CN101453036A - Non-aqueous electrolytic solution for lithium ion secondary battery and manufacturing method thereof - Google Patents
Non-aqueous electrolytic solution for lithium ion secondary battery and manufacturing method thereof Download PDFInfo
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Abstract
The invention provides a nonaqueous electrolytic solution for a lithium ion secondary battery. The nonaqueous electrolytic solution comprises a nonaqueous solvent, a lithium salt and an additive, wherein the additive is a composition of cyclic sultone and oxalyl lithium difluoroborate. The invention also provides a method for preparing the nonaqueous electrolytic solution for the lithium ion secondary battery. The solution has the advantages that the nonaqueous electrolytic solution has obviously improved effect, low cost and simple process, is applicable to practical application, and can improve the cycling performance by over 50 percent. On the other hand, as the nonaqueous electrolytic solution is not required to form more electrolytic solution, the characteristics of the prior electrolytic solution can not be affected, such as high ionic conductance, high energy and low capacity decline. The nonaqueous electrolytic solution is both applicable to a cylindrical cell, a button cell, and a computer battery, a mobile phone battery, a battery of a vehicle using motor, a solar cell and the like.
Description
Technical field
The present invention relates to a kind of nonaqueous electrolytic solution that is used for lithium rechargeable battery and preparation method thereof.
Background technology
Lithium ion battery has the advantage of specific energy height, in light weight, memory-less effect, is widely used in the powerful electronic installation, for example on notebook computer, digital camera, DV, the electric tool, even is used for electric motor car in groups.Cylindrical lithium ion secondary battery is used very extensive on electronic product market, the world, and occupation rate of market is higher than similar NI-G, Ni-MH battery far away, we can say, above-mentioned electronic product has be unable to do without lithium rechargeable battery.Lithium rechargeable battery output, sales volume at home is very huge.But the cylindrical lithium ion secondary battery performance of domestic production at present generally is inferior to japanese product, especially cycle performance.
Secondary cell can repeated charge-discharge cycles uses, and rechargeable battery is the battery that reversible variation takes place between electrode volume and the structure when discharge.The positive electrode of lithium rechargeable battery normally contains the reactive compound of lithium, and negative pole then is the carbon with special molecular structure.In charging, the electromotive force at load cell the two poles of the earth forces anodal compound to discharge lithium ion, embeds the negative pole molecules align and is in the carbon of lamellar structure; In the time of discharge, lithium ion is then separated out from the carbon of lamellar structure, combines with the compound of positive pole again, like this because moving of lithium ion then produced electric current.In general, service condition according to battery, require battery to have the characteristic of charge-discharge characteristic, cycle life characteristics, high temperature placement, for the battery that uses carbonaceous material as negative material, variation along with the electrolyte kind, the characteristic of battery has very big variation, under existing ethylene carbonate, dimethyl carbonate and vinylene carbonate the situation as solvent, solvent can be accompanied by the generation of gas in electrode process and decompose, and along with the carrying out of charge and discharge cycles, battery capacity reduces gradually.
Nonaqueous electrolytic solution determines the electrical property of battery to a great extent as the critical material of cylindrical lithium ion secondary battery, to the cycle performance of battery influence more so.The key reason that nonaqueous electrolytic solution influences cylindrical lithium ion secondary battery is, when lithium rechargeable battery changes into, electrolyte can form one deck solid electrolyte film (being called for short the SEI film) at both positive and negative polarity, this layer solid electrolyte film is low to the conductibility of lithium ion, therefore can cause the charge-discharge performance of battery significantly to reduce, the cycle performance of battery and high rate performance depend on this layer SEI film.And electrolyte is formed the quality that influences SEI film component, structure and performance.Therefore, develop the non-aqueous solution electrolysis formula of liquid that is fit to cylindrical lithium ion secondary battery,, have crucial meaning improving the performance of cylindrical lithium ion secondary battery, especially cycle performance.Do small change by electrolyte is formed, just may greatly improve the cycle performance of cylindrical lithium ion secondary battery.
Application number provides a kind of non-water system secondary battery with good charge-discharge characteristic, cycle life characteristics and high-temperature standing properties for 02140953.6 Chinese invention patent application.Contain vinylethylene carbonate and vinylene carbonate in the electrolyte of this battery, in electrolyte, also contain a kind of in ring-type sulphonic acid ester or cyclic sulfates, the cyclic acid anhydride in addition, preferred ring-type sulfonic acid is to be selected from 1,3-propane sultone, 1,4-butane sultones, 1,3-butane sultones and 1, a kind of in the 3-propene sulfonic acid lactone.This additives for battery can improve the flash-over characteristic of secondary cell and the cycle life of battery.
On " New Chemical Materials " magazine of 2007 the 6th phases, delivered one piece and be entitled as " the novel lithium salts that can be used for lithium ion battery " in this piece article, mentioned a kind of new compound that is used for electrolyte " oxalyl difluoro boric acid lithium salts " (the English LiODFB of abbreviation), structural formula:
And utilize LiODFB unique chemical structure, make it combine two oxalyl lithium borate (LiBOB) and LiBF4 (LiBF
4) advantage.Compare with LiBOB, LiODFB in carbonic ester dissolubility and the viscosity of solvent tangible improvement has been arranged, thereby make lithium battery have better cryogenic property and multiplying power discharging property.With LiBF
4Compare, LiODFB can promote the formation of solid electrolyte interface, improved the high-temperature behavior of lithium ion battery, it is good that this battery also has with the chemical stability of lithium metal, can be good at making the aluminium foil passivation and improve ion battery security performance and anti-over-charging ability under a high position.
U.S. Pat 7,172 discloses the electrolyte of being made up of nonaqueous solvents and salt mixture in 834, and this salt mixture comprises alkali metal electrolysis liquid salt and additive salt, and this additive salt contains the anion of the mixed acid anhydride of oxalic acid and boric acid.Additive salt also comprises two oxalyl lithium borates and oxalyl difluoro lithium borate, and electrolyte salt comprises LiPF
6And LiBF
4The amount of additive salt is the additive salt all in the electrolyte and the 0.1-60% of electrolyte salt integral molar quantity, and it is that it has improved in the first time charging process protective layer on the negative material at carbon containing or the formation of solid electrolyte interface as the advantage of the additive of electrolyte that this patent also discloses oxalyl difluoro boric acid lithium compound.
Summary of the invention
The purpose of this invention is to provide a kind of nonaqueous electrolytic solution that is used for lithium rechargeable battery that can improve lithium rechargeable battery cycle-index, useful life, high-temperature behavior and security performance.
One aspect of the present invention has provided a kind of nonaqueous electrolytic solution that is used for lithium rechargeable battery, and it comprises nonaqueous solvents, lithium salts and additive, and described additive is ring-type sultones and oxalyl difluoro lithium borate composition.Using oxalyl difluoro lithium borate is that it has improved protective layer or the formation of solid electrolyte interface on negative material in first time charging process as the advantage of additive.This solid electrolyte interface can effectively be protected based on the negative pole in the electrolyte solid of carbonate; thereby the lithium ion battery that uses this electrolyte is stable and has operating temperature range widely; further; the use of this additive, the irreversible capacity that is consumed that is used for forming the solid electrolyte interface has been greatly reduced.
When ring-type sultones and oxalyl difluoro lithium borate add the electrolyte of lithium secondary battery to as additive jointly, have than every kind of additive simple superposition more performance.The ring-type sultones has good filming performance, cheap, but this material is easy to variable color to be decomposed, discharge sulfonic acid class free acid, and under hot conditions, cause the electrolyte flavescence easily, discover, oxalyl difluoro lithium borate can improve the above-mentioned shortcoming of ring-type sultones, and oxalyl difluoro lithium borate can strengthen under the high temperature solid electrolyte interface film strength on the galvanic anode, thereby improve the long-time stability of the battery performance of battery under high power high current charge-discharge condition, guarantee the stability of battery high power operating mode.
Because ring-type sultones, oxalyl difluoro lithium borate all have the characteristic of improving cycle performance, when therefore the composition that combines when both is as additive, to compare with the non-aqueous eletrolyte before improving, cycle performance can improve greatly.Simultaneously, the security performance of battery is improved significantly.Simultaneously can not influence conductivity, the electrolytic conductivity maximum is 11.0mS/cm.And when oxalyl difluoro lithium borate and ring-type sultones during as additive, oxalyl difluoro lithium borate and PF
5 -Form chelate, stoped LiPF
6Catabolite PF
5 -And the chemical reaction between the electrolyte solvent, thereby the stability of whole electrolyte system and the fail safe of battery have been improved.
Preferably, the mass ratio of ring-type sultones in the described nonaqueous electrolytic solution and described oxalyl difluoro lithium borate is 1:0.1～12, more preferably 1:0.5～5, most preferably 1:1～3.
Described nonaqueous electrolytic solution preferably includes 1 weight portion nonaqueous solvents, 0.068-0.2 weight portion lithium salts, 0.005-0.2 weight portion additive.
Described nonaqueous electrolytic solution more preferably comprises 1 weight portion nonaqueous solvents, 0.1-0.164 weight portion lithium salts, 0.01-0.1 weight portion additive.
Described nonaqueous electrolytic solution most preferably comprises 1 weight portion nonaqueous solvents, 0.123-0.164 weight portion lithium salts, 0.06-0.08 weight portion additive.
When the ratio of additive during less than the aforementioned proportion scope; can not fully form and protect overlay film on the negative pole; thereby can not obtain the characteristic of satisfied charge and discharge circulation life; simultaneously when the ratio of additive during greater than above-mentioned proportion; oxidative decomposition can take place in superfluous additive on positive pole when high temperature is placed; and have gas to produce, so the expansion of battery increase, the conductivity of electrolyte may change and can reduce once in a while the characteristic of battery simultaneously.
Described ring-type sultones is preferably selected from 1,3-propane sultone, 1,4-butane sultones, 1,3-butane sultones and 1, any one or a few in the 3-propene sulfonic acid lactone.
Described ring-type sultones more preferably 1, the 3-propane sultone.1,180 ℃ of the boiling points of 3-propane sultone when therefore adding, can suppress labile carbonic ester near negative pole in nonaqueous electrolytic solution, thereby suppress the decomposition of nonaqueous solvents.
Described nonaqueous solvents is preferably carbonic ester.
Described carbonic ester is preferably any one or a few in ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, the gamma-butyrolacton.
Described carbonic ester is ethylene carbonate or propene carbonate more preferably.Studies show that, when containing ethylene carbonate or propene carbonate in the solution of carbonic ester, they be present in easily negative pole near, therefore make labile carbonic ester near negative pole, thereby suppress the decomposition of nonaqueous solvents.
Preferably, the moisture content of described carbonic ester is less than 0.0005%, and the purity of described carbonic ester is greater than 99.98%, is that the solvent that purity is approximately 99.5% technical grade carries out rectifying, the high neat solvent that obtains on special rectifying column.
Described lithium salts is preferably selected from any one or a few in lithium hexafluoro phosphate, LiBF4, diacetyl lithium borate and the arsenic hexafluoride lithium.
Another aspect of the present invention provides a kind of method for preparing nonaqueous electrolytic solution of the present invention, and it may further comprise the steps:
A) at first in reaction vessel, add nonaqueous solvents;
B) then in described nonaqueous solvents, add lithium salts, add thermal agitation, form basic non-aqueous eletrolyte;
C) treat described basic non-aqueous eletrolyte cool to room temperature, to wherein adding additive, i.e. ring-type sultones and oxalyl difluoro lithium borate composition, ultrasonic agitation forms water white nonaqueous electrolytic solution.
Preferably, the heating and temperature control that adds thermal agitation of described step b is at 44-55 ℃.
If when oxalyl difluoro lithium borate add at step b with when adding lithium salts fashionable since lithium salts add the affiliation evolution of heat, therefore cause between oxalyl difluoro lithium borate and the moisture chemical reaction take place, cause the consumption in advance of lithium salts, influenced the stability of system.And work as oxalyl difluoro lithium borate and ring-type sultones as additive, add to jointly in the basic non-aqueous eletrolyte, the existence of ring-type sultones can stop the chemical reaction between oxalyl difluoro lithium borate and the moisture, thereby has improved the stability of whole electrolyte system.
Advantage of the present invention is: the nonaqueous electrolytic solution that obtains according to the present invention has the effect of obvious improvement, and cost is lower, and technology is simple, very suitable practical application, and cycle performance can improve more than 50%.On the other hand, because nonaqueous electrolytic solution of the present invention does not require to form more electrolyte again, thereby can not influence the characteristics of existing electrolyte, for example: the macroion conductivity, high-energy and low capacity decline, described nonaqueous electrolytic solution is applicable to cylindrical battery, button cell, also is applicable to computer battery, battery of mobile phone, vehicle using motor battery, solar cell etc.
Description of drawings
Fig. 1 is the cycle performance comparison diagram of the embodiment of the invention 1 and Comparative Examples electrolyte.Test condition is: at first with constant current 0.2C with 18650 type lithium ion cell chargings to 4.2V, change the 4.2V constant voltage charge immediately over to, cut-off current is 40mA, is discharged to constant current 0.2C then to stop when cell voltage is 2.75V.After the circulation like this 3 times, the electric current of using 0.5C instead carries out charge and discharge cycles at 2.75V～4.2V, determines the cycle performance of battery with this, thereby obtains the cycle performance of electrolyte.
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Those of ordinary skills understand that following examples are unrestricted the present invention in order to technical scheme of the present invention to be described only.Although the present invention is had been described in detail with reference to embodiment, those of ordinary skill in the art is to be understood that, technical scheme of the present invention is made amendment or is equal to replacement, do not break away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Embodiment 1:
A) the three kinds of solvent ethylene carbonates (EC) that refine, gamma-butyrolacton (GBL), methyl ethyl carbonate (EMC) mix by weight 1:1:1, and the quality of the carbonate solution that obtains is 880 grams;
B) slowly add 1M 120 the gram LiPF
6, make it to dissolve fully, form basic non-aqueous eletrolyte;
C) in basic non-aqueous eletrolyte, add 2.0% 1, the 3-propane sultone, 0.5% oxalyl difluoro lithium borate composition additive, ultrasonic agitation also mixes, and obtains water white nonaqueous electrolytic solution, water white nonaqueous electrolytic solution is by 100%.
The electrolyte property test: for the moisture and the acidity of strictness control electrolyte, gained electrolyte is injected 18650 type cylindrical lithium ion secondary batteries in the Braun glove box, positive pole is spinel lithium manganate (LiMn
2O
4) material, negative pole be graphite, with commercially available specialized lithium ion secondary battery electro-chemical test instrument change into, the cycle performance test.Test condition is: at first with constant current 0.2C with 18650 type lithium ion cell chargings to 4.2V, change the 4.2V constant voltage charge immediately over to, cut-off current is 40mA, is discharged to constant current 0.2C then to stop when cell voltage is 2.75V.After the circulation like this 3 times, the electric current of using 0.5C instead carries out charge and discharge cycles at 2.75V～4.2V, determines the cycle performance of battery with this.The cycle performance of the electrolyte that obtains is seen Fig. 1 and table 2.
Comparative Examples 1
A) three kinds of solvent EC, GBL that refine, EMC mix by weight 1:1:1, and the quality that obtains carbonate solution is 880 grams,
B) slowly add 1M 120 the gram LiPF
6, make it to dissolve fully,
C) obtain electrolyte and test by the method for testing of embodiment 1, test result is seen Fig. 1 and table 2.
As can be seen, the cycle performance of embodiment 1 will obviously be better than Comparative Examples 1, and embodiment 1 cycle-index (80% capacity) can surpass 600 times, and the cycle-index of Comparative Examples (remaining 80% capacity) is less than 400 times.
Comparative Examples 2
A) the three kinds of solvent ethylene carbonates (EC) that refine, gamma-butyrolacton (6BL), methyl ethyl carbonate (EMC) mix by mass ratio 1:1:1, and the quality of the carbonate solution that obtains is 880 grams;
B) slowly add the LiPF of 1M
6Totally 120 restrain,, make it to dissolve fully, form basic non-aqueous eletrolyte;
C) in above-mentioned basic non-aqueous eletrolyte, add 1,3-propane sultone 20 grams, ultrasonic agitation also mixes, and obtains water white nonaqueous electrolytic solution, and water white nonaqueous electrolytic solution is by 100%.
Resulting nonaqueous electrolytic solution is injected 18650 type cylindrical lithium ion secondary batteries in the Braun glove box, positive pole is that spinel lithium manganate, negative pole are graphite, and the cycle performance of the electrolyte that obtains is seen Fig. 1 and table 2.
Comparative Examples 3
Step a is identical with Comparative Examples 2 with step b, at step c with 1, the 3-propane sultone changes oxalyl difluoro lithium borate 5 grams into, ultrasonic agitation also mixes, obtain water white nonaqueous electrolytic solution, water white nonaqueous electrolytic solution injects 18650 type cylindrical lithium ion secondary batteries by 100% with resulting nonaqueous electrolytic solution in the Braun glove box, positive pole is that spinel lithium manganate, negative pole are graphite, and the cycle performance of the electrolyte that obtains is seen Fig. 1 and table 2.
Embodiment 2
A) four kinds of solvent EC, DMC that refine, EMC, propene carbonate PC mix by weight 0.8:1:1:0.2, obtain 880 gram carbonic esters;
B) slowly add the LiPF of 1.1M
6132 grams make it to dissolve fully, form basic non-aqueous eletrolyte;
C) in basic non-aqueous eletrolyte, add 1.0% 1, the 3-propane sultone, the composition additive of 1.0% oxalyl difluoro lithium borate, ultrasonic agitation also mixes, and obtains water white nonaqueous electrolytic solution, water white nonaqueous electrolytic solution is by 100%.
Gained electrolyte is injected 18650 type cylindrical lithium ion secondary batteries in the Braun glove box, positive pole is that spinel lithium manganate, negative pole are graphite, with commercially available specialized lithium ion secondary battery electro-chemical test instrument change into, cycle performance test, the cycle performance that obtains battery sees Table 2 and Fig. 1.The contrast of the security performance (heavy impact test) of the box hat battery of making according to present embodiment and the box hat battery of embodiment 1 and Comparative Examples 1 sees Table 1.
Table 1 box hat battery (18650 type) security performance contrast test
| The electrolyte numbering | Quantity | Phenomenon | Result of determination |
| Embodiment 1 | 5 | Not on firely do not explode | Qualified |
| Embodiment 2 | 5 | 4 not on fire does not explode, and 1 is emitted a small amount of white cigarette | Qualified |
| Comparative Examples 1 | 3 | 2 not on fire does not explode, and 1 is emitted a large amount of black smokes, the case temperature height | Defective |
Embodiment 3:
A) four kinds of solvent EC, DMC that refine, EMC, DEC mix by weight 0.8:1:1:0.2, obtain carbonic ester 880 grams;
B) slowly add the LiPF of 1.2M
6, 144 grams make it to dissolve fully, form basic non-aqueous eletrolyte;
C) be sequentially added into 1 of 1.6% vinylene carbonate and 1.5%, the 3-propane sultone, the composition additive of 1.5% oxalyl difluoro lithium borate, and mix, mixed electrolyte is by 100%.
Gained electrolyte is injected 18650 type cylindrical lithium ion secondary batteries in the Braun glove box, positive pole is that spinel lithium manganate, negative pole are graphite, with commercially available specialized lithium ion secondary battery electro-chemical test instrument change into, cycle performance test, the cycle performance that obtains battery sees Table 2.
Embodiment 4:
A) two kinds of solvent EC, DMC that refine mix by weight 1:1, obtain carbonic ester EC, DMC440 gram
B) slowly add the LiPF of 1.1M
666 grams make it to dissolve fully, form basic non-aqueous eletrolyte;
C) in basic non-aqueous eletrolyte, add 1.0% 1, the composition additive of 3-propane sultone and 1.0% oxalyl difluoro lithium borate, ultrasonic agitation also mixes, and obtains water white nonaqueous electrolytic solution, and water white nonaqueous electrolytic solution is by 100%.
Gained electrolyte is injected 18650 type cylindrical lithium ion secondary batteries in the Braun glove box, positive pole is that spinel lithium manganate, negative pole are graphite, with commercially available specialized lithium ion secondary battery electro-chemical test instrument change into, cycle performance test, the cycle performance that obtains battery sees Table 2.
Embodiment 5
A) a kind of solvent EC587 gram and the DEC293 gram that refine
B) slowly add the LiPF of 1.1M
6132 grams add LiBF4 10 grams again, make it to dissolve fully, form basic non-aqueous eletrolyte;
C) in described basic non-aqueous eletrolyte, add 1.0% 1, the 3-propane sultone, the composition additive of 1.0% oxalyl difluoro lithium borate, ultrasonic agitation also mixes, obtain water white nonaqueous electrolytic solution, water white nonaqueous electrolytic solution is by 100%.
Gained electrolyte is injected 18650 type cylindrical lithium ion secondary batteries in the Braun glove box, positive pole is that spinel lithium manganate, negative pole are graphite, with commercially available specialized lithium ion secondary battery electro-chemical test instrument change into, cycle performance test, obtain the cycle performance of battery, see Table 2.
Embodiment 6
A) the three kinds of solvent ethylene carbonates (EC) that refine, dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) mix by weight 1:1:1, and the quality of the carbonate solution that obtains is 1000 grams;
B) slowly add 68 LiPF that restrain
6, make it to dissolve fully, form basic non-aqueous eletrolyte;
C) in basic non-aqueous eletrolyte, add 5 gram composition additives, wherein 1,3-propane sultone 4.5 grams, oxalyl difluoro lithium borate 0.5 gram, ultrasonic agitation also mixes, and obtains water white nonaqueous electrolytic solution, and water white nonaqueous electrolytic solution is by 100%.Method by a kind of embodiment is tested its cycle performance, sees Table 2.
Embodiment 7
A) the three kinds of solvent ethylene carbonates (EC) that refine, dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) mix by weight 1:1:1, and the quality of the carbonate solution that obtains is 1000 grams;
B) slowly add 100 LiPF that restrain
6, make it to dissolve fully, form basic non-aqueous eletrolyte;
C) in basic non-aqueous eletrolyte, add 10 gram composition additives, wherein 1,3-propane sultone 9.1 grams, oxalyl difluoro lithium borate 0.9 gram, ultrasonic agitation also mixes, and obtains water white nonaqueous electrolytic solution, and water white nonaqueous electrolytic solution is by 100%.Method by a kind of embodiment is tested its cycle performance, sees Table 2.
Embodiment 8
A) the three kinds of solvent ethylene carbonates (EC) that refine, dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) mix by weight 1:1:1, and the quality of the carbonate solution that obtains is 1000 grams;
B) slowly add 100 LiPF that restrain
6, make it to dissolve fully, form basic non-aqueous eletrolyte;
C) in basic non-aqueous eletrolyte, add 100 gram composition additives, wherein 1,3-propane sultone 66.7 grams, oxalyl difluoro lithium borate 33.3 grams, ultrasonic agitation also mixes, and obtains water white nonaqueous electrolytic solution, and water white nonaqueous electrolytic solution is by 100%.Method by a kind of embodiment is tested its cycle performance, sees Table 2.
Embodiment 9
A) the three kinds of solvent ethylene carbonates (EC) that refine, dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) mix by weight 1:1:1, and the quality of the carbonate solution that obtains is 1000 grams;
B) slowly add 160 LiPF that restrain
6, make it to dissolve fully, form basic non-aqueous eletrolyte;
C) in basic non-aqueous eletrolyte, add composition additive 60 grams, wherein 45 restrain 1, the 3-propane sultone, 15 gram oxalyl difluoro lithium borates, ultrasonic agitation also mixes, and obtains water white nonaqueous electrolytic solution, and water white nonaqueous electrolytic solution is by 100%.Method by a kind of embodiment is tested its cycle performance, sees Table 2.
Embodiment 10
A) the three kinds of solvent ethylene carbonates (EC) that refine, dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) mix by weight 1:1:1, and the quality of the carbonate solution that obtains is 1000 grams;
B) slowly add 160 LiPF that restrain
6, make it to dissolve fully, form basic non-aqueous eletrolyte;
C) in basic non-aqueous eletrolyte, add 50 grams 1, the 3-propane sultone, 10 gram oxalyl difluoro lithium borate composition additives, ultrasonic agitation also mixes, and obtains water white nonaqueous electrolytic solution, and water white nonaqueous electrolytic solution is by 100%.Method by a kind of embodiment is tested its cycle performance, sees Table 2.
Embodiment 11
A) the three kinds of solvent ethylene carbonates (EC) that refine, dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) mixed by weight 1: 1: 1, and the quality of the carbonate solution that obtains is 1000 grams;
B) slowly add 100 LiPF that restrain
6, make it to dissolve fully, form basic non-aqueous eletrolyte;
C) in basic non-aqueous eletrolyte, add 10 gram composition additives, wherein 1,3-propane sultone 9.0 grams, oxalyl difluoro lithium borate 1.0 grams, ultrasonic agitation also mixes, and obtains water white nonaqueous electrolytic solution, and water white nonaqueous electrolytic solution is by 100%.Test its cycle performance by the method among the embodiment 1, see Table 2.
The cycle performance of table 2 battery
| First charge-discharge efficiency (%) | Battery 0.5C capacity (mAh) | Cycle-index (capacity residue 80%) | |
| Embodiment 1 | 92.1 | 2045 | 613 |
| Comparative Examples 1 | 90.1 | 2008 | 383 |
| Comparative Examples 2 | 91.3 | 2023 | 435 |
| Comparative Examples 3 | 90.5 | 2010 | 478 |
| Embodiment 2 | 91.3 | 2032 | 584 |
| Embodiment 3 | 92.3 | 2050 | 490 |
| Embodiment 4 | 90.9 | 2020 | 625 |
| Embodiment 5 | 91.9 | 2040 | 583 |
| Embodiment 6 | 91.5 | 2009 | 588 |
| Embodiment 7 | 91.9 | 2056 | 600 |
| Embodiment 8 | 92.3 | 2078 | 635 |
| Embodiment 9 | 92.5 | 2095 | 655 |
| Embodiment 10 | 92.2 | 2081 | 623 |
| Embodiment 11 | 91.4 | 2000 | 580 |
Claims (10)
1. nonaqueous electrolytic solution that is used for lithium rechargeable battery, it comprises nonaqueous solvents, lithium salts and additive, it is characterized in that, described additive is ring-type sultones and oxalyl difluoro lithium borate composition.
2. nonaqueous electrolytic solution according to claim 1 is characterized in that, the weight ratio of described ring-type sultones and described oxalyl difluoro lithium borate is 1:0.1～12, preferred 1:0.5～5, more preferably 1:1～3.
3. nonaqueous electrolytic solution according to claim 1 and 2 is characterized in that, described nonaqueous electrolytic solution comprises:
1 weight portion nonaqueous solvents, 0.068-0.2 weight portion lithium salts, 0.005-0.2 weight portion additive; Preferably
1 weight portion nonaqueous solvents, 0.1-0.164 weight portion lithium salts, 0.01-0.1 weight portion additive; More preferably
1 weight portion nonaqueous solvents, 0.123-0.164 weight portion lithium salts, 0.06-0.08 weight portion additive.
4. nonaqueous electrolytic solution according to claim 1 and 2 is characterized in that, described ring-type sultones is selected from 1,3-propane sultone, 1,4-butane sultones, 1,3-butane sultones and 1, any one or a few in the 3-propene sulfonic acid lactone.
5. nonaqueous electrolytic solution according to claim 1 and 2 is characterized in that, described ring-type sultones is 1, the 3-propane sultone.
6. nonaqueous electrolytic solution according to claim 1 and 2, it is characterized in that, described nonaqueous solvents is a carbonic ester, be preferably selected from ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and the gamma-butyrolacton any one or a few, preferred ethylene carbonate or propene carbonate.
7. nonaqueous electrolytic solution according to claim 6 is characterized in that, the moisture content of described carbonic ester is less than 0.0005%, and the purity of described carbonic ester is greater than 99.98%.
8. nonaqueous electrolytic solution according to claim 1 and 2 is characterized in that, described lithium salts is to be selected from lithium hexafluoro phosphate, LiBF4, diacetyl lithium borate and the arsenic hexafluoride lithium any one or a few.
9. a method for preparing any described nonaqueous electrolytic solution of claim 1 to 8 is characterized in that, this method may further comprise the steps:
A) at first in reaction vessel, add nonaqueous solvents;
B) then in described nonaqueous solvents, add lithium salts, add thermal agitation, form basic non-aqueous eletrolyte;
C) treat described basic non-aqueous eletrolyte cool to room temperature, to wherein adding additive, i.e. ring-type sultones and oxalyl difluoro lithium borate composition, ultrasonic agitation forms water white nonaqueous electrolytic solution.
10. method according to claim 9 is characterized in that, the heating and temperature control that adds thermal agitation of described step b is at 40-55 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101787137A CN101453036A (en) | 2007-12-04 | 2007-12-04 | Non-aqueous electrolytic solution for lithium ion secondary battery and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101787137A CN101453036A (en) | 2007-12-04 | 2007-12-04 | Non-aqueous electrolytic solution for lithium ion secondary battery and manufacturing method thereof |
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| CN101453036A true CN101453036A (en) | 2009-06-10 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102055017A (en) * | 2010-07-22 | 2011-05-11 | 中信国安盟固利动力科技有限公司 | Carbonic ester electrolyte with annular sultone and oxalyl lithium tetraborate composition added |
| US20120293916A1 (en) * | 2011-05-20 | 2012-11-22 | Samsung Electro-Mechanics Co., Ltd. | Electrolyte solution for lithium-ion capacitor and lithium-ion capacitor including the same |
| CN102983362A (en) * | 2012-12-20 | 2013-03-20 | 中国东方电气集团有限公司 | Low-temperature electrolyte for LiFePO4 (lithium iron phosphate) lithium-ion batteries |
| CN106299479A (en) * | 2016-08-23 | 2017-01-04 | 四川金利声乐电子科技有限公司 | A kind of formula of the high function type eletrolysis solution for lithium ion battery |
| CN109346768A (en) * | 2018-09-30 | 2019-02-15 | 东莞市杉杉电池材料有限公司 | A kind of manganate lithium ion battery nonaqueous electrolytic solution |
| CN109891656A (en) * | 2017-03-17 | 2019-06-14 | 株式会社Lg化学 | Electrolyte additive and the electrolyte for lithium secondary battery including the electrolyte additive |
| CN111082144A (en) * | 2019-12-31 | 2020-04-28 | 广东博龙能源科技有限公司 | Lithium battery electrolyte and preparation method thereof |
| CN111384390A (en) * | 2018-12-27 | 2020-07-07 | 中国科学院上海硅酸盐研究所 | Acidification reaction modification method for solid electrolyte surface |
| CN116960319A (en) * | 2023-09-14 | 2023-10-27 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and electricity utilization device |
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- 2007-12-04 CN CNA2007101787137A patent/CN101453036A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102055017A (en) * | 2010-07-22 | 2011-05-11 | 中信国安盟固利动力科技有限公司 | Carbonic ester electrolyte with annular sultone and oxalyl lithium tetraborate composition added |
| US20120293916A1 (en) * | 2011-05-20 | 2012-11-22 | Samsung Electro-Mechanics Co., Ltd. | Electrolyte solution for lithium-ion capacitor and lithium-ion capacitor including the same |
| CN102983362A (en) * | 2012-12-20 | 2013-03-20 | 中国东方电气集团有限公司 | Low-temperature electrolyte for LiFePO4 (lithium iron phosphate) lithium-ion batteries |
| CN106299479A (en) * | 2016-08-23 | 2017-01-04 | 四川金利声乐电子科技有限公司 | A kind of formula of the high function type eletrolysis solution for lithium ion battery |
| CN106299479B (en) * | 2016-08-23 | 2020-06-12 | 台州市杰龙风机厂 | Formula of high-functional electrolyte for lithium ion battery |
| CN109891656A (en) * | 2017-03-17 | 2019-06-14 | 株式会社Lg化学 | Electrolyte additive and the electrolyte for lithium secondary battery including the electrolyte additive |
| CN109891656B (en) * | 2017-03-17 | 2022-05-13 | 株式会社Lg化学 | Electrolyte additive and electrolyte for lithium secondary battery comprising the same |
| CN109346768A (en) * | 2018-09-30 | 2019-02-15 | 东莞市杉杉电池材料有限公司 | A kind of manganate lithium ion battery nonaqueous electrolytic solution |
| CN111384390A (en) * | 2018-12-27 | 2020-07-07 | 中国科学院上海硅酸盐研究所 | Acidification reaction modification method for solid electrolyte surface |
| CN111082144A (en) * | 2019-12-31 | 2020-04-28 | 广东博龙能源科技有限公司 | Lithium battery electrolyte and preparation method thereof |
| CN116960319A (en) * | 2023-09-14 | 2023-10-27 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and electricity utilization device |
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