CN109888384A - Electrolyte and battery containing electrolyte - Google Patents
Electrolyte and battery containing electrolyte Download PDFInfo
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- CN109888384A CN109888384A CN201711277431.2A CN201711277431A CN109888384A CN 109888384 A CN109888384 A CN 109888384A CN 201711277431 A CN201711277431 A CN 201711277431A CN 109888384 A CN109888384 A CN 109888384A
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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
- H01M10/05—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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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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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- 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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- 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
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Abstract
Embodiments herein provides electrolyte and the battery containing the electrolyte, and the electrolyte of battery includes: carboxylate；Cyclic ethers and nitrile compound.The application is by the way that carboxylate to be introduced into dicyandiamide solution, in combination with the use of nitrile compound and cyclic ethers, hence it is evident that improves battery core high rate performance, while guaranteeing high-temperature storage performance and high temperature cyclic performance.
Description
Technical field
Embodiments herein is related to field of batteries, electrolyte more particularly, to battery and contains the electrolyte
Battery.
Background technique
Lithium ion battery is because of its higher energy density, the advantages that long circulation life and memory-less effect, is widely used
In fields such as smart phone, wearable device, consumer level unmanned plane and electric cars；With the extensive use of lithium ion battery,
The development of information technology, the requirement to lithium ion battery propose the requirement of fast charging and discharging, therefore such as other than traditional performance
The fast charging and discharging what meets lithium ion battery becomes current line urgent problem in the industry.
Influence many because being known as of the fast charging and discharging of lithium ion battery, wherein weight of the electrolyte as lithium ion battery
Component part is wanted, there is great influence to it.The dynamics of lithium ion battery can be effectively improved by improving electrolyte
Performance reduces big multiplying power polarization, reduces charging temperature rise.Chain carboxylate has the characteristics that low melting point, low viscosity, can effectively change
Kind lithium ion battery big multiplying power charge characteristic under room temperature and low temperature environment, can be effectively reduced lithium ion battery direct-current internal resistance from
And reduce the temperature rise of charging process.But carboxylate is applied to high voltage cobalt acid lithium (LiCoO2) etc. lithium ion battery when, due to
There are stronger oxidisability (LiCoO when lithium ion battery charge and discharge2Electrode, active oxygen), it is easy to cause the oxidation point of carboxylate
Solution.
Therefore, in order to further widen the use of carboxylate solvent, carboxylate electrolyte is improved in high voltage, high temperature system
In stability, need that more particularly suitable additive is added into carboxylate electrolyte.
Summary of the invention
This application provides (> 4.35V) under high voltages improve battery high-temperature stability electrolyte, solve because
The problem of improving dynamic performance and bring high-temperature storage performance and high temperature cyclic performance variation by carboxylate.
Carboxylate is introduced into dicyandiamide solution by the application, in combination with the use of nitrile and cyclic ethers, can be obviously improved battery core times
Rate performance, while guaranteeing high-temperature storage performance and high temperature cyclic performance.
Embodiments herein provides a kind of electrolyte, comprising: carboxylate；And cyclic ethers and nitrile compound.
In above-mentioned electrolyte, wherein the cyclic ethers account for the gross mass of the electrolyte percentage be 0.01%~
2%.
In above-mentioned electrolyte, wherein the nitrile compound account for the gross mass of the electrolyte percentage be 0.5%~
10%.
In above-mentioned electrolyte, wherein the cyclic ethers is selected from 1,3-dioxolane, 1,3- dioxane and Isosorbide-5-Nitrae-dioxy six
One of ring is a variety of.
In above-mentioned electrolyte, wherein the nitrile compound be selected from one of following below formula compound represented or
It is a variety of, wherein R11Selected from carbon atom number be 1~5 alkylidene, carbon atom number be 1~6 one of alkylene oxide group；R21、
R22It is each independently selected from the alkylidene that carbon atom number is 0~5；R31、R32、R33Being each independently selected from carbon atom number is 0~5
Alkylidene, carbon atom number R33
One of 1~5 alkylene oxide group: NC-R11-CN、
In above-mentioned electrolyte, wherein the nitrile compound is selected from one of following compound or a variety of:
In above-mentioned electrolyte, wherein further include lithium salts, the lithium salts include lithium hexafluoro phosphate, difluorophosphate,
One of LiBF4, hexafluoroarsenate lithium, lithium perchlorate, double fluorine sulfimide lithiums, double trifluoromethanesulfonimide lithiums or
It is a variety of.
In above-mentioned electrolyte, wherein the carboxylate account for the gross mass of the electrolyte percentage be 5%~
70%.
In above-mentioned electrolyte, wherein the chemical formula of the carboxylate isWherein, R1、R2Independently select
From carbon atom number between 1~5 alkyl or alkyl halide alkyl.
In the electrolyte of above-mentioned lithium ion battery, wherein the carboxylate includes methyl acetate, ethyl acetate, acetic acid
One of propyl ester, methyl propionate, ethyl propionate and propyl propionate are a variety of.
Another embodiment of the application provides the lithium ion battery including above-mentioned electrolyte, but the present invention is not limited to lithium from
Sub- battery.
The beneficial effects of the present application are as follows passing through the cyclic ethers that carboxylate, specific structure are added into conventional carbonate electrolyte
With the nitrile compound of specific structure, the collective effect of above-mentioned three kinds of compounds is given full play to, and then improves the height of lithium ion battery
Warm cycle performance, high-temperature storage performance and high rate performance.By the way that carboxylate is added into conventional carbonate electrolyte, lithium is improved
The dynamic performance of ion battery, but under high voltages, due to positive electrode less stable, discharge the object with strong oxidizing property
Matter causes carboxylate that oxidation reaction occurs in positive electrode surface.The nitrile compound of cyclic ethers and specific structure that specific structure is added is made
For additive, wherein the cyclic ethers open loop of specific structure forms a film, and nitrile compound inhibits the dissolution of Co ion, therefore stablizes anode,
Inhibit inflatable of the lithium ion battery during high temperature storage, improves the high temperature storing stabilization and high temperature circulation of lithium ion battery
Energy.The application by optimization electrolyte in carboxylate, the cyclic ethers of specific structure, specific structure nitrile compound usage ratio,
Further improve the multiplying power, high-temperature storage performance and high temperature cyclic performance of lithium ion battery.
Specific embodiment
Carboxylic containing chain is added by the present invention for the nitrile compound of the cyclic ethers of specific structure and specific structure
In the electrolyte of sour rouge, the mass percent of cyclic ethers in the electrolytic solution is 0.01%~2%, the matter of nitrile compound in the electrolytic solution
Measuring percentage is 0.5%~10%.Compared with prior art, lithium ion battery can be improved using electrolyte provided by the present application
Dynamic performance, while guaranteeing high temperature cyclic performance and high-temperature storage performance.
The oxidizing potential of the cyclic ethers of specific structure is lower, aoxidizes in cathode surface, open loop generates organic lithium salt, the organolithium
Salt is stablized, and the stability of solid electrolyte interface (SEI) film is enhanced, and alleviates the electrolyte of the lithium ion battery in pyroprocess
In the oxygenolysis of electrode surface, and then reach the mesh of the high-temperature storage performance and high temperature cyclic performance that improve lithium ion battery
's.
Transition metal atoms in the cathode active material of lone pair electrons energy level and lithium ion battery in nitrile functionality
The energy level of the vacant track of outermost layer is close, allows the organic molecule containing nitrile functionality that Absorptive complex wave occurs in cathode surface.
The organic molecule for being adsorbed on cathode surface can well separate component oxidizable in electrolyte with cathode surface, substantially reduce
The cathode surface of the lithium ion battery of Charging state is to the oxidation of electrolyte, so as to improve the cycle performance of lithium ion battery
And high-temperature storage performance.
The organic molecule containing nitrile functionality of different structure will generate different isolation effects from cathode surface to electrolyte.
With the increase of the nitrile functionality number in organic molecule, the isolation effect risen is more significant.Meanwhile having containing nitrile functionality
Machine bulk of molecule has an optimal value, and molecule is too small, and the insulating space of formation is limited, cannot effectively will be easy in electrolyte
Oxidation component is separated with cathode surface, and molecule is excessive, and the oxidizable component in electrolyte can be by containing the organic of nitrile functionality
The gap of molecule is in contact with cathode surface, cannot still play good isolation effect.
It, can be with present applicant have found that the cyclic ethers of specific structure is used in combination with the nitrile compound of specific structure
Largely improve the high-temperature storage performance and high temperature cyclic performance of the lithium ion battery containing carboxylate.Specifically, pass through ring
The collective effect of the Absorptive complex wave of the film forming and nitrile compound of ether, is effectively protected cathode surface, and carboxylate and yin has been isolated
The contact at pole interface, to effectively prevent the deterioration of carboxylate bring high temperature cyclic performance and high-temperature storage performance.
The electrolyte of the application includes organic solvent, lithium salts and additive.In embodiment, organic solvent is non-aqueous organic
Solvent.In some embodiments, organic solvent may include carboxylate compound and carbonats compound.Carbonic ester can be
The carbonic ester of any kind, as long as may be used as nonaqueous electrolyte organic solvent, for example, it may be cyclic carbonate or
Linear carbonate etc..Cyclic carbonate can be ethylene carbonate, propene carbonate, butylene carbonate, pentylene, fluoro
Ethylene carbonate etc., linear carbonate can be dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate etc., but
It is that the application is not limited to that, their halo derivatives can also be used.In addition, these compounds can be independent or several
Kind is used in mixed way.
The carboxylate of the application is chain carboxylate, selected from least one of 1 compound represented of chemical formula:Chemical formula 1
Wherein R1、R2For carbon atom number between 1~5 alkyl or alkyl halide alkyl.Specifically, chemical formula 1 indicates
Carboxylate include methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP) and
One of propyl propionate (PP) is a variety of.On the basis of the gross mass of electrolyte, the content of carboxylate be 5wt.%~
70wt.%.If the content of carboxylate is lower than 5wt.%, low temperature and high power performance improve unobvious.If carboxylate contains
Amount increases more than 70wt.%, irreversible side reaction.
Lithium salts in the electrolyte of the application may include one of inorganic lithium salt and organic lithium salt or a variety of.Specifically
Ground, lithium salts may include lithium hexafluoro phosphate (LiPF6), difluorophosphate (LiPO2F2), LiBF4 (LiBF4), hexafluoro arsenic
One of sour lithium, lithium perchlorate, double fluorine sulfimide lithiums (LiFSI), double trifluoromethanesulfonimide lithiums (LiTFSI) are more
Kind.Preferably, lithium salts is lithium hexafluoro phosphate (LiPF6).The concentration of lithium salts is 0.5M~1.5M.Lithium salt is too low, electrolyte
Conductivity it is low, will affect the multiplying power and cycle performance of entire lithium-ion battery system；Lithium salt is excessively high, is electrolysed fluid viscosity mistake
Greatly, the multiplying power of entire lithium-ion battery system is equally influenced.Preferably, the concentration of lithium salts is 0.8M~1.3M.However, this field
The skilled person will understand that the lithium salts of the application can be any other suitable lithium salts and concentration.
Additive in the electrolyte of the application may include the cyclic ethers of specific structure and the nitrile compounds of specific structure.
Cyclic ethers is the one or more of 1,3- dioxolane, 1,3- dioxane and 1,4- dioxane.Their chemical formula is respectively such as
Shown in lower:
1,3- dioxolane
1,3- dioxane
1,4- dioxane
In some embodiments of the present application, on the basis of the quality of electrolyte, the content of cyclic ethers be 0.01wt.%~
2wt.%, it is insufficient in the liquid film that electrode surface is formed if the content of cyclic ethers is lower than 0.01wt.%, to lithium ion battery
High-temperature storage performance improvement it is unobvious, when the content of cyclic ethers be higher than 2wt.% when, form a film it is thicker, impedance increase, to battery
Cycle performance can also deteriorate.
Nitrile compound in the electrolyte of the application is in chemical formula 2, chemical formula 3,4 compound represented of chemical formula
It is one or more.Wherein, R11Selected from carbon atom number be 1~5 alkylidene, carbon atom number be 1~6 alkylene oxide group in one
Kind；R21、R22It is each independently selected from the alkylidene that carbon atom number is 0~5；R31、R32、R33It is each independently selected from carbon atom number
For 0~5 alkylidene, carbon atom number be 1~5 one of alkylene oxide group.
NC-R11- CN chemical formula 2
Chemical formula 3
Chemical formula 4
According to some embodiments of the present application, nitrile compound can be selected from one of following compounds or a variety of:(compound 1),(compound 2),(change
Close object 3),(compound 4),(compound 5),(compound 6),(compound 7).
In some embodiments of the present application, mass percentage of the nitrile compound in nonaqueous electrolytic solution be 0.5%~
10%.When mass percentage of the nitrile compound in nonaqueous electrolytic solution is lower than 0.5%, in cathode surface and electrolyte
The buffer action of oxidizable component is unobvious, and the cycle performance and high-temperature storage performance to lithium ion battery are not obviously improved,
When mass percentage of the nitrile compound in nonaqueous electrolytic solution is higher than 10%, the cycle performance of lithium ion battery can be deteriorated,
This may be due to when the too high levels of nitrile compound, can viscosity, conductivity to electrolyte have an adverse effect.
The electrolyte of the lithium ion battery of the application can also contain other additives, for example, SEI film film for additive, resistance
Fire additive, anti-overcharge additive, conductive additive etc..
According to some embodiments of the present application, electrolyte can be prepared using conventional method, such as will be each in electrolyte
Kind material is uniformly mixed.
Embodiments herein additionally provides the lithium ion battery including above-mentioned electrolyte.Lithium ion battery further include containing
The positive plate of positive electrode active materials, the negative electrode tab containing negative electrode active material and isolation film.Positive electrode active materials can be selected from
Cobalt acid lithium (LiCoO2), nickel manganese cobalt acid lithium ternary material, nickel manganese lithium aluminate ternary material, LiFePO4, lithium nickelate, LiMn2O4
(LiMn2O4) one of or it is a variety of, the above positive electrode active materials include in the prior art through overdoping or cladding processing anode
Active material.Negative electrode active material can selected from natural graphite, artificial graphite, carbonaceous mesophase spherules (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 of Li-Al alloy or a variety of.Isolation film can use polypropylene isolation film or polyethylene separators, with
Upper isolation film further includes the isolation film that surface is coated with inorganic coating or organic coating.It will be understood by those skilled in the art, however, that
Positive electrode active materials, negative electrode active material and the isolation film of the application can be other suitable materials.
Illustrate the preparation of lithium ion battery, the following examples 1-21 and comparative example 1-13 below with reference to specific embodiment
In lithium ion battery be prepared by the following method.It will be apparent to one skilled in the art that preparation side described in this application
Method is only example, other any suitable preparation methods are within the scope of application.
The preparation process of the lithium ion battery of embodiments herein and comparative example is as follows:
Comparative example 1
(1) preparation of electrolyte
In dry argon atmosphere glove box, by ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate
(DEC) it is that EC:PC:DEC=30:30:40 is mixed according to mass ratio, lithium salts LiPF is added after dissolving and being sufficiently stirred6, mix
Electrolyte is obtained after closing uniformly.Wherein, LiPF6Concentration be 1.05mol/L.It should be understood that above-mentioned mass ratio and concentration are only
Example can use other any suitable mass ratioes and concentration.
(2) preparation of positive plate
By positive electrode active materials cobalt acid lithium (LiCoO2), conductive black (conductive agent Super P), binder gather inclined difluoro second
Alkene is mixed according to weight ratio 97:1.4:1.6, is added N-Methyl pyrrolidone (NMP), is stirred under de-airing mixer effect
To transparent and homogeneous shape, anode sizing agent is obtained；Anode sizing agent is evenly applied on plus plate current-collecting body aluminium foil；By aluminium foil at 85 DEG C
Drying, then after cold pressing, cut-parts, cutting, dry 4h, obtains positive plate under 85 DEG C of vacuum condition.
(3) preparation of negative electrode tab
By negative electrode active material artificial graphite, conductive agent Super P, thickener sodium carboxymethylcellulose (CMC), binder
Butadiene-styrene rubber (SBR) is mixed according to weight ratio 96.4:1.5:0.5:1.6, and deionized water is added, and is acted in de-airing mixer
Lower acquisition negative electrode slurry；Negative electrode slurry is coated uniformly on negative current collector copper foil；Copper foil is dried at 85 DEG C, is then passed through
After crossing cold pressing, cut-parts, cutting, dry 12h, obtains negative electrode tab under 120 DEG C of vacuum condition.
(4) preparation of isolation film
Select the polyethylene separators of 16 μ m-thicks.
(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 winds or stacking obtains naked battery core；Naked battery core is placed in outer packing foil aluminum plastic film after soldering polar ear, by above-mentioned system
The electrolyte got ready is injected into the naked battery core after drying, and by Vacuum Package, standing, chemical conversion, (0.02C constant-current charge is arrived
3.3V, then with 0.1C constant-current charge to the processes such as 3.6V), shaping, volume test, obtain soft bag lithium ionic cell.
Comparative example 2
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 1, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30。
Comparative example 3
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while 1, the 3- dioxolane that mass fraction is 0.5% is added.
Comparative example 4
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while 1, the 3- dioxane that mass fraction is 0.5% is added.
Comparative example 5
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while Isosorbide-5-Nitrae-dioxane that mass fraction is 0.5% is added.
Comparative example 6
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while the compound 2 that mass fraction is 3% is added.
Comparative example 7
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while the compound 4 that mass fraction is 3% is added.
Comparative example 8
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:50:10。
Comparative example 9
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:10:50。
Comparative example 10
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
The mass ratio of enester (EC), propene carbonate (PC) and ethyl acetate (EA) is EC:PC:EA=20:20:60.
Comparative example 11
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and methyl acetate (MA) mass ratio be EC:PC:DEC:MA=
20:20:30:30。
Comparative example 12
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and methyl propionate (MP) mass ratio be EC:PC:DEC:MP=
20:20:30:30。
Comparative example 13
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl propionate (EP) mass ratio be EC:PC:DEC:EP=
20:20:30:30。
Embodiment 1
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that ethylene carbonate in electrolysis
Ester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 3% compound 2 and 0.5% 1,3- dioxolane that mass fraction, which is added,.
Embodiment 2
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 3% compound 2 and 0.5% 1,3- dioxane that mass fraction, which is added,.
Embodiment 3
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 3% compound 2 and 0.5% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 4
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 3% compound 4 and 0.5% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 5
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 3% compound 4 and 0.5% 1,3- dioxane that mass fraction, which is added,.
Embodiment 6
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 3% compound 4 and 0.5% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 7
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 1% compound 4 and 0.5% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 8
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 5% compound 4 and 0.5% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 9
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 7% compound 4 and 0.5% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 10
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 9% compound 4 and 0.5% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 11
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 3% compound 2 and 0.1% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 12
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 3% compound 4 and 0.3% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 13
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that electrolyte is in addition to solvent
Ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC) and the mass ratio of ethyl acetate (EA) are EC:PC:
DEC:EA=20:20:30:30, while it is 3% compound 2 and 0.8% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 14
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 3% compound 2 and 1% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 15
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:30:30, while it is 3% compound 2 and 2% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 16
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:50:10, while it is 3% compound 4 and 0.5% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 17
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl acetate (EA) mass ratio be EC:PC:DEC:EA=
20:20:10:50, while it is 3% compound 4 and 0.5% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 18
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
The mass ratio of enester (EC), propene carbonate (PC) and ethyl acetate (EA) is EC:PC:EA=20:20:60, while matter is added
Measuring score is 3% compound 4 and 0.5% 1,4- dioxane.
Embodiment 19
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and methyl acetate (MA) mass ratio be EC:PC:DEC:MA=
20:20:30:30, while it is 3% compound 4 and 0.5% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 20
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and methyl propionate (MP) mass ratio be EC:PC:DEC:MP=
20:20:30:30, while it is 3% compound 4 and 0.5% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
Embodiment 21
Electrolyte and lithium ion battery are prepared according to method identical with comparative example 2, the difference is that carbonic acid second in electrolyte
Enester (EC), propene carbonate (PC), diethyl carbonate (DEC) and ethyl propionate (EP) mass ratio be EC:PC:DEC:EP=
20:20:30:30, while it is 3% compound 4 and 0.5% Isosorbide-5-Nitrae-dioxane that mass fraction, which is added,.
The type and content of comparative example 1-13 and the additive in embodiment 1-21 are as shown in table 1 below.
The type and content of 1 additive of table
Later, the cycle performance of lithium ion battery, high-temperature storage performance and 2C discharging efficiency are tested:
(1) the big multiplying power discharging property test of lithium ion battery
By comparative example 1~13 and the resulting lithium ion battery of Examples 1 to 21 with the charging of 0.5C constant current/constant voltage at 25 DEG C
To 4.40V, 10min is shelved, with 0.5C constant-current discharge to blanking voltage 3.0V, records discharge capacity.With 0.5C perseverance at 25 DEG C
Stream/constant-voltage charge shelves 10min to 4.40V, with 2C constant-current discharge to blanking voltage 3.0V, records discharge capacity.At 25 DEG C
0.5C capacity is compared and obtains 2C discharging efficiency.Comparative example 1~13 and the test of the lithium ion battery 2C discharge performance of Examples 1 to 21
Data are referring to table 2.
(2) the cycle performance test of lithium ion battery
Lithium ion battery is placed in 45 DEG C of insulating boxs, 30 minutes is stood, lithium ion battery is made to reach constant temperature.It is up to perseverance
The lithium ion battery of temperature with 1C constant-current charge to voltage is 4.4V, is then 0.05C with 4.4V constant-voltage charge to electric current, then with
1C constant-current discharge to voltage is 3.0V, this is a charge and discharge cycles.Such charge/discharge, calculate separately circulating battery 50 times,
Capacity retention ratio after 100 times, 200 times and 300 times.Comparative example 1~13 and 45 DEG C of the lithium ion battery of Examples 1 to 21 follow
Ring test data are referring to table 2.
Capacity retention ratio (%)=n-th circulation discharge capacity/discharge capacity for the first time after lithium ion battery n times circulation
× 100%.
(3) the high-temperature storage performance test of lithium ion battery
By comparative example 1~13 and the resulting lithium ion battery of Examples 1 to 21, at room temperature extremely with 0.5C constant-current charge
4.40V, then constant-voltage charge to electric current is 0.05C, tests the thickness of lithium ion battery and is denoted as h0；Later by lithium ion battery
It is put into 60 DEG C of insulating box, keeps the temperature 30 days, and every the thickness of 6 days test lithium ion batteries and is denoted as hn, n is lithium ion battery
The number of days of high temperature storage.60 DEG C of storage test datas of comparative example 1~13 and the lithium ion battery of Examples 1 to 21 are referring to table 2.
Thickness swelling (%)=(hn-h0)/h0 × 100% after high-temperature lithium ion battery storage n days.
The performance test results of table 2 comparative example 1-13 and embodiment 1-21 sum
Compare comparative example 1 and comparative example 2, after 8-13 can be seen that addition carboxylate, improves big times of lithium ion battery
Rate discharge performance, but the high temperature cyclic performance of lithium ion battery and high-temperature storage performance deteriorate.
After comparing comparative example 2 and comparative example 3-7 it is found that individually adding 0.5% cyclic ethers or 3% nitrile compound, lithium
The high temperature cyclic performance and high-temperature storage performance of ion battery have obtained different degrees of improvement.
Compare comparative example 2-13 and embodiment 1-6, implementation column 16-21 it is found that be added specific simultaneously in nonaqueous electrolytic solution
The cyclic ethers of structure and the nitrile compound of specific structure, high temperature cyclic performance and high-temperature storage performance to lithium ion battery change
Kind effect becomes apparent.
Compare comparative example 5 and embodiment 6-10 it is found that the specific cyclic ethers containing mass fraction 0.5%, while adding quality
When the specific nitrile compound that score is 1~9%, the high temperature cyclic performance and high-temperature storage performance of lithium ion battery are obviously improved.
But nitrile compound content is when being more than 5%, then when increasing the content of nitrile compound, high temperature cyclic performance and big multiplying power discharging
It can reduce, this is because the nitrile compound of high-content increases the viscosity of electrolyte, lead to high temperature cyclic performance and big multiplying power
Discharge performance reduces.
Compare comparative example 6 and embodiment 3,11-15 it is found that containing mass fraction be 3% nitrile compound while addition
When the cyclic ethers that mass fraction is 0.1%~2%, the high temperature cyclic performance and high-temperature storage performance of lithium ion battery obviously change
It is kind.But the additional amount of cyclic ethers, when being more than 1%, the high temperature cyclic performance of lithium ion battery and big multiplying power discharging property reduce.
This is because the impedance of lithium ion battery increases when cyclic ether content is high, causes Capacity fading to accelerate, be degrading lithium-ion electric
The cycle performance in pond and big multiplying power discharging property.
The above results explanation, carboxylate, the cyclic ethers of specific structure, specific structure being used in conjunction with for nitrile compound can have
Effect improves the performances such as dynamics, high temperature circulation, the high temperature storage of lithium ion battery.
The above is only several embodiments of the present invention, not any type of limitation is done to the present invention, although this hair
It is bright to be disclosed as above with preferred embodiment, however be not intended to limit the invention, any person skilled in the art, it is not taking off
In the range of technical solution of the present invention, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of electrolyte, comprising:
Carboxylate；And
Cyclic ethers and nitrile compound.
2. electrolyte according to claim 1, wherein the percentage that the cyclic ethers accounts for the gross mass of the electrolyte is
0.01%~2%.
3. electrolyte according to claim 1, wherein the nitrile compound accounts for the percentage of the gross mass of the electrolyte
It is 0.5%~10%.
4. electrolyte according to claim 1, wherein the cyclic ethers be selected from 1,3-dioxolane, 1,3- dioxane and
One of 1,4- dioxane is a variety of.
5. electrolyte according to claim 1, wherein the nitrile compound is in following below formula compound represented
It is one or more, wherein R11Selected from carbon atom number be 1~5 alkylidene, carbon atom number be 1~6 alkylene oxide group in one
Kind；R21、R22It is each independently selected from the alkylidene that carbon atom number is 0~5；R31、R32、R33It is each independently selected from carbon atom number
For 0~5 alkylidene, carbon atom number be 1~5 one of alkylene oxide group: NCR11CN、
6. electrolyte according to claim 1, wherein the nitrile compound is selected from one of following compound or more
Kind:
7. electrolyte according to claim 1, wherein further include lithium salts, the lithium salts includes lithium hexafluoro phosphate, two
Lithium fluophosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, double fluorine sulfimide lithiums, in double trifluoromethanesulfonimide lithiums
It is one or more.
8. electrolyte according to claim 1, wherein the percentage that the carboxylate accounts for the electrolyte gross mass is
5%~70%.
9. electrolyte according to claim 1, wherein the chemical formula of the carboxylate is
Wherein, R1、R2For carbon atom number between 1~5 alkyl or alkyl halide alkyl；
In the preferred methyl acetate of the carboxylate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and propyl propionate
It is one or more.
10. a kind of battery, wherein including electrolyte according to claim 1 to 9.
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