CN106505249B - Lithium ion battery electrolyte and lithium ion battery containing same - Google Patents
Lithium ion battery electrolyte and lithium ion battery containing same Download PDFInfo
- Publication number
- CN106505249B CN106505249B CN201611156600.2A CN201611156600A CN106505249B CN 106505249 B CN106505249 B CN 106505249B CN 201611156600 A CN201611156600 A CN 201611156600A CN 106505249 B CN106505249 B CN 106505249B
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- Prior art keywords
- electrolyte
- lithium
- lithium ion
- ion battery
- additive
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 76
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- 239000000654 additive Substances 0.000 claims abstract description 70
- 230000000996 additive effect Effects 0.000 claims abstract description 61
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 21
- -1 cyano, trimethylsilyl Chemical group 0.000 claims description 44
- 239000007774 positive electrode material Substances 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 3
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 3
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- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
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- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims description 2
- NEILRVQRJBVMSK-UHFFFAOYSA-N B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C NEILRVQRJBVMSK-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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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- 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
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M10/42—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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery electrolyte and a lithium ion battery containing the same. The film-forming additive A forms an SEI film on the surface of the negative electrode of the battery, and reduces side reactions between the negative electrode interface and an electrolyte, so that the film-forming additive A is a necessary premise that the battery has better cycle performance; the stabilizing additive B can form a CEI film on the surface of the anode, inhibit the activity of an anode interface and electrolyte, reduce the direct contact oxidation of the anode and the electrolyte, and simultaneously improve the structural stability of the anode material, so that the anode material is not easy to collapse and break due to stress generation.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery electrolyte and a lithium ion battery containing the same.
Background
At present, lithium ion batteries are widely applied to the fields of digital products, electric automobiles and the like, and people put higher requirements on the energy density of the lithium ion batteries. In order to improve the energy density of the lithium ion battery, two schemes are mainly adopted in the prior art, namely, the charge cut-off voltage of the lithium ion battery is improved, for example, the charge cut-off voltage is improved to be more than 4.35V; and the capacity of the anode material is improved, for example, a high-nickel ternary anode material is adopted. However, both the high voltage scheme and the high capacity material scheme place higher demands on the cycle performance and high temperature storage performance of the electrolyte.
On one hand, the oxidation performance of the material is enhanced due to excessive lithium removal of the anode material under high voltage, so that the side reaction between unstable organic components in the electrolyte and the unstable organic components in the electrolyte is increased, the concentration of free acid substances in the electrolyte is increased under a high-temperature environment, the free acid easily damages a passivation film of the lithium ion battery, and the anode and cathode active substances are exposed in the electrolyte, so that the battery is easy to generate gas, and the cycle performance of the battery is deteriorated. In order to reduce or even inhibit the oxidation of the cathode material at high voltage, it is common practice to add some aromatic compounds, such as biphenyl or cyclohexylbenzene, and other homologues or derivatives of benzene, to the electrolyte.
For example, chinese patent CN1632983A discloses a safe lithium ion battery electrolyte, which is prepared by adding aryl compound and phenylcyclohexane into common lithium ion battery electrolyte, wherein the addition amounts of the aryl compound and the phenylcyclohexane are 0.5-5% and 1-10% of the weight of the lithium ion battery electrolyte respectively. When the battery is cycled at high voltage (such as 4.5V), the action mechanism of adding some aromatic compounds (such as biphenyl and the like) into the electrolyte is to form a layer of conductive polymer on the surface of the positive electrode material to reduce the oxidability of the positive electrode, but the thickness of the layer of polymer is continuously increased along with the increase of the cycling frequency, so that the internal impedance of the battery is continuously increased, and the cycle performance attenuation of the battery is accelerated. Therefore, the addition of aromatic compounds is not conducive to high voltage cycling of lithium ion batteries. And when the battery is fully charged to a high voltage (e.g., 4.5V) and stored at a relatively high temperature (e.g., 85 c), the above-mentioned partially aromatic compound undergoes an irreversible polymerization reaction to cover the surface of the active material, and thus, the capacity and internal resistance properties are deteriorated when the battery is returned to normal temperature, i.e., the high-temperature storage properties at a high voltage of the battery are poor.
On the other hand, the surface of the high-nickel ternary cathode material is strong in alkalinity, metal ions (such as Co, Mn and Ni) in the cathode material are easy to dissolve out and enter into electrolyte in the charging and discharging processes, especially under the high-temperature condition, and the dissolved out metal ions have strong catalytic activity and can generate side reaction with the electrolyte, so that the high-temperature storage performance and the cycle performance of the battery are reduced.
In view of the above, it is necessary to optimize the existing lithium ion battery electrolyte to improve the high-temperature storage performance and the high-temperature cycle performance of the high-energy density lithium ion battery.
Disclosure of Invention
The invention aims to: aiming at the defects of poor high-temperature storage and cycle performance of the electrolyte for the conventional high-energy-density lithium ion battery, the electrolyte for the lithium ion battery is provided to improve the stability of the electrolyte and positive and negative electrode interfaces, and reduce the capacity attenuation and high-temperature gas generation in the use process of the battery, so that the high-temperature storage performance and the high-temperature cycle performance of the lithium ion battery are improved.
In order to achieve the above object, the present invention adopts the following solutions:
the lithium ion battery electrolyte comprises lithium salt, a non-aqueous organic solvent and an additive, wherein the additive comprises a film forming additive A and a stabilizing additive B, and the stabilizing additive B is a chain disulfonate compound shown in a formula I and/or a formula II;
wherein R is1，R2，R3，R4Independently selected from aryl and its substitute, alkyl and its substitute with 1-10 carbon atoms, cyano, trimethylsilyl, allyl and amino substitute; the R is5Is a dimethylsilyl group or a methylene group having 1 to 10 carbon atoms.
Preferably, the content of the film forming additive A is 0.2-10% of the total mass of the electrolyte, and the content of the stabilizing additive B is 0.1-5% of the total mass of the electrolyte.
Preferably, the stabilizing additive B is one or more of the following structural formulas,
preferably, the aromatic group and the substituent thereof are at least one of a phenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a 2-propylphenyl group, a 2-isopropylphenyl group, a 2-fluorophenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-propylphenyl group, a 4-isopropylphenyl group, a 2-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, a 2, 4-dimethylphenyl group, a 2, 4-bis (trifluoromethyl) phenyl group, a 2,4, 6-trimethylphenyl group and a 2,4, 6-tris (trifluoromethyl) phenyl group.
Preferably, the alkyl group having 1 to 10 carbon atoms and the substituent thereof is at least one of a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a trifluoromethyl group, a perfluoroethyl group, a perfluoroisopropyl group, a n-hexyl group, a perfluorohexyl group, a n-heptyl group, a n-octyl group, a perfluorooctyl group, a n-nonyl group, a perfluorononyl group, and a n-decyl group.
Preferably, the film-forming additive A is at least one of Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS), lithium difluorooxalate borate (DFOB), lithium bis-oxalate borate (BOB), vinyl sulfate (DTD), 4-methyl vinyl sulfate (4-methyl DTD), Succinic Anhydride (SA), and 4-ethyl vinyl sulfate (4-ethyl DTD).
Preferably, the additive further comprises at least one of ethylene carbonate (VEC), tris (trimethylsilane) borate, tris (trimethylsilane) phosphate, lithium difluorophosphate, lithium difluorosulfonimide (FSI), lithium Difluorophosphate (DFP), diphenyl carbonate (DPC), tolyl carbonate (MPC), lithium bistrifluoromethanesulfonimide (TFSI), Succinonitrile (SN), Adiponitrile (AND), hexanetrinitrile AND ethylene glycol bis (propionitrile) ether, AND the content of the additive is 0.1-5% of the total mass of the electrolyte.
Preferably, the lithium salt is at least one of lithium hexafluorophosphate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium bis (fluorosulfonyl) imide, lithium tetrafluoroborate and lithium bis (trifluoromethanesulfonyl) imide; the content of the lithium salt is 6-20% of the total mass of the electrolyte.
Preferably, the non-aqueous organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, propyl propionate, Ethyl Propionate (EP), methyl propyl carbonate, tetrahydrofuran, dioxacycloalkane, γ -butyrolactone, Ethyl Acetate (EA), propyl acetate, Methyl Butyrate (MB), Ethyl Butyrate (EB), propyl butyrate; the content of the non-aqueous organic solvent is 65-85% of the total mass of the electrolyte. The non-aqueous organic solvent comprises solvents with high dielectric constants such as ethylene carbonate, propylene carbonate and the like, and is beneficial to dissolving lithium salt and improving the high temperature and cycle performance of the battery; in addition, the electrolyte contains a solvent component with low viscosity and wide electrochemical window, so that the electrolyte can not be decomposed by a high-potential positive electrode, and the low viscosity can meet the soaking requirement of the electrolyte on a pole piece; therefore, the non-aqueous organic solvent has higher decomposition potential and better thermal stability and electrochemical stability under high temperature and high voltage, thereby providing a stable electrochemical environment for the electrical property of the high-voltage lithium ion battery with the voltage of 4.35V or above.
Another object of the present invention is to provide a lithium ion battery, which includes a positive electrode plate, a negative electrode plate, a diaphragm disposed between the positive electrode plate and the negative electrode plate, and an electrolyte, wherein the positive electrode plate includes a positive current collector and a positive electrode diaphragm coated on the surface of the positive current collector, the negative electrode plate includes a negative current collector and a negative electrode diaphragm coated on the surface of the negative current collector, the positive electrode diaphragm includes a positive active material, a positive conductive agent, and a positive binder, and the electrolyte is the lithium ion battery electrolyte in any of the above sections.
Preferably, the positive active material is at least one of lithium cobaltate, lithium nickelate, lithium manganate, lithium vanadate, lithium iron phosphate, lithium manganese iron phosphate and a ternary positive material, and the ternary positive material is LiNi1-x-y-zCoxMnyAlzO2Wherein 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, and x + y + z is more than or equal to 0 and less than or equal to 1.
Preferably, the charge cut-off voltage of the lithium ion battery is greater than or equal to 4.35V, and more preferably greater than or equal to 4.4V.
Preferably, the compacted density of the positive pole piece is greater than or equal to 3.5g/cm3Said negativeThe compacted density of the pole piece is more than or equal to 1.55g/cm3。
The kind of the positive electrode current collector is well known to those skilled in the art, and may be selected from aluminum foil, copper foil, punched steel strip; aluminum foil is preferred as the positive electrode current collector.
The kind of the positive electrode binder is well known to those skilled in the art, for example, one or more of fluorine-containing resin and polyolefin compound such as polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), and Styrene Butadiene Rubber (SBR).
The positive electrode conductive agent is not particularly limited in the present invention, and may be a positive electrode conductive agent conventional in the art, such as at least one of acetylene black, conductive carbon black, and conductive graphite.
Wherein the negative electrode diaphragm comprises a negative electrode active material, a negative electrode conductive agent and a negative electrode binder; the negative electrode active material is not particularly limited, and negative electrode active materials that can intercalate and release lithium, which are conventional in the art, may be used, for example: natural graphite, coated natural graphite, artificial graphite, petroleum coke, organic pyrolysis carbon, mesocarbon microbeads, carbon fibers, silicon carbon materials, silicon materials, metal oxides (oxides of metal elements such as Sn, Ti, Cr, Bo, Fe, V, Mn, Cu, Mo, Ni, W, Zr, Zn) and alloy materials such as Li-Sn, Li-Sn-O, Li-Al, Li-Ti, Li-Mg, Li-Ge, Li-Si and the like.
The negative electrode current collector is various negative electrode current collectors known to those skilled in the art, and may be selected from aluminum foil, copper foil, nickel-plated steel strip, punched steel strip, for example; copper foil is preferred as the negative electrode current collector.
The negative electrode conductive agent is not particularly limited, and may be one or more of negative electrode conductive agents conventional in the art, such as carbon black, acetylene black, carbon fibers, conductive carbon black, and conductive graphite.
The kind of the negative electrode binder is well known to those skilled in the art, such as fluorine-containing resin and/or polyolefin compound (e.g., one or more of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE)/styrene-butadiene rubber (SBR)); it is also possible to use a mixture of a cellulose-based polymer and a rubber latex, such as a mixture of a cellulose-based polymer and styrene-butadiene rubber (SBR).
The invention has at least the following beneficial effects:
1) according to the invention, through the combination of the additives A and B, the lithium ion battery electrolyte has excellent high-temperature storage and high-temperature cycle performance. The film-forming additive A forms an SEI film on the surface of the negative electrode of the lithium ion battery, and reduces side reactions between the negative electrode interface and an electrolyte, so that the negative electrode film-forming additive A is a necessary prerequisite for better cycle performance of the battery. The stabilizing additive B can form a CEI film on the surface of the anode, inhibit the activity of an anode interface and electrolyte, reduce the direct contact oxidation of the anode and the electrolyte, and simultaneously improve the structural stability of the anode material, so that the anode material is not easy to collapse and break due to stress; the stabilizing additive B is a chain multifunctional additive with two sulfonic acid esters, alpha-H on carbon connected with the sulfonic acid esters can interact with transition metal ions, the dissolution of metal ions such as Co/Mn/Ni is reduced, and the stability of the anode material is improved; when the electrolyte containing the additive acts on a high-voltage type positive electrode material and a high-nickel ternary material, the problems of crystal structure distortion and thermal runaway caused by excessive lithium removal are not easy to generate, the dissolution of metal ions in the positive electrode material can be effectively reduced, the catalytic decomposition of transition metal ions on the electrolyte is inhibited, and meanwhile, the additive B contains multiple functional groups, so that the synergistic effect can be generated, the electrochemical performance of the electrolyte containing the additive is enhanced, and the high-temperature storage performance and the cycle performance of a battery are improved.
2) By adjusting the synergistic effect generated by the proportion of the film forming additive A and the stabilizing additive B, the lithium ion battery prepared by using the electrolyte has the excellent performances of long cycle life and low high-temperature storage expansion under the high-voltage condition of 4.35V or above, and has wide application prospect.
Detailed Description
The present invention and its advantageous effects will be described in further detail with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Preparing an electrolyte:
in a glove box filled with argon (the water content is less than 10ppm, the oxygen content is less than 1ppm), ethylene carbonate, propylene carbonate, diethyl carbonate and ethyl methyl carbonate are uniformly mixed and continuously stirred according to the mass ratio of 30:5:35:30, 1.0 mass percent of vinylene carbonate, 2 mass percent of 1, 3-propane sulfonic acid lactone and 0.5 mass percent of additive B6 are added into the mixed solution, and then 12.5 mass percent of LiPF is slowly added6And stirring until the solution is completely dissolved, thus obtaining the lithium ion battery electrolyte of the embodiment 1.
Preparing a lithium ion battery:
LiNi as positive electrode active material0.6Co0.2Mn0.2O2The conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) are fully stirred and uniformly mixed in an N-methyl pyrrolidone solvent system according to the mass ratio of 95: 3: 2, and then coated on an Al foil for drying and cold pressing to obtain the positive pole piece, wherein the compaction density of the positive pole piece is 3.5g/cm3。
Fully stirring and uniformly mixing the negative active material graphite, the conductive agent acetylene black, the binder Styrene Butadiene Rubber (SBR) and the thickening agent carboxymethylcellulose sodium (CMC) in a deionized water solvent system according to the mass ratio of 96: 2: 1, coating the mixture on a Cu foil, drying and cold pressing to obtain a negative pole piece, wherein the compaction density of the negative pole piece is 1.55g/cm3。
Polyethylene (PE) is used as a base film (14 μm) and a nano alumina coating (2 μm) is coated on the base film to be used as a diaphragm.
And stacking the positive pole piece, the diaphragm and the negative pole piece in sequence to enable the diaphragm to be positioned between the positive pole piece and the negative pole piece to play an isolating role, and winding to obtain the bare cell. And placing the bare cell in an outer package, injecting the prepared electrolyte, and performing procedures of packaging, shelving, formation, aging, secondary packaging, capacity grading and the like to obtain the 504848-type high-nickel ternary positive electrode material soft package lithium ion battery.
Preparation of the electrolytes of examples 2 to 22 and comparative examples 1 to 6:
examples 2 to 22 and comparative examples 1 to 6 the electrolyte was prepared in a similar manner to the electrolyte of example 1, i.e., in an argon-filled glove box (moisture content < 10ppm, oxygen content < 1ppm) in the proportions of the solvents and various additives listed in table 1, wherein lithium hexafluorophosphate was added in an amount of 12.5%. Wherein the additives listed under B1-B13 correspond to the following compounds, respectively:
Preparation of lithium ion batteries of examples 2 to 18 and comparative examples 1 to 5 (ternary NCM batteries):
the preparation methods of the lithium ion batteries of the examples 2-18 and the comparative examples 1-5 are similar to those of the example 1, the adopted positive electrode active material is consistent with the ternary positive electrode material (NCM) used in the example 1, then the electrolytes corresponding to the examples 2-18 and the comparative examples 1-5 are respectively injected, and the high-nickel ternary positive electrode material soft package lithium ion batteries of the examples 2-18 and the comparative examples 1-5 are obtained through the processes of packaging, laying aside, formation, aging, secondary packaging, capacity grading and the like.
Preparation of lithium ion batteries (LCO batteries) for examples 19-22 and comparative example 6:
lithium cobaltate LiCoO as a positive electrode active material2The conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) are fully stirred and uniformly mixed in an N-methyl pyrrolidone solvent system according to the mass ratio of 95: 3: 2, and then coated on an Al foil for drying and cold pressing to obtain the positive pole piece, wherein the compaction density of the positive pole piece is 4.1g/cm3。
Fully stirring and uniformly mixing the negative active material graphite, the conductive agent acetylene black, the binder Styrene Butadiene Rubber (SBR) and the thickening agent carboxymethylcellulose sodium (CMC) in a deionized water solvent system according to the mass ratio of 96: 2: 1, coating the mixture on a Cu foil, drying and cold pressing to obtain a negative pole piece, wherein the compaction density of the negative pole piece is 1.65g/cm3。
Polyethylene (PE) was used as a base film (14 μm) and a PVDF coating (2 μm) was applied on the base film as a separator.
And stacking the positive pole piece, the diaphragm and the negative pole piece in sequence to enable the diaphragm to be positioned between the positive pole piece and the negative pole piece to play an isolating role, and winding to obtain the bare cell. And (3) placing the bare cell in an outer package, respectively injecting the electrolytes prepared in the embodiments 19-22 and the comparative example 6, and carrying out the procedures of packaging, laying aside, formation, aging, secondary packaging, capacity grading and the like to obtain the high-voltage lithium cobaltate soft package lithium ion batteries of the embodiments 19-22 and the comparative example 6.
TABLE 1 composition of electrolytes of examples 1 to 22 and comparative examples 1 to 6
The following performance tests were performed on the lithium ion batteries of examples 1 to 22 and comparative examples 1 to 6, respectively:
1. and (3) testing the normal-temperature 1C/1C cycle performance: in the environment of 25 ℃ +/-2 ℃, the ternary NCM battery and the LCO battery prepared in comparative examples 1-6 and examples 1-22 are respectively charged at constant current of 1.0C (the capacity 1C of the ternary NCM battery is 1000mAh, and the capacity 1C of the LCO battery is 1300mAh) to the limit voltage of 4.35V and 4.4V, then changed to constant voltage charging, and left to stand for 5min until the charging current is less than or equal to the cutoff current of 0.02C, and then discharged at 1.0C to the cutoff voltage of 3.0V and left to stand for 5 min; the above procedure was followed for a cycle charge and discharge experiment for over 500 weeks with the test results shown in table 2.
2. 55-1C/1C cycle performance test of the ternary NCM battery: under the constant temperature environment with the temperature of 55 ℃, the batteries prepared in the comparative examples 1 to 5 and the examples 1 to 18 are changed into constant voltage charging after being charged at the constant current of 1.0 ℃ to the limiting voltage of 4.35V, and are kept stand for 5min until the charging current is less than or equal to the cutoff current of 0.02C, and then the batteries are discharged at the 1.0C to the cutoff voltage of 3.0V and kept stand for 5 min; the cyclic charge and discharge experiment was performed according to the above procedure, and the test results are shown in table 2 after more than 300 cycles.
3. And (3) testing the cycle performance of the LCO battery at 45-1C/1C: under the constant temperature environment of 45 ℃, the batteries prepared in the comparative example 6 and the examples 19 to 22 are changed into constant voltage charging after being charged to the limiting voltage of 4.4V at the constant current of 1.0C until the charging current is less than or equal to the cutoff current of 0.02C, and are stood for 5min, and then the batteries are discharged to the cutoff voltage of 3.0V at the constant current of 1.0C and are stood for 5 min; the cyclic charge and discharge experiment was performed according to the above procedure, and the test results are shown in table 2 after more than 400 weeks of cycling.
4. Ternary NCM cells were tested in 30 days storage at 60 ℃ high temperature: the batteries prepared in comparative examples 1 to 5 and examples 1 to 18 are changed into constant voltage charging after being charged to 4.35V limiting voltage at 0.2C until the charging current is less than or equal to 0.02C of cutoff current, and then are stood for 5min and then discharged at 0.2C, wherein the current discharge capacity is the initial capacity; charging at 0.5C to 4.35V, limiting voltage, changing into constant voltage charging until the charging current is less than or equal to the cut-off current, standing for 2h when the charging current is open, and measuring the initial thickness and the initial internal resistance; storing the battery cell at the temperature of 60 +/-2 ℃ and opening the circuit for 30 days; then taking out the battery core, immediately testing the thickness, recovering for 2h at room temperature, and testing the internal resistance of the battery; and then, discharging the battery cell at 0.2C, and then charging and discharging at 0.2C, and testing the residual capacity and the recovery capacity. The rate of change of thickness, internal resistance, etc. was calculated before and after storage of the cell and the test results are shown in table 2.
5. LCO battery 85 ℃ high temperature storage 6H test: the batteries prepared in the comparative example 6 and the examples 19 to 22 are changed into constant voltage charging after being charged to the limiting voltage of 4.4V at the temperature of 0.2C until the charging current is less than or equal to the cutoff current of 0.02C, the batteries are kept stand for 5min and then discharged at the temperature of 0.2C, and the current discharge capacity is the initial capacity; charging at 0.5C to 4.4V, limiting voltage, changing into constant voltage charging, standing for 2h when the charging current is less than or equal to the cut-off current, and measuring the initial thickness and the initial internal resistance; storing the battery cell at 85 +/-2 ℃ and opening the circuit for 6H; then taking out the battery core, immediately testing the thickness, recovering for 2h at room temperature, and testing the internal resistance of the battery; and then, discharging the battery cell at 0.2C, and then charging and discharging at 0.2C, and testing the residual capacity and the recovery capacity. The rate of change of thickness, internal resistance, etc. was calculated before and after storage of the cell and the test results are shown in table 2.
TABLE 2 ternary NCM and LCO cells cycling performance and high temperature storage Performance test results
From the test results in table 2, it can be seen that when comparative example 1 contains only 1% of VC additive, the thickness expansion rate of the ternary NCM cell reaches about 73% after 30 days of high temperature storage at 60 ℃, while comparative example 2 is reduced to 43% after 1.5% of PS is added, and comparative example 4 is reduced to 35% after 1.5% of DTD is added, indicating that the cyclic sulfonate improves the high temperature storage performance of the cell. In the comparative example, VC mainly has the effect of forming an SEI film on the interface of the negative electrode, but has a weak passivation effect on the positive electrode; the anode has high activity in a high-temperature environment, can generate side reaction with unstable components in the electrolyte, and the battery system can generate HF in the high-temperature environment, wherein the HF can react with the cathode to generate a large amount of gas and can act with the anode to accelerate the dissolution of metal ions in the anode material, and the dissolved transition metal ions can increase the self-discharge of the battery and further catalyze the decomposition and consumption of the electrolyte under the high-temperature condition. The introduction of the film forming additives A such as PS, DTD and the like has certain inhibiting effect on the processes, and the high-temperature storage performance of the battery is improved.
After the stabilizing additive B containing two sulfonic acid esters is further added on the basis of the additive containing 1% of VC and 1.5% of PS, the high-temperature performance of the battery is obviously improved; for example, after 1% of B1, B3, B5, B6, B7, B8 or B11 is added on the basis of 1% of VC + 1.5% of PS additive, the thickness expansion change rate of the battery is further reduced to 11.8-15.9% after the battery is stored at the high temperature of 60 ℃ for 30 days. Furthermore, the improvement of the high-temperature storage performance has a certain relationship with the addition amount of the stabilizing additive B, for example, in examples 1 to 4, when the addition amount of the additive B6 is 0.5 to 5%, the high-temperature storage expansion rate of the battery decreases with the increase of the addition amount of B6, and the thickness expansion rate decreases from 19.4% (example 1) to 5.8% (example 4). Further experiments show that the high-temperature performance of the battery is greatly related to the solvent composition of the electrolyte, the high-temperature storage performance of the battery is obviously deteriorated due to the introduction of the carboxylic ester (such as EP and EA), and the high-temperature storage performance of the battery is obviously improved after the stabilizing additive B (such as B1) is introduced. The reason for this is that, on the one hand, carboxylic acid esters have a low boiling point and are easily vaporized and expanded due to a high vapor pressure under high temperature conditions; on the other hand, compared with carbonic ester, carboxylic ester is easier to be decomposed under the catalysis of acid under the high-temperature environment and is easier to be oxidized on the surface of the positive electrode; the stabilizing additive B is used as a high-boiling-point additive, has good thermal stability, and more importantly, the stabilizing additive B can form a passivation film on the interface of the positive electrode, so that the activity of the positive electrode material is inhibited, and the gas production risk is reduced.
In addition, the high temperature performance of the stabilizing additive B also has a relationship with the substituted functional group when R is1，R2，R3，R4After being substituted by nitrile, phenyl, fluorine-containing phenyl and trimethylsilyl substituents, the modified nitrile has better high-temperature performance; this is mainly related to the nature of the substituted functional group, which on the one hand is structurally more stable and has a certain electron withdrawing effect and is not easily oxidized and decomposed; on the other hand, the functional group can also interact with water and HF, so that active substances such as water, acid and the like and positive and negative electrodes are delayed to a certain extent(ii) a reaction between the two. And slightly inferior in high temperature performance when substituted with amino group, allyl group, etc., as in example 7, additive B5 containing allyl functional group; this is because the electron cloud density and distribution of the allyl functional group are more prone to electron donating, and the electron is more easily given to the functional group with respect to electron withdrawing to cause an oxidation reaction, thereby easily increasing the self-discharge of the battery in a high-temperature storage environment.
As can be seen from the 55 c high temperature cycle data of the ternary NCM cell in table 2, comparative example 1, which contained only 1% VC, had poor high temperature performance. The reason is that on one hand, the battery produces more gas in the long circulation process, and the positive electrode and the negative electrode are separated by the gas and cannot be charged and discharged normally; on the other hand, as can be seen from the normal-temperature cycle performance test in the comparative example, the role of VC on the cycle performance of the ternary cathode material is not very obvious, the internal phase change and Li content change of the ternary cathode material in the cycle process can cause the expansion of crystals, so that stress is generated inside electrode particles, and the current distribution inside the electrode particles is uneven, thereby causing large difference of different local SOC states; and different stress states among different particles cause the link fracture among the particles and cracks on the particle surfaces, the existence of the cracks promotes the dissolution of metal ions in the ternary cathode material, the dissolved transition metal ions (such as Mn) can migrate to the negative electrode through the electrolyte, and are reduced and precipitated on the surface of the negative electrode to damage the structure of a negative electrode SEI film, and finally, the battery performance is deteriorated (such as voltage drop, internal resistance increase and battery thickening).
The stable additive B capable of forming a stable anode passivation layer on the anode interface is added into the system, so that the activity of the anode material can be reduced, the structure of the anode material is more stable due to the formed passivation layer, the anode material is not easy to break and collapse due to the stress, the stability of the anode material is improved, and the anode material is ensured to have better lithium releasing and embedding capacity in the long-term charging and discharging process. After PS, DFOB and DTD are added in comparative examples 2-4 respectively, the normal-temperature cycle performance of the battery is improved to a certain extent, and particularly the two additives, namely DTD and DFOB, can participate in the formation of an SEI film of a negative electrode and have a certain promotion effect on the passivation of a positive electrode, but the effects of the additives need to be further improved and improved. The stable additive B is further added on the basis of the additive, so that the normal-temperature cycle performance of the battery is further improved; meanwhile, by comparing examples 10-12 with comparative examples 2-4, the 55 ℃ high-temperature cycle performance is also greatly improved, and after 300 cycles, the capacity retention rate of the battery is higher than 30%. Comparing the effect of different contents of additive B6 on the cycle performance, it is found that the addition of too much B6 has a certain negative effect on the cycle performance of the battery, especially the normal temperature performance, for example, the cycle performance is obviously reduced when the addition amount is 5% in example 4 compared with the addition amount of 1% in example 2 or 3% in example 3. The compound increases the viscosity of the electrolyte, reduces the permeability of the electrolyte, and increases the impedance of a battery system due to excessive addition of the additive B6, so that the internal consumption of the battery is increased in the charging and discharging processes; however, the addition of the additive B6 is too little, and the additive B does not obviously help to improve the high-temperature performance of the battery, so that the addition amount of the stabilizing additive B is preferably 0.5-5%, and preferably 0.3-3%.
In addition, the test results in table 2 also show that the combination of various additives has an obvious effect on improving the comprehensive performance of the battery, and as in examples 14 to 18 of the present invention, by using the combination of the VC/DTD/DFOB/PS negative electrode film-forming additive a and introducing the FSI additive that reduces the impedance and improves the protection of the positive electrode, a synergistic effect can be further generated, so that the cycle life and the storage performance of the battery can be better.
In addition, the stabilizing additive B also has an obvious effect on improving the cycle performance of a 4.4V lithium cobalt oxide high-voltage battery system; as in comparative example 6, when the stabilizing additive B was not introduced, the battery exhibited significant gassing after 6H storage at 85 ℃, at which time the thickness expansion rate of the battery in comparative example 6 reached 18%; after additives such as B1, B6, B11 and the like are introduced, the high-temperature storage performance of the battery is obviously improved, and the thickness expansion of the battery is obviously reduced. Under the high-voltage working condition, after the positive material is subjected to transition lithium removal, the oxidation activity is enhanced, and a certain amount of HF is generated in the high-temperature storage process, so that the damage to a negative electrode SEI film and a positive electrode material is accelerated, and the storage performance of the battery is reduced; the introduced stabilizing additive B is a multifunctional additive and contains two sulfonate groups, alpha-H on carbon connected with sulfonate can interact with transition metal ions, the dissolution of metal ions (such as Co) is reduced, and the structural stability of the anode material is effectively enhanced. In addition, in order to further improve the performance of the 4.4V cobalt acid lithium battery, additives such as ADN, FSI, DENE and the like can be further introduced into the electrolyte, so that the electrolyte has better comprehensive performance.
Through the analysis, the electrolyte can work normally in a battery with a high-nickel ternary positive electrode material and a 4.4V or above lithium cobaltate high-voltage system, has better cycle life and high-temperature storage performance, and can completely meet the requirements of a power battery and a high-energy-density power battery.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and the present invention is not limited to the disclosed embodiments, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A lithium ion battery electrolyte comprises a lithium salt, a non-aqueous organic solvent and an additive, and is characterized in that: the additive comprises a film forming additive A and a stabilizing additive B, wherein the stabilizing additive B is a chain disulfonate compound shown in a formula II; the content of the film forming additive A is 0.2-10% of the total mass of the electrolyte, and the content of the stabilizing additive B is 0.1-5% of the total mass of the electrolyte; the charge cut-off voltage of the lithium ion battery is greater than or equal to 4.35V;
wherein R is3，R4Each independently selected from one of aryl and its substitute, cyano, trimethylsilyl, allyl and amino substitute, wherein the aryl does not contain phenyl;
in addition, the electrolyte is used for a high-nickel ternary positive electrode material battery system.
2. The lithium ion battery electrolyte of claim 1, wherein: the aryl and the substitute thereof are at least one of 2-fluorophenyl, 4-fluorophenyl, 2-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2, 4-bis (trifluoromethyl) phenyl and 2,4, 6-tris (trifluoromethyl) phenyl.
3. The lithium ion battery electrolyte of claim 1, wherein: the film forming additive A is at least one of vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, lithium difluoro oxalate borate, lithium bis-oxalate borate, vinyl sulfate, 4-methyl vinyl sulfate, succinic anhydride and 4-ethyl vinyl sulfate.
4. The lithium ion battery electrolyte of claim 1, wherein: the additive also comprises at least one of ethylene carbonate, tris (trimethylsilane) borate, tris (trimethylsilane) phosphate, lithium difluorophosphate, lithium bis (fluorosulfonyl) imide, lithium difluorophosphate, diphenyl carbonate, tolyl carbonate, lithium bis (trifluoromethanesulfonyl) imide, succinonitrile, adiponitrile, hexanetricarbonitrile and ethylene glycol bis (propionitrile) ether, and the content of the additive is 0.1-5% of the total mass of the electrolyte.
5. The lithium ion battery electrolyte of claim 1, wherein: the lithium salt is at least one of lithium hexafluorophosphate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium bis (fluorosulfonyl) imide, lithium tetrafluoroborate and lithium bis (trifluoromethanesulfonyl) imide; the content of the lithium salt is 6-20% of the total mass of the electrolyte.
6. The lithium ion battery electrolyte of claim 1, wherein: the non-aqueous organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, propyl propionate, ethyl propionate, methyl propyl carbonate, tetrahydrofuran, dioxane, gamma-butyrolactone, ethyl acetate, propyl acetate, methyl butyrate, ethyl butyrate and propyl butyrate; the content of the non-aqueous organic solvent is 65-85% of the total mass of the electrolyte.
7. The utility model provides a lithium ion battery, includes positive pole piece, negative pole piece, sets up positive pole piece with diaphragm and electrolyte between the negative pole piece, positive pole piece includes the anodal mass flow body and the anodal diaphragm of coating on anodal mass flow body surface, negative pole piece includes the negative pole mass flow body and the negative diaphragm of coating on negative mass flow body surface, anodal diaphragm includes anodal active material, anodal conductive agent and anodal binder, its characterized in that: the electrolyte is the lithium ion battery electrolyte of any one of claims 1 to 6.
8. The lithium ion battery of claim 7, wherein: the compacted density of the positive pole piece is more than or equal to 3.5g/cm3The compacted density of the negative pole piece is more than or equal to 1.55g/cm3。
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Effective date of registration: 20231011 Address after: No.62 Huayin North Road, Kecheng District, Quzhou City, Zhejiang Province Patentee after: New Asia Shanshan New Material Technology (Quzhou) Co.,Ltd. Address before: 523000 workshop 5, phase II plant area, Pengdong Industrial Zone, Hengmei shuilian, Nancheng District, Dongguan City, Guangdong Province Patentee before: DONGGUAN SHANSHAN BATTERY MATERIALS Co.,Ltd. |