CN103107355B - Lithium ion battery and electrolyte thereof - Google Patents
Lithium ion battery and electrolyte thereof Download PDFInfo
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- CN103107355B CN103107355B CN201310044901.6A CN201310044901A CN103107355B CN 103107355 B CN103107355 B CN 103107355B CN 201310044901 A CN201310044901 A CN 201310044901A CN 103107355 B CN103107355 B CN 103107355B
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Abstract
The invention provides a kind of lithium ion battery and electrolyte thereof.The electrolyte of described lithium ion battery comprises nonaqueous solvents, the lithium salts be dissolved in nonaqueous solvents, not branched cyclic sulfates or sulphonic acid ester and branched cyclic sulfates.Described lithium ion battery comprises: positive plate; Negative plate; Barrier film, is arranged between positive/negative plate; And aforementioned electrolyte.Lithium ion battery of the present invention and electrolyte thereof have superior low temperature charge-discharge performance, also ensure that the performances such as suitable high temperature storage and circulation simultaneously.
Description
Technical field
The present invention relates to a kind of secondary cell, particularly relate to a kind of lithium ion battery and electrolyte thereof.
Background technology
Lithium ion battery has that operating voltage is high, energy density is high, has extended cycle life, memory-less effect, the advantage such as environmentally friendly, nowadays become the main power source of mobile electronic product, also demonstrate powerful application prospect in fields such as electric automobile, military project, space flight.
In order to improve the cycle life of lithium ion battery, usually adding film for additive in the electrolytic solution, wishing that film for additive can form the form compact and stable chemical films of one deck at electrode surface.Because this layer of chemical films can block the migration of electronics between electrode and electrolyte, thus the side reaction between them can be suppressed, slow down the aging of battery, extend working time.Meanwhile, because this layer of chemical films is lithium ion conducting, thus can not impact the charge-discharge performance of lithium ion battery itself.The form compact and stable performance of chemical films can ensure these the two kinds long-term existence acted on, and therefore can reduce the consumption of additive, and then reduces the harmful effect of additive.Film for additive conventional at present comprises vinylene carbonate (VC), fluoroethylene carbonate (FEC), vinyl ethylene carbonate (VEC), PS (PS), vinylacetate (VA) and di-oxalate lithium borate (LiBOB) etc.
But additive known is at present also imperfect, the chemical films that they are formed not is the chemical films of desirable form compact and stable lithium ion conducting and electron-block, therefore can bring certain side effect to the performance of battery.Such as PS is a kind of comparatively conventional additive, and it is the not branched cyclic sulfonic acid ester of one, after adding PS in the electrolytic solution, can be improved high temperature storage and the cycle performance of battery by the chemical films formed.But found by testing impedance, add separately PS and the internal resistance of cell can be made to increase, namely chemical films is not perfect lithium ion conducting, but has certain resistance; Under normal temperature or hot environment, lithium ion has the resistance that enough energy bring to cross this layer of chemical films, therefore not obvious on the impact of battery performance; But at low ambient temperatures, the resistance that this layer of chemical films is brought is also very important, therefore causes battery discharge capacity at low temperatures on the low side, and has the precipitation of lithium metal at anode surface.
Summary of the invention
In view of background technology Problems existing, the object of the present invention is to provide a kind of lithium ion battery and electrolyte thereof, it can improve low temperature charge-discharge performance.
Another object of the present invention is to provide a kind of lithium ion battery and electrolyte thereof, it can ensure the high temperature cyclic performance of battery.
Another object of the present invention is to provide a kind of lithium ion battery and electrolyte thereof, and it can ensure the high-temperature storage performance of battery.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of lithium ion battery electrolyte it comprise nonaqueous solvents, the lithium salts be dissolved in nonaqueous solvents, not branched cyclic sulfates or sulphonic acid ester and branched cyclic sulfates.
In a second aspect of the present invention, the invention provides a kind of lithium ion battery, it comprises: positive plate; Negative plate; Barrier film, is arranged between positive/negative plate; And electrolyte, wherein said electrolyte is the electrolyte of lithium ion battery described according to a first aspect of the present invention.
Beneficial effect of the present invention is as follows:
The present invention is on the electrolyte basis containing not branched cyclic sulfates or sulphonic acid ester, add a certain amount of branched cyclic sulfates again, optimize the structure of the chemical films that it is formed at electrode surface, the final membrane structure formed is made to be more conducive to passing through of lithium ion, ensure that the lithium ion battery containing this electrolyte has superior low temperature charge-discharge performance, also ensure that the performances such as suitable high temperature storage and circulation simultaneously.
Accompanying drawing explanation
Fig. 1 is the curve chart of cycle performance at 10 DEG C;
Fig. 2 is the curve chart of cycle performance at 45 DEG C.
Embodiment
The following detailed description of lithium ion battery according to the present invention and electrolyte thereof and embodiment.
First the electrolyte of lithium ion battery is according to a first aspect of the present invention described.
The electrolyte of lithium ion battery according to a first aspect of the present invention, comprises nonaqueous solvents, the lithium salts be dissolved in nonaqueous solvents, not branched cyclic sulfates or sulphonic acid ester and branched cyclic sulfates.
According in the electrolyte of lithium ion battery of the present invention, preferably, described not branched cyclic sulfates or sulphonic acid ester comprise ethyl sulfate (its structural formula represents such as formula 1), PS (its structural formula represents such as formula 2).
According in the electrolyte of lithium ion battery of the present invention, preferably, the weight percentage of weight percentage in the electrolyte of described lithium ion battery of not branched cyclic sulfates or sulphonic acid ester is 0.5 ~ 5%, preferably 1 ~ 3%.This is because when not branched cyclic sulfates or sulphonic acid ester content too low time, the chemical films that its open loop is formed is not enough to the surface of coated electrode, can not stop the side reaction caused by the electro transfer between electrolyte and electrode, thus the high temperature caused and cycle performance are deteriorated; And when not branched cyclic sulfates or sulphonic acid ester too high time, thicker chemical films can be formed at electrode surface, consider simultaneously unbranched structure form the compactness of chemical films, it shows larger lithium ion mobility resistance, causes the variation of battery low temperature and high rate performance.Therefore, its weight percentage is preferably 0.5 ~ 5%, is further preferably 1 ~ 3%.
According in the electrolyte of lithium ion battery of the present invention, preferably, described branched cyclic sulfates represents such as formula 3
Wherein n is the integer of 0 ~ 3, R
1, R
2in the alkyl of at least one C1 ~ C3 or the thiazolinyl of C2 ~ C3, the hydrogen atom on described alkyl and thiazolinyl can partly or entirely be replaced by halogen atom.
According in the electrolyte of lithium ion battery of the present invention, preferably, the branched cyclic sulfates that employing formula 3 represents comprises 4-methyl ethyl sulfate (its structural formula represents such as formula 4)
According in the electrolyte of lithium ion battery of the present invention, preferably, weight percentage weight percentage in the electrolyte of described lithium ion battery of branched cyclic sulfates is 0.5 ~ 5%, preferably 1 ~ 3%, its content is no more than the weight percentage of not branched cyclic sulfates or sulphonic acid ester simultaneously.When in electrolyte simultaneously containing not branched cyclic sulfates or sulphonic acid ester and branched cyclic sulfates time, they can participate in filming function jointly.Due to the sterically hindered effect of the side chain of branched cyclic sulfates, can ensure that formed chemical films has certain three-D space structure in microstructure, ensure the passage of lithium ion transition, lessen the impedance of formed chemical films like this, improve the cryogenic property of lithium ion battery.But the more use of branched cyclic sulfates can form the chemical films of short texture, can not the electro transfer between electrolyte and electrode be stoped and show very poor cycle performance.Can think that branched cyclic sulfates just plays the effect of modifying formed chemical films time used in combination, itself should as the bulk composition forming chemical films, and therefore its content should not exceed the weight percentage of not branched cyclic sulfates or sulphonic acid ester.
After circulus in 4-methyl ethyl sulfate is opened, also the course of reaction that electrode surface forms chemical films can be participated in, its side chain comprised has certain sterically hindered effect, can ensure that formed chemical films has three-D space structure in microstructure, ensure that the passage that lithium ion is crossed, lessen the impedance of formed chemical films like this, improve the cryogenic property of lithium ion battery.
In the electrolyte of the lithium ion battery according to the application, preferably, the weight percentage of weight percentage in the electrolyte of described lithium ion battery of not branched cyclic sulfates or sulphonic acid ester is 0.5 ~ 5%, preferably 1 ~ 3%; The weight percentage of weight percentage in the electrolyte of described lithium ion battery of branched cyclic sulfates is 0.5 ~ 5%, preferably 1 ~ 3%; The weight percentage of described branched cyclic sulfates is no more than the weight percentage of not branched cyclic sulfates or sulphonic acid ester.
According in the electrolyte of lithium ion battery of the present invention, preferably, described nonaqueous solvents comprises cyclic carbonate and linear carbonate; Cyclic carbonate is selected from a kind of in ethylene carbonate, propene carbonate, butyl lactone, butylene or their mixing; Linear carbonate is selected from a kind of in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, dipropyl carbonate, ethyl propyl carbonic acid ester or their mixing.
According in the electrolyte of lithium ion battery of the present invention, preferably, described lithium salts is LiPF
6, LiBF
4, LiClO
4, LiAsF
6, LiBOB, LiCF
3sO
3in one or more.
Secondly lithium ion battery is according to a second aspect of the present invention described.
Lithium ion battery according to a second aspect of the present invention comprises: positive plate; Negative plate; Barrier film, is arranged between positive/negative plate; And electrolyte, described electrolyte is the electrolyte of described lithium ion battery according to a first aspect of the present invention.
Comparative example and the embodiment according to lithium ion battery of the present invention and electrolyte thereof are finally described.
Comparative example 1
The preparation of A electrolyte
Ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC) are mixed with the weight ratio of 30:30:40, and dissolve 1MLiPF6 lithium salts, based on electrolyte.
The preparation of B battery core
Prepared by positive plate: by active material LiNi
0.5co
0.2mn
0.3o
2(LNCM), conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF) by weight after 96:2:2 is fully uniformly mixed in 1-METHYLPYRROLIDONE dicyandiamide solution, be coated on Al paper tinsel and dry, cold pressing, obtain positive plate.
The preparation of negative plate: after active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickener carboxymethyl cellulose sodium (CMC) are fully uniformly mixed in deionized water solvent system according to weight ratio 95:2:2:1, be coated on oven dry on Cu paper tinsel, cold pressing, obtain negative plate.
Barrier film: using PE porous polymer film as barrier film.
Anode ring forming: positive plate, barrier film, negative plate are folded in order, make barrier film be in the effect playing isolation in the middle of anode and cathode, and winding obtains naked battery core.Naked battery core is placed in external packing, and the basic electrolyte that injection prepares also carries out Vacuum Package, charges to 3.4V afterwards with 0.02C, charge to 3.85V with 0.1C again to change into, the battery after changing into is placed in 60 DEG C of baking ovens, after ageing 12h, exhaust edge sealing, obtains lithium ion battery.
Comparative example 2
The preparation of A electrolyte
Electrolyte is prepared according to the method identical with comparative example 1, be ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), 1 unlike this electrolyte, 3-N-morpholinopropanesulfonic acid lactone (1,3-PS) mix with the weight ratio of 29.1:29.1:38.8:3, and dissolve 1M lithium hexafluoro phosphate (LiPF
6).
The preparation of B battery core
With comparative example 1.
Comparative example 3
The preparation of A electrolyte
Electrolyte is prepared according to the method identical with comparative example 1, unlike this electrolyte be ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), 4-methyl ethyl sulfate mix with the weight ratio of 29.1:29.1:38.8:3, and dissolve 1MLiPF
6.
The preparation of B battery core
With comparative example 1.
Comparative example 4
The preparation of A electrolyte
Electrolyte is prepared according to the method identical with comparative example 1, unlike this electrolyte be ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl sulfate mix with the weight ratio of 29.1:29.1:38.8:3, and dissolve 1MLiPF
6.
The preparation of B battery core
With comparative example 1.
Embodiment 1
The preparation of A electrolyte
Electrolyte is prepared according to the method identical with comparative example 1, be ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), 1 unlike this electrolyte, 3-N-morpholinopropanesulfonic acid lactone, 4-methyl ethyl sulfate mix with the weight ratio of 28.8:28.8:38.4:3:1, and dissolve 1MLiPF
6.
The preparation of B battery core
With comparative example 1.
Embodiment 2
The preparation of A electrolyte
Electrolyte is prepared according to the method identical with comparative example 1, be ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), 1 unlike this electrolyte, 3-N-morpholinopropanesulfonic acid lactone, 4-methyl ethyl sulfate mix with the weight ratio of 28.5:28.5:38:3:2, and dissolve 1MLiPF6.
The preparation of B battery core
With comparative example 1.
Embodiment 3
The preparation of A electrolyte
Electrolyte is prepared according to the method identical with comparative example 1, unlike this electrolyte be ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), 4-methyl ethyl sulfate, ethyl sulfate mix with the weight ratio of 28.8:28.8:38.4:1:3, and dissolve 1MLiPF
6.
The preparation of B battery core
With comparative example 1.
Contrast for the ease of comparative example 1-4 and embodiments of the invention 1-3, the component of the electrolyte of these examples and ratio are listed by following table 1.
The electrolysis composition of table 1 comparative example and embodiment and ratio
Finally provide the testing result of the embodiment 1-3 of comparative example 1-4 and lithium ion battery of the present invention.
(1) internal resistance of cell test
By the battery folder of comparative example 1-4, embodiment 1-3 in burn-in board, adopt the internal resistance of Agilent 34401A type universal instrument test battery core under 1000Hz frequency, test result is as shown in table 2.
1000Hz internal resistance under table 2 normal temperature (m Ω)
As can be seen from Table 2, band side chain or not branched cyclic sulfates or sulphonic acid ester (comparative example 2-4) is added separately in the basic electrolyte of comparative example 1, the internal resistance of cell all can be made to increase, this demonstrate it, in chemical films that electrode surface becomes, resistance is had to lithium ion mobility.Can find out simultaneously, in comparative example 2-4, the impedance of branched 4-methyl ethyl sulfate (comparative example 3) institute film forming is significantly less than not branched 1, the impedance of 3-N-morpholinopropanesulfonic acid lactone (comparative example 2) and ethyl sulfate (comparative example 4) institute film forming, this shows that branched structure can affect the structure forming chemical films really, and then affects its performance.Especially comparative example 2, compared with 4-methyl ethyl sulfate, 1,3-N-morpholinopropanesulfonic acid lactone is not with side chain, although the course of reaction that participate in the chemical films that form electrode surface similar to 4-methyl ethyl sulfate, but chemical films is tightly overlying on electrode surface after film forming, result in the negative effect that foregoing membrane impedance is larger.After branched cyclic sulfates is mixed (embodiment 1-3) with not branched cyclic sulfates or sulphonic acid ester, the internal resistance of battery is also significantly less than the internal resistance of the battery being used alone not branched cyclic sulfates or sulphonic acid ester (comparative example 4 or comparative example 2), this shows that branched cyclic sulfates can optimize the structure of the chemical films that not branched cyclic sulfates or sulphonic acid ester are formed, thus produces active influence to battery performance.
(2) low temperature performance test
By the battery of comparative example 1-4, embodiment 1-3 at normal temperatures, with the constant current charge of 0.5C multiplying power to voltage higher than 4.2V, then under 4.2V constant voltage, charge to electric current lower than 0.05C, be discharged to voltage lower than 3.0V with 0.5C multiplying power constant current further; The discharge capacity of getting final step 0.5C constant current, as battery normal temperature discharge capacity D0, by the quality of this capacity divided by positive pole effective active matter, obtains the specific discharge capacity of the positive active material of each lithium ion battery.Average data (the first half) and the ratio (the latter half) of the positive discharge specific capacity of each Battery pack are as shown in table 3.
Again by battery at normal temperatures with 0.5C multiplying power constant current charge to voltage higher than 4.2V, under 4.2V constant voltage, charge to electric current lower than 0.05C further, make battery be in fully charged state; Maintain 2h under battery core after completely filling is placed in-20 DEG C of environment, make battery reach the stable state of this temperature, then with 0.1C multiplying power constant-current discharge to 3.0V, obtain the specific discharge capacity of 0.1C multiplying power under its-20 DEG C of environment.
Change the discharge-rate under-20 DEG C of environment into 0.2C, 0.3C, repeat above process, the specific discharge capacity of 0.2C, 0.3C multiplying power under-20 DEG C of environment can be obtained.
Table 3 normal temperature (RT) and-20 DEG C of positive discharge specific capacities (mAh/g)
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| 0.5C DC(RT) | 147.3 | 148.4 | 148.4 | 148.2 | 147.9 | 148.0 | 147.9 |
| 0.1C DC(-20℃) | 106.3 | 96.0 | 117.7 | 112.7 | 111.3 | 115.2 | 118.1 |
| 0.2C DC(-20℃) | 62.7 | 46.1 | 78.2 | 70.0 | 66.6 | 75.2 | 85.2 |
| 0.3C DC(-20℃) | 21.2 | 4.9 | 40.3 | 33.3 | 26.5 | 38.2 | 65.1 |
| 0.5C DC(RT) | 100.0% | 100.0% | 100.0% | 100.0% | 100.0% | 100.0% | 100.0% |
| 0.1C DC(-20℃) | 72.1% | 64.7% | 79.3% | 76.1% | 75.3% | 77.8% | 79.9% |
| 0.2C DC(-20℃) | 42.5% | 31.0% | 52.7% | 47.3% | 45.0% | 50.8% | 57.6% |
| 0.3C DC(-20℃) | 14.4% | 3.3% | 27.2% | 22.5% | 17.9% | 25.8% | 44.0% |
As can be seen from Table 3, cyclic sulfonic acid ester or cyclic sulfates be used alone or (comparative example 2-4, embodiment 1-3) used in combination can't cause harmful effect to the normal temperature capacity of battery; And due to the filming function of cyclic sulfonic acid ester and cyclic sulfates, inhibit the further reduction of anode surface electrolyte, make positive discharge specific capacity be increased to about 148mAh/g by 147.3mAh/g.Can see being used alone (comparative example 2) of PS, the specific discharge capacity of meeting severe exacerbation battery at-20 DEG C, when 0.3C only can release 3.3% of normal temperature specific discharge capacity simultaneously.And after with the addition of 4-methyl ethyl sulfate (embodiment 1-2), the low temperature discharge ability of battery can be significantly improved.Wherein, (embodiment 3) used in combination effect of 3% ethyl sulfate and 1%4-methyl ethyl sulfate is the most obvious, and under its-20 DEG C of environment, 0.3C can release 44.0% of normal temperature capacity, for not adding any sulphonic acid ester or sulfuric ester more than three times in comparative example 1.
(3) low temperature charging performance test
By the battery of comparative example 1-4, embodiment 1-3 under normal temperature environment, 0.5C multiplying power current charges higher than 4.2V, is then less than 0.05C with 4.2V constant voltage charge to electric current to cell voltage, further with 0.5C multiplying power current discharge to cell voltage lower than 3.0V.Get the discharge capacity of final step 0.5C multiplying power as battery normal temperature discharge capacity D1.
Maintain 2h under the battery core of comparative example 1-4, embodiment 1-3 being tested normal temperature capacity is placed in 10 DEG C of environment, make battery reach the stable state of this temperature.Again with 0.5C multiplying power constant current charge to cell voltage higher than 4.2V, further with 4.2V constant voltage charge to electric current lower than 0.05C, further with 0.5C multiplying power constant-current discharge to cell voltage lower than 3.0V.Repeat above charge and discharge process 10 times, and final completely to fill end, the discharge capacity of 0.5C multiplying power under 10 DEG C of environment can be obtained.With D1 for 100%, the percentage of the discharge capacity under each battery core 10 DEG C of environment can be obtained, as shown in Figure 1.
, the battery that 0.5C multiplying power under 10 DEG C of environment is completely filled is taken apart meanwhile, observe anode surface and analyse lithium situation, the charging ability of battery under low-temperature condition can be obtained.
As can be seen from Figure 1, not branched PS (comparative example 2) is significantly degrading the discharge capability of battery 10 DEG C time; Branched 4-methyl ethyl sulfate (comparative example 3) then increases at 10 DEG C of discharge capabilities to battery; And a certain amount of branched cyclic sulfates (embodiment 1-3) is added again in the electrolyte containing not branched cyclic sulfonic acid ester or sulfuric ester, the discharge capability of battery 10 DEG C time is further enhanced.Because discharge capacity can characterize the situation of charging last time, therefore, that can think branched cyclic sulfates adds the low temperature charging ability that can improve further and only add not branched cyclic sulfonic acid ester or sulfuric ester battery.Meanwhile, the lithium ion battery of embodiment 1-3 take apart after anode surface without obviously analysing lithium, and in comparative example 1-4 especially comparative example 2 have and serious analyse lithium phenomenon, confirm the improvement of electrolyte provided by the present invention to low temperature charging performance.
(4) 85 DEG C of memory properties
By the battery of comparative example 1-4, embodiment 1-3 at normal temperatures with 0.5C multiplying power current charges to cell voltage higher than 4.2V, 0.05C is less than to battery current further with 4.2V constant voltage charge, make battery be in fully charged state, adopt height gage test battery thickness, and thickness T0 before being designated as storage; Being placed in 85 DEG C of baking ovens by completely filling the battery core after thickness measuring, taking out after 4h, and using height gage test battery thickness immediately, be designated as thickness T1 after storing; According to the thickness swelling in following formulae discovery battery core storing process
ε=(T1-T0)/T0 × 100%, the thickness swelling of each Battery pack of gained is as shown in table 4.
85 DEG C, table 4 battery stores thickness swelling
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Thickness swelling | 53.4% | 6.7% | 6.8% | 6.7% | 6.9% | 7.1% | 6.8% |
As can be seen from Table 3, compared with the basic electrolyte (comparative example 1) of the additive without any sulphonic acid ester or sulfuric ester, add the high-temperature storage performance that not branched cyclic sulfonic acid ester or sulfuric ester (comparative example 2, comparative example 4) can significantly improve battery, the thickness swelling after this battery stores 4h at 85 DEG C can be reduced to about 7% by 53.4%; After adding branched 4-methyl ethyl sulfate (comparative example 3, embodiment 1-3), thickness swelling still remains on about 7%, this shows that the use of branched 4-methyl ethyl sulfate can not worsen the high-temperature storage performance of battery, and battery still can keep good high temperature storage ability.
(5) cycle performance test
Under the battery of comparative example 1-4, embodiment 1-3 being placed in 45 DEG C of environment, with 0.5C multiplying power electric current constant current charge to cell voltage higher than 4.2V, again with 4.2V constant voltage charge to electric current lower than 0.05C, be discharged to cell voltage lower than 3.0V with 0.5C multiplying power constant current more further; Circulation like this 500 times.
As can be seen from Figure 2, electrolyte in comparative example 1 is not containing any cyclic sulfonic acid ester or sulfuric ester, its battery core filming performance is poor, therefore at 45 DEG C of circulation times, is easy to occur the reaction of electrolyte and electrode and causes capacity rapid decay and occur that battery core capacity is dived after circulating at 200 times; And the electrolyte in comparative example 2,4 adds 1 of 3% weight respectively, 3-N-morpholinopropanesulfonic acid lactone and ethyl sulfate, its battery core has excellent cycle performance, not only there is not phenomenon of diving, and maintain capacity attenuation rate comparatively slowly all the time, the capability retention of 500 circulations still can reach 87.8% and 86.6%, and this illustrates that not branched cyclic sulfates and sulphonic acid ester have good filming function, significantly can improve the cycle performance of battery; In comparative example 3, be used alone the 4-methyl ethyl sulfate that weight percentage is 3%, battery core capacity rapid decay, and after 200 circulations, there is diving phenomenon, this illustrates that 4-methyl ethyl sulfate is used alone the short texture of time institute's film forming, also be not enough to the reaction suppressing electrolyte and electrode, it is used alone and can not meets performance requirement.But this does not hinder it to improve the character of institute's film forming as a kind of in common film for additive, as in embodiment 1-3, basis containing not branched cyclic sulfonic acid ester or cyclic sulfates adds a certain amount of branched 4-methyl ethyl sulfate, can see, adding of branched cyclic sulfates does not significantly worsen the cycle performance of battery, and the capability retention after 500 circulations still can reach more than 85%.This illustrates and suitably adds the agent structure that branched cyclic sulfates can't affect the chemical films of not branched cyclic sulfonic acid ester or sulfuric ester formation, therefore can not worsen the cycle performance of battery significantly.
To sum up analyze and can find out, according to lithium-ion battery electrolytes of the present invention, add not branched cyclic sulfonic acid ester or cyclic sulfates, improve high temperature and the cycle performance of battery; Add branched cyclic sulfates simultaneously, the internal resistance of this battery can be reduced, improve the low temperature charge-discharge performance of battery.Compared to prior art, lithium ion battery provided by the present invention and electrolyte thereof, under the prerequisite not endangering cycle life and high-temperature behavior, significantly improve battery charge-discharge performance at low ambient temperatures, in other words lithium ion battery of the present invention and electrolyte thereof have superior low temperature charge-discharge performance and battery can be made to keep the performances such as suitable high temperature storage and circulation simultaneously, thus can adapt to the practical application in more large-temperature range environment.
Claims (9)
1. an electrolyte for lithium ion battery, comprises nonaqueous solvents and is dissolved in the lithium salts in nonaqueous solvents, it is characterized in that,
The electrolyte of described lithium ion battery also comprises:
Not branched cyclic sulfates or not branched cyclic sulfonic acid ester; And
Branched cyclic sulfates;
Described not branched cyclic sulfates or the weight percentage of not branched cyclic sulfonic acid ester in the electrolyte of described lithium ion battery are 0.5 ~ 5%;
The weight percentage of described branched cyclic sulfates in the electrolyte of described lithium ion battery is 0.5 ~ 5%;
The weight percentage of not branched cyclic sulfates or not branched cyclic sulfonic acid ester described in described branched cyclic sulfates is no more than;
Not branched cyclic sulfates or not branched cyclic sulfonic acid ester and branched cyclic sulfates participate in filming function jointly, by sterically hindered being used for of side chain, branched cyclic sulfates ensures that the chemical films formed has certain three-D space structure in microstructure, ensure the passage of lithium ion transition, branched cyclic sulfates does not affect the agent structure of the chemical films of not branched cyclic sulfates or the formation of not branched cyclic sulfonic acid ester.
2. the electrolyte of lithium ion battery according to claim 1, is characterized in that, described not branched cyclic sulfates or not branched cyclic sulfonic acid ester comprise ethyl sulfate, 1,3-N-morpholinopropanesulfonic acid lactone, the structure of ethyl sulfate represents such as formula 1,1,3-N-morpholinopropanesulfonic acid lactone represents such as formula 2
3. the electrolyte of lithium ion battery according to claim 1, is characterized in that, described branched cyclic sulfates represents such as formula 3
Wherein n is the integer of 0 ~ 3, R
1, R
2in at least one is the alkyl of C1 ~ C3 or the thiazolinyl of C2 ~ C3.
4. the electrolyte of lithium ion battery according to claim 3, is characterized in that, the hydrogen moiety on described alkyl and thiazolinyl or all replaced by halogen atom.
5. the electrolyte of lithium ion battery according to claim 3, is characterized in that, the branched cyclic sulfates that employing formula 3 represents comprises 4-methyl ethyl sulfate, and 4-methyl ethyl sulfate represents such as formula 4
6. the electrolyte of lithium ion battery according to claim 1, is characterized in that,
Described not branched cyclic sulfates or the weight percentage of not branched cyclic sulfonic acid ester in the electrolyte of described lithium ion battery are 1 ~ 3%;
The weight percentage of described branched cyclic sulfates in the electrolyte of described lithium ion battery is 1 ~ 3%.
7. the electrolyte of lithium ion battery according to claim 1, is characterized in that, described nonaqueous solvents comprises cyclic carbonate and linear carbonate;
Cyclic carbonate is selected from a kind of in ethylene carbonate, propene carbonate, butyl lactone, butylene or their combination;
Linear carbonate is selected from a kind of in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, dipropyl carbonate, ethyl propyl carbonic acid ester or their combination.
8. the electrolyte of lithium ion battery according to claim 1, is characterized in that, described lithium salts is LiPF
6, LiBF
4, LiClO
4, LiAsF
6, LiBOB, LiCF
3sO
3in a kind of or their mixing.
9. a lithium ion battery, comprising:
Positive plate;
Negative plate;
Barrier film, is arranged between positive/negative plate; And
Electrolyte;
It is characterized in that, the electrolyte of the lithium ion battery of described electrolyte according to any one of claim 1-8.
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| EP3146588B1 (en) * | 2014-05-23 | 2018-07-25 | Solvay Sa | Nonaqueous electrolyte compositions comprising cyclic sulfates and lithium borates |
| CN111769329B (en) * | 2015-07-31 | 2022-07-12 | 宁德新能源科技有限公司 | Lithium ion battery |
| CN105576283A (en) * | 2016-02-03 | 2016-05-11 | 东莞市凯欣电池材料有限公司 | High voltage electrolyte considering high and low temperature performance and lithium ion battery using the electrolyte |
| CN107403950A (en) * | 2016-05-19 | 2017-11-28 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery |
| CN108242557B (en) * | 2016-12-26 | 2020-08-28 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| KR102449844B1 (en) | 2017-09-06 | 2022-09-29 | 삼성에스디아이 주식회사 | Rechargeable lithium battery and rechargeable lithium battery including same |
| KR20190027188A (en) | 2017-09-06 | 2019-03-14 | 삼성에스디아이 주식회사 | Non-electrolyte for rechargeable lithium battery and rechargeable lithium battery including same |
| CN110970664A (en) * | 2018-09-28 | 2020-04-07 | 宁德时代新能源科技股份有限公司 | Non-aqueous electrolyte and lithium ion battery |
| CN111490291A (en) * | 2020-04-09 | 2020-08-04 | 东莞市杉杉电池材料有限公司 | High-voltage quick-charging type lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN114122493B (en) * | 2020-08-31 | 2024-08-09 | 深圳新宙邦科技股份有限公司 | Nonaqueous electrolyte for lithium ion battery and lithium ion battery |
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