CN106340672A - Lithium ion battery non-aqueous electrolyte and lithium ion battery - Google Patents
Lithium ion battery non-aqueous electrolyte and lithium ion battery Download PDFInfo
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- CN106340672A CN106340672A CN201610538401.1A CN201610538401A CN106340672A CN 106340672 A CN106340672 A CN 106340672A CN 201610538401 A CN201610538401 A CN 201610538401A CN 106340672 A CN106340672 A CN 106340672A
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- aqueous 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
- 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
- H01M10/0567—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
- 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 invention discloses a lithium ion battery non-aqueous electrolyte and a lithium ion battery. The lithium ion battery non-aqueous electrolyte comprises an unsaturated phosphate ester compound and a sulfone compound, and the sulfone compound comprises a cyclic sulfone compound and/or a linear sulfone compound; the unsaturated phosphate ester compound has a structure represented by formula 1; and the cyclic sulfone compound has a structure represented by formula 2, and the linear sulfone compound has a structure represented by formula 3. The non-aqueous electrolyte is characterized in that the unsaturated phosphate ester compound and the sulfone compound are simultaneously added to the electrolyte in order to form a protection film with the advantages of uniform components, moderate thickness and good compactness on an electrode interface; the unsaturated phosphate ester compound cooperates with the sulfone compound to make the electrolyte have good stability on a positive electrode in order to make the battery have excellent high-temperature performances and excellent cycle performances, and the unsaturated phosphate ester compound and the sulfone compound are combined to make the battery have low impedance in order to make the battery have excellent low-temperature performances. The electrolyte lays a foundation for the production of high-quality power batteries.
Description
Technical field
The application is related to lithium-ion battery electrolytes field, more particularly to a kind of non-aqueous electrolyte for lithium ion cell and lithium
Ion battery.
Background technology
Lithium ion battery, compared with other batteries, has light weight, small volume, running voltage is high, energy density is high, output
Power is big, charge efficiency is high, memory-less effect and the advantages of have extended cycle life, and has more and more been used for 3c consumption at present
Electronic product market.And the development with new-energy automobile, non-aqueous electrolyte lithium ion battery is as the power current of automobile
Origin system is also increasingly popularized.The continuous improvement requiring with new-energy automobile course continuation mileage, increasingly requires lithium ion power
The high-energy-density of battery.Ternary nickel cobalt manganese anode material is because of its higher energy density, low cost, function admirable, safety
The advantage such as property is relatively preferable, becomes the study hotspot of current new energy resource power battery positive electrode, and with electrokinetic cell energy
The continuous improvement of density, ternary nickel cobalt manganese material electrokinetic cell just develops towards high-tension direction.
But as positive electrode, ternary nickel cobalt manganese material haves the shortcomings that high-temperature behavior is not enough, in ternary nickel cobalt manganese material
In, nickel element has very strong catalytic action to electrolyte, understands the decomposition of catalytic electrolysis liquid, thus reducing discharge capacity, and
The accumulation of catabolite can lead to obvious internal resistance to increase；This situation high voltage, high temperature and nickel content higher under conditions of,
Can become to be particularly acute, thus deterioration significantly, hinder high voltage ternary nickel cobalt manganese material battery to lead in electrokinetic cell
Domain practical.
Electrolyte is the key factor of impact battery combination property, and especially, the additive in electrolyte is each to battery
The performance of item performance is even more important.Therefore, to give full play to the performance of the electrokinetic cell of ternary nickel cobalt manganese material, electrolyte
It is crucial for joining.Lithium-ion battery electrolytes practical at present are to add traditional film for additive such as vinylene carbonate (contracting
Write vc) or fluorinated ethylene carbonate (abbreviation fec) nonaqueous electrolytic solution, excellent the following of battery is ensured by the interpolation of vc and fec
Ring performance.But the high voltage less stable of vc, easily decomposes aerogenesis under fec high temperature.Therefore, under high voltage hot conditionss,
These additives are difficult to meet the performance requirement of high temperature circulation.
A kind of new film for additive of phosphate compound containing three keys is disclosed in patent application 201410534841.0,
It not only can improve high temperature cyclic performance moreover it is possible to be obviously improved storge quality.Sulfone compound also sees document report very early
(journal of power sources 179 (2008) 770 779), mainly improves the stability of high-voltage battery, improves
Cycle performance.But the scientific worker of this area finds under study for action, the phosphate ester additive of three keys is formed in electrode interface
Passivation film conductivity poor, leading to interface impedance larger hence it is evident that deteriorating cryogenic property, being particularly easy to lead to battery in low temperature
The lower analysis lithium that charges is it is suppressed that the application under cryogenic of nonaqueous lithium ion battery.
Content of the invention
The purpose of the application is to provide a kind of new non-aqueous electrolyte for lithium ion cell and lithium ion battery.
To achieve these goals, the application employs technical scheme below:
The one side of the application discloses a kind of non-aqueous electrolyte for lithium ion cell, including unsaturated phosphoric acid ester and sulfone class
Compound, sulfone compound includes ring-type sulfone compound and/or straight chain sulfone compound；
Unsaturated phosphate compounds have structure shown in formula one,
Wherein, r1、r2、r3Separately it is selected from the alkyl that carbon number is 1-4, and r1、r2、r3In at least one be containing
There are double bond or the unsaturated alkyl of three key；
Ring-type sulfone compound has structure shown in formula two, and straight chain sulfone compound has structure shown in formula three,
Wherein, r4、r5、r6、r7Separately be selected from hydrogen atom, halogen or carbon number are the alkyl of 1-5, a be including
The substituted or non-substituted alkylidene of 2～6 carbon numbers, the functional group that it replaces can be halogen or carbon number is 1-3
Alkyl.
It should be noted that the application's it is critical that with the addition of above-mentioned in non-aqueous electrolyte for lithium ion cell simultaneously
Unsaturated phosphate compounds and sulfone compound, overcome the boundary that the unsaturated phosphate compounds of independent interpolation are led to
Face impedance is big, charge under low temperature the defects such as analysis lithium.Wherein, sulfone compound can be ring-type sulfone compound or straight chain sulfone class
Compound or both be used in mixed way.
Also, it should be noted sulfone compound be applied to electrolyte not the application take the lead in propose, the application pass through
Substantial amounts of research and test find, sulfone compound and above-mentioned unsaturation phosphate compounds are used cooperatively, is obtained in that
Preferably high temperature performance and cycle performance, thus propose the application.It is appreciated that the application is in patent application
On the basis of 201410534841, and proposed with patent application 201510397735.7 as priority, therefore, above two pieces
Correlation technique content in patent application and term are applied to the application.Additionally, the application's it is critical only that sulfone compound
Use cooperatively with above-mentioned unsaturation phosphate compounds, as specific sulfone compound and above-mentioned unsaturation phosphoric acid ester
Compound, the compound that can be commonly used using existing laboratory or be of little use；But, in order to ensure the performance of nonaqueous electrolytic solution,
In the preferred scheme of the application, particular type to sulfone compound and above-mentioned unsaturation phosphate compounds, or even specifically
Compound is illustrated and limits, and this will be discussed in detail in technical scheme below.
Preferably, the unsaturated phosphate compounds of the application are selected from the compound of structural formula shown in table 1 at least
One kind, that is, unsaturated phosphate compounds are selected from least one to compound 6 for the compound 1.
Table 1 is used for the unsaturated phosphate compounds of non-aqueous electrolyte for lithium ion cell
It is appreciated that either unsaturated phosphate compounds shown in formula one, or compound 1 arrives compound 6
Unsaturated phosphate compounds, are all the preferred technical schemes of the application however not excluded that other has similar physicochemical properties
Unsaturated phosphate compounds.
It is furthermore preferred that ring-type sulfone compound is formula four and/or at least one of structural compounds shown in formula five,
Wherein, r8-r16Separately it is selected from the alkyl that hydrogen atom, halogen or carbon number are 1-5.
It is furthermore preferred that sulfone compound be selected from sulfolane, 3- methyl sulfolane, 3,3,4,4- tetrafluoro sulfolane, ring penta sulfone,
At least one in dimethyl sulfone, Methylethyl sulfone and diethyl sulfone.
It is appreciated that either sulfone compound shown in formula five for the formula two, or the concrete several sulfone class chemical combination limiting
Thing, is all the optimal technical scheme of the application however not excluded that other has the sulfone compound of similar physicochemical properties.
Preferably, in the non-aqueous electrolyte for lithium ion cell of the application, unsaturated phosphate compounds account for lithium-ion electric
The 0.1%～2% of pond nonaqueous electrolytic solution gross weight.
Preferably, in the non-aqueous electrolyte for lithium ion cell of the application, unsaturated phosphate compounds account for lithium-ion electric
The 0.2%～1% of pond nonaqueous electrolytic solution gross weight.
Preferably, in the non-aqueous electrolyte for lithium ion cell of the application, sulfone compound accounts for lithium ion battery non-aqueous solution electrolysis
The 0.1%～30% of liquid gross weight.
Preferably, sulfone compound accounts for the 0.1%～10% of non-aqueous electrolyte for lithium ion cell gross weight.
It is further preferred that sulfone compound accounts for the 0.5～10% of non-aqueous electrolyte for lithium ion cell gross weight.
It is furthermore preferred that sulfone compound accounts for the 1～10% of non-aqueous electrolyte for lithium ion cell gross weight.
In the non-aqueous electrolyte for lithium ion cell of the application, when the consumption of unsaturated phosphate compounds is less than 0.1%
When, both positive and negative polarity film-formation result is poor, and does not have the effect improving performance；And it is too high to work as its consumption, during more than 2%, can make electrode
The one-tenth thickness at interface, increases battery impedance, deterioration.
Meanwhile, when the content of sulfone compound is less than 0.1%, sulfone compound cannot effectively play a role；When sulfone class
When the content of compound is more than 10%, it is true that within the specific limits, such as less than 30%, remain to embody preferable performance.
When the content of sulfone compound is more than 30%, electrolysis fluid viscosity can be led to excessive, simultaneously thicker in electrode interface film forming, increase
Battery impedance, deterioration.
It should be noted that unsaturated phosphate compounds are made by it is critical only that of the application with sulfone compound cooperation
With thus improving high temperature performance and cycle performance；It is appreciated that both consumption changes will necessarily directly affect electrolyte
Performance, thus affect high temperature performance and the cycle performance of battery.Therefore, in the preferred version of the application, in order to ensure electricity
Solution liquid and the performance of battery, are particularly limited to both consumptions.It is appreciated that in scope defined herein,
The nonaqueous electrolytic solution being configured has good high temperature performance and cycle performance；If exceeding this scope, its corresponding performance
Will necessarily be impacted, but, require in relatively low or more secondary use demand for some, equally can be to a certain degree
On improve high temperature performance or the cycle performance of battery.
Further, in the non-aqueous electrolyte for lithium ion cell of the application, sulfone compound and unsaturated phosphoric acid ester
The weight of compound is than more than or equal to 0.2.When the content of unsaturated phosphate compounds is high and sulfone compound content is relatively low
When, cryogenic property is substantially not enough.
Preferably, the organic solvent of nonaqueous electrolytic solution is selected from ethylene carbonate, Allyl carbonate, butylene, carbonic acid
At least one in dimethyl ester, diethyl carbonate, Ethyl methyl carbonate and methyl propyl carbonate.
Preferably, the lithium salts of nonaqueous electrolytic solution is selected from lithium hexafluoro phosphate, lithium perchlorate, LiBF4, double fluorine oxalic acid boron
At least one in sour lithium, two (trimethyl fluoride sulfonyl) imine lithium and imidodisulfuryl fluoride lithium salt.
The another side of the application discloses a kind of lithium ion battery, including positive pole, negative pole, is placed between positive pole and negative pole
Barrier film, and electrolyte, wherein, electrolyte is the non-aqueous electrolyte for lithium ion cell of the application.
The charge cutoff voltage of the lithium ion battery of the application is more than or equal to 4.35v.
Preferably, in the lithium ion battery of the application, positive pole is selected from licoo2、linio2、limn2o4、lico1-ymyo2、
lini1-ymyo2、limn2-ymyo4And linixcoymnzm1-x-y-zo2In at least one；, wherein, m be selected from fe, co, ni, mn,
At least one in mg, cu, zn, al, sn, b, ga, cr, sr, v and ti, and 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤
1.
It should be noted that the nonaqueous electrolytic solution of the application, develop for lithium ion battery, therefore, it can fit
For various lithium ion batteries, include but are not limited to the type cited by the application.
Because using above technical scheme, the application has the beneficial effects that:
The nonaqueous electrolytic solution of the application, phosphate compounds unsaturated shown in formula one and sulfone compound are coordinated, with
When be added in electrolyte, form one layer of uniform ingredients, thickness in electrode interface moderate, and the good protecting film of compactness；Both
Use cooperatively, so that electrolyte is just having good stability so that battery obtains excellent high performance and circulation
Performance, furthermore, it is possible to making the relatively low impedance of battery holding, making battery obtain excellent cryogenic property.The non-water power of the application
Solution liquid is that the electrokinetic cell of preparation high-quality is laid a good foundation.
Specific embodiment
The application's it is critical that coordinates the unsaturated phosphate compounds shown in formula one and sulfone compound, plus
In the nonaqueous electrolytic solution entering, while not affecting high-temperature behavior and cycle performance, so that battery keeps relatively low interior
Resistance, and then make battery obtain excellent cryogenic property.
Wherein, the unsaturated phosphate compounds shown in formula one can form stable passivating film in negative terminal surface, can
Largely stop the reduction decomposition of electrolyte.Additionally, unsaturated phosphate compounds also can form protection in positive electrode surface
Film, can stop electrolyte in the oxidized decomposition of positive electrode surface further, suppress the dissolution of cathode metal ion, especially simultaneously
When charging voltage is equal to or more than 4.35v, its effect becomes apparent from, and can significantly improve high-temperature behavior and the circulation of lithium battery
Performance, but the interpolation of the unsaturated phosphate compound of formula one also causes internal resistance to increase simultaneously, thus the asking of deteriorated low temperature performance
Topic.
For the problems referred to above, the application, on the basis of phosphate compounds unsaturated shown in adding type one, adds sulfone
Class compound.Because the oxidizing potential of sulfone compound is relatively low, can form that a layer thickness is relatively thin in positive pole, composition uniformly, cause
The good protecting film of close property.The compactness of protecting film can be effectively improved well the decomposition reaction in positive pole for the electrolyte, stops positive pole gold
Belong to the dissolution of ion；The thickness of protecting film and the uniform property of composition, can effectively reduce impedance；And the reduction of impedance can make
Obtain battery and obtain excellent cryogenic property.
Therefore, the having the beneficial effects that of the non-aqueous electrolyte for lithium ion cell of the application:
(1) unsaturated phosphate compounds can form a fine and close passivating film so that electrolyte has preferably in positive pole
Stability so that battery has excellent high-temperature behavior and cycle performance.Sulfone compound can also in electrode film forming,
Formed membrane component uniformly, fine and close so that battery has relatively low impedance so that battery has excellent cryogenic property.
(2) by phosphate compounds unsaturated shown in formula one and sulfone compound cooperation, it is added simultaneously in electrolyte,
Moderate in electrode interface formation one layer of uniform ingredients, thickness, and the good protecting film of compactness；Both use cooperatively, and can make electricity
Pond obtains excellent high performance and cycle performance, and, both combinations can make battery keep relatively low impedance, and then makes battery
Obtain excellent cryogenic property.
Additionally, for the performance ensureing nonaqueous electrolytic solution, the application unsaturated phosphate compounds, sulfone class to formula one
The consumption of compound is defined.Wherein, sulfone compound account for non-aqueous electrolyte for lithium ion cell gross weight 0.5%～
30% it is preferred that account for the 1～10% of non-aqueous electrolyte for lithium ion cell gross weight, and this is higher in order to obtain in the electrolytic solution
Chemical stability, give full play to the performance of electrolyte.And, in a kind of preferred implementation of the application, add simultaneously
Ring-type sulfone compound and chain sulfone compound, both synergism are added, the content of ring-type sulfone compound is electrolyte
The 1-3% of gross weight, the content of chain sulfone compound is the 1-2% of electrolyte gross weight, and both synergism are in positive pole
The protection film thickness being formed is more uniform, and compactness is good, can effectively reduce impedance, and improve the performance of battery.
Below by specific embodiment, the application is described in further detail.Following examples only are entered to advance to the application
One step explanation, should not be construed as the restriction to the application.
Embodiment 1
The preparation method of this example lithium ion battery, including positive pole preparation process, negative pole preparation process, electrolyte preparation step
Suddenly, barrier film preparation process and battery number of assembling steps.Specific as follows:
Positive pole preparation process is: by 96.8:2.0:1.2 quality than blended anode active material
lini0.5co0.2mn0.3o2, conductive carbon black and binding agent polyvinylidene fluoride, be dispersed in n- N-methyl-2-2-pyrrolidone N, obtain
Anode sizing agent, anode sizing agent is uniformly coated on the two sides of aluminium foil, through drying, rolling and be vacuum dried, and uses ultrasound wave
Welding machine is burn-on and is obtained positive plate after aluminum lead-out wire, and the thickness of pole plate is between 120-150 μm.
Negative pole preparation process is: by 96:1:1.2:1.8 quality than admixed graphite, conductive carbon black, binding agent butadiene-styrene rubber
And carboxymethyl cellulose, disperse in deionized water, to obtain cathode size, cathode size is coated on the two sides of Copper Foil, warp
Cross drying, calendering and be vacuum dried, and burn-on with supersonic welder and obtain negative plate after nickel lead-out wire, the thickness of pole plate exists
Between 120-150 μm.
Electrolyte preparation process is: ethylene carbonate, Ethyl methyl carbonate and diethyl carbonate is by volume ec:emc:
Dec=3:3:4 is mixed, and adds the lithium hexafluoro phosphate that concentration is 1.0mol/l, add and be based on electrolyte gross weight after mixing
The three propargyl phosphate esters of 0.1wt% and the sulfolane of 0.5wt%.
Barrier film preparation process is: using polypropylene, polyethylene and three layers of isolating membrane of polypropylene, thickness is 20 μm.
Battery number of assembling steps is: places three layers of isolating membrane that thickness is 20 μm between positive plate and negative plate, then will
The sandwich structure of positive plate, negative plate and barrier film composition is wound, then puts into square aluminum metal after coiling body is flattened
In shell, the lead-out wire of both positive and negative polarity is respectively welded on the relevant position of cover plate, and with laser-beam welding machine by cover plate and metal-back
It is welded as a whole, obtain the battery core treating fluid injection；The electrolyte of above-mentioned preparation is injected in battery core by liquid injection hole, the amount of electrolyte
Ensure full of the space in battery core.
Then carry out the conventional chemical conversion of initial charge: 0.05c constant-current charge 3min, 0.2c constant-current charge according to the following steps
5min, 0.5c constant-current charge 25min, shelves 1h, shaping, after-teeming liquid, sealing, then further with the electric current constant-current charge of 0.2c
To 4.2v, after normal temperature shelf 24h, 0.2c constant-current constant-voltage charging to 4.2v, then with the electric current constant-current discharge of 0.2c to 3.0v.Obtain
Obtain the lithium ion battery of this example.
The lithium ion battery of this example preparation is tested as follows:
(1) high temperature cyclic performance test: at 45 DEG C, the battery after chemical conversion is charged to 4.35v with 1c constant current constant voltage, then
With 1c constant-current discharge to 3.0v.After 300 circulations of charge/discharge, calculate the conservation rate of the 300th circulation volume, high to assess it
Warm cycle performance.Computing formula is as follows:
300th circulation volume conservation rate (%)=(the 300th cyclic discharge capacity/first time cyclic discharge capacity) ×
100%.
(2) normal-temperature circulating performance test: at 25 DEG C, the battery after chemical conversion is charged to 4.35v with 1c constant current constant voltage, then
With 1c constant-current discharge to 3.0v.The conservation rate of the 500th circulation volume is calculated, to assess its room temperature after 500 circulations of charge/discharge
Cycle performance.Computing formula is as follows:
500th circulation volume conservation rate (%)=(the 500th cyclic discharge capacity/first time cyclic discharge capacity) ×
100%；
(3) high-temperature storage performance: the battery after chemical conversion is charged to 4.35v with 1c constant current constant voltage at normal temperatures, measures battery
Initial discharge capacity, then after 60 DEG C of storages 30 days, is discharged to 3.0v with 1c, the holding capacity of measurement battery and recovery are held
Amount.Computing formula is as follows:
Battery capacity conservation rate (%)=holding capacity/initial capacity × 100%；
Capacity resuming rate (%)=recovery capacity/initial capacity × 100%.
(4) low temperature performance test: at 25 DEG C, the battery after chemical conversion is charged to 4.35v with 1c constant current constant voltage, then
With 1c constant-current discharge to 3.0v, record discharge capacity.Then 1c constant current constant voltage is full of, and is placed in -20 DEG C of environment and shelves 12h
Afterwards, 1c constant-current discharge, to 3.0v, records discharge capacity.
- 20 DEG C of low temperature discharging efficiency value=1c discharge capacity (- 20 DEG C)/1c discharge capacity (25 DEG C).
(5) often low temperature direct impedance (dcir) performance test: at 25 DEG C, the battery 1c after chemical conversion is charged to half electric shape
State, uses 0.1c, 0.2c, 0.5c, 1c and 2c charge and discharge ten seconds respectively, records discharge and recharge blanking voltage respectively.Then, with different multiplying
Charging and discharging currents be abscissa (unit: a), the blanking voltage corresponding to charging and discharging currents, as vertical coordinate, makees linear relationship
Figure (unit: mv).
The slope value of the linear graph of charging dcir value=difference charging current and corresponding blanking voltage.
The slope value of the linear graph of electric discharge dcir value=difference discharge current and corresponding blanking voltage.
(6) in addition, after to the battery after chemical conversion is charged with 0.3c at 0 DEG C, measuring the analysis lithium degree of negative pole, and adopt 5
Point system is estimated, and fraction is lower, illustrates to analyse lithium more serious.Specifically, lithium, 4 expressions more slightly analysis lithium, 3 tables are not analysed in 5 points of expressions
Show that typically lithium is seriously analysed in analysis lithium, 2 expression more serious analysis lithium, 1 expression.
All test results of this example are as shown in table 3.
Embodiment 2-20
In embodiment 2-20, except the particular compound of sulfone compound and unsaturated phosphate compounds, and its use
Beyond amount difference, other is all same as Example 1.The particular compound of each embodiment, and its consumption is as shown in table 2, wherein uses
Amount is to calculate according to the percentage ratio that each material accounts for non-aqueous electrolyte for lithium ion cell gross weight.
In addition, the application have also been devised 6 comparative examples, i.e. comparative example 1-6, likewise, 6 comparative examples and embodiment 1 or
Other embodiments are compared, and are also only that the particular compound added is different with consumption, other is all same as Example 1.Each contrast
The particular compound of example, and its consumption is as shown in table 2, likewise, wherein consumption is to account for lithium ion battery according to the material adding
The percentage ratio of nonaqueous electrolytic solution gross weight calculates.
The material of each embodiment of table 2 and comparative example and its consumption
In table, the corresponding embodiment of blank expression or comparative example do not add this corresponding material, three propargyl phosphate esters
I.e. compound 1 in table 1, diallyl ethyl phosphonic acid ester is the compound 4 in table 1.
The test result of embodiment 1-20 and comparative example 1-6 is as shown in table 3.
The each embodiment of table 3 and the test result of comparative example
In table 2,0 DEG C of 0.3c charges, and in negative pole analysis lithium Tachistoscope, lithium is not analysed in 5 expressions, lithium, 3 tables are more slightly analysed in 4 expressions
Show that typically lithium is seriously analysed in analysis lithium, 2 expression more serious analysis lithium, 1 expression.
By the test result contrast of comparative example 1-6, it can be found that when unsaturated phosphate compounds are used alone, following
Preferably, cryogenic property is very poor for ring performance and high temperature storage.When sulfone compound is used alone, cycle performance and high-temperature storage performance
Poor, cryogenic property is preferable.
And in the test result of embodiments herein 1-20, by the contrast of comparative example 1 and embodiment 3-5,8-13, can
To find, on the basis of unsaturated phosphate compounds, to add sulfone compound, not only cryogenic property can substantially be changed
Kind, cycle performance and high-temperature behavior also have more apparent improvement simultaneously.
Meanwhile, in the test result of embodiments herein 1-20, with respect to comparative example 1-6, it can be found that comprise simultaneously
The high-temperature behavior of all embodiments of unsaturated phosphate compounds and sulfone compound and cryogenic property all make moderate progress.Logical
Cross embodiment 4,6,7 contrast, 17 and 19 contrasts, with the increase of unsaturated phosphate compounds, its high-temperature behavior has carried
Height, but cryogenic property relative drop, particularly impedance, with the increase of consumption, impedance also increases therewith.Especially work as unsaturation
The content of phosphate compounds is high and when sulfone compound content is relatively low, cryogenic property is substantially not enough.
In sum, unsaturated phosphate compounds and sulfone compound are used cooperatively by the application, suitable than
Under example, battery can be made to obtain excellent high-temperature behavior and cycle performance and good cryogenic property.Wherein, in consumption side
Face, unsaturated phosphoric acid ester consumption 0.1%～2%, sulfone compound consumption 0.1%～30% can act as improving high/low temperature
Performance and the effect of cycle performance；And the feelings in unsaturated phosphate ester consumption 0.2%～1%, sulfone compound consumption 1～10%
Under condition, better.
Above content is further description the application made with reference to specific embodiment it is impossible to assert this Shen
Being embodied as please is confined to these explanations.For the application person of an ordinary skill in the technical field, do not taking off
On the premise of the application design, some simple deduction or replace can also be made, all should be considered as belonging to the protection of the application
Scope.
Claims (9)
1. a kind of non-aqueous electrolyte for lithium ion cell it is characterised in that: include unsaturated phosphate compounds and sulfone class chemical combination
Thing, described sulfone compound includes ring-type sulfone compound and/or straight chain sulfone compound；
Described unsaturation phosphate compounds have structure shown in formula one,
Wherein, r1、r2、r3Separately it is selected from the alkyl that carbon number is 1-4, and r1、r2、r3In at least one is containing double
Key or the unsaturated alkyl of three key；
Described ring-type sulfone compound has structure shown in formula two, and described straight chain sulfone compound has structure shown in formula three,
Wherein, r4、r5、r6、r7Separately it is selected from the alkyl that hydrogen atom, halogen or carbon number are 1-5, a is including 2～6
The substituted or non-substituted alkylidene of individual carbon number, the functional group that it replaces is halogen or carbon number is the alkyl of 1-3.
2. non-aqueous electrolyte for lithium ion cell according to claim 1 it is characterised in that: described ring-type sulfone compound is
Formula four and/or at least one of structural compounds shown in formula five,
Wherein, r8-r16Separately it is selected from the alkyl that hydrogen atom, halogen or carbon number are 1-5.
3. non-aqueous electrolyte for lithium ion cell according to claim 1 it is characterised in that: described sulfone compound be selected from ring
In fourth sulfone, 3- methyl sulfolane, 3,3,4,4- tetrafluoro sulfolane, ring penta sulfone, dimethyl sulfone, Methylethyl sulfone and diethyl sulfone
At least one.
4. the non-aqueous electrolyte for lithium ion cell according to any one of claim 1-3 it is characterised in that: described unsaturation phosphorus
Acid esters compound accounts for the 0.1%～2% of non-aqueous electrolyte for lithium ion cell gross weight it is preferred that to account for lithium ion battery non-aqueous
The 0.2%～1% of electrolyte gross weight.
5. the non-aqueous electrolyte for lithium ion cell according to any one of claim 1-3 it is characterised in that: described sulfone class chemical combination
Thing accounts for the 0.1%～30% of non-aqueous electrolyte for lithium ion cell gross weight it is preferred that accounting for non-aqueous electrolyte for lithium ion cell gross weight
The 0.1～10% of amount, it is further preferred that accounting for the 0.5～10% of non-aqueous electrolyte for lithium ion cell gross weight, it is furthermore preferred that
Account for the 1～10% of non-aqueous electrolyte for lithium ion cell gross weight.
6. the non-aqueous electrolyte for lithium ion cell according to any one of claim 1-3 it is characterised in that: described sulfone class chemical combination
Thing with described unsaturation phosphate compounds weight than more than or equal to 0.2.
7. a kind of lithium ion battery, including positive pole, negative pole, the barrier film being placed between positive pole and negative pole, and electrolyte, its feature
It is: described electrolyte is the non-aqueous electrolyte for lithium ion cell described in any one of claim 1-6.
8. lithium ion battery according to claim 7 it is characterised in that: described positive pole be selected from licoo2、linio2、
limn2o4、lico1-ymyo2、lini1-ymyo2、limn2-ymyo4And linixcoymnzm1-x-y-zo2One of or two or more,
Wherein, m is selected from one of fe, co, ni, mn, mg, cu, zn, al, sn, b, ga, cr, sr, v and ti or two or more, and 0≤
Y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
9. lithium ion battery according to claim 7 it is characterised in that: the charge cutoff voltage of described lithium ion battery is big
In or be equal to 4.35v.
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| CN201910517222.3A CN110233292B (en) | 2015-07-08 | 2016-07-08 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
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| WO2017004885A1 (en) | 2017-01-12 |
| CN110233292A (en) | 2019-09-13 |
| CN110233292B (en) | 2021-02-12 |
| CN105140561A (en) | 2015-12-09 |
| WO2018006563A1 (en) | 2018-01-11 |
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