CN114122493A - Lithium ion battery non-aqueous electrolyte and lithium ion battery - Google Patents
Lithium ion battery non-aqueous electrolyte and lithium ion battery Download PDFInfo
- Publication number
- CN114122493A CN114122493A CN202010899847.3A CN202010899847A CN114122493A CN 114122493 A CN114122493 A CN 114122493A CN 202010899847 A CN202010899847 A CN 202010899847A CN 114122493 A CN114122493 A CN 114122493A
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- CN
- China
- Prior art keywords
- lithium ion
- ion battery
- carbonate
- nonaqueous electrolyte
- equal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 109
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 53
- 150000001875 compounds Chemical class 0.000 claims description 76
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 239000000654 additive Substances 0.000 claims description 27
- 229910003002 lithium salt Inorganic materials 0.000 claims description 23
- 159000000002 lithium salts Chemical class 0.000 claims description 23
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 20
- 230000000996 additive effect Effects 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 15
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 14
- -1 methylvinyl Chemical group 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000001188 haloalkyl group Chemical group 0.000 claims description 11
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000011149 active material Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 150000005678 chain carbonates Chemical class 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 8
- 229930195735 unsaturated hydrocarbon Chemical group 0.000 claims description 8
- 229910012265 LiPO2F2 Inorganic materials 0.000 claims description 7
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 5
- 229910013188 LiBOB Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 3
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 3
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- 229910015818 MPO4 Inorganic materials 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- LEGITHRSIRNTQV-UHFFFAOYSA-N carbonic acid;3,3,3-trifluoroprop-1-ene Chemical compound OC(O)=O.FC(F)(F)C=C LEGITHRSIRNTQV-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000005394 methallyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
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- SVTMLGIQJHGGFK-UHFFFAOYSA-N carbonic acid;propa-1,2-diene Chemical compound C=C=C.OC(O)=O SVTMLGIQJHGGFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 16
- 239000003792 electrolyte Substances 0.000 abstract description 13
- 230000002829 reductive effect Effects 0.000 abstract description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 21
- 238000007600 charging Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 210000004027 cell Anatomy 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 229910013716 LiNi Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910032387 LiCoO2 Inorganic materials 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 4
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
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- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 3
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 3
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- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 2
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of lithium ion battery electrolyte, and discloses a lithium ion battery non-aqueous electrolyte and a lithium ion battery prepared from the same. When the lithium ion battery non-aqueous electrolyte provided by the invention is used for further preparing the lithium ion battery, the high-temperature storage and high-temperature cycle performance of the battery can be improved simultaneously, and the thickness expansion rate of the battery in storage is effectively reduced.
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrolyte, in particular to a lithium ion battery non-aqueous electrolyte and a lithium ion battery.
Background
Lithium ion batteries have been developed in the field of portable electronic products for a series of advantages such as high operating voltage, high safety, long life, no memory effect, etc. With the development of new energy automobiles, the lithium ion battery has a huge application prospect in a power supply system for the new energy automobiles.
As blood of a lithium ion battery, the electrolyte plays a crucial role in improving the energy density, the cycle stability and the like of the lithium ion battery. During the charging and discharging process of the lithium ion battery, the accompanying Li+The electrolyte and the electrode material undergo a series of reactions by reversible intercalation/deintercalation reactions, forming a solid electrolyte interface film (SEI film) covering the surface of the electrode material. As an electronic insulator and a lithium ion conductor, the stable SEI film can prevent further contact of an electrolyte with an electrode material, and has a great influence on the electrochemical performance and safety performance of a lithium ion battery. On the contrary, the unstable SEI film may cause the continuous consumption and reaction of the electrolyte, and generate a series of irreversible byproducts, which may cause the increase of the internal resistance and the volume expansion of the battery, and even cause fire or explosion in case of serious conditions, thereby causing great hidden troubles to the safety of the battery. Therefore, the stability of the SEI film may determine the performance of the lithium ion battery.
The optimization of the composition of the electrolyte is an important method for improving the stability of the SEI film of the lithium ion battery, and compared with an organic solvent and a lithium salt, the electrolyte has the advantages of small additive requirement, obvious effect and low cost, so that many researchers choose to use different film-forming additives (such as vinylene carbonate, fluoroethylene carbonate and ethylene carbonate) to improve various performances of the battery. And D, researching Vinylene Carbonate (VC) serving as an additive by using an electrochemical method and a spectral method, wherein the VC is found to improve the cycle performance of the battery, particularly the cycle performance of the battery at high temperature and reduce irreversible capacity. The main reason is that VC can be polymerized on the surface of graphite to generate a polyalkyl lithium carbonate film, thereby inhibiting the reduction of solvent and salt anions. LiClO at 1mol/L of G.H.Wrodnigg et al4The addition of 5 volume percent of Ethylene Sulfite (ES) or Propylene Sulfite (PS) into PC can effectively prevent PC molecules from being embedded into a graphite electrode, and can also improve the low-temperature performance of the electrolyte. The reason for this may be that the reduction potential of ES is about 2V (vs. Li/Li)+) The solvent can be reduced in preference to the solvent, and an SEI film can be formed on the surface of the graphite negative electrode.
Although the above studies play an important role in improving the performance of the battery, the research work in this respect is not mature so far, for example, there are few reports on additives for increasing the operating temperature range of the lithium ion battery, and particularly, the types of additives applied to the improvement of the high temperature performance of the lithium ion battery are limited.
Disclosure of Invention
The invention aims to solve the problem of poor performance of a lithium ion battery at high temperature in the prior art, and provides a lithium ion battery non-aqueous electrolyte and a lithium ion battery prepared by using the electrolyte.
In order to achieve the above object, a first aspect of the present invention provides a nonaqueous electrolyte for lithium ion batteries,
the nonaqueous electrolytic solution contains an organic solvent, a lithium salt, and a compound represented by the following formula (1) and/or formula (2):
in the formulae (1) and (2), R1-R6Each independently selected from hydrogen, alkyl or haloalkyl groups of 1 to 6 carbon atoms, ether or haloether groups of 1 to 8 carbon atoms, unsaturated hydrocarbon groups of 2 to 6 carbon atoms or ester groups of 1 to 6 carbon atoms.
Preferably, the alkyl group of 1 to 6 carbon atoms is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, neo-butyl or tert-butyl.
Preferably, the haloalkyl group with 1 to 6 carbon atoms is selected from haloalkyl groups with 1 to 6 carbon atoms, wherein at least one hydrogen in the alkyl group is replaced by halogen element; more preferably, the halogen element is fluorine.
Preferably, the unsaturated hydrocarbon group of 2 to 6 carbon atoms is selected from vinyl, propenyl, allyl, propynyl, propargyl, methylvinyl or methallyl.
Preferably, the compound represented by the formula (1) is selected from one or more compounds having the following structure:
Preferably, the compound represented by formula (2) is selected from one or more compounds having the following structure:
Preferably, the content of the compound represented by the formula (1) is 10ppm or more based on the total weight of the lithium ion battery nonaqueous electrolyte; more preferably, the content of the compound represented by the formula (1) is 10ppm to 3 wt% based on the total weight of the nonaqueous electrolyte solution for a lithium ion battery.
Preferably, the content of the compound represented by the formula (2) is 10ppm to 1 wt% of the total weight of the lithium ion battery nonaqueous electrolyte solution; more preferably, the content of the compound represented by the formula (2) is 10ppm to 0.8 wt% based on the total weight of the nonaqueous electrolyte solution for a lithium ion battery.
Preferably, the organic solvent is a mixture of cyclic carbonate and chain carbonate.
Preferably, the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate and butylene carbonate.
Preferably, the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and propyl methyl carbonate.
Preferably, the lithium salt is selected from LiPF6、LiBF4、LiPO2F2、LiTFSI、LiBOB、LiDFOB、LiTFSI、LiSbF6、LiAsF6、LiN(SO2CF3)2、LiC(SO2CF3)3And LiN (SO)2F)2One or more of (a).
Preferably, the content of the lithium salt in the lithium ion battery nonaqueous electrolyte is 0.5-3 mol/L; more preferably, the content of the lithium salt in the non-aqueous electrolyte of the lithium ion battery is 0.7-1.5 mol/L.
Preferably, the lithium salt is selected from LiPF6And/or LiPO2F2。
Preferably, the nonaqueous electrolytic solution further comprises an additive selected from one or more of unsaturated cyclic carbonate, fluorinated cyclic carbonate, cyclic sultone and cyclic sulfate.
Preferably, the unsaturated cyclic carbonate is selected from one or more of vinylene carbonate, ethylene carbonate and methylene ethylene carbonate.
Preferably, the fluorinated cyclic carbonate is selected from one or more of fluoroethylene carbonate, trifluoromethyl ethylene carbonate and difluoroethylene carbonate.
Preferably, the cyclic sultone is selected from one or more of 1, 3-propane sultone, 1, 4-butane sultone and propenyl-1, 3-sultone.
Preferably, the cyclic sulfate is selected from the group consisting of vinyl sulfate, 4-methyl vinyl sulfate and
one or more of (a).
More preferably, the additive is vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone,
And vinyl sulfate.
Preferably, the content of the additive is 0.1-5 wt% of the total weight of the lithium ion battery nonaqueous electrolyte.
In a second aspect, the present invention provides a lithium ion battery, which includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and the lithium ion battery nonaqueous electrolyte according to the first aspect of the present invention.
Preferably, the active material of the lithium ion battery positive electrode is selected from LiNixCoyMzL(1-x-y-z)O2、LiCox’L(1-x’)O2、LiNix”L’y’M(2-x”-y’)O4And Liz’MPO4One or more of (a) or (b),
wherein, L is one or more of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe;
l' is one or more of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe;
m is one or more of Fe, Al, Mn and Co;
and x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is more than 0 and less than or equal to 1, x ' is more than or equal to 0 and less than or equal to 0.3 and less than or equal to 0.6, y ' is more than or equal to 0.01 and less than or equal to 0.2, and z ' is more than or equal to 0.5 and less than or equal to 1.
By adopting the technical scheme, when the lithium ion battery non-aqueous electrolyte is adopted and the lithium ion battery is further prepared, the capacity retention rate of the lithium ion battery during storage and use at high temperature can be obviously improved, and the thickness expansion rate of the battery during storage is effectively reduced.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides, in a first aspect, a nonaqueous electrolyte for a lithium ion battery, which contains an organic solvent, a lithium salt, and a compound represented by the following formula (1) and/or formula (2):
in the formulae (1) and (2), R1-R6Each independently selected from hydrogen, alkyl or haloalkyl groups of 1 to 6 carbon atoms, ether or haloether groups of 1 to 8 carbon atoms, unsaturated hydrocarbon groups of 2 to 6 carbon atoms or ester groups of 1 to 6 carbon atoms.
According to the present invention, preferably, the alkyl group of 1 to 6 carbon atoms is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, neo-butyl or tert-butyl.
Preferably, the haloalkyl group with 1 to 6 carbon atoms is selected from haloalkyl groups with 1 to 6 carbon atoms, wherein at least one hydrogen in the alkyl group is replaced by halogen element; more preferably, the halogen element is fluorine.
Preferably, the unsaturated hydrocarbon group of 2 to 6 carbon atoms is selected from vinyl, propenyl, allyl, propynyl, propargyl, methylvinyl or methallyl.
According to the present invention, preferably, the compound represented by the formula (1) is selected from one or more compounds having the following structures:
According to the present invention, preferably, the compound represented by the formula (1) is selected from one or more compounds having the following structures:
In the present invention, the compound represented by the formula (1) can be synthesized by the following method:
reacting the compound represented by the formula (A) with the compound represented by the formula (B-1) and/or the compound represented by the formula (B-2) at-10 ℃ to 20 ℃ in the presence of an acid-binding agent to obtain the compound represented by the formula (1).
Wherein, in the formula (A) and the formula (B), R1-R4May each be independently selected from hydrogen, alkyl or haloalkyl groups of 1 to 6 carbon atoms, ether or haloether groups of 1 to 8 carbon atoms, unsaturated hydrocarbon groups of 2 to 6 carbon atoms or ester groups of 1 to 6 carbon atoms.
Wherein, the acid scavenger can be selected conventionally in the field, and for example, it can be N, N-Diisopropylethylamine (DIEA), pyridine, triethylamine, etc., in the present invention, preferably, the acid scavenger is triethylamine.
After the reaction, the target compound may be obtained by a conventional treatment method in the art, and for example, the target compound may be obtained by a method such as column chromatography.
In the present invention, the compound represented by the formula (2) can be synthesized by the following method: firstly, reacting a compound represented by the following formula (C) with thionyl chloride at 30-60 ℃ to obtain a compound represented by the formula (D); then, reacting the compound represented by the formula (D) with the compound represented by the formula (E) at 0-60 ℃ to obtain a compound represented by the formula (F); finally, the compound shown in the formula (F) and an oxidant are subjected to catalytic reaction at the temperature of minus 10-50 ℃ in the presence of ruthenium trichloride to obtain the compound shown in the formula (2).
Wherein R is5-R6May each be independently selected from hydrogen, alkyl or haloalkyl groups of 1 to 6 carbon atoms, ether or haloether groups of 1 to 8 carbon atoms, unsaturated hydrocarbon groups of 2 to 6 carbon atoms or ester groups of 1 to 6 carbon atoms.
Wherein the oxidizing agent can be selected conventionally in the art, and preferably, the oxidizing agent is one or more of sodium periodate, sodium hypochlorite and calcium hypochlorite.
The inventors of the present invention have intensively studied and found that when the compound represented by the formula (1) and/or the formula (2) is contained in the nonaqueous electrolytic solution of a lithium ion battery, both the high-temperature cycle performance and the storage performance of the lithium ion battery are significantly improved. This is probably because the compound represented by the formula (1) or (2) can react on the electrode surface to form a passivation film during the first charge, thereby inhibiting further decomposition of the solvent molecules. In addition, the passivation film formed by the compound is high-temperature resistant and cannot be damaged in the high-temperature cycle and storage process, and the compound represented by the formula (1) or the formula (2) can repair other components in the passivation film damaged by high temperature, so that the stability of the interface film of the battery at high temperature is ensured, and the high-temperature cycle and high-temperature storage performance of the battery are improved.
According to the present invention, when used for preparing a nonaqueous electrolytic solution, the content of the compound represented by the formula (1) may be 10ppm or more based on the total weight of the nonaqueous electrolytic solution for a lithium ion battery; preferably, the content of the compound represented by the formula (1) is 10ppm to 3 wt% of the total weight of the lithium ion battery nonaqueous electrolyte. The content of the compound represented by the formula (2) may be 10ppm to 1 wt% based on the total weight of the lithium ion battery nonaqueous electrolyte solution; preferably, the content of the compound represented by the formula (2) is 10ppm to 0.8 wt% based on the total weight of the lithium ion battery nonaqueous electrolyte.
When the content of the compound represented by formula (1) and/or formula (2) is within this range, the storage and cycle performance of the lithium ion battery at high temperatures can be effectively improved. When the content of the compound represented by the formula (1) and/or the formula (2) is less than this range, the effect is not sufficiently remarkable although there is a certain improvement effect; when the content of the compound represented by formula (1) and/or formula (2) is in this range, the storage and cycling performance of the lithium ion battery at high temperature may be adversely affected, which may be caused by the fact that the viscosity of the electrolyte increases after the compound represented by formula (1) and/or formula (2) is added in a higher content, which further increases the overall resistance of the battery, thereby decreasing the storage and cycling performance at high temperature.
In the present invention, the organic solvent in the lithium ion battery nonaqueous electrolyte may be any of various organic solvents commonly used in the art for preparing nonaqueous electrolytes, and is not particularly limited, and for example, one or more of cyclic carbonates, chain carbonates, carboxylates, ethers, and the like may be used as the organic solvent.
According to the present invention, preferably, the organic solvent is a mixture of cyclic carbonate and chain carbonate, and when the organic solvent is selected from a mixture of cyclic carbonate and chain carbonate, the nonaqueous electrolytic solution can be made to have a higher dielectric constant and a lower viscosity. More preferably, the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate and butylene carbonate; the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and methyl propyl carbonate.
In a particularly preferred embodiment of the present invention, the organic solvent is a mixture of Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC), and the ratio of the three is 1:1: by using the three compounds in the above ratio range as the organic solvent, the nonaqueous electrolytic solution can obtain higher conductivity, which is beneficial to improving the comprehensive performance of the battery.
According to the present invention, various lithium salts commonly used in the art for preparing lithium ion batteries can be used as the lithium salt in the nonaqueous electrolyte of the lithium ion battery, and are not particularly limited, and for example, LiPF can be selected6、LiPO2F2、LiBF4、LiBOB、LiClO4、LiCF3SO3、LiDFOB、LiN(SO2CF3)2、LiN(SO2F)2One or more of LiTFSI, and litdob. In the present invention, preferably, the lithium salt is selected from LiPF6、LiBF4、LiPO2F2LiTFSI, LiBOB, LiDFOB and LiN (SO)2F)2One or more of (a). More preferably, the lithium salt is selected from LiPF6And/or LiPO2F2. When the lithium salt is used, the conductivity of the non-aqueous electrolyte can be obviously improved, the performance of the lithium ion battery is improved, and the production cost is reduced.
In the present invention, the content of the lithium salt may be a content generally used in lithium ion batteries in the art, and is not particularly limited. In the invention, the content of the lithium salt in the lithium ion battery non-aqueous electrolyte is 0.5-3 mol/L; preferably, the content of the lithium salt in the non-aqueous electrolyte of the lithium ion battery is 0.7-1.5 mol/L. When the content of the lithium salt is within the range, the high conductivity of the nonaqueous electrolyte can be ensured, and the comprehensive performance of the battery is excellent.
In the present invention, the nonaqueous electrolyte solution for a lithium ion battery may further contain various additives commonly used in the art for improving the performance of a lithium ion battery, in addition to the compound represented by the formula (1) and/or the formula (2), and examples of such additives include: may be selected from unsaturated cyclic carbonates, fluorinated cyclic carbonates, cyclic sultones, cyclic sulfates, and the like.
In the present invention, preferably, the unsaturated cyclic carbonate is selected from one or more of vinylene carbonate (CAS: 872-36-6), ethylene carbonate (CAS: 4427-96-7) and methylene vinyl carbonate (CAS: 124222-05-5).
In the present invention, preferably, the fluorinated cyclic carbonate is selected from one or more of fluoroethylene carbonate (CAS: 114435-02-8), trifluoromethyl ethylene carbonate (CAS: 167951-80-6) and difluoroethylene carbonate (CAS: 311810-76-1).
In the present invention, preferably, the cyclic sultone is selected from one or more of 1, 3-propane sultone (CAS: 1120-71-4), 1, 4-butane sultone (CAS: 1633-83-6) and propenyl-1, 3-sultone (CAS: 21806-61-1).
In the present invention, preferably, the cyclic sulfate is selected from the group consisting of vinyl sulfate (CAS: 1072-53-3), 4-methyl vinyl sulfate (CAS: 5689-83-8) and
one or more of (a).
In the present invention, more preferably, the additive is Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS),
And vinyl sulfate (DTD).
The inventors of the present invention have found that when the above additive is further added to a lithium ion battery, the additive can exert a synergistic effect with the compound represented by formula (1) and/or formula (2), thereby further improving the overall performance of the lithium ion battery.
In addition, in addition to the above additives, a second lithium salt may be further added as an additive to improve the performance of the lithium ion battery, for example, in a preferred embodiment of the present invention, the second lithium salt LiN (SO) is added2F)2As an additive, by adding LiN (SO) as an additive2F)2The capacity retention rate and the capacity recovery rate of the lithium ion battery can be further improved.
In the present invention, the content of the additive may be the content conventionally used in lithium ion batteries for various additives in the art. For example, the content of the additive can be 0.1-5 wt% of the total weight of the lithium ion battery nonaqueous electrolyte; preferably, the content of the additive can be 0.1-3 wt% of the total weight of the lithium ion battery nonaqueous electrolyte; more preferably, the content of the additive may be 0.5 to 1 wt% of the total weight of the lithium ion battery nonaqueous electrolyte.
In a second aspect, the present invention provides a lithium ion battery, which includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and the lithium ion battery nonaqueous electrolyte according to the first aspect of the present invention.
According to the invention, the active material of the lithium ion battery positive electrode may be selected from the group consisting of LiNixCoyMzL(1-x-y-z)O2、LiCox’L(1-x’)O2、LiNix”L’y’M(2-x”-y’)O4And Liz’MPO4Wherein, L is one or more of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe; l' is one or more of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe; m is one or more of Fe, Al, Mn and Co; x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is more than 0 and less than or equal to 1, 0<x’≤1，0.3≤x”≤0.6，0.01≤y’≤0.2，0.5≤z’≤1。
For example, LiNi can be used as the active material of the positive electrode of the lithium ion batteryxCoyMzL(1-x-y-z)O2Wherein x may be 0.5, y may be 0.2, z may be 0.3, and M may be Mn, i.e., the active material of the lithium ion battery positive electrode thus represented is LiNi0.5Co0.2Mn0.3O2。
According to the present invention, the active material of the negative electrode may be selected from various materials commonly used in the art for negative electrode active materials of lithium ion batteries, without particular limitation, and may be, for example, one or more of metallic lithium, graphite-based carbon materials, hard carbon materials, soft carbon materials, silicon-based, tin-based, antimony-based, aluminum-based, transition metal compounds; in the present invention, preferably, the active material of the negative electrode is one or more of artificial graphite, natural graphite, and silicon carbon.
In the present invention, the preparation of the positive electrode and the negative electrode of the lithium ion battery may be performed according to a method commonly used in the art for preparing the positive electrode and the negative electrode of the lithium ion battery, and is not particularly limited. For example, the active materials of the positive and negative electrodes may be mixed with a conductive agent and a binder, and the mixture may be dispersed in an organic solvent to prepare a slurry, and then the obtained slurry may be coated on a current collector and subjected to drying, calendering, and the like. The conductive agent, binder, organic solvent and current collector can be materials and substances commonly used in the art, and are not described in detail herein.
According to the present invention, the separator disposed between the positive electrode and the negative electrode may be any of various materials commonly used as separators in the art, and is not particularly limited, and may be, for example, one or more of a polyolefin-based separator, a polyamide-based separator, a polysulfone-based separator, a polyphosphazene-based separator, a polyethersulfone-based separator, a polyetherketoneketone-based separator, a polyetheramide-based separator, and a polyacrylonitrile-based separator; preferably, the diaphragm is selected from a polyolefin diaphragm and/or a polyacrylonitrile diaphragm.
In the invention, the lithium ion battery can be prepared by a sandwich method commonly used in the field, for example, a diaphragm is arranged between a positive plate and a negative plate coated with active materials, then the whole is coiled, a coiled body is flattened and then placed into a packaging bag for vacuum baking and drying to obtain a battery cell, then electrolyte is injected into the battery cell, and the battery cell is formed after vacuum packaging and standing. This method is conventional in the art and will not be described further herein.
The present invention will be described in detail below by way of examples. In the following examples, all materials used are commercially available unless otherwise specified.
In the following examples, the production method of a compound represented by formula (2) represented by compound 2 is as follows:
reacting the compound represented by the formula (D-1) with the compound represented by the formula (E-1) at 0-60 ℃ under stirring to obtain a compound represented by the formula (F-1); then, the compound shown in the formula (F-1) and oxidants such as sodium periodate, sodium hypochlorite, calcium hypochlorite and the like are catalyzed by ruthenium trichloride at the temperature of-10 to 50 ℃ to obtain a compound 2.
In the following examples, the production method of a compound represented by formula (1) represented by compound 7 is as follows:
under stirring, in the presence of an acid-binding agent triethylamine, reacting the compound represented by the formula (A-1) with the compound represented by the formula (B-3) at-10-20 ℃ to obtain a compound 7.
Test example 1: high temperature cycle performance test
The lithium ion batteries prepared in the following examples and comparative examples were placed in an oven maintained at a constant temperature of 45 ℃ and were constant-current charged to 4.4V (LiNi) with a current of 1C0.5Co0.2Mn0.3O2Artificial graphite battery) or 4.2V (LiNi)0.8Co0.15Al0.05O2Artificial graphite battery) or 4.48V (LiCoO)2Artificial graphite battery) or 3.65V (LiFePO)4Artificial graphite cell), constant voltage charging until the current drops to 0.02C, and constant current discharging at 1C to 3.0V (LiNi)0.5Co0.2Mn0.3O2Artificial graphite Battery, LiNi0.8Co0.15Al0.05O2Artificial graphite Battery, LiCoO2Artificial graphite cell) or discharged at a constant current of 1C to 2.5V (LiFePO)4Artificial graphite battery), thus cycled 300 times, and the 1 st discharge capacity and the 300 th discharge capacity were recorded.
The capacity retention for the high temperature cycle was calculated as follows:
capacity retention rate is 300-th discharge capacity/1-th discharge capacity × 100%.
Test example 2: high temperature storage Performance test
Lithium ion batteries prepared in the following examples and comparative examples were charged to 4.4V (LiNi) at room temperature with a constant current of 1C and a constant voltage0.5Co0.2Mn0.3O2Artificial graphite battery) or 4.2V (LiNi)0.8Co0.15Al0.05O2Artificial graphite battery) or 4.48V (LiCoO)2Artificial graphite battery) or 3.65V (LiFePO)4Artificial graphite battery), measuring initial discharge capacity of the battery andinitial cell thickness, and then after storage at 60 ℃ for 30 days, discharge to 3.0V (LiNi) at a constant current of 1C0.5Co0.2Mn0.3O2Artificial graphite Battery, LiNi0.8Co0.15Al0.05O2Artificial graphite Battery, LiCoO2Artificial graphite cell), or discharged at a constant current of 1C to 2.5V (LiFePO)4V/artificial graphite battery), measuring the retention capacity and recovery capacity of the battery at that time and the thickness of the battery after storage, and calculating the capacity retention rate, capacity recovery rate and thickness expansion rate of the battery according to the following calculation formulas:
battery capacity retention (%) — retention capacity/initial capacity × 100%;
battery capacity recovery (%) — recovery capacity/initial capacity × 100%;
thickness expansion (%) (battery thickness after storage-initial battery thickness)/initial battery thickness × 100%.
Example 1
1) Preparation of non-aqueous electrolyte of lithium ion battery
Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) were mixed in a weight ratio of EC: DEC: EMC ═ 1:1:1, and then lithium hexafluorophosphate (LiPF) was added6) Adding compound 1 with 10ppm of total weight of the nonaqueous electrolyte solution until the molar concentration is 1 mol/L;
2) preparation of Positive plate
The positive active material LiNi-Co-Mn oxide LiNi0.5Co0.2Mn0.3O2Uniformly mixing conductive carbon black Super-P serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder according to the weight ratio of 93:4:3, and then dispersing the obtained mixture in N-methyl-2-pyrrolidone (NMP) to obtain positive electrode slurry; and uniformly coating the positive electrode slurry on two surfaces of the aluminum foil, drying, rolling and vacuum drying, and welding an aluminum outgoing line by using an ultrasonic welding machine to obtain the positive electrode plate, wherein the thickness of the positive electrode plate is 120-150 mu m.
3) Preparation of negative plate
Uniformly mixing artificial graphite serving as a negative electrode active material, conductive carbon black Super-P serving as a conductive agent, Styrene Butadiene Rubber (SBR) serving as a binder and carboxymethyl cellulose (CMC) according to a weight ratio of 94:1:2.5:2.5, and dispersing the mixture in deionized water to obtain negative electrode slurry; and coating the negative electrode slurry on two sides of the copper foil, drying, rolling and vacuum drying, and welding a nickel outgoing line by using an ultrasonic welding machine to obtain a negative electrode plate, wherein the thickness of the negative electrode plate is 120-150 mu m.
4) Preparation of cell
And placing three layers of isolating films with the thickness of 20 mu m between the positive plate and the negative plate, then winding the sandwich structure consisting of the positive plate, the negative plate and the diaphragm, flattening the wound body, then placing the wound body into an aluminum foil packaging bag, and baking for 48h at 75 ℃ in vacuum to obtain the battery cell to be injected with liquid.
5) Liquid injection and formation of battery core
In a glove box with the dew point below-40 ℃, injecting the electrolyte prepared in the step 1) into the battery cell prepared in the step 4), and standing for 24 hours after vacuum packaging;
then the first charge is normalized according to the following steps: charging at 0.05C for 180min, charging at 0.2C to 3.95V, vacuum sealing for the second time, further charging at 0.2C to 4.4V, standing at room temperature for 24hr, and discharging at 0.2C to 3.0V.
Examples 2 to 29 and comparative examples 1 to 10
The procedure of example 1 was followed, except that the types and contents of the positive electrode active material of the lithium ion battery, the compound represented by formula (1) or formula (2) and the other additives added to the nonaqueous electrolytic solution were varied, as shown in table 1.
In addition, the formation method differs for different positive electrode active materials, specifically, LiNi0.8Co0.15Al0.05O2Artificial graphite battery: charging at 0.05C for 180min, charging at 0.1C for 180min, charging at 0.2C for 120min, vacuum sealing for the second time, constant-current and constant-voltage charging at 0.2C to 4.2V, stopping current at 0.05C, standing at room temperature for 5min, and discharging at 0.2C to 3V.
LiCoO2Artificial graphite battery: adopts the thermal pressing formation, the upper limit voltage is 3.8V and the pressure is 8Kg/CC after the constant current of 0.1C is charged for 45min,charging at 0.2C constant current for 30min with upper limit voltage of 4.4V and pressure of 8Kg/CC, charging at 0.5C constant current for 75min with upper limit voltage of 4.4V and pressure of 8Kg/CC, vacuum sealing for the second time, further charging at 0.2C constant current and constant voltage to 4.48V, stopping current at 0.03C, standing at room temperature for 5min, and discharging at 0.2C constant current to 3V.
LiFePO4Artificial graphite battery: the method comprises the steps of adopting thermal compression, charging at a constant current of 0.03C for 120min with an upper limit voltage of 3.65V and a pressure of 3Kg/CC, charging at a constant current of 0.1C for 60min with an upper limit voltage of 3.65V and a pressure of 3Kg/CC, charging at a constant current of 0.2C for 60min with an upper limit voltage of 3.65V and a pressure of 6Kg/CC, performing secondary vacuum sealing, further charging at a constant current of 0.2C for 3.65V and a constant voltage, stopping the current for 0.05C, standing at normal temperature for 5min, and then discharging at a constant current of 0.2C for 2.5V.
The relevant properties of the lithium ion batteries prepared in examples 1 to 29 and comparative examples 1 to 10 are shown in table 1.
TABLE 1
Note: table 1/shows no addition of the corresponding substances.
From the results of examples 1 to 8 and comparative example 1, it can be seen that when the compound represented by formula (1) or formula (2) of the present invention is contained in the nonaqueous electrolytic solution for a lithium ion battery, the storage and cycle performance of the lithium ion battery at high temperatures can be significantly improved as compared with the comparative example in which the above compound is not used.
Further, as is clear from comparison of the results of examples 4, 9 to 14 and comparative examples 2 to 7, it was found that when other additives (vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, methyl ethyl ketone, ethyl methyl ketone, ethyl ketone, and ethyl ketone) were further added to the nonaqueous electrolytic solution of the lithium ion battery,
Vinyl sulfate and LiN (SO)2F)2) In this case, the cycle and storage performance of the lithium ion battery at high temperature can be further improved.
As can also be seen from table 1, increasing the addition amount of compound 1 (refer to examples 1 and 4) can significantly improve the capacity retention rate and capacity recovery rate of the lithium ion battery, but when the addition amount of compound 1 continues to increase (refer to examples 7 and 8), the performance of the lithium ion battery is rather decreased.
As can be seen from the results of examples 15 to 29 and comparative examples 8 to 10, LiNi was used as a material other than the positive electrode active material0.5Co0.2Mn0.3O2Besides, when the positive active material of the lithium ion battery is LiNi0.8Co0.15Al0.05O2、LiCoO2And LiFePO4And when the nonaqueous electrolyte contains the compound represented by the formula (1) and/or the formula (2) provided by the invention, the high-temperature cycle and the storage performance of the obtained lithium ion battery can be remarkably improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A nonaqueous electrolyte for a lithium ion battery, characterized in that the nonaqueous electrolyte contains an organic solvent, a lithium salt, and a compound represented by the following formula (1) and/or formula (2):
in the formulae (1) and (2), R1-R6Each independently selected from hydrogen, alkyl or haloalkyl groups of 1 to 6 carbon atoms, ether or haloether groups of 1 to 8 carbon atoms, unsaturated hydrocarbon groups of 2 to 6 carbon atoms or 1 to 6 carbon atomsAn ester group of a molecule.
2. The nonaqueous electrolyte solution for lithium-ion batteries according to claim 1, wherein the alkyl group having 1 to 6 carbon atoms is selected from a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a neo-butyl group, or a tert-butyl group;
preferably, the haloalkyl group with 1 to 6 carbon atoms is selected from haloalkyl groups with 1 to 6 carbon atoms, wherein at least one hydrogen in the alkyl group is replaced by halogen element;
more preferably, the halogen element is fluorine;
preferably, the unsaturated hydrocarbon group of 2 to 6 carbon atoms is selected from vinyl, propenyl, allyl, propynyl, propargyl, methylvinyl or methallyl.
3. The nonaqueous electrolyte solution for lithium-ion batteries according to claim 1 or 2, wherein the compound of formula (1) is one or more selected from compounds having the following structures:
4. the nonaqueous electrolyte solution for lithium-ion batteries according to claim 1 or 2, wherein the compound of formula (2) is one or more selected from compounds having the following structures:
5. the nonaqueous electrolyte solution for lithium ion batteries according to any one of claims 1 to 4, wherein the content of the compound represented by formula (1) is 10ppm or more based on the total weight of the nonaqueous electrolyte solution for lithium ion batteries;
preferably, the content of the compound represented by the formula (1) is 10ppm to 3 wt% of the total weight of the lithium ion battery nonaqueous electrolyte solution;
preferably, the content of the compound represented by the formula (2) is 10ppm to 1 wt% of the total weight of the lithium ion battery nonaqueous electrolyte solution;
preferably, the content of the compound represented by the formula (2) is 10ppm to 0.8 wt% based on the total weight of the lithium ion battery nonaqueous electrolyte.
6. The nonaqueous electrolyte solution for a lithium ion battery according to any one of claims 1 to 4, wherein the organic solvent is a mixture of a cyclic carbonate and a chain carbonate;
preferably, the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate and butylene carbonate;
preferably, the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and propyl methyl carbonate.
7. The nonaqueous electrolyte for lithium ion batteries according to any one of claims 1 to 4, wherein the lithium salt is selected from LiPF6、LiBF4、LiPO2F2、LiTFSI、LiBOB、LiDFOB、LiTFSI、LiSbF6、LiAsF6、LiN(SO2CF3)2、LiC(SO2CF3)3And LiN (SO)2F)2One or more of (a) or (b),
preferably, the content of the lithium salt in the lithium ion battery nonaqueous electrolyte is 0.5-3 mol/L;
preferably, the lithium salt is selected from LiPF6And/or LiPO2F2；
Preferably, the content of the lithium salt in the non-aqueous electrolyte of the lithium ion battery is 0.7-1.5 mol/L.
8. The lithium-ion battery nonaqueous electrolyte solution of any one of claims 1 to 4, wherein the lithium-ion battery nonaqueous electrolyte solution further comprises an additive selected from one or more of unsaturated cyclic carbonates, fluorinated cyclic carbonates, cyclic sultones, and cyclic sulfates;
preferably, the unsaturated cyclic carbonate is selected from one or more of vinylene carbonate, ethylene carbonate and methylene ethylene carbonate;
preferably, the fluorinated cyclic carbonate is selected from one or more of fluoroethylene carbonate, trifluoromethyl ethylene carbonate and difluoroethylene carbonate;
preferably, the cyclic sultone is selected from one or more of 1, 3-propane sultone, 1, 4-butane sultone and propenyl-1, 3-sultone;
preferably, the cyclic sulfate is selected from the group consisting of vinyl sulfate, 4-methyl vinyl sulfate and
one or more of;
more preferably, the additive is vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone,
And vinyl sulfate;
preferably, the content of the additive is 0.1-5 wt% of the total weight of the lithium ion battery nonaqueous electrolyte.
9. A lithium ion battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and the lithium ion battery nonaqueous electrolyte solution according to any one of claims 1 to 8.
10. The lithium ion battery according to claim 9, wherein the active material of the positive electrode of the lithium ion batteryThe material is selected from LiNixCoyMzL(1-x-y-z)O2、LiCox’L(1-x’)O2、LiNix”L’y’M(2-x”-y’)O4And Liz’MPO4One or more of (a) or (b),
wherein, L is one or more of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe;
l' is one or more of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe;
m is one or more of Fe, Al, Mn and Co;
and x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is more than 0 and less than or equal to 1, x ' is more than or equal to 0 and less than or equal to 0.3 and less than or equal to 0.6, y ' is more than or equal to 0.01 and less than or equal to 0.2, and z ' is more than or equal to 0.5 and less than or equal to 1.
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| CN103053060A (en) * | 2010-08-05 | 2013-04-17 | 和光纯药工业株式会社 | Non-aqueous electrolyte, and non-aqueous electrolyte cell using the same |
| JP2016029650A (en) * | 2014-07-17 | 2016-03-03 | 三菱化学株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte battery using the same |
| CN105474452A (en) * | 2013-09-25 | 2016-04-06 | 三井化学株式会社 | Method for manufacturing rectangular battery cell using metal plates |
| WO2017069278A1 (en) * | 2015-10-23 | 2017-04-27 | 宇部興産株式会社 | Non-aqueous electrolyte solution and power storage device using same |
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| CN103053060A (en) * | 2010-08-05 | 2013-04-17 | 和光纯药工业株式会社 | Non-aqueous electrolyte, and non-aqueous electrolyte cell using the same |
| CN105474452A (en) * | 2013-09-25 | 2016-04-06 | 三井化学株式会社 | Method for manufacturing rectangular battery cell using metal plates |
| JP2016029650A (en) * | 2014-07-17 | 2016-03-03 | 三菱化学株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte battery using the same |
| WO2017069278A1 (en) * | 2015-10-23 | 2017-04-27 | 宇部興産株式会社 | Non-aqueous electrolyte solution and power storage device using same |
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