CN109309253A - Electrolyte and electrochemical energy storage device - Google Patents

Electrolyte and electrochemical energy storage device Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
electrolyte
unsubstituted
substituted
quaternary ammonium
ammonium salts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710625287.0A
Other languages
Chinese (zh)
Inventor
王小梅
付成华
韩昌隆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Contemporary Amperex Technology Co Ltd
Original Assignee
Contemporary Amperex Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Contemporary Amperex Technology Co Ltd filed Critical Contemporary Amperex Technology Co Ltd
Priority to CN201710625287.0A priority Critical patent/CN109309253A/en
Publication of CN109309253A publication Critical patent/CN109309253A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0567Liquid materials characterised by the additives
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/0025Organic electrolyte
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

This application involves a kind of electrolyte and electrochemical energy storage devices.The electrolyte includes electrolytic salt and additive.The additive includes sulphonic acid ester cyclic quaternary ammonium salts and cyclic phosphazene compound.The two cooperation 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, the solid electrolyte interface film of Low ESR and densification is especially capable of forming in negative terminal surface, corrosion of the hydrofluoric acid to positive and negative electrode in electrolyte can be also reduced simultaneously, under the synergistic effect of the two, electrochemical energy storage device has preferable cycle performance and high-temperature storage performance.

Description

Electrolyte and electrochemical energy storage device
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.
CN201710625287.0A 2017-07-27 2017-07-27 Electrolyte and electrochemical energy storage device Pending CN109309253A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710625287.0A CN109309253A (en) 2017-07-27 2017-07-27 Electrolyte and electrochemical energy storage device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710625287.0A CN109309253A (en) 2017-07-27 2017-07-27 Electrolyte and electrochemical energy storage device

Publications (1)

Publication Number Publication Date
CN109309253A true CN109309253A (en) 2019-02-05

Family

ID=65202314

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710625287.0A Pending CN109309253A (en) 2017-07-27 2017-07-27 Electrolyte and electrochemical energy storage device

Country Status (1)

Country Link
CN (1) CN109309253A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160285125A1 (en) * 2015-03-27 2016-09-29 Mason K. Harrup All-inorganic solvents for electrolytes
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
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Similar Documents

Publication Publication Date Title
CN105633466B (en) Nonaqueous electrolytic solution and lithium ion battery comprising it
CN105047995A (en) Electrolyte, lithium ion battery comprising same and preparation method of lithium ion battery
CN108242567A (en) Electrolyte and secondary cell
CN109309246A (en) Electrolyte and electrochemical energy storage device
CN106159330A (en) A kind of PC base high-voltage electrolyte and a kind of lithium ion battery
CN109309226A (en) Electrochemical energy storage device
CN105161753B (en) Lithium ion battery and its electrolyte
CN102231441A (en) Sulfur-containing electrolyte with film forming function for lithium ion battery as well as preparation method and application thereof
CN109390629B (en) Electrolyte and battery
CN108242557B (en) Electrolyte solution and secondary battery
CN109888384A (en) Electrolyte and battery containing electrolyte
CN105811009B (en) A kind of electrolyte and the lithium ion battery including the electrolyte
CN107017433B (en) Nonaqueous electrolytic solution and lithium ion battery
CN107293776A (en) Electrolyte and lithium ion battery
CN109728340B (en) Lithium ion battery
CN109802176A (en) Electrolyte and lithium ion battery containing electrolyte
CN109309192A (en) Electrode slice and electrochemical energy storage device
CN109309253A (en) Electrolyte and electrochemical energy storage device
CN108258297A (en) Electrolyte and lithium ion battery
CN109309254B (en) Electrolyte and electrochemical energy storage device
CN108242566A (en) Electrolyte and secondary cell
CN106558728A (en) A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery
CN109309245A (en) Electrolyte and electrochemical energy storage device
CN109786832A (en) Electrolysis additive, electrolyte and lithium ion secondary battery
CN109638351A (en) A kind of high-voltage electrolyte that taking into account high temperature performance and its lithium ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20190205