclic quaternary ammonium salts and/or cyclic sulfates
Content it is excessive, then the passivating film formed is blocked up, and the interface impedance of positive and negative electrode can to a certain extent increased, and is also unfavorable for pair
The improvement of electrochemical energy storage device chemical property.But required in relatively low or more secondary use demand for some,
Carboxylate, sulphonic acid ester cyclic quaternary ammonium salts and cyclic sulfates are added can improve electrification to a certain extent simultaneously in electrolyte
Learn high temperature cyclic performance, high-temperature storage performance and the high rate performance of energy storage device.Preferably, the sulphonic acid ester cyclic quaternary ammonium salts
Content be the 0.1%~5% of the electrolyte gross mass, the contents of the cyclic sulfates is the electrolyte gross mass
0.5%~3%.
In the electrolyte according to the application first aspect, the electrolytic salt in the electrolyte can be selected from lithium salts or
Sodium salt.
In the electrolyte according to the application first aspect, the content of the electrolytic salt is not limited specifically,
It can be selected according to actual needs.Specifically, the content of the electrolytic salt can for the electrolyte gross mass 6%~
25%, it is preferable that the content of the electrolytic salt can be the 6%~20% of the electrolyte gross mass, it is further preferred that institute
The content for stating electrolytic salt can be the 10%~15% of the electrolyte gross mass.
In the electrolyte according to the application first aspect, the type of the lithium salts is not limited specifically, can root
It is selected according to actual demand.Preferably, the lithium salts includes at least LiPF6.The lithium salts can further include LiBF4、
LiClO4、LiAsF6、LiSbF6、LiBOB、LiDFOB、LiFSI、LiTFSI、LiPO2F2、LiTFOP、LiN(SO2RF)2、LiN
(SO2F)(SO2RF one or more of), wherein RF=CnF2n+1, indicate that saturation perfluoroalkyl, n are the integer in 1~10
In the electrolyte according to the application first aspect, the type of the sodium salt is not limited specifically, can root
It is selected according to actual demand.Specifically, the sodium salt can be selected from NaPF6、NaBF4、NaClO4、NaAsF6、NaCF3SO3、NaN
(CF3SO2)2、NaN(C2F5SO2)2、NaN(FSO2)2One or more of.
In the electrolyte according to the application first aspect, the non-aqueous organic solvent may also include carbonic ester.Institute
State the mixture that carbonic ester may include cyclic carbonate and linear carbonate.The non-aqueous organic solvent may also include above-mentioned carbon
The halogenated compound of acid esters.Specifically, specifically, the non-aqueous organic solvent may also include ethylene carbonate, propylene carbonate,
Butylene carbonate, pentylene, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbonic acid first
One or more of ethyl ester, gamma-butyrolacton, tetrahydrofuran.
Secondly illustrate the electrochemical energy storage device according to the application second aspect.
It include the electricity according to the application first aspect according to electrochemical energy storage device described in the application second aspect
Solve liquid.
In the electrochemical energy storage device according to the application second aspect, the electrochemical energy storage device further includes just
Pole piece, negative electrode tab, isolation film and pack case etc..
In the electrochemical energy storage device according to the application second aspect, it should be noted that the electrochemistry storage
Energy device can be lithium ion battery, sodium-ion battery, Zinc ion battery or supercapacitor.In embodiments herein, only
The embodiment that electrochemical energy storage device is lithium ion battery is shown, but the application is without being limited thereto.
In lithium ion battery, positive plate includes plus plate current-collecting body and the positive diaphragm that is set on plus plate current-collecting body.Institute
Stating plus plate current-collecting body is aluminium foil.The anode diaphragm includes positive electrode active materials, and the anode diaphragm may also include conductive agent, glue
Tie agent.Positive electrode active materials can be selected from cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), the LiMn2O4 of spinel-type
(LiMn2O4), the LiMPO of olivine-type4, ternary material LiaNixAyB(1-x-y)O2One or more of.Wherein, in olivine
The LiMPO of type4In, M is selected from one or more of Co, Ni, Fe, Mn, V；In ternary material LiaNixAyB(1-x-y)O2In, A, B
It is each independently selected from one of Co, Al, Mn, and A and B be not identical, 0.95≤a≤1.2,0 < x < 1,0 < y < 1, and x+y < 1.
The not specific limitation of the type of conductive agent and binder, can be selected according to actual needs.
In lithium ion battery, negative electrode tab includes negative current collector and the cathode membrane that is set on negative current collector.Institute
Stating negative current collector is copper foil.The cathode membrane includes negative electrode active material, and the cathode membrane may also include conductive agent, glue
Tie agent.Negative electrode active material can be selected from lithium metal, and the negative electrode active material is also selected from voltage < 2V (vs.Li/Li+)
When can be embedded in the material of lithium, specifically, the negative electrode active material can be selected from the micro- carbon of natural graphite, artificial graphite, interphase
Ball (referred to as MCMB), hard carbon, soft carbon, silicon, silico-carbo compound, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO2, point
The lithiumation TiO of spinel structure2-Li4Ti5O12, one or more of Li-Al alloy.The type of conductive agent and binder is not specific
Limitation, can be selected according to actual needs.
In lithium ion battery, the type of the isolation film is not specifically limited, and can be selected according to actual needs, tool
Body, the isolation film can be selected from polyethylene film, polypropylene screen, polyvinylidene fluoride film and their multilayer complex films.
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
, used sulphonic acid ester cyclic quaternary ammonium salts can refer to Chinese patent CN105845981A disclosed on August 10th, 2016.
Lithium ion battery in embodiment 1-22 and comparative example 1-8 is prepared by the following method:
(1) preparation of positive plate
By positive electrode active materials LiNi0.6Co0.2Mn0.2O2, conductive agent acetylene black, binder polyvinylidene fluoride press quality
Than for LiNi0.6Co0.2Mn0.2O2: acetylene black: polyvinylidene fluoride=98:1:1 is mixed, and Solvents N-methyl pyrrolidines is added
Ketone, stirring obtains anode sizing agent to system at transparent and homogeneous shape under de-airing mixer effect；Anode sizing agent is evenly applied to
With a thickness of on 12 μm of plus plate current-collecting body aluminium foil；Aluminium foil is transferred to 120 DEG C of oven drying 1h after room temperature is dried, is then passed through
Cold pressing, cutting obtain positive plate.
(2) preparation of negative electrode tab
By negative electrode active material artificial graphite, thickener sodium carboxymethylcellulose (CMC), binder butadiene-styrene rubber according to matter
Amount is mixed than 98:1:1, and deionized water is added, and obtains negative electrode slurry under de-airing mixer effect；Negative electrode slurry is uniform
Coated on the negative current collector copper foil with a thickness of 8 μm；Copper foil is transferred to 120 DEG C of oven drying 1h after room temperature is dried, so
Afterwards by being cold-pressed, cutting to obtain negative electrode tab.
(3) preparation of electrolyte
In water content < 10ppm argon atmosphere glove box, by ethylene carbonate (EC), methyl ethyl carbonate (EMC), carbon
Diethyl phthalate (DEC) is that EC:EMC:DEC=1:1:1 is mixed according to volume ratio, and carboxylate is then added to above-mentioned mixing
It in liquid and is sufficiently stirred, then by sufficiently dry lithium salts LiPF6It is dissolved in mixing non-aqueous organic solvent, sulfonic acid is added later
Ester cyclic quaternary ammonium salts, cyclic sulfates, obtain electrolyte after mixing.Wherein, LiPF6Content be electrolyte gross mass
12.5%.Used carboxylate in electrolyte, sulphonic acid ester cyclic quaternary ammonium salts and cyclic sulfates specific type and
Content is as shown in table 1, and wherein the content of carboxylate compound is the volume that the total volume based on non-aqueous organic solvent is calculated
Percentage, sulphonic acid ester cyclic quaternary ammonium salts and cyclic annular sulfuric acid content are the quality percentage that the gross mass based on electrolyte is calculated
Number.
(4) preparation of isolation film
Select the polypropylene isolation film of 16 μ m-thicks (model A273 is provided by Celgard company).
(5) preparation of lithium ion battery
Positive plate, isolation film, negative electrode tab are folded in order, isolation film is between positive and negative plate and plays isolation
Effect, then winding obtains naked battery core；Naked battery core is placed in outer packing shell, the above-mentioned electrolyte prepared is injected into drying
In naked battery core afterwards, by processes such as Vacuum Package, standing, chemical conversion, shapings, lithium ion battery is obtained.
The parameter of table 1 embodiment 1-22 and comparative example 1-8
The test process of lithium ion battery will be illustrated next.
(1) the high temperature cyclic performance test of lithium ion battery
At 45 DEG C, by lithium ion battery first with 1C (nominal capacity) constant-current charge to voltage be 4.4V, further with
4.4V constant-voltage charge to electric current is 0.05C, is then 3.0V with 1C constant-current discharge to voltage, this is a charge and discharge cycles mistake
Journey, this discharge capacity are the discharge capacity recycled for the first time.Lithium ion battery is carried out to 300 circulations according to the method described above to fill
Electricity/discharge test, detection obtain the discharge capacity of the 300th circulation.15 lithium ion batteries of every group of test, are averaged.
45 DEG C of lithium ion battery circulation 300 times after capacity retention ratio (%)=(lithium ion battery the 300th time circulation put
The discharge capacity that capacitance/lithium ion battery recycles for the first time) × 100%.
(2) the high-temperature storage performance test of lithium ion battery
At 25 DEG C, by lithium ion battery with 1C (nominal capacity) constant-current charge to voltage for 4.4V, then with 4.4V perseverance
Pressure charges to electric current less than 0.05C, is later 3.0V with 0.5C constant-current discharge to voltage；Again with 1C constant-current charge to 4.4V, so
0.05C is less than with 4.4V constant-voltage charge to electric current afterwards, test the discharge capacity of lithium ion battery at this time and is denoted as D0；Then by lithium
Ion battery is placed at 60 DEG C and stores 30 days, after storing, is discharged to voltage to lithium ion battery with 1C constant current as 3.0V；
It is again 4.4V with 1C constant-current charge to voltage, 0.05C is then less than with 4.4V constant-voltage charge to electric current, later with 0.5C constant current pair
It is 3.0V that lithium ion battery, which is discharged to voltage, tests lithium ion discharge capacity at this time and is denoted as D1.15 lithium ions of every group of test
Battery is averaged.
60 DEG C of lithium ion battery storage 30 days after capacity retention ratio (%)=[D1/D0] × 100%.
(3) 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 voltage for 4.4V, then with 4.4V perseverance
Pressure charges to electric current≤0.05C, after shelving 5min, with 0.2C constant-current discharge extremely by voltage 3V, at this time by lithium ion battery
Actual discharge capacity is denoted as D0.It then is 4.4V with 1C constant-current charge to voltage by lithium ion battery, then with 4.4V constant-voltage charge
To electric current≤0.05C, after shelving 5min, with 6C constant-current discharge to by voltage 3V, the discharge capacity of lithium ion battery is remembered at this time
For D1.15 lithium ion batteries of every group of test, are averaged.
High rate performance (%)=D1/D0 × 100% of lithium ion battery 6C/0.2C.
(4) the low temperature direct resistance test of lithium ion battery
At 25 DEG C, by lithium ion battery with 1C (nominal capacity) constant-current charge to voltage for 4.4V, further with 4.4V
Constant-voltage charge shelves 5min, is 3V with 1C constant-current discharge to blanking voltage to electric current≤0.05C, records actual discharge capacity, and
Lithium ion battery is adjusted to 50%SOC by (100%SOC) on the basis of the discharge capacity, tests lithium-ion electric after the completion of adjusting
The voltage in pond, is denoted as U1, and lithium ion battery is shelved 4h or more at -25 DEG C, so that the temperature of lithium ion battery reaches -25 DEG C,
With electric current (I) continuous discharge 10s of 0.3C, the voltage of lithium ion battery is tested after electric discharge, is denoted as U2.Every group test 15
Lithium ion battery is averaged.
D.C. resistance DCR=(U1-U2)/I at -25 DEG C of lithium ion battery.
The performance test results of table 2 embodiment 1-22 and comparative example 1-8
From the Correlative data analysis in above-mentioned table 2 it is found that in comparative example 1, carboxylate is not added in electrolyte, while also not
Sulphonic acid ester cyclic quaternary ammonium salts, cyclic sulfates are added, high temperature storage capacity retention ratio, the high temperature circulation capacity of lithium ion battery are protected
Holdup, high rate performance and low temperature direct resistance are poor.In comparative example 2, carboxylate, lithium ion battery are only added in electrolyte
High rate performance be significantly improved, the low temperature direct resistance of lithium ion battery has obtained slight improvement, but due to carboxylic
The poor high temperature stability of acid esters is degrading the high temperature cyclic performance and high-temperature storage performance of lithium ion battery.In comparative example 3, electricity
Sulphonic acid ester cyclic quaternary ammonium salts are only added in solution liquid, the high temperature cyclic performance and high-temperature storage performance and low temperature of lithium ion battery are straight
Leakage resistance is improved, but the high rate performance of lithium ion battery is not obviously improved.In comparative example 4, ring is only added in electrolyte
The high temperature cyclic performance of shape sulfuric ester, lithium ion battery is improved, but the high-temperature storage performance of lithium ion battery and low temperature are straight
The improvement of leakage resistance is then unobvious.In comparative example 5, carboxylate and sulphonic acid ester cyclic quaternary ammonium salts is added simultaneously in electrolyte, it can be with
Improve high-temperature storage performance and low temperature direct resistance while improving lithium ion battery high rate performance, but to high temperature circulation
The improvement of energy is unobvious.In comparative example 6, in electrolyte simultaneously carboxylate and cyclic sulfates is added, can improve simultaneously lithium from
The high rate performance and high temperature cyclic performance of sub- battery, but the high-temperature storage performance of lithium ion battery is poor.In comparative example 7, electricity
Sulphonic acid ester cyclic quaternary ammonium salts and cyclic sulfates, the high temperature cyclic performance of lithium ion battery, high temperature storage are added simultaneously in solution liquid
Performance and low thermal resistance can be improved simultaneously, but to the high rate performance of lithium ion battery almost without improvement.
The analysis in Examples 1 to 22 it is found that when containing carboxylate, sulphonic acid ester cyclic quaternary ammonium salts and ring-type simultaneously in electrolyte
When sulfuric ester, although carboxylate, sulphonic acid ester cyclic quaternary ammonium salts are different with the specific type and content of cyclic sulfates, lithium-ion electric
The chemical property in pond is variant, but can make lithium ion battery while have good high rate performance, high temperature cyclic performance
And high-temperature storage performance, lithium are totally good from the chemical property of battery, can satisfy the demand of actual use.
In Examples 1 to 6, with the increase of carboxylic acid ester content, the high temperature storage capacity retention ratio of lithium ion battery and
High temperature circulation capacity retention ratio gradually decreases, but the high rate performance of lithium ion battery and low temperature direct resistance gradually improve.
In embodiment 7~10 and embodiment 3, with the increase of sulphonic acid ester cyclic quaternary salt content, lithium ion battery
High temperature storage capacity retention ratio, high temperature circulation capacity retention ratio, high rate performance can be improved to a certain extent, while low
Warm D.C. resistance also can be improved.
In embodiment 11~14 and embodiment 3, as cyclic sulfates content increases, the high temperature storage of lithium ion battery
Capacity retention ratio, high temperature circulation capacity retention ratio and high rate performance can be improved, but the low temperature direct of lithium ion battery
Resistance has the tendency that slight deterioration.
Therefore the content of carboxylate, sulphonic acid ester cyclic quaternary ammonium salts and cyclic sulfates is too little or too much is unfavorable for from total
Improve the performance of lithium ion battery on body, but requires equally may be used in relatively low or more secondary use demand for some
To improve the high rate performance, high temperature cyclic performance and high-temperature storage performance of lithium ion battery to a certain extent, at the same make lithium from
Sub- battery has lesser low temperature direct resistance.
The analysis in embodiment 3 and comparative example 8 is it is found that use cyclic sulfates in the additive of the electrolyte of the application
When, although the improvement of the high-temperature storage performance of lithium ion battery and high temperature cyclic performance is weaker than the lithium using 1,3-propane sultone
Ion battery, but the high rate performance of lithium ion battery and low temperature direct resistance can be significantly improved, lithium ion battery totality
Chemical property is good, can satisfy its use demand in complex environment and high rate charge-discharge.
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 (11)
1. a kind of electrolyte, comprising:
Electrolytic salt；
Non-aqueous organic solvent；And
Additive；
It is characterized in that,
The non-aqueous organic solvent includes carboxylate；
The additive includes sulphonic acid ester cyclic quaternary ammonium salts and cyclic sulfates.
2. electrolyte according to claim 1, which is characterized in that the carboxylate is in 1 compound represented of formula
It is one or more of；
In formula 1, R11Selected from H, C1~and 10 alkyl, one of the halogenated alkyl of C1~10, R12Alkyl selected from C1~10,
One of halogenated alkyl of C1~10.
3. electrolyte according to claim 2, which is characterized in that the carboxylate is selected from methyl formate, Ethyl formate, second
Sour methyl esters, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, propionic acid
Pentyl ester, isoamyl propionate, isopropyl acetoacetic ester, ethyl butyrate, ethyl isobutyrate, butyl butyrate, butyl isobutyrate, amyl butyrate,
Isoamyl butyrate, ethyl valerate, ethyl isovalerate, propyl valerate, propyl isovalerate and above compound are by halogen atom
One or more of parts replace or one or more of the compound all replaced.
4. electrolyte according to claim 1, which is characterized in that the sulphonic acid ester cyclic quaternary ammonium salts are selected from shown in formula 2
One or more of compound；
In formula 2, R21The alkenyl of alkyl, substituted or unsubstituted C2~12 selected from-CN, substituted or unsubstituted C1~12,
The alkynyl of substituted or unsubstituted C2~12, the alkoxy of substituted or unsubstituted C1~12, substituted or unsubstituted C1~12
One of acyloxy；
R22The alkenylene of alkylidene, substituted or unsubstituted C2~12 selected from substituted or unsubstituted C1~12 replaces or not
One of the alkynylene of substituted C2~12, alkylene acyl group of substituted or unsubstituted C1~12；
R23It is the alkenyl of alkyl, substituted or unsubstituted C2~12 selected from substituted or unsubstituted C1~12, substituted or unsubstituted
The alkynyl of C2~12, the alkoxy of substituted or unsubstituted C1~12, substituted or unsubstituted C1~12 acyloxy, replace
Or one of the aryl of unsubstituted C6~22, heterocyclic base of substituted or unsubstituted C5~22；
R24Alkylidene selected from substituted or unsubstituted C1~3；
Substituent group is selected from one or more of-CN, halogen atom；
Indicate anion,Selected from F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、(FSO2)2N-、
One of.
5. electrolyte according to claim 4, which is characterized in that the cation group of the sulphonic acid ester cyclic quaternary ammonium salts selects
From
One of.
6. electrolyte according to claim 5, which is characterized in that the sulphonic acid ester cyclic quaternary ammonium salts are selected from following compounds
One or more of:
7. electrolyte according to claim 1, the cyclic sulfates are selected from one of 3 compound represented of formula or several
Kind；
In formula 3, n is the integer in 1~3, R31、R32、R33、R34It is each independently selected from the alkane of H, F, Cl, Br, I, C1~10
One of base or halogenated alkyl, the alkoxy of C1~10 or halogenated alkoxy.
8. electrolyte according to claim 7, which is characterized in that the cyclic sulfates in following compounds one
Kind is several:
9. electrolyte according to claim 1, which is characterized in that
The volume of the carboxylate is the 5%~50% of the non-aqueous organic solvent total volume, it is preferable that the body of the carboxylate
Product is the 10%~40% of the non-aqueous organic solvent total volume, it is further preferred that the volume of the carboxylate is described non-
The 20%~35% of aqueous organic solvent total volume.
10. electrolyte according to claim 1, which is characterized in that
The content of the sulphonic acid ester cyclic quaternary ammonium salts is the 0.05%~10% of the electrolyte gross mass, it is preferable that the sulphur
The content of acid esters cyclic quaternary ammonium salts is the 0.1%~5% of the electrolyte gross mass；
The content of the cyclic sulfates is the 0.1%~5% of the electrolyte gross mass, it is preferable that the cyclic sulfates
Content be the electrolyte gross mass 0.5%~3%.
11. a kind of electrochemical energy storage device, which is characterized in that including electrolysis according to claim 1 to 10
Liquid.
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| JP2021106144A (en) * | 2019-12-27 | 2021-07-26 | トヨタ自動車株式会社 | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery |
| CN116435601A (en) * | 2023-06-14 | 2023-07-14 | 广州天赐高新材料股份有限公司 | Electrolyte and application thereof |
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| CN105655642A (en) * | 2016-03-30 | 2016-06-08 | 宁德时代新能源科技股份有限公司 | Electrolyte and high-nickel anode lithium ion battery containing same |
| CN106099184A (en) * | 2016-06-28 | 2016-11-09 | 宁德新能源科技有限公司 | A kind of electrolyte and use the lithium ion battery of this electrolyte |
| CN106920988A (en) * | 2017-04-01 | 2017-07-04 | 上海中聚佳华电池科技有限公司 | A kind of sodium-ion battery electrolyte, its preparation method and application |
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| CN105655642A (en) * | 2016-03-30 | 2016-06-08 | 宁德时代新能源科技股份有限公司 | Electrolyte and high-nickel anode lithium ion battery containing same |
| CN106099184A (en) * | 2016-06-28 | 2016-11-09 | 宁德新能源科技有限公司 | A kind of electrolyte and use the lithium ion battery of this electrolyte |
| CN106920988A (en) * | 2017-04-01 | 2017-07-04 | 上海中聚佳华电池科技有限公司 | A kind of sodium-ion battery electrolyte, its preparation method and application |
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| JP2021106144A (en) * | 2019-12-27 | 2021-07-26 | トヨタ自動車株式会社 | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery |
| JP7340147B2 (en) | 2019-12-27 | 2023-09-07 | トヨタ自動車株式会社 | Non-aqueous electrolytes and non-aqueous electrolyte secondary batteries |
| CN116435601A (en) * | 2023-06-14 | 2023-07-14 | 广州天赐高新材料股份有限公司 | Electrolyte and application thereof |
| CN116435601B (en) * | 2023-06-14 | 2024-03-22 | 广州天赐高新材料股份有限公司 | Electrolyte and application thereof |
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Application publication date: 20190205 |