CN105514489A - Electrolyte and lithium ion battery containing electrolyte - Google Patents
Electrolyte and lithium ion battery containing electrolyte Download PDFInfo
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- CN105514489A CN105514489A CN201610057504.6A CN201610057504A CN105514489A CN 105514489 A CN105514489 A CN 105514489A CN 201610057504 A CN201610057504 A CN 201610057504A CN 105514489 A CN105514489 A CN 105514489A
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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
-
- 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
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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
-
- 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 relates to the field of lithium ion batteries, in particular to an electrolyte and a lithium ion battery containing the electrolyte. The electrolyte comprises lithium salt, an organic solvent and additives. The additives comprise fluoroethylene carbonate, silazane compounds and cyclic sulphate. The invention further relates to the lithium ion battery containing the electrolyte. Silazane compounds and cyclic sulphate are combined to be applied to a nonaqueous electrolyte containing fluoroethylene carbonate, an excellent SEI film forming effect of cyclic sulphate and fluoroethylene carbonate in graphite, silicon or tin-based anodes is utilized, damage of cyclic sulphate to cathode and anode interfaces can be avoided, and therefore the effect of improving the circulation performance, the rate and the safety performance of lithium ion batteries with graphite, silicon or tin bases as anodes can be achieved.
Description
Technical field
The present invention relates to field of lithium ion battery, specifically, relate to a kind of electrolyte and comprise the lithium ion battery of this electrolyte.
Background technology
The high-energy-density of lithium ion battery, long circulation life, wide operating temperature range and environmental protection have made it become the main energy sources of current mobile electronic device.But the develop rapidly of mobile electronic device particularly smart mobile phone (gentlier, thinner), also proposed higher demand to the energy density of lithium ion battery in recent years.
In order to improve the energy density of lithium ion battery, two kinds of conventional at present methods are the operating voltage of raising positive electrode respectively and use the negative material with more high discharge capacity.Wherein, Si or Sn and alloy material of cathode thereof are because its theoretical specific capacity far above graphite (4200mAh/g) makes it become an important development direction of improving lithium ion battery energy density.But compared with graphite anode system, Si or Sn and alloy anode interface less stable thereof, affect circulation volume conservation rate, main cause may be that the SEI film on Si or Sn and alloy anode surface thereof easily destroys: the destruction of SEI film result in the side reaction of solvent at anode surface, accelerates lithium ion battery Capacity fading.
In view of this, necessaryly a kind of electrolyte improving Si or Sn and alloy anode lithium ion battery charge-discharge performance thereof is provided.
Summary of the invention
Primary goal of the invention of the present invention is to propose a kind of electrolyte.
Second goal of the invention of the present invention is to propose the lithium ion battery containing this electrolyte.
In order to complete object of the present invention, the technical scheme of employing is:
The present invention relates to a kind of electrolyte, described electrolyte comprises lithium salts, organic solvent and additive, comprises fluorinated ethylene carbonate, such as formula the silicon nitrogen silane compound shown in I with such as formula the cyclic sulfates shown in II in described additive;
Wherein, in formula I, R
1, R
2, R
3, R
4, R
5, R
6, R
7independently be selected from hydrogen, C separately
1 ~ 6alkyl, n is selected from the integer of 1 ~ 5;
In formula II, R
11, R
12independently be selected from hydrogen, C separately
1 ~ 6alkyl, C
1 ~ 6alkoxyl, n is selected from the integer of 0 ~ 2.
Preferably, in formula I, R
1be selected from hydrogen or C
1 ~ 3alkyl, R
2, R
3, R
4, R
5, R
6, R
7independently be selected from C separately
1 ~ 3alkyl, n is selected from 1,2 or 3;
In formula II, R
11, R
12independently be selected from hydrogen or C separately
1 ~ 3alkyl, n is selected from 0 or 1.
Preferably, described silicon nitrogen silane compound is selected from least one in hexamethyldisiloxane, heptamethyldisilazane, hexaethyl disilazine or six propyl group disilazanes.
Preferably, described cyclic sulfates is selected from least one in sulfuric acid vinyl ester, sulfuric acid propylene, 4-methylsulfuric acid vinyl acetate.
Preferably, described cyclic sulfates mass percentage is in the electrolytic solution 0.1% ~ 5%.
Preferably, described silicon nitrogen silane compound mass percentage is in the electrolytic solution 0.1% ~ 5%.
Preferably, described organic solvent is selected from least one in ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate or ethyl butyrate;
Described lithium salts is selected from least one in lithium hexafluoro phosphate, difluorophosphate, LiBF4, two trifluoromethanesulfonimide lithium, two (fluorine sulphonyl) imine lithium, di-oxalate lithium borate or difluorine oxalic acid boracic acid lithium.
The invention still further relates to a kind of lithium ion battery, comprise the positive plate containing positive electrode active materials, negative plate, lithium battery diaphragm and electrolyte of the present invention containing negative active core-shell material.
Preferably, described negative material be selected from carbon materials, silicon based anode material, tin base cathode material, alloy material of cathode containing silicon, containing at least one in the alloy material of cathode of tin.
Preferably, at least one in graphite, element silicon or tin element is contained in described negative active core-shell material.
Technical scheme of the present invention can reach beneficial effect:
Cyclic sulfates and fluorinated ethylene carbonate (FEC) have excellent SEI film-formation result at graphite, silicon or tinbase anode, but cyclic sulfates poor stability, and easily reaction generates H
+or lewis acid, FEC and LiPF
6reaction also easily generates H
+or lewis acid, SEI is damaged, causes Capacity fading to accelerate.Silicon nitrogen silane compound has absorption H
+or it is lewis acidic and the effect of ring-opening reaction occurs.The discovery that inventor is pleasantly surprised under study for action; the silicon nitrogen silane compound of certain content is added in the nonaqueous electrolytic solution containing FEC and cyclic sulfates; electrolyte surface tension force and viscosity can be reduced largely; improve the wettability of electrolyte antianode pole piece; and the side chain of the length of silicon nitrogen silane compound launches, and can form network structure, and have induction to cyclic sulfates and fluorinated ethylene carbonate; make it dispersed, and form the diaphragm of even compact at anode surface by mesh.Three also can form the passivating film of stable and uniform at positive electrode surface, significantly improve circulation, multiplying power and security performance under lithium ion battery high-voltage.
Embodiment
According to the one side of the application, provide the nonaqueous electrolytic solution in a kind of lithium ion battery, this nonaqueous electrolytic solution can improve the charge and discharge cycles capability retention of the lithium ion battery containing element silicon and/or tin element in anode.
This electrolyte comprises lithium salts, organic solvent and additive, comprises fluorinated ethylene carbonate (FEC), such as formula the silicon nitrogen silane compound shown in I with such as formula the cyclic sulfates shown in II in described additive.
Silicon nitrogen silane compound of the present invention is such as formula shown in I:
In formula I, R
1, R
2, R
3, R
4, R
5, R
6, R
7independently be selected from hydrogen, C separately
1 ~ 6alkyl, n is selected from the integer of 1 ~ 5;
Preferably, R
1be selected from hydrogen or C
1 ~ 6alkyl, R
2, R
3, R
4, R
5, R
6, R
7independently be selected from C separately
1 ~ 3alkyl, n is selected from 1,2 or 3.
One as electrolyte of the present invention is improved, the structural formula of silicon nitrogen silane compound such as formula (I a) shown in:
In formula I a, R
2, R
3, R
4, R
5, R
6, R
7independently be selected from C separately
1 ~ 3alkyl, n is selected from 1,2 or 3.
One as electrolyte of the present invention is improved, and silicon nitrogen silane compound can be selected from:
Cyclic sulfates of the present invention is such as formula shown in II:
In formula II, R
11, R
12independently be selected from hydrogen, C separately
1 ~ 6alkyl, C
1 ~ 6alkoxyl, n is selected from the integer of 0 ~ 2.
Preferably, R
11, R
12independently be selected from hydrogen or C separately
1 ~ 3alkyl, n is selected from 0 or 1.
One as electrolyte of the present invention is improved, the structural formula of cyclic sulfates such as formula (II a) shown in:
One as electrolyte of the present invention is improved, the structural formula of cyclic sulfates such as formula (II b) shown in:
One as electrolyte of the present invention is improved, and cyclic sulfates can be selected from:
In abovementioned alkyl, the preferred upper limit value of carbon number is followed successively by 6,5,4,3,2,1; Such as, when the higher limit of carbon number is 6, the carbon atom number range of alkyl refers to 1 ~ 6; The most preferably carbon number of alkyl is 1 ~ 5, and further preferably 1 ~ 3.Alkyl can be alkyl group or cycloalkyl: alkyl group comprises straight chained alkyl and the alkyl with side chain; Cycloalkyl is the saturated alkyl containing alicyclic structure, alicyclic ring can contain or do not contain substituting group.
Above-mentioned C
1-6alkyl includes but not limited to :-CH
3,-CH
2cH
3,-(CH
2)
2cH
3,-CH (CH
3)
2, cyclopropyl ,-(CH
2)
3cH
3,-CH
2cH (CH
3)
2,-CH (CH
3) CH
2cH
3,-CH
2cH (CH
3)
2,-C (CH
3)
3,-(CH
2)
4cH
3,-CH
2cH
2cH (CH
3)
2,-CH (CH
3) CH
2cH
2cH
3,-CH
2cH (CH
3) CH
2cH
3,-CH
2c (CH
3)
3, cyclohexyl.
One as electrolyte of the present invention is improved, and cyclic sulfates mass percentage is in the electrolytic solution 0.1% ~ 5%, and preferably 1% ~ 5%; Silicon nitrogen silane compound mass percentage is in the electrolytic solution 0.1% ~ 5%, and preferably 0.1% ~ 3%.
One as electrolyte of the present invention is improved, the nonaqueous solvents of non-water organic electrolyte is selected from ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), ethyl propionate (EP), propyl propionate (PP), methyl propionate (MP), at least one in propyl acetate (PA).
One as electrolyte of the present invention is improved, and fluorinated ethylene carbonate (FEC) mass fraction in the electrolytic solution in electrolyte is 1% ~ 30%.
One as electrolyte of the present invention is improved, and the lithium salts that non-water organic electrolyte uses is selected from lithium hexafluoro phosphate LiPF
6, LiBF4 LiBF
4, two trifluoromethanesulfonimide lithium LiN (CF
3sO
2)
2(being abbreviated as LiTFSI), di-oxalate lithium borate LiB (C
2o
4)
2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF
2(C
2o
4) at least one in (being abbreviated as LiDFOB); Preferably, described lithium salt is 0.9M ~ 1.2M.
The another aspect of the present patent application provides a kind of lithium ion battery, comprises the positive plate containing positive electrode active materials, negative plate, lithium battery diaphragm and electrolyte of the present invention containing negative active core-shell material.
Preferably, described negative material be selected from carbon materials, silicon based anode material, tin base cathode material, alloy material of cathode containing silicon, containing at least one in the alloy material of cathode of tin.Preferably, at least one in graphite, element silicon or tin element is contained in described negative active core-shell material.The positive electrode active materials of described lithium ion battery is selected from least one in lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminum oxide.
Concrete, negative active core-shell material is selected from native graphite, Delanium, mesophase spherule micro-carbon ball, hard carbon, soft carbon, silicon, silico-carbo compound, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO
2, spinel structure lithiumation TiO
2-Li
4ti
5o
12, at least one in Li-Al alloy.
Below in conjunction with embodiment, set forth the application further.Should be understood that these embodiments are only not used in the scope of restriction the application for illustration of the application.
As nothing specializes, the content in embodiment is mass percentage.Wherein, the quality of each constituent mass/organic solvent of the mass percentage=100% × organic solvent of each component in organic solvent; The gross mass of each constituent mass/nonaqueous electrolytic solution of the percentage composition=100% × additive of each component in additive.
Embodiment 1 ~ 9
The preparation of electrolyte: ethylene carbonate (being abbreviated as EC) and diethyl carbonate (being abbreviated as DEC) are mixed with mass ratio EC:DEC=30:70, adds the lithium hexafluoro phosphate (LiPF of certain mass
6), make its concentration in the electrolytic solution be 1M; Additive is made up of FEC, silicon nitrogen silane compound and cyclic sulfates; Wherein silicon nitrogen silane compound is hexamethyldisiloxane, and cyclic sulfates is DTD.
The concrete addition manner of electrolyte is as shown in table 1, and wherein, FEC, hexamethyldisiloxane and DTD addition are the mass percentage content accounting for electrolyte.
Table 1: electrolyte addition manner
| Embodiment | Non-aqueous organic solvent | Lithium salts | FEC | Hexamethyldisiloxane | DTD |
| Embodiment 1 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 0.2 | 1 |
| Embodiment 2 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 0.5 | 1 |
| Embodiment 3 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 1 | 1 |
| Embodiment 4 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 2 | 1 |
| Embodiment 5 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 3 | 1 |
| Embodiment 6 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 1 | 0.2 |
| Embodiment 7 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 1 | 0.5 |
| Embodiment 8 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 1 | 3 |
| Embodiment 9 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 1 | 5 |
The preparation of anode pole piece: by cobalt acid lithium, conductive carbon black (SuperP), binding agent polyvinylidene fluoride (PVDF) in mass ratio 97:1.4:1.6 and 1-METHYLPYRROLIDONE (NMP) mix and make lithium ion battery anode glue size, be coated in current collector aluminum foil; Cold pressing after drying at 85 DEG C; Then, after carrying out trimming, cut-parts, itemize, under the vacuum condition of 85 DEG C, dry 4h, soldering polar ear, makes anode slice of lithium ion battery.
The preparation of cathode pole piece: using as the graphite of active material of positive electrode and SiO
2(75:25) with conductive carbon black (SuperP), thickener sodium carboxymethylcellulose (being abbreviated as CMC), bonding agent polyacrylic acid (being abbreviated as PAA) in mass ratio 92:1.0:1.0:5 and pure water mix and make slurry, to be coated on copper foil of affluxion body and oven dry at 85 DEG C; Then, after carrying out trimming, cut-parts, itemize, under 120 DEG C of vacuum conditions, dry 12h, soldering polar ear, make lithium ion battery negative electrode.
The preparation of lithium ion battery: using polyethylene (being abbreviated as PE) porous polymer film as barrier film; Obtained positive plate, barrier film, negative plate are folded in order, make barrier film be in the middle of positive/negative plate, winding obtains naked battery core; Naked battery core is placed in external packing, the electrolyte of above-mentioned preparation is injected in dried battery, encapsulate, leave standstill, change into that (0.02C constant current charge is to 3.4V, again with 0.1C constant current charge to 3.85V), shaping, volume test, complete the preparation (the thickness 4.2mm of soft-package battery, width 32mm, length 82mm) of lithium ion battery.
Comparative example 1 ~ 8
Prepare lithium ion battery according to the method for embodiment, difference is only that the composition of additive in electrolyte is different.The concrete addition manner of electrolyte is as shown in table 2, and wherein, FEC, hexamethyldisiloxane and DTD addition are the mass percentage content accounting for electrolyte.
Table 2: electrolyte addition manner
| Embodiment | Non-aqueous organic solvent | Lithium salts | FEC | Hexamethyldisiloxane | DTD |
| Comparative example 1 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | — | — |
| Comparative example 2 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | — | 1 |
| Comparative example 3 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 1 | — |
| Comparative example 4 | EC:DEC＝3:7 | 1M LiPF 6 | — | 1 | 1 |
| Comparative example 5 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 1 | 0.05 |
| Comparative example 6 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 1 | 6 |
| Comparative example 7 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 0.05 | 1 |
| Comparative example 8 | EC:DEC＝3:7 | 1M LiPF 6 | 10 | 6 | 1 |
(1) cycle performance of lithium ion battery test
Test the cycle performance of the lithium ion battery prepared in embodiment 1 ~ 9 and comparative example 1 ~ 8 respectively, method is as follows:
At 25 DEG C, after lithium ion battery is left standstill 30 minutes, with 0.5C multiplying power constant current charge to 4.4V, then 4.4V constant voltage charge is to 0.05C, and leave standstill 5 minutes, then with 0.5C multiplying power constant-current discharge to 3.0V, this is a charge and discharge cycles process, this discharge capacity is the discharge capacity first of lithium ion battery, carries out 200 charge and discharge cycles processes afterwards.
Discharge capacity/discharge capacity × 100% first of capability retention (the %)=the N time circulation after lithium ion battery N circulation.
Cycle performance of battery test result is as shown in table 3.
Table 3: cycle performance of lithium ion battery
As can be seen from the test result of embodiment 1 ~ 5 and comparative example 7,8, containing mass fraction be 10% FEC electrolyte in add the DTD that mass fraction is 1%, add mass fraction is in the electrolytic solution the hexamethyldisiloxane of 0.2% ~ 3% simultaneously, the cycle performance of lithium ion battery has obvious improvement, and the addition of hexamethyldisiloxane is preferably 0.5% ~ 2%; Hexamethyldisiloxane addition is too high or too low, can not play the effect of improvement to cycle performance of battery.
From embodiment 3, 6 ~ 9 and comparative example 5, the test result of 6 can be found out, containing mass fraction be 10% FEC electrolyte in add the hexamethyldisiloxane that mass fraction is 1%, add mass fraction is the DTD of 0.2% ~ 5% simultaneously, the cycle performance of lithium ion battery has clear improvement, when the content of DTD is 0.2%, anode film forming is insufficient, performance of lithium ion battery improves less, when DTD content is greater than 0.5%, lithium ion battery shows optimum cycle performance, continue to increase DTD content to 5%, the SEI film generated due to the DTD of high-load is thicker, impedance increases, the side reaction that DTD brings simultaneously significantly increases, the cycle performance of lithium ion battery fails to improve further, the addition of DTD is preferably 0.5% ~ 3%.DTD addition is too high or too low, can not play the effect of improvement to cycle performance of battery.
As can be seen from the test result of comparative example 1 ~ 3, containing mass fraction be 10% FEC electrolyte in after to add mass fraction be the DTD of 1%, the circulation volume conservation rate of battery is significantly improved.And an interpolation mass fraction is the hexamethyldisiloxane of 1% in electrolyte, the cycle performance of lithium ion battery only has slight improvement.
As can be seen from the test result of comparative example 4, do not add FEC in electrolyte, the cycle performance of lithium ion battery is poor, because the SEI film that FEC generates is unstable, in cyclic process, SEI film is destroyed, and causes capability retention to reduce.
(2) the high rate performance test of battery
The battery obtained in embodiment 1 ~ 9 and comparative example 1 ~ 8 is all carried out following test:
By battery with 0.5C constant-current discharge to 3.0V, shelve 5min, then with 0.5C constant current charge to 4.4V, and constant voltage charge is 0.05C by electric current, leaves standstill 5min, more respectively with 0.2C, 1C, 1.5C, 2C constant-current discharge to by voltage 3.0V.Discharge capacity under record 0.2C, 1C, 1.5C, 2C condition is D1, discharge capacity under record 0.2C is D0, and based on the discharge capacity under 0.2C, calculate the discharge capacitance of battery under different multiplying by following formula and (survey 15 batteries, get its mean value), then the high rate performance of characterizing battery is carried out by the discharge capacitance of battery under different multiplying.In addition, the discharge capacitance of each battery under different multiplying is as shown in table 4.
Discharge capacitance=[(D1-D0)/D0] × 100% of battery
Table 4: discharge capacity of lithium ion battery conservation rate
(3) hot case test
The battery obtained in embodiment 1 ~ 9 and comparative example 1 ~ 8 is all carried out following test:
1) with the constant current of 1.0C electric current, battery is charged to 4.4V, then constant voltage charge is down to 0.05C to electric current, and charging stops; 2) battery is placed in hot case, from 25 DEG C, 150 DEG C are warming up to the programming rate of 5 DEG C/min, after arriving 150 DEG C, holding temperature is constant, then timing is started, observe the state of battery after 1h, by the standard of this test be: battery without smoldering, without on fire, without blast, wherein often organize 5 batteries.The result of the hot case test of each battery is as shown in table 5.By above-mentioned hot case test, the security performance of characterizing battery.
Table 5: the hot case test of lithium ion battery
| State after hot case test | |
| Embodiment 1 | 5 batteries all pass through, and do not smolder, on fire, explosion phenomenon |
| Embodiment 2 | 4 batteries all pass through, and 1 battery in addition has phenomenon on fire |
| Embodiment 3 | 5 batteries all pass through, and do not smolder, on fire, explosion phenomenon |
| Embodiment 4 | 5 batteries all pass through, and do not smolder, on fire, explosion phenomenon |
| Embodiment 5 | 5 batteries all pass through, and do not smolder, on fire, explosion phenomenon |
| Embodiment 6 | 5 batteries all pass through, and do not smolder, on fire, explosion phenomenon |
| Embodiment 7 | 5 batteries all pass through, and do not smolder, on fire, explosion phenomenon |
| Embodiment 8 | 5 batteries all pass through, and do not smolder, on fire, explosion phenomenon |
| Embodiment 9 | 5 batteries all pass through, and do not smolder, on fire, explosion phenomenon |
| Comparative example 1 | 5 batteries all have phenomenon on fire |
| Comparative example 2 | 5 batteries all have phenomenon on fire |
| Comparative example 3 | 1 battery passes through, and 4 batteries in addition all have phenomenon on fire |
| Comparative example 4 | 1 battery passes through, and 4 batteries in addition all have phenomenon on fire |
| Comparative example 5 | 2 batteries pass through, and 3 batteries in addition all have phenomenon on fire |
| Comparative example 6 | 2 batteries pass through, and 3 batteries in addition all have phenomenon on fire |
| Comparative example 7 | 2 batteries pass through, and 3 batteries in addition all have phenomenon on fire |
| Comparative example 8 | 2 batteries pass through, and 3 batteries in addition all have phenomenon on fire |
Can learn from the related data above-mentioned table 4, table 5, compared with the battery prepared in comparative example, the battery prepared by the embodiment of the present application, the high rate performance under 1C, 1.5C, 2C and the thermal stability at 150 DEG C all have lifting by a relatively large margin.
Embodiment 10 ~ 18
Prepare lithium ion battery according to the method for previous embodiment, difference is only that the composition of electrolyte is different.The concrete addition manner of electrolyte is as shown in table 6, and wherein, FEC, hexamethyldisiloxane and DTD addition are the mass percentage content accounting for electrolyte.
Table 6:
The performance of the lithium ion battery adopting the electrolyte prescription of embodiment 10 ~ 18 to prepare is close with previous embodiment.
Although the application with preferred embodiment openly as above; but be not for limiting claim; any those skilled in the art are under the prerequisite not departing from the application's design; can make some possible variations and amendment, the scope that therefore protection range of the application should define with the application's claim is as the criterion.
Claims (10)
1. an electrolyte, is characterized in that, described electrolyte comprises lithium salts, organic solvent and additive, comprises fluorinated ethylene carbonate, such as formula the silicon nitrogen silane compound shown in I with such as formula the cyclic sulfates shown in II in described additive;
Wherein, in formula I, R
1, R
2, R
3, R
4, R
5, R
6, R
7independently be selected from hydrogen, C separately
1 ~ 6alkyl, n is selected from the integer of 1 ~ 5;
In formula II, R
11, R
12independently be selected from hydrogen, C separately
1 ~ 6alkyl, C
1 ~ 6alkoxyl, n is selected from the integer of 0 ~ 2.
2. electrolyte according to claim 1, is characterized in that, in formula I, and R
1be selected from hydrogen or C
1 ~ 3alkyl, R
2, R
3, R
4, R
5, R
6, R
7independently be selected from C separately
1 ~ 3alkyl, n is selected from 1,2 or 3;
In formula II, R
11, R
12independently be selected from hydrogen or C separately
1 ~ 3alkyl, n is selected from 0 or 1.
3. electrolyte according to claim 2, is characterized in that, described silicon nitrogen silane compound is selected from least one in hexamethyldisiloxane, heptamethyldisilazane, hexaethyl disilazine or six propyl group disilazanes.
4. according to electrolyte according to claim 2, it is characterized in that, described cyclic sulfates is selected from least one in sulfuric acid vinyl ester, sulfuric acid propylene, 4-methylsulfuric acid vinyl acetate.
5. electrolyte according to claim 1, is characterized in that, described cyclic sulfates mass percentage is in the electrolytic solution 0.1% ~ 5%.
6. electrolyte according to claim 1, is characterized in that, described silicon nitrogen silane compound mass percentage is in the electrolytic solution 0.1% ~ 5%.
7. electrolyte according to claim 1, is characterized in that,
Described organic solvent is selected from least one in ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate or ethyl butyrate;
Described lithium salts is selected from least one in lithium hexafluoro phosphate, difluorophosphate, LiBF4, two trifluoromethanesulfonimide lithium, two (fluorine sulphonyl) imine lithium, di-oxalate lithium borate or difluorine oxalic acid boracic acid lithium.
8. a lithium ion battery, is characterized in that, comprises the positive plate containing positive electrode active materials, the electrolyte according to any one of negative plate, lithium battery diaphragm and claim 1 ~ 7 containing negative active core-shell material.
9. lithium ion battery according to claim 8, is characterized in that, described negative material be selected from carbon materials, silicon based anode material, tin base cathode material, alloy material of cathode containing silicon, containing at least one in the alloy material of cathode of tin.
10. lithium ion battery according to claim 9, is characterized in that, containing at least one in graphite, element silicon or tin element in described negative active core-shell material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610057504.6A CN105514489A (en) | 2016-01-28 | 2016-01-28 | Electrolyte and lithium ion battery containing electrolyte |
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| CN106058316A (en) * | 2016-08-10 | 2016-10-26 | 东莞市凯欣电池材料有限公司 | High-nickel ternary lithium ion power battery electrolyte and high-nickel ternary lithium ion power battery |
| CN107403950A (en) * | 2016-05-19 | 2017-11-28 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery |
| CN108808091A (en) * | 2018-07-19 | 2018-11-13 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery high wellability electrolyte and lithium ion battery |
| CN110518286A (en) * | 2019-08-30 | 2019-11-29 | 宁德新能源科技有限公司 | Electrolyte and electrochemical appliance and electronic device including electrolyte |
| CN111108642A (en) * | 2017-09-22 | 2020-05-05 | 三菱化学株式会社 | Nonaqueous electrolyte, nonaqueous electrolyte secondary battery, and energy device |
| CN112768769A (en) * | 2021-01-15 | 2021-05-07 | 惠州锂威新能源科技有限公司 | Non-aqueous electrolyte for high-voltage lithium ion battery and lithium ion battery |
| CN113396500A (en) * | 2018-12-05 | 2021-09-14 | 昭和电工材料株式会社 | Electrolyte solution and electrochemical device |
| CN113851716A (en) * | 2021-09-24 | 2021-12-28 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte and lithium ion battery thereof |
| CN113964384A (en) * | 2021-10-18 | 2022-01-21 | 南京航空航天大学 | Multifunctional organic silicon electrolyte suitable for lithium ion battery based on silicon cathode and preparation and application thereof |
| CN115189029A (en) * | 2022-09-13 | 2022-10-14 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
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| CN107403950A (en) * | 2016-05-19 | 2017-11-28 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery |
| CN106058316A (en) * | 2016-08-10 | 2016-10-26 | 东莞市凯欣电池材料有限公司 | High-nickel ternary lithium ion power battery electrolyte and high-nickel ternary lithium ion power battery |
| CN111108642A (en) * | 2017-09-22 | 2020-05-05 | 三菱化学株式会社 | Nonaqueous electrolyte, nonaqueous electrolyte secondary battery, and energy device |
| CN111108642B (en) * | 2017-09-22 | 2024-04-02 | 三菱化学株式会社 | Nonaqueous electrolyte, nonaqueous electrolyte secondary battery, and energy device |
| CN108808091A (en) * | 2018-07-19 | 2018-11-13 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery high wellability electrolyte and lithium ion battery |
| CN108808091B (en) * | 2018-07-19 | 2020-04-17 | 合肥国轩高科动力能源有限公司 | High-wettability electrolyte for lithium ion battery and lithium ion battery |
| CN113396500A (en) * | 2018-12-05 | 2021-09-14 | 昭和电工材料株式会社 | Electrolyte solution and electrochemical device |
| CN110518286B (en) * | 2019-08-30 | 2022-04-15 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device including the same, and electronic device |
| CN110518286A (en) * | 2019-08-30 | 2019-11-29 | 宁德新能源科技有限公司 | Electrolyte and electrochemical appliance and electronic device including electrolyte |
| CN112768769A (en) * | 2021-01-15 | 2021-05-07 | 惠州锂威新能源科技有限公司 | Non-aqueous electrolyte for high-voltage lithium ion battery and lithium ion battery |
| CN113851716A (en) * | 2021-09-24 | 2021-12-28 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte and lithium ion battery thereof |
| CN113964384A (en) * | 2021-10-18 | 2022-01-21 | 南京航空航天大学 | Multifunctional organic silicon electrolyte suitable for lithium ion battery based on silicon cathode and preparation and application thereof |
| CN113964384B (en) * | 2021-10-18 | 2024-01-05 | 南京航空航天大学 | Multifunctional organic silicon electrolyte suitable for lithium ion battery based on silicon negative electrode and preparation and application thereof |
| CN115189029A (en) * | 2022-09-13 | 2022-10-14 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
| CN115189029B (en) * | 2022-09-13 | 2023-01-17 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
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