CN109309253A - Electrolyte and electrochemical energy storage device - Google Patents
Electrolyte and electrochemical energy storage device Download PDFInfo
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- CN109309253A CN109309253A CN201710625287.0A CN201710625287A CN109309253A CN 109309253 A CN109309253 A CN 109309253A CN 201710625287 A CN201710625287 A CN 201710625287A CN 109309253 A CN109309253 A CN 109309253A
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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
- 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
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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 relates to an electrolyte and an electrochemical energy storage device. The electrolyte includes an electrolyte salt and an additive. The additive comprises a sulfonate cyclic quaternary ammonium salt and a cyclic phosphazene compound. The electrochemical energy storage device has the advantages that a layer of compact, uniform and stable passive film can be formed on the surface of the positive electrode and the surface of the negative electrode of the electrochemical energy storage device through the cooperation of the positive electrode and the negative electrode, particularly, a low-impedance and compact solid electrolyte interface film can be formed on the surface of the negative electrode, meanwhile, the corrosion of hydrofluoric acid in electrolyte to the positive electrode and the negative electrode can be reduced, and under the synergistic effect of the positive electrode and the negative electrode, the electrochemical energy storage device has better cycle performance and high-temperature.
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, making it currently becomes the preferred option of new-energy automobile electrical source of power.However as the expansion of electronics market demand
Big and power, energy storage device development, requirement of the people to lithium ion battery are continuously improved, and exploitation has high-energy density and full
The lithium ion battery of sufficient fast charging and discharging becomes the task of top priority.Currently, effective method be improve the voltage of electrode active material,
Compacted density and the suitable electrolyte of selection.
Currently, widely applied electrolyte is usually using lithium hexafluoro phosphate as electrolytic salt and with ring in lithium ion battery
Shape carbonic ester and the mixture of linear carbonate are the electrolyte of organic solvent, however above-mentioned electrolyte is there are many deficiencies,
Specifically under high voltages, the high-temperature storage performance of lithium ion battery is poor, and lithium ion battery faces below in long-term circulation
The problem of capacity rapid decay.Wherein, important component of the electrolyte as lithium ion battery, to the electricity of lithium ion battery
Chemical property has great influence, and the composition by improving electrolyte can improve the property of lithium ion battery to a certain extent
Energy.
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, electrochemical energy storage device has preferable cycle performance and high-temperature storage performance.
In order to achieve the above object, in the one side of the application, this application provides a kind of electrolyte comprising electrolyte
Salt and additive.The additive includes sulphonic acid ester cyclic quaternary ammonium salts and cyclic phosphazene compound.
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
The electrolyte.
Compared with the existing technology, the application has the beneficial effect that
The electrolysis additive of the application includes sulphonic acid ester cyclic quaternary ammonium salts and cyclic phosphazene compound, can make electrochemistry
The positive and negative electrode surface of energy storage device is respectively formed one layer of densification, uniform and stable passivating film, especially negative terminal surface being capable of shape
At Low ESR and the solid electrolyte interface film (SEI film) of densification, while hydrofluoric acid can be also reduced in electrolyte to positive and negative electrode
Corrosion, under the synergistic effect of the two, electrochemical energy storage device has preferable cycle performance and high-temperature storage performance.
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 and additive.The additive includes sulphonic acid ester
Cyclic quaternary ammonium salts and cyclic phosphazene compound.
According in the electrolyte of the application first aspect, the sulphonic acid ester cyclic quaternary ammonium salts are selected from shown in formula 1
One or more of compound；In formula 1, R11Alkyl 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；R12Alkylidene 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；R13The 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；R14Selected from taking
The alkylidene of generation or unsubstituted C1~3；Substituent group is selected from one or more of-CN, halogen atom；
In formula 1,Indicate anion,Selected from F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、 One of.
In the electrolyte according to the application first aspect, the cyclic phosphazene compound, which is selected from shown in formula 2, to be changed
Close one or more of object；In formula 2, R21、R22、R23、R24、R25、R26It is each independently selected from H, halogen atom, C1~20
Alkyl, the alkenyl of C2~20, the alkynyl of C2~20, the aryl of C6~20, the halogenated alkyl of C1~20, C2~20 haloalkene
Base, the halo alkynyl of C2~20, the halogenated aryl of C6~20, the alkoxy of C1~20, the alkenyloxy group of C2~20, C2~20 alkynes
Oxygroup, the aryloxy group of C6~20, the halogenated alkoxy of C1~20, the haloalkenyloxy of C2~20, C2~20 halogenated alkynyloxy group,
One of haloaryloxy of C6~20, and R22、R24、R26In at least two be selected from halogen atom.Wherein it is preferred to halogen
Plain atom can be selected from one or more of F, Cl, Br.
In the electrolyte according to the application first aspect, the electrolyte is liquid electrolyte, solid polymer
Electrolyte or gel polymer electrolytes.Due to liquid electrolyte and solid polymer electrolyte, gel polymer electrolytes
The mechanism of action is similar, therefore is only illustrated in this application with liquid electrolyte citing.
In the electrolyte according to the application first aspect, the sulphonic acid ester cyclic quaternary ammonium salts and ring phosphonitrile chemical combination
Object can make the positive and negative electrode surface of electrochemical energy storage device be respectively formed 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, reduces connecing for positive and negative electrode and electrolyte
Touching, so as to avoid electrolyte that lasting oxidation reaction and reduction reaction occur on positive and negative electrode surface, and then reduces electrolysis
The decomposition of liquid, avoids internal resistance from rising, while can also weaken corrosion of the electrolyte to positive and negative electrode, significantly improves electrochemistry storage
The cycle performance and high-temperature storage performance of energy device.The reason is that electrochemical energy storage device chemical conversion when, positive and negative electrode table
Face can form one layer of passivating film, when containing sulphonic acid ester cyclic quaternary ammonium salts in electrolyte, special knot that cation group has
(the cation group part of the i.e. described sulphonic acid ester cyclic quaternary ammonium salts is by the cyclic quaternary head of tape unit positive charge and functionality for structure
Sulphonic acid ester tail portion formed by intermediate organic carbon chain link), the cyclic quaternary head of tape unit positive charge can be made also
When former current potential is 1.5V, it is able to drive entire cation group and is actively broken close to cathode by preferential reduction decomposition, and discharge
Functional sulphonic acid ester tail portion out can preferentially establish one layer by alkyl sulfonic acid metal salt (RSO in negative terminal surface3The objects such as X)
The SEI film of matter composition due to alkyl sulfonic acid metal salt intrinsic ionic conductivity with higher, and has very high thermostabilization
Property, therefore thus in the SEI film that negative terminal surface is formed there is internal structure to cause the spies such as dense and uniform, impedance low and high temperature is had excellent performance
Point can improve the high-temperature storage performance of electrochemical energy storage device.When containing lithium hexafluoro phosphate in the electrolytic salt of electrolyte,
Stability is poor at high temperature for it, decomposition product PF5It can generate hydrofluoric acid in the presence of having micro-moisture, and cyclic phosphazene compound
The hydrofluoric acid in electrolyte then can be absorbed, to can reduce corrosion of the hydrofluoric acid to positive and negative electrode passivating film, improve electrochemistry storage
The cycle performance of energy device.Therefore, when sulphonic acid ester cyclic quaternary ammonium salts and cyclic phosphazene compound is added simultaneously in electrolyte,
Under the collective effect of the two, electrochemical energy storage device has preferable cycle performance and high-temperature storage performance.
In the electrolyte according to the application first aspect, in formula 1, it is preferable that R11Selected from substituted or unsubstituted
C1~6 alkyl or one of halogenated alkyl, R12One of alkylidene selected from substituted or unsubstituted C1~12,
R13One of alkyl or halogenated alkyl selected from substituted or unsubstituted C1~6, R14Selected from substituted or unsubstituted C1~2
One of alkylidene.
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, specifically, the sulphonic acid ester cyclic quaternary ammonium salts are selected from down
State one or more of compound；But the application is without being limited thereto；
In the electrolyte according to the application first aspect, in formula 2, it is preferable that R21、R23、R25In at least one
A alkoxy or halogenated alkoxy selected from C1~20, the alkenyloxy group of C2~20 or haloalkenyloxy, C2~20 alkynyloxy group or
One of halogenated alkynyloxy group, the aryloxy group of C6~20 or haloaryloxy.
In the electrolyte according to the application first aspect, in formula 2, it is further preferred that R21、R22、R23、R24、
R25、R26Be each independently selected from H, halogen atom, the alkyl of C1~10 or halogenated alkyl, the alkenyl of C2~10 or halogenated alkenyl,
The alkynyl or halo alkynyl of C2~10, the aryl of C6~10 or halogenated aryl, the alkoxy of C1~10 or halogenated alkoxy, C2~
The aryloxy group or haloaryloxy of 10 alkenyloxy group or haloalkenyloxy, the alkynyloxy group of C2~10 or halogenated alkynyloxy group, C6~10
One of, and R22、R24、R26In at least two be selected from halogen atom, R21、R23、R25At least one of be selected from C1~10
Alkoxy or halogenated alkoxy, the alkenyloxy group of C2~10 or haloalkenyloxy, C2~10 alkynyloxy group or halogenated alkynyloxy group, C6
One of~10 aryloxy group or haloaryloxy.
In the electrolyte according to the application first aspect, specifically, the cyclic phosphazene compound is selected from followingization
Close one or more of object；But the application is without being limited thereto；
In the electrolyte according to the application first aspect, the content of the sulphonic acid ester cyclic quaternary ammonium salts is the electricity
Solve the 0.05%~10% of liquid gross mass.Content is very few, and the positive and negative anodes passivating film of formation is not sufficient to prevent electrolyte further
Reaction, it is also unobvious to the improvement of electrochemical energy storage device performance.And too high levels, the then impedance on positive and negative anodes increase, meeting
Deteriorate electrochemical energy storage device performance.Preferably, the content of the sulphonic acid ester cyclic quaternary ammonium salts is the electrolyte gross mass
0.1%~5%.
In the electrolyte according to the application first aspect, the content of the cyclic phosphazene compound is the electrolyte
The 0.1%~8% of gross mass.Content is very few, unobvious to the improvement of electrochemical energy storage device performance.And too high levels, due to
The conductivity of electrolyte reduces, and can deteriorate electrochemical energy storage device dynamic performance.Preferably, the cyclic phosphazene compound contains
Amount is the 1%~5% of the electrolyte gross mass.
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.Specifically, the content of the electrolytic salt be the electrolyte gross mass 6%~
25%.Preferably, the content of the electrolytic salt is the 6%~20% of the gross mass of the electrolyte.It is further preferred that institute
State electrolytic salt content be the electrolyte gross mass 10%~15%.
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 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、LiN(SO2F)2、LiTFSI、LiPO2F2、LiTFOP、LiN(SO2RF)2、
LiN(SO2F)(SO2RF one or more of), wherein RF=CnF2n+1, indicate that saturation perfluoroalkyl, n are whole in 1~10
Number.
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 electrolyte further includes organic solvent, described organic
The type of solvent can be selected according to actual needs there is no specific limitation.Preferably, using non-aqueous organic solvent.Institute
State the carbonic ester and/or carboxylate that non-aqueous organic solvent may include any kind.The carbonic ester may include cyclic carbonate with
And the mixture of linear carbonate.The non-aqueous organic solvent may also include the halogenated compound of carbonic ester.Specifically, described to have
Solvent can be selected from ethylene carbonate, propylene carbonate, butylene carbonate, pentylene, fluoroethylene carbonate, carbonic acid two
Methyl esters, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl acetate, propyl propionate, third
One or more of acetoacetic 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..
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, positive plate includes plus plate current-collecting body and the positive diaphragm that is set on plus plate current-collecting body.Institute
Stating positive diaphragm includes positive electrode active materials, and the anode diaphragm may also include conductive agent, binder.Positive electrode active materials are optional
From cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), the LiMn2O4 (LiMn of spinel-type2O4), the LiMPO of olivine-type4, ternary
Material LiaNixAyB(1-x-y)O2One or more of.Wherein, in the LiMPO of olivine-type4In, M is selected from Co, Ni, Fe, Mn, V
One or more of；In ternary material LiaNixAyB(1-x-y)O2In, A, B are 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 limit of the type of conductive agent and binder
System, 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 cathode membrane includes negative electrode active material, and the cathode membrane may also include conductive agent, binder.Negative electrode active material is optional
Comfortable voltage < 2V (vs.Li/Li+) when can be embedded in the material of lithium.Specifically, the negative electrode active material can be selected from natural stone
The micro- carbon ball of ink, artificial graphite, interphase (referred to as MCMB), 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.It leads
The not specific limitation of the type of electric agent and binder, can be selected according to actual needs.The negative electrode tab also can be used directly
Metal lithium sheet.
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 1~12 and comparative example 1~7 is prepared by the following method:
(1) preparation of positive plate
By positive electrode active materials LiNi0.33Co0.33Mn0.33O2, conductive agent acetylene black, binder polyvinylidene fluoride press matter
Amount is mixed than 98:1:1, and solvent N-methyl pyrilidone is added, and stirring is equal to stable system under de-airing mixer effect
One, obtain anode sizing agent；Anode sizing agent is evenly applied on the plus plate current-collecting body aluminium foil with a thickness of 12 μm；By aluminium foil in room temperature
It is transferred to 120 DEG C of oven drying 1h after drying, then obtains positive plate by cold pressing, cutting.
(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, then by sufficiently dry lithium salts LiPF6
It is dissolved in mixed organic solvents, sulphonic acid ester cyclic quaternary ammonium salts and cyclic phosphazene compound is added later, obtains after mixing
Electrolyte.Wherein, LiPF6Content be electrolyte gross mass 12.5%.Used sulphonic acid ester cyclic annular season in electrolyte
The specific type and content of ammonium salt and cyclic phosphazene compound are as shown in table 1, and in table 1, sulphonic acid ester cyclic quaternary ammonium salts and ring
The content of phosphazene compound is the mass percent that the gross mass based on electrolyte is calculated.
(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 1~12 and comparative example 1~7
The test process of lithium ion battery will be illustrated next.
(1) the high-temperature storage performance test of lithium ion battery
It with 1C constant-current charge to voltage is 4.4V by lithium ion battery, then with 4.4V constant-voltage charge to electricity at 25 DEG C
Stream is less than 0.05C, is later 3.0V with 0.5C constant-current discharge to voltage；Be again 4.4V with 1C constant-current charge to voltage, then with
4.4V constant-voltage charge to electric current is less than 0.05C, tests 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, is 3.0V with 1C constant-current discharge to voltage after storing；Again extremely with 1C constant-current charge
Voltage is 4.4V, is then less than 0.05C with 4.4V constant-voltage charge to electric current, is later 3.0V with 0.5C constant-current discharge to voltage,
It tests the discharge capacity of lithium ion battery at this time and is denoted as D1.
Capacity retention ratio (%)=[D1/D0] × 100% behind 60 DEG C of storages 30 days of lithium ion battery.
(2) the cycle performance test of lithium ion battery
It is first 4.4V with 1C constant-current charge to voltage by lithium ion battery, further with 4.4V constant-voltage charge at 25 DEG C
It is 0.05C to electric current, is then 3.0V with 1C constant-current discharge to voltage, this is a charge and discharge cycles process, this electric discharge
Capacity is the discharge capacity recycled for the first time.Lithium ion battery is carried out to 400 cycle charging/discharge tests according to the method described above,
Detection obtains the discharge capacity of the 400th circulation.
Capacity retention ratio (%)=(electric discharge appearance of lithium ion battery the 400th time circulation after lithium ion battery circulation 400 times
The discharge capacity that amount/lithium ion battery recycles for the first time) × 100%.
The performance test results of table 2 embodiment 1~12 and comparative example 1~7
From the Correlative data analysis of table 2 it is found that lithium ion battery is in sulphonic acid ester cyclic quaternary ammonium salts and cyclic phosphazene compound
Collective effect under can have preferable cycle performance and high-temperature storage performance.
The analysis in comparative example 1~3 is it is found that sulphonic acid ester cyclic quaternary ammonium salts and ring phosphonitrile chemical combination is not added in comparative example 1
Compounds, the cycle performance and high-temperature storage performance of lithium ion battery are all poor；When only cyclic annular containing sulphonic acid ester in electrolyte
When quaternary ammonium salt (comparative example 2), the cycle performance and high-temperature storage performance of lithium ion battery can be improved to a certain degree,
In, the improvement of the high-temperature storage performance of lithium ion battery is more significant, and the improvement of cycle performance is then relatively unobvious；Work as electrolysis
When only containing cyclic phosphazene compound (comparative example 3) in liquid, the cycle performance of lithium ion battery is improved, and high temperature storage
It can be without improvement, in some instances it may even be possible to will appear slight deterioration.
The analysis in embodiment 1~12 and comparative example 4~7 it is found that be added sulphonic acid ester cyclic quaternary ammonium salts simultaneously in electrolyte
And cyclic phosphazene compound, lithium ion battery have preferable cycle performance and high-temperature storage performance, while it is understood that
The variation of the specific type and dosage of sulphonic acid ester cyclic quaternary ammonium salts and cyclic phosphazene compound necessarily directly influences the performance of electrolyte,
To influence the improvement to performance of lithium ion battery.
In comparative example 4, the content of sulphonic acid ester cyclic quaternary ammonium salts is insufficient, improves to the high-temperature storage performance of lithium ion battery
It is unobvious.In Examples 1 to 5, with the increase of sulphonic acid ester cyclic quaternary salt content, the circulation volume of lithium ion battery is kept
Rate and high temperature storage capacity retention ratio are improved.When the too high levels of sulphonic acid ester cyclic quaternary ammonium salts, such as in comparative example 5
In, the cycle performance and high-temperature storage performance of lithium ion battery can be deteriorated.
In comparative example 6, the content of cyclic phosphazene compound is insufficient, to the circulation volume conservation rate of lithium ion battery improve compared with
It is weak.In embodiment 6~9, as cyclic phosphazene compound content increases, in high-temperature lithium ion battery memory capacity conservation rate without bright
In the case where aobvious degradating trend, the circulation volume conservation rate of lithium ion battery be can be improved.When containing for cyclic phosphazene compound
When measuring excessively high, such as in comparative example 7, since the conductivity of electrolyte reduces, the high temperature storage capacity of lithium ion battery is kept
Rate will appear deterioration, while the dynamic performance of lithium ion battery is deteriorated, and leads to the circulation volume conservation rate of lithium ion battery
Deteriorate.
Therefore the content of sulphonic acid ester cyclic quaternary ammonium salts and cyclic phosphazene compound is too little or too much is unfavorable for changing on the whole
The performance of kind lithium ion battery, but required in relatively low or more secondary use demand for some, it equally can be one
Determine the cycle performance and high-temperature storage performance that improve lithium ion battery in degree.
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 sulphonic acid ester cyclic quaternary ammonium salts and cyclic phosphazene compound.
2. electrolyte according to claim 1, which is characterized in that the sulphonic acid ester cyclic quaternary ammonium salts are selected from shown in formula 1
One or more of compound；
In formula 1, R11The 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；
R12The 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；
R13It 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；
R14Alkylidene 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.
3. electrolyte according to claim 2, which is characterized in that the cation group of the sulphonic acid ester cyclic quaternary ammonium salts selects
From
One of.
4. electrolyte according to claim 3, which is characterized in that the sulphonic acid ester cyclic quaternary ammonium salts are selected from following compounds
One or more of:
5. electrolyte according to claim 1, which is characterized in that the cyclic phosphazene compound is selected from chemical combination shown in formula 2
One or more of object；
In formula 2, R21、R22、R23、R24、R25、R26It is each independently selected from H, halogen atom, the alkyl of C1~20, C2~20
Alkenyl, the alkynyl of C2~20, the aryl of C6~20, the halogenated alkyl of C1~20, the halogenated alkenyl of C2~20, C2~20 it is halogenated
Alkynyl, the halogenated aryl of C6~20, the alkoxy of C1~20, the alkenyloxy group of C2~20, the alkynyloxy group of C2~20, C6~20 virtue
Oxygroup, the halogenated alkoxy of C1~20, the haloalkenyloxy of C2~20, the halogenated alkynyloxy group of C2~20, C6~20 halogenated virtue
One of oxygroup, and R22、R24、R26In at least two be selected from halogen atom.
6. electrolyte according to claim 5, which is characterized in that the cyclic phosphazene compound is in following compounds
It is one or more of；
7. 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 phosphazene compound is the 0.1%~8% of the electrolyte gross mass, it is preferable that the ring phosphonitrile
The content for closing object is the 1%~5% of the electrolyte gross mass.
8. electrolyte according to claim 1, which is characterized in that the content of the electrolytic salt is the total matter of the electrolyte
The 6%~25% of amount, it is preferable that the content of the electrolytic salt is the 6%~20% of the electrolyte gross mass, further excellent
Selection of land, the content of the electrolytic salt are the 10%~15% of the electrolyte total weight.
9. electrolyte according to claim 1, which is characterized in that the electrolyte is liquid electrolyte, solid polymer
Electrolyte or gel polymer electrolytes.
10. a kind of electrochemical energy storage device, which is characterized in that including electrolyte according to claim 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110336075A (en) * | 2019-06-25 | 2019-10-15 | 宁德新能源科技有限公司 | Electrolyte and electrochemical appliance and electronic device comprising it |
| CN113471533A (en) * | 2021-05-25 | 2021-10-01 | 合肥国轩高科动力能源有限公司 | Electrolyte of silicon-carbon negative electrode lithium ion battery and lithium ion battery |
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| CN105489936A (en) * | 2016-01-22 | 2016-04-13 | 宁德新能源科技有限公司 | Non-aqueous electrolyte and lithium ion battery comprising same |
| US20160285125A1 (en) * | 2015-03-27 | 2016-09-29 | Mason K. Harrup | All-inorganic solvents for electrolytes |
| 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 |
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| CN105047994A (en) * | 2015-09-22 | 2015-11-11 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery comprising same |
| CN105489936A (en) * | 2016-01-22 | 2016-04-13 | 宁德新能源科技有限公司 | Non-aqueous electrolyte and lithium ion battery comprising same |
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| CN110336075A (en) * | 2019-06-25 | 2019-10-15 | 宁德新能源科技有限公司 | Electrolyte and electrochemical appliance and electronic device comprising it |
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Application publication date: 20190205 |