CN108110318A - A kind of nonaqueous electrolytic solution and lithium ion battery for lithium ion battery - Google Patents
A kind of nonaqueous electrolytic solution and lithium ion battery for lithium ion battery Download PDFInfo
- Publication number
- CN108110318A CN108110318A CN201611063485.4A CN201611063485A CN108110318A CN 108110318 A CN108110318 A CN 108110318A CN 201611063485 A CN201611063485 A CN 201611063485A CN 108110318 A CN108110318 A CN 108110318A
- Authority
- CN
- China
- Prior art keywords
- nonaqueous electrolytic
- electrolytic solution
- unsaturated
- compound
- lithium ion
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
This application discloses a kind of nonaqueous electrolytic solutions and lithium ion battery for lithium ion battery.The nonaqueous electrolytic solution of the application, including unsaturated phosphate ester class compound and annular unsaturated carboxylic acid anhydride compound, the unsaturated phosphate ester class compound has structure shown in formula one, formula one：Wherein, R1, R2, R3 are separately selected from the alkyl that carbon number is 15, and at least one in R1, R2, R3 is the unsaturated alkyl containing double bond or three key；The unsaturated cyclic carboxyanhydrides compound has structure shown in formula two, formula two：Wherein, R4 is selected from the alkenylene that carbon number is 24 or the alkenylene that fluorine substitution carbon number is 24.The nonaqueous electrolytic solution of the application is acted synergistically by the first compound and second compound, on the one hand with excellent high temperature cyclic performance and storage performance, while has relatively low impedance, cryogenic property is excellent.
Description
Technical field
This application involves lithium-ion battery electrolytes field, more particularly to a kind of non-aqueous solution electrolysis for lithium ion battery
Liquid and lithium ion battery.
Background technology
Lithium ion battery has the characteristics that higher than energy, specific power is big, has extended cycle life, and is mainly used in 3C numbers at present
Class consumer electronics product field and new energy power vehicle and energy storage field.With new-energy automobile course continuation mileage requirement not
Disconnected improve is increasingly miniaturized with the size of digital class consumption electronic product so that high-energy density chemical conversion is current lithium ion battery
Main Trends of The Development.It is to improve the effective way of battery energy density to improve lithium ion battery operating voltage.
The operating voltage for improving lithium ion battery often brings the deterioration of performance.It is because under high voltages, on the one hand electric
The crystal structure of pond anode is there are certain unstability, during charge and discharge, it may occur that structure collapse so as to cause
The deterioration of performance；On the other hand, under high voltages, positive electrode surface is under high oxidation state, active higher, easy catalytic electrolysis liquid
Oxygenolysis, the decomposition product of electrolyte are easily deposited in positive electrode surface, the deintercalation passage of lithium ion are blocked, so as to deteriorate
Battery performance.
Electrolyte is the key factor for influencing battery comprehensive performance, and particularly, the additive in electrolyte is to each of battery
The performance of item performance is even more important.Therefore, the performance of the power battery of ternary nickel cobalt manganese material, of electrolyte to be given full play to
With being crucial.Lithium-ion battery electrolytes practical at present are addition traditional film for additive such as vinylene carbonate (contractings
Write VC) or fluorinated ethylene carbonate (abbreviation FEC) nonaqueous electrolytic solution, ensure that battery is excellent by the addition of VC and FEC and follow
Ring performance.But the high voltage stability of VC is poor, and aerogenesis is easily decomposed under FEC high temperature.Therefore, under high voltage hot conditions,
These additives are difficult the performance requirement for meeting lithium ion battery under high voltages with the cycling under high temperature.
A kind of new film for additive of the phosphate compound for containing three keys is disclosed in patent application 201410534841.0,
It can not only improve high temperature cyclic performance, moreover it is possible to be obviously improved storge quality.But the scientific worker of this field is under study for action
It was found that the phosphate ester additive of three keys can not only form a film in anode, and can be in cathode film formation, it can be apparent in the film forming of cathode
Increase the impedance of cathode, hence it is evident that deteriorate cryogenic property.
And annular unsaturated carboxylic acid anhydride compound also sees some related texts as lithium battery electrolytes additive very early
It offers in patent, annular unsaturated carboxylic acid anhydrides are similar with the phosphate functional characteristics of three keys and can be obviously improved high-temperature behavior,
But it can also increase battery impedance simultaneously, deteriorate cryogenic property, it is suppressed that the application of nonaqueous lithium ion battery under cryogenic.
The content of the invention
The purpose of the application is to provide a kind of for non-aqueous electrolyte for lithium ion cell and using the non-of the lithium ion battery
Water electrolysis liquid.
To achieve these goals, the application employs following technical scheme：
The one side of the application discloses a kind of nonaqueous electrolytic solution for lithium ion battery, including unsaturated phosphate ester class
Compound and unsaturated cyclic carboxyanhydrides compound, the unsaturated phosphate ester class compound have structure shown in formula one,
Formula one：
Wherein, R1, R2, R3 are separately the alkyl of 1-5 selected from carbon number, and at least one in R1, R2, R3 are
Unsaturated alkyl containing double bond or three key；
The unsaturated cyclic carboxyanhydrides compound has structure shown in formula two,
Formula two：
Wherein, R4 is selected from the alkenylene that carbon number is 2-4 or the alkenylene that fluorine substitution carbon number is 2-4.
Under normal circumstances, two type high temp performances are good, and impedance is big, and the additive of poor performance at low temperatures is used in combination, meeting
So that battery further obtains better high-temperature behavior, but impedance can further increase, and cryogenic property can further be deteriorated.But this
The scientific worker in field has found under study for action, and above-mentioned three keys phosphoric acid ester is added simultaneously in non-aqueous electrolyte for lithium ion cell
Compound and annular unsaturated carboxylic acid anhydride compound, compared with three key phosphate compounds are used alone, find high temperatures
Can be improved significantly, and discovery interface impedance beyond expectation is substantially reduced, cryogenic property is obviously improved.
The technical principle for adding unsaturated phosphate ester class compound and annular unsaturated carboxylic acid anhydride compound simultaneously is：
During initial charge, unsaturated phosphate ester class compound can be in cathode film formation, such compound is in passivating film formed by cathode
Electric conductivity is poor, can significantly increase cathode impedance, significantly bigger than normal so as to cause battery overall impedance, poor performance at low temperatures.And insatiable hunger
During initial charge also there is very strong cathode film formation with cyclic carboxylic acids compound anhydride, be mainly reflected in such change
Close the higher into film potential of object cathode, can preferentially unsaturated phosphate ester class compound is in cathode film formation, so as to inhibit subsequently not
Saturation phosphate compounds cathode film forming, so as to reduce battery impedance.The application is by unsaturated phosphate ester class chemical combination
Object is used together with unsaturated cyclic carboxyanhydrides compound, the two coordinative role, is generated the two and is used alone what is do not had
Special-effect.
By foregoing description, while add the skill of unsaturated phosphate ester class compound and annular unsaturated carboxylic acid anhydride compound
Art principle can illustrate that the Blank in figure is blank electrolysis liquid with Fig. 1 and Fig. 2：EC/EMC/DEC=1/1/1 (volume ratio),
LiPF6：1M.From Fig. 1 and Fig. 2, unsaturated phosphate ester class (compound 1) is about left in 2.7V during initial charge
The right side starts from cathode film formation, and the impedance that can cause cathode in cathode film formation at this time significantly increases；In unsaturated phosphate ester class (chemical combination
Object 1) on the basis of add in annular unsaturated carboxylic acid anhydride compound (CA), annular unsaturated carboxylic acid anhydride compound (CA) can be preferential
In 1.5V and 2V or so film, and the film meeting that annular unsaturated carboxylic acid anhydride compound (CA) preferentially forms are formed in negative terminal surface
Inhibit film forming of the unsaturated phosphate ester class (compound 1) at follow-up 2.7V, so as to reduce the impedance of cathode.
Specifically, the unsaturated phosphate ester class compound shown in above-mentioned formula one can be selected from the compound of following structural formula：
It is appreciated that the unsaturated phosphate ester class compound or compound 1 either shown in formula one arrive compound 6
Unsaturated phosphate ester class compound is all the preferred technical solution of the application, however not excluded that other with similar physicochemical properties
Unsaturated phosphate ester class compound.
Specifically, the annular unsaturated carboxylic acid anhydrides shown in above-mentioned formula two can be selected from maleic anhydride (being abbreviated as MA), 2- first
It is one or more in base maleic anhydride (being abbreviated as CA).
It is appreciated that annular unsaturated carboxylic acid anhydride compound or MA or CA either shown in formula two, are all these
The preferred technical solution of application, however not excluded that other annular unsaturated carboxylic acid anhydride compounds with similar physicochemical properties.
Preferably, in the non-aqueous electrolyte for lithium ion cell of the application, unsaturated phosphate ester class compound accounts for lithium-ion electric
The 0.1%~3% of pond nonaqueous electrolytic solution total weight, more preferably 0.1%~2%.
Seen from the above description, when the dosage of above-mentioned unsaturated phosphate ester class compound is less than 0.1%, anode film forming effect
Fruit is deteriorated, and the protective effect of anode is declined, and the effect for improving performance declines；When its dosage is more than 2%, electrode interface can be made
Film forming it is partially thick, increase the impedance of electrode interface impedance, particularly cathode interface, so as to increase battery overall impedance, deterioration electricity
Pond performance.
Preferably, in the non-aqueous electrolyte for lithium ion cell of the application, annular unsaturated carboxylic acid anhydride compound account for lithium from
The 0.1%~3% of sub- battery nonaqueous electrolytic solution total weight, more preferably 0.1%~2%.
Meanwhile seen from the above description, when the content of unsaturated cyclic carboxyanhydrides compound is less than 0.1%,
The film-formation result of cathode is deteriorated, it is difficult to effectively prevent unsaturated phosphate ester class compound in cathode film formation；When unsaturated cyclic carboxylic
It when the content of anhydride compound is more than 2%, also results in that the film forming of electrode interface is partially thick, increases the impedance of electrode interface, it is special
It is not the impedance of cathode interface, so as to increase battery overall impedance, deterioration.
Further, the non-aqueous electrolyte for lithium ion cell of the application further includes unsaturated cyclic carbonic ester or annular sulfonic acid
At least one of lactone or cyclic sulfates.
Further, the unsaturated cyclic carbonate products dosage accounts for the 0.1%-5% of nonaqueous electrolytic solution total weight.
Annular sultone compounds dosage accounts for the 0.1%-5% of nonaqueous electrolytic solution total weight.Cyclic sulfates compound amount accounts for non-
The 0.1%-5% of water electrolysis liquid total weight.
Further, the unsaturated cyclic carbonic ester in vinylene carbonate, vinylethylene carbonate at least
It is a kind of.
The ring-type sultones is selected from 1,3- propane sultones, 1,4- butane sultones, 1,3- propene sultones and first
At least one of alkane disulfonic acid methylene ester.
The cyclic sulfates are selected from one or both of sulfuric acid vinyl ester and sulfuric acid acrylic ester.
In the nonaqueous electrolytic solution of the application, comprising non-aqueous organic solvent, organic solvent is selected from ethylene carbonate, propylene carbonate
At least one of ester, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate.
Further, in the nonaqueous electrolytic solution of the application, lithium salts is selected from lithium hexafluoro phosphate, LiBF4, two (fluoroforms
Base sulphonyl) at least one of imine lithium and imidodisulfuryl fluoride lithium salt.
The another side of the application discloses a kind of lithium ion battery, including anode, cathode, is placed between positive electrode and negative electrode
Membrane 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 greater than or equal to 4.3V.
Further, in the lithium ion battery of the application, anode is selected from LiCoO2、LiNiO2、LiMn2O4、LiCo1-yMyO2、
LiNi1-yMyO2、LiMn2-yMyO4And LiNixCoyMnzM1-x-y-zO2At least one of；, wherein, M be selected from Fe, Co, Ni, Mn,
At least one of 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, can be adapted for various lithium ion batteries, including but not only limit
In the type cited by the application.
Description of the drawings
Fig. 1 is the initial charge differential capacity figure of blank electrolysis liquid, embodiment 6 and comparative example 1；
Fig. 2 is the AC impedance figure of blank electrolysis liquid, embodiment 6 and comparative example 1.
Specific embodiment
The application is described in further detail below by specific embodiments and the drawings.Following embodiment is only to the application
It is further described, should not be construed as the limitation to the application.
Embodiment
This example prepares electrolyte according to the component shown in table 1 and proportioning, wherein, devise multiple the application for lithium from
The nonaqueous electrolytic solution of sub- battery and multiple comparative examples, refer to table 1.
The lithium salts of this example uses lithium hexafluoro phosphate.It is appreciated that lithium salts is a specific implementation used by this example
Mode, the other common lithium salts in this field, such as LiBF4、LiBOB、LiDFOB、LiPO2F2、LiSbF6、LiAsF6、LiN
(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3With LiN (SO2F)2, this example is can be equally used for, does not do specific limit herein
It is fixed.
The preparation method of the electrolyte of this example is：Volume ratio according to EC/EMC/DEC=1/1/1 (volume ratio) is prepared non-
Then aqueous organic solvent adds in the lithium hexafluoro phosphate that ultimate density is 1.0mol/L, then adds in additive by table 1 thereto.Table 1
In percentage be weight percentage, i.e., additive accounts for the percentage of electrolyte total weight.
Each component and dosage in 1 electrolyte of table
The lithium ion battery of this example, positive active material use LiNi0.5Co0.2Mn0.3O2, cathode use Delanium, every
Film is using three layers of polypropylene, polyethylene and polypropylene isolation film.4.35V lithium ion batteries are made.It is specific as follows：
Anode preparation method is：By 96.8：2.0：1.2 quality is than blended anode active material
LiNi0.5Co0.2Mn0.3O2, conductive carbon black and binding agent polyvinylidene fluoride, be dispersed in n-methyl-2-pyrrolidone, obtain
Anode sizing agent is uniformly coated on the two sides of aluminium foil by anode sizing agent, by drying, rolling and be dried in vacuo, and uses ultrasonic wave
Welding machine burn-ons and obtains positive plate after aluminum lead-out wire, and the thickness of pole plate is between 120-150 μm.
Cathode preparation method is：By 96：1：1.2：1.8 quality is than admixed graphite, conductive carbon black, binding agent butadiene-styrene rubber
And carboxymethyl cellulose, disperse in deionized water, to obtain negative electrode slurry, negative electrode slurry is coated on the two sides of copper foil, pass through
Drying, calendering and vacuum drying are crossed, and is burn-on with supersonic welder and obtains negative plate after nickel lead-out wire, the thickness of pole plate exists
Between 120-150 μm.
Membrane preparation method is：Using three layers of polypropylene, polyethylene and polypropylene isolation film, thickness is 20 μm.
Battery assembly method is：Three layers of isolation film that thickness is 20 μm are placed between positive plate and negative plate, then will
The sandwich structure of positive plate, negative plate and membrane composition is wound, then is put into aluminum foil sack after coiling body is flattened,
Vacuum bakeout 48h at 75 DEG C, obtains battery core to be injected；The electrolyte of above-mentioned preparation is injected in battery core, it is quiet through Vacuum Package
Only for 24 hours.
Battery formation：0.05C constant-current charges 180min, 0.1C constant-current charge is to 3.95V, and secondary vacuum sealing, 45 DEG C are put
48h is put, then further with the electric current constant-current charge of 0.2C to 4.4V, with the electric current constant-current discharge of 0.2C to 3.0V.
45 DEG C of 1C that this example tests each electrolyte battery respectively cycle 300 times and room temperature 1C cycles, 500 capacity guarantors
Holdup, stored 30 days at 60 DEG C after capacity retention ratio, capacity restoration rate and thickness swelling, -20 DEG C of 1C discharging efficiencies with
And often low temperature direct impedance.Specific test method is as follows：
(1) 45 DEG C of 1C cycles 300 weeks capacity retention ratios, and the high temperature cyclic performance of the battery actually measured is specific to survey
Method for testing includes：At 45 DEG C, the battery after chemical conversion is charged to 4.35V with 1C constant current constant voltages, by electric current be 0.01C, then
With 1C constant-current discharges to 3.0V.After such 300 Xun Huans of charge/discharge, the conservation rate of capacity after the 300th Xun Huan is calculated, to comment
Estimate its high temperature cyclic performance.It is as follows that 45 DEG C of 1C cycle 300 capacity retention ratio calculation formula：
300th circulation volume conservation rate (%)=(the 300th cyclic discharge capacity/first time cyclic discharge capacity) ×
100%.
(2) normal-temperature circulating performance is tested：At 25 DEG C, the battery after chemical conversion is charged to 4.35V with 1C constant current constant voltages, then
With 1C constant-current discharges to 3.0V.The conservation rate of the 500th circulation volume is calculated after 500 Xun Huans of charge/discharge, to assess its room temperature
Cycle performance.Calculation formula is as follows：
500th circulation volume conservation rate (%)=(the 500th cyclic discharge capacity/first time cyclic discharge capacity) ×
100%.
The test method of capacity retention ratio, capacity restoration rate and thickness swelling after being stored 30 days at (3) 60 DEG C includes：
Battery after chemical conversion is charged to 4.35V with 1C constant current constant voltages at normal temperatures, by electric current be 0.01C, then with 1C constant-current discharges extremely
3.0V measures battery initial discharge capacity, then with 1C constant-current constant-voltage chargings to 4.35V, is 0.01C by electric current, measures battery
Original depth, then battery is measured the thickness of battery, then with 1C constant-current discharges to 3.0V, surveyed after 60 DEG C of storages 30 days
Measure the holding capacity of battery, then with 1C constant-current constant-voltage chargings to 4.35V, by electric current be 0.01C, then with 1C constant-current discharges extremely
3.0V, measurement recover capacity.The calculation formula of capacity retention ratio, capacity restoration rate and thickness swelling is as follows：
Battery capacity conservation rate (%)=holding capacity/initial capacity × 100%
Capacity resuming rate (%)=recovery capacity/initial capacity × 100%
Cell thickness expansion rate (%)=(thickness-original depth after 30 days)/original depth × 100%.
(4) low temperature performance is tested：At 25 DEG C, the battery after chemical conversion is charged to 4.35V with 1C constant current constant voltages, then
With 1C constant-current discharges to 3.0V, discharge capacity is recorded.Then 1C constant current constant voltages are full of, and are placed in -20 DEG C of environment and are shelved 12h
Afterwards, 1C constant-current discharges record discharge capacity to 3.0V.
- 20 DEG C of low temperature discharging efficiency value=1C discharge capacities (- 20 DEG C)/1C discharge capacities (25 DEG C).
(5) room temperature DC impedance (DCIR) performance test：At 25 DEG C, the battery 1C after chemical conversion is charged to SOC=
50% state, respectively with 0.1C, 0.2C, 0.5C, 1C and 2C charge and discharges ten seconds record charge and discharge blanking voltage respectively.Then, with not
Charging and discharging currents with multiplying power are abscissa (unit：A), using the blanking voltage corresponding to charging and discharging currents as ordinate, line is made
Sexual intercourse figure (unit：mV).
The slope value of electric discharge DCIR values=difference discharge current and the linear graph of corresponding blanking voltage.
Every test result is as shown in table 2.
2 test result of table
By test, the initial charge differential capacity figure of blank electrolysis liquid, embodiment 6 and comparative example 1 is formed (such as Fig. 1 institutes
Show) and AC impedance figure (as shown in Figure 2).
From Fig. 1 and Fig. 2, unsaturated phosphate ester class (compound 1) is during initial charge, about in 2.7V or so
Start from cathode film formation, the impedance that can cause cathode in cathode film formation at this time significantly increases；In unsaturated phosphate ester class (compound
1) annular unsaturated carboxylic acid anhydride compound (CA) is added on the basis of, annular unsaturated carboxylic acid anhydride compound (CA) can preferentially exist
1.5V and 2V or so form film in negative terminal surface, and the film that annular unsaturated carboxylic acid anhydride compound (CA) preferentially forms can press down
Film forming of the unsaturated phosphate ester class (compound 1) processed at follow-up 2.7V, so as to further reduce the impedance of cathode.
It is compared by the test result of comparative example 1-2, it can be found that when unsaturated phosphate ester class compound is used alone, followed
Ring performance and high temperature storage are preferable, but impedance is very big, and cryogenic property is very poor.Unsaturated cyclic carboxyanhydrides compound is used alone
When, impedance is relatively low, and cryogenic property is preferable, but cycle performance and high temperature storage are poor.
And in the test result of embodiments herein 1-18, by comparative example 1 and embodiment 2,6,8 comparison can be with
It was found that on the basis of unsaturated phosphate ester class compound, unsaturated cyclic carboxyanhydrides compound is added, not only cycle performance
It has clear improvement with high-temperature behavior, cryogenic property is also obviously improved, and impedance is significantly reduced.
Meanwhile in the test result of embodiments herein 1-18, compared with comparative example 1, it can be found that simultaneously comprising not
The high-temperature behavior and cryogenic property of all embodiments of saturation phosphate compounds and unsaturated cyclic carboxyanhydrides compound
All make moderate progress.It is compared by embodiment 2,5,6,7, with the increase of unsaturated phosphate ester class compound, high-temperature behavior has
It is improved, but cryogenic property relative drop, with the increase of dosage, impedance also increases therewith for particularly impedance.Especially when
Unsaturated phosphate ester kind compound content is very high and when unsaturated cyclic carboxyanhydrides compounds content is very low, and impedance is larger, low
Warm nature can apparent deficiency.
In conclusion the application makes unsaturated phosphate ester class compound and the cooperation of unsaturated cyclic carboxyanhydrides compound
With the high-temperature behavior and cycle performance and good cryogenic property that under suitable ratio battery acquisition can be made excellent.
The foregoing is a further detailed description of the present application in conjunction with specific implementation manners, it is impossible to assert this Shen
Specific implementation please is confined to these explanations.For those of ordinary skill in the art to which this application belongs, do not taking off
On the premise of conceiving from the application, several simple deduction or replace can also be made, should all be considered as belonging to the protection of the application
Scope.
Claims (10)
1. a kind of nonaqueous electrolytic solution for lithium ion battery, which is characterized in that including unsaturated phosphate ester class compound and ring
Shape unsaturated carboxylic acid anhydride compound, the unsaturated phosphate ester class compound have structure shown in formula one,
Formula one：
Wherein, R1, R2, R3 separately selected from carbon number be 1-5 alkyl, and in R1, R2, R3 it is at least one be containing
The unsaturated alkyl of double bond or three key；
The unsaturated cyclic carboxyanhydrides compound has structure shown in formula two,
Formula two：
Wherein, R4 is selected from the alkenylene that carbon number is 2-4 or the alkenylene that fluorine substitution carbon number is 2-4.
2. nonaqueous electrolytic solution according to claim 1, which is characterized in that the unsaturated phosphate ester class compound is selected from In one or more.
3. nonaqueous electrolytic solution according to claim 1, which is characterized in that the ring-type unsaturated carboxylic acid anhydrides are selected from maleic acid
It is one or more in acid anhydride, 2- methyl maleic anhydrides.
4. nonaqueous electrolytic solution according to claim 1, which is characterized in that in the nonaqueous electrolytic solution, unsaturated phosphate ester
Class compound accounts for the 0.1%~3% of non-aqueous electrolyte for lithium ion cell total weight, and annular unsaturated carboxylic acid anhydride compound accounts for lithium
The 0.1%~3% of ion battery nonaqueous electrolytic solution total weight.
5. according to the nonaqueous electrolytic solution described in any one in claim 1-4, which is characterized in that in the nonaqueous electrolytic solution also
Including at least one of unsaturated cyclic carbonic ester, annular sultones, cyclic sulfates.
6. nonaqueous electrolytic solution according to claim 5, which is characterized in that it is sub- that the unsaturated cyclic carbonic ester is selected from carbonic acid
At least one of vinyl acetate, vinylethylene carbonate；
The ring-type sultones is selected from 1,3- propane sultones, 1,4- butane sultones, 1,3- propene sultones and methane two
At least one of sulfonic acid methylene ester；
The cyclic sulfates are selected from one or both of sulfuric acid vinyl ester and sulfuric acid acrylic ester；
The unsaturated cyclic carbonate products dosage accounts for the 0.1%-5% of nonaqueous electrolytic solution total weight.Annular sultones
Compound amount accounts for the 0.1%-5% of nonaqueous electrolytic solution total weight.Cyclic sulfates compound amount accounts for nonaqueous electrolytic solution gross weight
The 0.1%-5% of amount.
7. nonaqueous electrolytic solution according to claim 1, which is characterized in that the nonaqueous electrolytic solution includes non-aqueous organic solvent
And lithium salts, the non-aqueous organic solvent are selected from ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, carbonic acid two
At least one of ethyl ester, methyl ethyl carbonate and methyl propyl carbonate；The lithium salts is selected from lithium hexafluoro phosphate, LiBF4, two
(trimethyl fluoride sulfonyl) at least one of imine lithium and imidodisulfuryl fluoride lithium salt.
8. a kind of lithium ion battery, which is characterized in that including anode, cathode, the membrane being placed between positive electrode and negative electrode, Yi Ji electricity
Liquid is solved, wherein, electrolyte is the nonaqueous electrolytic solution described in any one in claim 1-7.
9. lithium ion battery according to claim 8, which is characterized in that the anode includes positive electrode active materials, described
Positive electrode active materials are selected from LiCoO2、LiNiO2、LiMn2O4、LiCo1-yMyO2、LiNi1-yMyO2、LiMn2-yMyO4With
LiNixCoyMnzM1-x-y-zO2At least one of；Wherein, M be selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr,
At least one of Sr, V and Ti, and 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
10. lithium ion battery according to claim 8 or claim 9, which is characterized in that the charge cutoff voltage of lithium ion battery is big
In or equal to 4.3V.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611063485.4A CN108110318B (en) | 2016-11-25 | 2016-11-25 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery |
| EP16922345.0A EP3547433A4 (en) | 2016-11-25 | 2016-12-30 | Non-aqueous electrolyte for lithium-ion battery and lithium-ion battery |
| PCT/CN2016/113649 WO2018094843A1 (en) | 2016-11-25 | 2016-12-30 | Non-aqueous electrolyte for lithium-ion battery and lithium-ion battery |
| JP2018564811A JP6814821B2 (en) | 2016-11-25 | 2016-12-30 | Non-aqueous electrolyte for lithium-ion batteries |
| US16/316,621 US11362370B2 (en) | 2016-11-25 | 2016-12-30 | Non-aqueous electrolyte for lithium-ion battery and lithium-ion battery |
| JP2020136214A JP6963068B2 (en) | 2016-11-25 | 2020-08-12 | Non-aqueous electrolyte for lithium-ion batteries |
| JP2021169184A JP7208330B2 (en) | 2016-11-25 | 2021-10-14 | Non-aqueous electrolyte for lithium-ion batteries |
| US17/735,109 US11757132B2 (en) | 2016-11-25 | 2022-05-02 | Non-aqueous electrolyte for lithium-ion battery and lithium-ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611063485.4A CN108110318B (en) | 2016-11-25 | 2016-11-25 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108110318A true CN108110318A (en) | 2018-06-01 |
| CN108110318B CN108110318B (en) | 2021-05-14 |
Family
ID=62204614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611063485.4A Active CN108110318B (en) | 2016-11-25 | 2016-11-25 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108110318B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109346771A (en) * | 2018-09-21 | 2019-02-15 | 杉杉新材料（衢州）有限公司 | A kind of lithium ion battery high-voltage electrolyte and lithium ion battery |
| CN110323487A (en) * | 2019-07-10 | 2019-10-11 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and electric equipment comprising same |
| CN111354978A (en) * | 2020-03-09 | 2020-06-30 | 东莞维科电池有限公司 | High-voltage ternary lithium ion battery electrolyte and high-voltage ternary lithium ion battery |
| CN111864262A (en) * | 2019-04-29 | 2020-10-30 | 诺莱特电池材料(苏州)有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN111916825A (en) * | 2020-06-30 | 2020-11-10 | 珠海冠宇电池股份有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same |
| CN111934017A (en) * | 2020-08-28 | 2020-11-13 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery containing same |
| CN114267882A (en) * | 2021-12-17 | 2022-04-01 | 珠海冠宇电池股份有限公司 | Battery with a battery cell |
| WO2023045948A1 (en) * | 2021-09-23 | 2023-03-30 | 深圳新宙邦科技股份有限公司 | Secondary battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1507669A (en) * | 2001-05-10 | 2004-06-23 | �����֯��ʽ���� | Nonaqueous electrolytic solution, composition for polymer gel electrolyte, polymer gel electrolyte, secondary cell, and electric double-layer capacitor |
| CN103346350A (en) * | 2013-06-27 | 2013-10-09 | 深圳市崧鼎科技有限公司 | Electrolyte for improving performance of lithium ion battery and battery |
| CN105140564A (en) * | 2015-07-28 | 2015-12-09 | 东莞市凯欣电池材料有限公司 | Lithium-ion battery electrolyte for high-voltage ternary positive electrode material system |
| CN105140566A (en) * | 2015-08-03 | 2015-12-09 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN105161763A (en) * | 2015-08-03 | 2015-12-16 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| JP2016173987A (en) * | 2015-03-16 | 2016-09-29 | 三菱化学株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte battery arranged by use thereof |
-
2016
- 2016-11-25 CN CN201611063485.4A patent/CN108110318B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1507669A (en) * | 2001-05-10 | 2004-06-23 | �����֯��ʽ���� | Nonaqueous electrolytic solution, composition for polymer gel electrolyte, polymer gel electrolyte, secondary cell, and electric double-layer capacitor |
| CN103346350A (en) * | 2013-06-27 | 2013-10-09 | 深圳市崧鼎科技有限公司 | Electrolyte for improving performance of lithium ion battery and battery |
| JP2016173987A (en) * | 2015-03-16 | 2016-09-29 | 三菱化学株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte battery arranged by use thereof |
| CN105140564A (en) * | 2015-07-28 | 2015-12-09 | 东莞市凯欣电池材料有限公司 | Lithium-ion battery electrolyte for high-voltage ternary positive electrode material system |
| CN105140566A (en) * | 2015-08-03 | 2015-12-09 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN105161763A (en) * | 2015-08-03 | 2015-12-16 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109346771A (en) * | 2018-09-21 | 2019-02-15 | 杉杉新材料（衢州）有限公司 | A kind of lithium ion battery high-voltage electrolyte and lithium ion battery |
| CN111864262A (en) * | 2019-04-29 | 2020-10-30 | 诺莱特电池材料(苏州)有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| KR20210008355A (en) * | 2019-07-10 | 2021-01-21 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Lithium ion battery and electric device including same |
| CN110323487A (en) * | 2019-07-10 | 2019-10-11 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and electric equipment comprising same |
| EP3793013A4 (en) * | 2019-07-10 | 2021-09-01 | Contemporary Amperex Technology Co., Limited | Lithium ion battery and powered device comprising same |
| US11329319B2 (en) | 2019-07-10 | 2022-05-10 | Contemporary Amperex Technology Co., Limited | Lithium-ion battery and electrical apparatus including the same |
| EP4087006A1 (en) * | 2019-07-10 | 2022-11-09 | Contemporary Amperex Technology Co., Limited | Lithium-ion battery and electrical apparatus including the same |
| KR102471591B1 (en) | 2019-07-10 | 2022-11-25 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Lithium ion battery and electric device including the same |
| CN111354978A (en) * | 2020-03-09 | 2020-06-30 | 东莞维科电池有限公司 | High-voltage ternary lithium ion battery electrolyte and high-voltage ternary lithium ion battery |
| CN111916825A (en) * | 2020-06-30 | 2020-11-10 | 珠海冠宇电池股份有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same |
| CN111916825B (en) * | 2020-06-30 | 2022-03-18 | 珠海冠宇电池股份有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same |
| CN111934017A (en) * | 2020-08-28 | 2020-11-13 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery containing same |
| WO2023045948A1 (en) * | 2021-09-23 | 2023-03-30 | 深圳新宙邦科技股份有限公司 | Secondary battery |
| CN114267882A (en) * | 2021-12-17 | 2022-04-01 | 珠海冠宇电池股份有限公司 | Battery with a battery cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108110318B (en) | 2021-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104617333B (en) | A kind of nonaqueous electrolytic solution and lithium rechargeable battery | |
| CN108110318A (en) | A kind of nonaqueous electrolytic solution and lithium ion battery for lithium ion battery | |
| CN106340672A (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| WO2016049953A1 (en) | Electrolyte of high-voltage lithium ion battery and high-voltage lithium ion battery | |
| CN107591557B (en) | A kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery using the electrolyte | |
| CN109950620A (en) | A kind of nonaqueous electrolytic solution and lithium ion battery | |
| CN104979589A (en) | High-voltage electrolyte and lithium ion battery using electrolyte | |
| CN106953118B (en) | Non-aqueous electrolyte for lithium ion battery and lithium ion battery | |
| JP6814821B2 (en) | Non-aqueous electrolyte for lithium-ion batteries | |
| CN105336987A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery | |
| CN103107363B (en) | Non-water electrolysis solution of lithium ion battery and corresponding lithium ion battery thereof | |
| CN108110317A (en) | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery | |
| CN103367804B (en) | A kind of lithium ion battery nonaqueous electrolytic solution and use the lithium ion battery of this nonaqueous electrolytic solution | |
| CN105789698B (en) | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery | |
| CN103594727B (en) | A kind of lithium ion battery nonaqueous electrolytic solution and use the lithium ion battery of this nonaqueous electrolytic solution | |
| CN105140566A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery | |
| CN111354978A (en) | High-voltage ternary lithium ion battery electrolyte and high-voltage ternary lithium ion battery | |
| CN111883839A (en) | High-voltage electrolyte and lithium ion battery based on same | |
| CN109768327B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same | |
| CN108110322A (en) | A kind of nonaqueous electrolytic solution and lithium ion battery for lithium ion battery | |
| WO2023206921A1 (en) | Lithium-ion battery | |
| CN108390098A (en) | A kind of high-voltage lithium-ion battery electrolyte and high-voltage lithium ion batteries | |
| CN105119017A (en) | Nonaqueous electrolyte solution for high-voltage lithium ion secondary battery and high-voltage lithium secondary battery | |
| CN109390630A (en) | A kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery using the electrolyte | |
| CN107919498A (en) | Non-aqueous electrolyte for lithium ion cell and the lithium ion battery using the electrolyte |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |