CN105449279A - Non-aqueous electrolyte solution and lithium-ion battery using same - Google Patents
Non-aqueous electrolyte solution and lithium-ion battery using same Download PDFInfo
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- CN105449279A CN105449279A CN201511030610.7A CN201511030610A CN105449279A CN 105449279 A CN105449279 A CN 105449279A CN 201511030610 A CN201511030610 A CN 201511030610A CN 105449279 A CN105449279 A CN 105449279A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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 belongs to the field of lithium-ion batteries, and particularly relates to a non-aqueous electrolyte solution and a lithium-ion battery using the same. The non-aqueous electrolyte solution comprises a non-aqueous organic solvent, lithium salts and additives; the non-aqueous organic solvent comprises at least one cyclic lactone compound; the additives comprise at least a negative electrode film-forming additive and at least a positive electrode passivation protective agent; and the positive electrode passivation positive agent is selected from at least one of 3,4-ethylenedioxythiophene, a cyclic anhydride phosphonate compound and a nitrile compound. The reduction potential of the negative electrode film-forming additive in the non-aqueous electrolyte solution is higher than that of the cyclic lactone compound, and a steady negative electrode passivation film can be formed; the positive electrode passivation protective agent can suppress oxygenolysis of the cyclic lactone compound at the positive electrode, so that the overcharging performance of the lithium-ion battery not only can be improved, but the cycle performance of the battery is also not affected.
Description
Technical field
The invention belongs to field of lithium ion battery, specifically, relate to a kind of nonaqueous electrolytic solution and use the lithium ion battery of this nonaqueous electrolytic solution.
Background technology
Lithium ion battery because of have specific energy high, have extended cycle life, the advantage such as self discharge is little, be widely used in consumer electronics product and energy storage and electrokinetic cell.Along with the extensive use of lithium ion battery, its environment for use is also tending towards varied already, requires more and more higher to the security performance of battery.Such as, in order to ensure the charging safety of electronic product, require that battery core has higher anti-overcharge performance.
Research shows, macrolide compounds cuts off electric current because its oxidizing potential lower than conventional carbonic ester and oxidation reaction form insulating barrier at positive electrode surface, thus obviously improve the over-charging of battery, but form that impedance is very large, unstable negative pole passivating film (SEI) because its too high reduction potential affects EC, FEC etc., affect the cycle performance (Journalofpowersources of battery, 2008,183,755-760).And the oxidizing potential of macrolide compounds is also lower than conventional carbonic ester, can in positive pole oxidation in cyclic process, product can increase the impedance of battery, affects the cycle performance of battery.Improve the cycle performance containing macrolide compounds electrolyte, need to find suitable cathode film formation additive and the agent of positive pole passivation protection.
Given this, special proposition the present invention.
Summary of the invention
First goal of the invention of the present invention is to provide a kind of electrolyte obviously can improve the over-charging of battery, and does not affect the cycle performance of battery.
Second goal of the invention of the present invention is to provide a kind of lithium ion battery using nonaqueous electrolytic solution of the present invention.
In order to realize foregoing invention object, the technical solution used in the present invention is:
The present invention relates to a kind of nonaqueous electrolytic solution, comprise non-aqueous organic solvent, lithium salts and additive, non-aqueous organic solvent contains at least one macrolide compounds, and additive package is containing at least one cathode film formation additive and the agent of at least one positive pole passivation protection; The agent of positive pole passivation protection be selected from 3,4-rthylene dioxythiophene, such as formula the phosphonic acid cyclic anhydridization compound shown in I, such as formula II shown in nitrile compound at least one:
Wherein, in formula I, R
11, R
12, R
13be selected from C independently of one another
1 ~ 6alkyl, substituted or unsubstituted phenyl; In formula II, R
14, R
15and R
16independently selected from C
1-5alkylidene, substituted or unsubstituted phenylene; Substituting group is C
1-3alkyl.
Preferably, described type I compound is selected from least one in triphenyl phosphonic acids cyclic anhydride, tripropyl phosphonic acids cyclic anhydride, triethyl group phosphonic acids cyclic anhydride, trimethyl phosphonic acids cyclic anhydride.
Preferably, described formula II compound is selected from least one in formula II a, formula II b, formula II c:
Preferably, described cathode film formation additive is selected from vinylene carbonate, vinylethylene carbonate, succinic anhydride, maleic anhydride, LiBF4 (LiBF
4), at least one in di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB), 1,3-propane sultone, ethyl sulfate.
Preferably, described macrolide compounds is selected from least one of formula III, formula IV:
Wherein, in formula III, n is the integer of 1 ~ 3, R
1~ R
6be selected from hydrogen atom, halogen atom, substituted or unsubstituted C independently of one another
1 ~ 10alkyl, substituting group is selected from F, Cl, Br.Preferably, described formula III compound is selected from least one in gamma-butyrolacton, δ-butyrolactone, 6-caprolactone, formula III a, formula III b, formula III c:
Preferably, the mass fraction of described positive pole passivation protection agent in nonaqueous electrolytic solution is 0.1% ~ 10%, is preferably 0.5% ~ 5%.
Preferably, the mass fraction of described cathode film formation additive in nonaqueous electrolytic solution is 0.1% ~ 20%, is preferably 0.5% ~ 8%.
Preferably, described solvent also comprises one or more in ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, methyl butyrate, ethyl acetate, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, sulfolane, dimethyl sulfoxide (DMSO), glycol sulfite, the sub-propyl ester of sulfurous acid, methyl sulfide, sulfurous acid diethyl ester, dimethyl sulfite.
The invention still further relates to a kind of lithium ion battery, comprise electrolyte, positive plate, negative plate, barrier film and package foil, described electrolyte is nonaqueous electrolytic solution of the present invention.
Embodiment
The invention provides a kind of nonaqueous electrolytic solution; comprise non-aqueous organic solvent, lithium salts and additive; non-aqueous organic solvent contains at least one macrolide compounds, and additive package contains at least one reduction potential cathode film formation additive higher than described macrolide compounds and the agent of at least one positive pole passivation protection.
Nonaqueous electrolytic solution of the present invention overcome macrolide compounds due to reduction potential too high thus EC, FEC etc. can be affected form very large, the unstable negative pole passivating film (SEI) of impedance.First, need use reduction potential higher than EC's and the film for additive of stable SEI can be formed; Secondly, needing to use can the positive pole passivation protection agent of passivation positive pole oxidation activity, suppresses macrolide compounds in the oxidation Decomposition of positive pole, thus improves the cycle performance containing macrolide compounds electrolyte.
One as nonaqueous electrolytic solution of the present invention is improved, and additive package, containing the agent of at least one positive pole passivation protection, is specifically selected from 3,4-rthylene dioxythiophene, has the compound of the phosphonic acids cyclic anhydride of structure shown in formula I, at least one had in the nitrile compound of formula II structure:
Wherein, in formula I, R
11, R
12, R
13be selected from C independently of one another
1 ~ 6alkyl, substituted or unsubstituted phenyl;
In formula II, R
14, R
15and R
16independently selected from C
1-5alkylidene, substituted or unsubstituted phenylene; Substituting group is C
1-3alkyl.
The preferred upper limit value of the carbon number of abovementioned alkyl or alkylidene is followed successively by 5,4,3; Such as, the preferred carbon number of alkyl is 1 ~ 5, and most 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.
As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, cyclobutyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, cyclopenta, 2,2-dimethyl propyl, 1-ethyl propyl, 1-methyl butyl, 2-methyl butyl, n-hexyl, isohesyl, 2-hexyl, 3-hexyl, cyclohexyl, 2-methyl amyl, 3-methyl amyl, 1,1,2-thmethylpropyl, 3,3-dimethylbutyls.
As the example of alkylidene, specifically can enumerate: methylene, ethylidene, sub-n-pro-pyl, isopropylidene, cyclopropylidene, sub-normal-butyl, isobutylene, sub-sec-butyl, the sub-tert-butyl group, sub-cyclobutyl, sub-n-pentyl, isoamylidene, sub-different tertiary pentyl, sub-different neopentyl, sub-different cyclopenta, 2,2-dimethylpropylidene, 1-ethylisopropyl base, 1-methyl-isobutyl, 2-methyl-isobutyl.
Phenylene can be 1,2-phenylene, 1,3-phenylene or Isosorbide-5-Nitrae-phenylene, and preferred Isosorbide-5-Nitrae-phenylene.
One as nonaqueous electrolytic solution of the present invention is improved, and formula II compound is selected from least one in formula II a, formula II b, formula II c:
One as nonaqueous electrolytic solution of the present invention is improved, and the agent of positive pole passivation protection is preferably at least one in tripropyl phosphonic acids cyclic anhydride, 3,4-rthylene dioxythiophene, the compound shown in formula II a.
One as nonaqueous electrolytic solution of the present invention is improved, and the mass fraction of positive pole passivation protection agent in nonaqueous electrolytic solution is 0.1% ~ 10%.This is because when the agent of positive pole passivation protection content lower than 0.05% time, can not passivation positive electrode surface completely, thus effectively can not stop the side reaction caused by electro transfer between electrolyte and electrode; And when positive pole passivation protection agent content is greater than 10%, thicker passivating film can be formed at positive electrode surface, cause lithium ion mobility resistance to increase, be unfavorable for the positive pole interface stability of battery in cyclic process.Further preferably, the mass fraction of described positive pole passivation protection agent in nonaqueous electrolytic solution is 0.5% ~ 5%.
One as nonaqueous electrolytic solution of the present invention is improved; tripropyl phosphonic acids cyclic anhydride is 0.05% ~ 3% as the mass fraction during agent of positive pole passivation protection in nonaqueous electrolytic solution; further preferably, the mass fraction of tripropyl phosphonic acids cyclic anhydride in nonaqueous electrolytic solution is 0.1% ~ 2%.
One as nonaqueous electrolytic solution of the present invention is improved; 3,4-rthylene dioxythiophene is 0.05% ~ 3% as the mass fraction during agent of positive pole passivation protection in nonaqueous electrolytic solution, further preferably; the mass fraction of 3,4-rthylene dioxythiophene in nonaqueous electrolytic solution is 0.1% ~ 0.5%.
One as nonaqueous electrolytic solution of the present invention is improved; compound shown in formula II is 0.05% ~ 3% as the mass fraction during agent of positive pole passivation protection in nonaqueous electrolytic solution; further preferably, the mass fraction of the compound shown in formula II in nonaqueous electrolytic solution is 0.1% ~ 2%.
One as nonaqueous electrolytic solution of the present invention is improved, described additive package contains at least one reduction potential cathode film formation additive higher than described macrolide compounds, specifically be selected from vinylene carbonate (VC), vinylethylene carbonate, succinic anhydride, maleic anhydride, LiBF4 (LiBF
4), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB), 1,3-propane sultone (PS) and ethyl sulfate (DTD).
One as nonaqueous electrolytic solution of the present invention is improved, described cathode film formation additive is preferably vinylene carbonate (VC), LiBF4 (LiBF4), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB) and 1,3-propane sultone (PS).
One as nonaqueous electrolytic solution of the present invention is improved, and the mass fraction of described cathode film formation additive in nonaqueous electrolytic solution is 0.1% ~ 20%.This is because when cathode film formation additive content lower than 0.05% time, complete SEI film can not be formed in negative terminal surface, thus effectively can not stop the side reaction caused by electro transfer between electrolyte and electrode; And when cathode film formation additive level is greater than 20%, thicker SEI film can be formed in negative terminal surface, cause lithium ion mobility resistance to increase, be unfavorable for the cathode interface stability of battery in cyclic process.Further preferably, the mass fraction of described cathode film formation additive in nonaqueous electrolytic solution is 0.5% ~ 8%.
One as nonaqueous electrolytic solution of the present invention is improved, vinylene carbonate (VC) is 0.05% ~ 3% as mass fraction during cathode film formation additive in nonaqueous electrolytic solution, further preferably, the mass fraction of VC in nonaqueous electrolytic solution is 0.1% ~ 1.5%.
One as nonaqueous electrolytic solution of the present invention is improved, LiBF4 (LiBF
4) be 0.05% ~ 1% as mass fraction during cathode film formation additive in nonaqueous electrolytic solution, further preferably, LiBF
4mass fraction in nonaqueous electrolytic solution is 0.1% ~ 0.5%.
One as nonaqueous electrolytic solution of the present invention is improved, di-oxalate lithium borate (LiBOB) is 0.05% ~ 1% as mass fraction during cathode film formation additive in nonaqueous electrolytic solution, further preferably, the mass fraction of LiBOB in nonaqueous electrolytic solution is 0.1% ~ 0.5%.
One as nonaqueous electrolytic solution of the present invention is improved, difluorine oxalic acid boracic acid lithium (LiDFOB) is 0.05% ~ 1% as mass fraction during cathode film formation additive in nonaqueous electrolytic solution, further preferably, the mass fraction of LiDFOB in nonaqueous electrolytic solution is 0.1% ~ 0.5%.
One as nonaqueous electrolytic solution of the present invention is improved, 1,3-propane sultone (PS) is 0.05% ~ 7% as mass fraction during cathode film formation additive in nonaqueous electrolytic solution, and further preferably, the mass fraction of PS in nonaqueous electrolytic solution is 0.1% ~ 5%.
One as nonaqueous electrolytic solution of the present invention is improved, and contains at least one of formula III or the macrolide compounds shown in formula IV in described non-aqueous organic solvent:
Wherein, in formula III, n is the integer of 1 ~ 3, R
1~ R
6be selected from hydrogen atom, halogen atom, substituted or unsubstituted C independently of one another
1 ~ 10alkyl, substituting group is selected from F, Cl, Br.
As the example of the compound shown in formula V and formula VI, specifically can enumerate: compound shown in gamma-butyrolacton, δ-butyrolactone, 6-caprolactone, formula III a, formula III b, formula III c, formula IV:
One as nonaqueous electrolytic solution of the present invention is improved, and the mass fraction of macrolide compounds in nonaqueous electrolytic solution is 0.1% ~ 40%.This is because when cyclic lactone chemical combination content lower than 0.1% time, complete dielectric film can not be formed at positive electrode surface, thus effectively can not block and overcharge the over-charging that electric current improves battery; And when macrolide compounds content is greater than 40%, electrolyte viscosity is too large, cause lithium ion mobility resistance to increase, and positive pole passivation protection film cannot effectively suppress electrolyte in the oxidation reaction of positive electrode surface.Further preferably, the mass fraction of cathode film formation additive in nonaqueous electrolytic solution is 1% ~ 30%.
One as nonaqueous electrolytic solution of the present invention is improved, and solvent also comprises at least one in ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, methyl butyrate, ethyl acetate, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, sulfolane, dimethyl sulfoxide (DMSO), glycol sulfite, the sub-propyl ester of sulfurous acid, methyl sulfide, sulfurous acid diethyl ester, dimethyl sulfite.
One as nonaqueous electrolytic solution of the present invention is improved, at least one of lithium salts optionally in organic lithium salt or inorganic lithium salt.
One as nonaqueous electrolytic solution of the present invention is improved, containing at least one in fluorine element, boron element, P elements in lithium salts.
One as nonaqueous electrolytic solution of the present invention is improved, and lithium salts is selected from lithium hexafluoro phosphate LiPF
6, two trifluoromethanesulfonimide lithium LiN (CF
3sO
2)
2(being abbreviated as LiTFSI), two (fluorine sulphonyl) imine lithium Li (N (SO
2f)
2) at least one in (being abbreviated as LiFSI).
In order to realize foregoing invention object, present invention also offers a kind of lithium ion battery, it comprises electrolyte, positive plate, negative plate, barrier film and package foil; Electrolyte is nonaqueous electrolytic solution of the present invention.
One as lithium ion battery of the present invention is improved, and positive pole diaphragm comprises positive electrode active materials, binding agent and conductive agent.
One as lithium ion battery of the present invention is improved, and positive electrode active materials is optionally from cobalt acid lithium LiCoO
2, lithium-nickel-manganese-cobalt ternary material, LiFePO 4, at least one in LiMn2O4, or the mixture of cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material.
One as lithium ion battery of the present invention is improved, and cathode membrane comprises negative active core-shell material, binding agent and conductive agent.
One as lithium ion battery of the present invention is improved, described negative active core-shell material be selected from graphite, silicon, silicide one or more, wherein, silicon can be selected from one or more of nano silicon particles, silicon nanowires, nano-tube, silicon thin film, 3D loose structure silicon and hollow porous silicon, but is not limited to above-mentioned enumerated silicon.
In above-mentioned lithium ion battery, the concrete kind of described lithium battery diaphragm is not subject to concrete restriction, the any conventional lithium battery diaphragm material used in lithium ion battery can be selected, the such as multilayer complex films of polyethylene, polypropylene, Kynoar and above-mentioned polyethylene, polypropylene, Kynoar, but be not limited to above-mentioned enumerated lithium battery diaphragm material.
The preparation method of the lithium ion battery that the application provides is known in the art, can manufacture the lithium ion battery that the application provides by existing preparation method of lithium ion battery.
Compared with prior art, the invention provides the over-charging that a kind of electrolyte obviously can improve battery, and do not affect the cycle performance of battery.
The application is further described below by way of instantiation.But these examples are only exemplary, do not form any restriction to the protection range of the application.
In following embodiment, comparative example and test example, the reagent used, material and instrument, as not having specified otherwise, all can obtain from commercial channels.
In the following embodiments, in comparative example and test example, used material is as follows:
Solvent: ethylene carbonate (EC), diethyl carbonate (being abbreviated as DEC), propene carbonate (being abbreviated as PC), lithium salts: LiPF
6.
Compound: vinylene carbonate (VC), LiBF
4, LiBOB, LiDFOB, 1,3-propane sultone (PS), tripropyl phosphonic acids cyclic anhydride (T3P), 3,4-rthylene dioxythiophene (EDOT), formula II a compound, gamma-butyrolacton (GBL), δ-butyrolactone, 6-caprolactone, formula III a, formula III b, formula III c, the compound shown in formula IV a:
Lithium battery diaphragm: the polypropylene barrier film (model is A273, is provided by Celgard company) of 16 micron thickness.
The preparation of embodiment electrolyte
Electrolyte is prepared by the following method:
In drying shed, after EC, PC and DEC are mixed, add lithium salts, then macrolide compounds and additive is added, mix, obtain electrolyte, wherein, the addition of EC, PC and DEC is EC:PC:DEC=1:1:3 for making EC, PC and DEC weight ratio, and the addition of lithium salts is make LiPF6 molar concentration in the electrolytic solution be 1mol/L.
In the process of above-mentioned preparation, concrete kind and the consumption thereof of used macrolide compounds and additive are as shown in table 1 below.
Electrolysis additive formula and addition in table 1, embodiment (1# ~ 25#) and comparative example (D1 ~ D8)
By experiment performance test will be carried out to the lithium ion battery that each comparative example of the present invention and embodiment obtain below.
Test one, loop test
The lithium ion battery prepared is carried out following test respectively:
At 25 DEG C, by lithium ion battery, with 0.5C constant current charge to 4.35V, then constant voltage charge is 0.05C to electric current, then uses 0.5C constant-current discharge to 3.0V, now for circulate first, to carry out time so repeatedly cycle charging/electric discharge according to above-mentioned condition, calculate lithium ion battery respectively and to circulate the capability retention after 50 times, 100 times, 200 times and 300 times, often organize each 5 batteries, wherein, the capability retention after circulation calculates according to the following formula.Electrolyte selected in each lithium ion battery and the relevant test data that obtains are see table 2.
Capability retention after circulation=(discharge capacity of corresponding circulation/circulate first discharge capacity) × 100%, the result of loop test is as shown in table 2.
Capability retention (%) after table 2, circulation
Can learn from the related data above-mentioned table 2, compare battery D1 ~ D5, battery 1 ~ 19, respectively through after 50 times, 100 times, 200 times, 300 times circulations, all has higher capability retention.From D7, D8, only add the one in cathode film formation additive or the agent of positive pole passivation protection, to keeping, the capability retention effect of battery is poor.
Can learn that electrolyte the application provided is applied to after in lithium ion battery, can not affect the cycle performance of battery thus, further increase the cycle performance of battery under the high voltage of more than 4.35V.In addition, when including cathode film formation additive provided by the invention and the agent of positive pole passivation protection in electrolyte simultaneously, the cycle performance of battery can be improved further, especially, further increase the cycle performance of battery under the high voltage of more than 4.35V.
Test two, overcharge test
At 25 DEG C, lithium ion battery is respectively got 5 and start charging with the constant voltage of the constant current of 1C and 10V, until overcharge, the peak temperature of Simultaneously test lithium ion battery and reach the peak temperature time used, and observe the state overcharging rear lithium ion battery.The result overcharging test is as shown in table 3.
25 DEG C of batteries result after overcharging test that table 3, each comparative example and embodiment are obtained
Can learn from the correlated results above-mentioned table 3, compare battery D1, D4, D5 and D6, overcharge the state that test presents and compare, after the battery of the electrolyte containing macrolide compounds overcharges test, generally speaking all not easily there is phenomenon on fire in battery.
Can learn thus, the electrolyte that the application provides, be applied to after in lithium ion battery, the over-charging of lithium ion battery can be improved, and do not affect the cycle performance of battery.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also carry out suitable change and amendment to above-mentioned execution mode.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a nonaqueous electrolytic solution, comprise non-aqueous organic solvent, lithium salts and additive, it is characterized in that: described non-aqueous organic solvent contains at least one macrolide compounds, described additive package is containing at least one cathode film formation additive and the agent of at least one positive pole passivation protection; The agent of described positive pole passivation protection be selected from 3,4-rthylene dioxythiophene, such as formula the phosphonic acid cyclic anhydridization compound shown in I, such as formula II shown in nitrile compound at least one:
Wherein, in formula I, R
11, R
12, R
13be selected from C independently of one another
1 ~ 6alkyl, substituted or unsubstituted phenyl; In formula II, R
14, R
15and R
16independently selected from C
1-5alkylidene, substituted or unsubstituted phenylene; Substituting group is C
1-3alkyl.
2. nonaqueous electrolytic solution according to claim 1, is characterized in that, described type I compound is selected from least one in triphenyl phosphonic acids cyclic anhydride, tripropyl phosphonic acids cyclic anhydride, triethyl group phosphonic acids cyclic anhydride, trimethyl phosphonic acids cyclic anhydride.
3. nonaqueous electrolytic solution according to claim 1, is characterized in that, described formula II compound is selected from least one in formula II a, formula II b, formula II c:
4. nonaqueous electrolytic solution according to claim 1, it is characterized in that, described cathode film formation additive is selected from least one in vinylene carbonate, vinylethylene carbonate, succinic anhydride, maleic anhydride, LiBF4, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, 1,3-propane sultone, ethyl sulfate.
5. nonaqueous electrolytic solution according to claim 1, is characterized in that, described macrolide compounds is selected from least one of formula III, formula IV:
Wherein, in formula III, n is the integer of 1 ~ 3, R
1~ R
6be selected from hydrogen atom, halogen atom, substituted or unsubstituted C independently of one another
1 ~ 10alkyl; Substituting group is selected from F, Cl, Br.
6. nonaqueous electrolytic solution according to claim 5, is characterized in that, described formula III compound is selected from least one in gamma-butyrolacton, δ-butyrolactone, 6-caprolactone, formula III a, formula III b, formula III c;
7. nonaqueous electrolytic solution according to claim 1, is characterized in that, the mass fraction of described positive pole passivation protection agent in nonaqueous electrolytic solution is 0.1% ~ 10%, is preferably 0.5% ~ 5%.
8. nonaqueous electrolytic solution according to claim 1, is characterized in that: the mass fraction of described cathode film formation additive in nonaqueous electrolytic solution is 0.1% ~ 20%, is preferably 0.5% ~ 8%.
9. electrolyte according to claim 1, it is characterized in that, described solvent also comprise in ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, methyl butyrate, ethyl acetate, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, sulfolane, dimethyl sulfoxide (DMSO), glycol sulfite, the sub-propyl ester of sulfurous acid, methyl sulfide, sulfurous acid diethyl ester, dimethyl sulfite one or more.
10. a lithium ion battery, it comprises electrolyte, positive plate, negative plate, barrier film and package foil, it is characterized in that, the nonaqueous electrolytic solution of described electrolyte according to any one of claim 1 to 9.
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Cited By (9)
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| CN105826606A (en) * | 2016-05-16 | 2016-08-03 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery containing same |
| CN106252715A (en) * | 2016-09-30 | 2016-12-21 | 合肥国轩高科动力能源有限公司 | A kind of high-temperature electrolyte of lithium ion battery |
| CN106410279A (en) * | 2016-11-30 | 2017-02-15 | 宁德时代新能源科技股份有限公司 | Electrolyte and secondary battery |
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| CN106252715A (en) * | 2016-09-30 | 2016-12-21 | 合肥国轩高科动力能源有限公司 | A kind of high-temperature electrolyte of lithium ion battery |
| CN106410279A (en) * | 2016-11-30 | 2017-02-15 | 宁德时代新能源科技股份有限公司 | Electrolyte and secondary battery |
| EP3754775A4 (en) * | 2018-02-16 | 2022-03-16 | Daikin Industries, Ltd. | Electrolysis solution, electrochemical device, lithium-ion secondary battery, and module |
| CN108461808A (en) * | 2018-03-21 | 2018-08-28 | 上海力信能源科技有限责任公司 | A kind of lithium ion battery of high-energy density and preparation method thereof |
| CN110299561A (en) * | 2018-03-21 | 2019-10-01 | 比亚迪股份有限公司 | Nonaqueous electrolytic solution, the lithium ion battery containing the nonaqueous electrolytic solution |
| CN110299561B (en) * | 2018-03-21 | 2022-02-08 | 比亚迪股份有限公司 | Non-aqueous electrolyte and lithium ion battery containing same |
| CN112585794A (en) * | 2018-08-11 | 2021-03-30 | 于利奇研究中心有限公司 | Liquid electrolyte comprising organic carbonate and cyclic sulfoxide for use in lithium secondary battery |
| CN109841903A (en) * | 2019-03-29 | 2019-06-04 | 山东海容电源材料股份有限公司 | A kind of high voltage nonaqueous electrolytic solution of resistance to combustion |
| WO2023072110A1 (en) * | 2021-10-25 | 2023-05-04 | 珠海冠宇电池股份有限公司 | Battery |
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