CN114156534A - Electrolyte containing nitrogen heterocyclic compound, preparation method and lithium secondary battery - Google Patents
Electrolyte containing nitrogen heterocyclic compound, preparation method and lithium secondary battery Download PDFInfo
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- CN114156534A CN114156534A CN202111490505.7A CN202111490505A CN114156534A CN 114156534 A CN114156534 A CN 114156534A CN 202111490505 A CN202111490505 A CN 202111490505A CN 114156534 A CN114156534 A CN 114156534A
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- electrolyte
- heterocyclic compound
- nitrogen
- containing heterocyclic
- carbonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 158
- -1 nitrogen heterocyclic compound Chemical class 0.000 title claims abstract description 146
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 43
- 238000002360 preparation method Methods 0.000 title description 4
- 239000002904 solvent Substances 0.000 claims abstract description 67
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 63
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 62
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 36
- 239000008151 electrolyte solution Substances 0.000 claims description 29
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 20
- 239000012535 impurity Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002808 molecular sieve Substances 0.000 claims description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 18
- 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 8
- 238000000034 method Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 claims description 4
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 claims description 4
- 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
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- 238000009831 deintercalation Methods 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 claims description 2
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 2
- 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 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 25
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 21
- 229910002804 graphite Inorganic materials 0.000 description 21
- 239000010439 graphite Substances 0.000 description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 20
- 150000005676 cyclic carbonates Chemical class 0.000 description 20
- 238000002156 mixing Methods 0.000 description 20
- 229910013872 LiPF Inorganic materials 0.000 description 16
- 101150058243 Lipf gene Proteins 0.000 description 16
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 14
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 7
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910016118 LiMn1.5Ni0.5O4 Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical class C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910001170 xLi2MnO3-(1−x)LiMO2 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
- H01M10/0567—Liquid materials characterised by the additives
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, and discloses an electrolyte of a nitrogen-containing heterocyclic compound, which comprises a solvent, a solute and an additive, and also comprises at least one nitrogen-containing heterocyclic compound shown in the following structural general formula (1) or structural general formula (2):
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an electrolyte containing nitrogen heterocyclic compounds, a preparation method and a lithium secondary battery.
Background
In recent years, with the increase in the level of consumption, there has been a rapidly increasing demand for not only power storage systems for small-sized and high-energy density applications, such as information-related devices, communication devices including personal computers, video cameras, digital cameras, cellular phones, smart phones, and the like; but also there is an increasing demand for power cells having large capacity, high output and high energy density, which are used in auxiliary power systems of electric vehicles, hybrid vehicles and fuel cell vehicles. Furthermore, even in power storage systems for large and high power applications, the requirements of batteries, such as power storage; as a candidate thereof, a nonaqueous electrolyte battery such as a lithium ion battery, a lithium ion capacitor, or a sodium ion battery has been actively developed.
A large number of nonaqueous electrolyte batteries have been put to practical use, but none of these batteries has satisfactory characteristics for various applications. In particular, in a lithium secondary battery using a highly-crystallized carbon material such as natural graphite or artificial graphite as a negative electrode material, since a non-aqueous solvent in a non-aqueous electrolyte is reductively decomposed on the surface of the negative electrode during charging, the decomposed product or gas generated therefrom inhibits the electrochemical reaction of the battery itself, and thus the cycle characteristics are degraded. In addition to the normal temperature cycle characteristics, such a battery is required to have high temperature cycle characteristics such that the decrease in capacity is small even when charge and discharge are repeatedly performed under a high temperature environment (high temperature cycle characteristics) and self-discharge is small even when the battery is left in a fully charged state for a long time under a high temperature environment (high temperature storage characteristics).
In order to improve battery performance represented by long-term durability and output characteristics, it is important to form a stable SEI having high ion conductivity and low electron conductivity for a long period of time, and there has been a wide attempt in the industry to positively form a good SEI (solid Electrolyte interface) by adding a small amount (usually 0.01 mass% or more and 10 mass% or less) of a compound called an additive to an Electrolyte. As a means for improving high-temperature characteristics and battery characteristics (cycle characteristics) of repeated charge and discharge, optimization of various battery components such as active materials of a positive electrode and a negative electrode has been studied. The non-aqueous electrolyte related art is no exception, and it is proposed to suppress deterioration caused by decomposition of an electrolyte on the surface of a positive electrode active material or a negative electrode active material by various additives. For example, Japanese patent laid-open No. 2013-051122 discloses a method in which a salt containing a phosphoryl group or a sulfonyl group is added to an electrolyte solution and examined, and a specific sulfonyl imide salt or phosphoryl imide salt is combined with an oxalic acid complex to improve high-temperature cycle characteristics or high-temperature storage characteristics; and Japanese patent laid-open publication No. 2013-030465 discloses a method of improving cycle characteristics or output characteristics by combining a specific fluorophosphate with a sulfonimide salt.
The research effectively improves the high-temperature circulation and high-temperature storage performance of the battery, and more electrolyte technical schemes need to be provided in order to promote the research and development of the battery electrolyte; and the above studies have not been further developed with respect to the suppression of the increase in acidity and chromaticity of the electrolyte, which also indirectly affects the quality of a battery product using the electrolyte.
Disclosure of Invention
One of the objectives of the present invention is to provide an electrolyte containing a nitrogen heterocyclic compound, which can significantly inhibit the increase of the charge-discharge cycle number of a battery and the high-temperature gas generation phenomenon of the battery under a high-temperature condition for a long time, and effectively improve the high-temperature cycle and high-temperature storage performance of the battery.
Another object of the present invention is to provide a method for preparing an electrolyte solution containing a nitrogen heterocyclic compound, which can effectively improve cycle characteristics and high-temperature storage characteristics of a battery and suppress gassing when the battery is stored at a high temperature of 60 ℃, when the prepared electrolyte solution is used in a non-aqueous electrolyte battery.
Meanwhile, the invention also provides a lithium secondary battery, which forms a stable passive film on the surface of an electrode, inhibits the high-temperature gas generation of the battery, prevents the decomposition of electrolyte and the dissolution of transition metal ions, and improves the cycle performance and the high-temperature performance of the battery.
In order to achieve the above object, the present invention provides an electrolyte solution of nitrogen-containing heterocyclic compounds, which comprises a solvent, a solute and an additive, and further comprises at least one nitrogen-containing heterocyclic compound represented by the following structural general formula (1) or structural general formula (2):
wherein R represents C, S or S ═ O.
In the electrolyte containing the nitrogen-containing heterocyclic compound, the nitrogen-containing heterocyclic compound accounts for 0.01-2% of the total mass of the electrolyte according to mass percentage.
In the above-mentioned electrolyte solution containing a nitrogen heterocyclic compound, the solvent includes at least two non-aqueous solvents, and the non-aqueous solvents include ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl acetate, and propyl acetate.
In the electrolyte of the nitrogen-containing heterocyclic compound, the solute is electrolyte lithium salt, and the concentration of the electrolyte lithium salt in the solvent is 0.8-1.5 mol/L.
In the above-mentioned electrolyte solution containing a nitrogen-containing heterocyclic compound, the electrolyte lithium salt includes at least one of lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium bis (fluorosulfonyl) imide, and lithium bis (trifluoromethylsulfonyl) imide.
In the above-mentioned electrolyte solution containing a nitrogen-containing heterocyclic compound, the additive includes at least one of vinyl sulfate, tris (trimethylsilyl) phosphate, tris (trimethylsilyl) borate, lithium difluorooxalato borate, vinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, and 1, 3-propanesultone.
Furthermore, the addition amount of the additive is 0.5 to 5 percent of the total mass of the electrolyte according to the weight percentage
The invention also provides a preparation method of the electrolyte containing the nitrogen heterocyclic compound, which comprises the following steps:
(1) purifying the solvent to remove impurities and water;
(2) adding a solute into the solvent obtained in the step (1) at room temperature, and uniformly stirring;
(3) and adding a nitrogen-containing heterocyclic compound and an additive, and uniformly stirring to obtain the electrolyte of the nitrogen-containing heterocyclic compound.
Further, the purification, impurity removal and water removal in the step (1) are preferably carried out by any one or more of molecular sieve, activated carbon, calcium hydride, lithium hydride, anhydrous calcium oxide, calcium chloride, phosphorus pentoxide, alkali metal or alkaline earth metal.
Meanwhile, the invention also provides a lithium secondary battery, which comprises a positive plate, a negative plate and the electrolyte containing the nitrogen heterocyclic ring compound, wherein the positive plate comprises a positive active material, a conductive agent, a current collector and a binding agent, wherein the positive active material is used for embedding or releasing lithium ions, and the binding agent is used for combining the positive active material and the conductive agent with the current collector; the negative electrode sheet includes a negative electrode active material capable of intercalating or deintercalating lithium ions, a conductive agent, a current collector, and a binder binding the negative electrode active material and the conductive agent to the current collector.
Advantageous effects
Compared with the prior art, the invention provides the electrolyte for the non-aqueous electrolyte battery, which is characterized in that the nitrogenous heterocyclic compound with a specific structure is used, so that when the electrolyte is used for the non-aqueous electrolyte battery, the cycle characteristic and the high-temperature storage characteristic of the battery can be effectively improved, and the gas generation phenomenon of the battery during high-temperature storage is inhibited; when the electrolyte of the nitrogenous heterocyclic compound provided by the invention contains an unstable additive, the nitrogenous heterocyclic compound with a specific structure can effectively inhibit the acidity and chromaticity of the electrolyte from increasing.
Detailed Description
The invention will now be further described with reference to the following examples, which are not to be construed as limiting the invention in any way, and any limited number of modifications which can be made within the scope of the claims of the invention are still within the scope of the claims of the invention.
In order to explain the technical contents of the present invention in detail, the following description is further made in conjunction with the embodiments.
The structural formulas of the nitrogen-containing heterocycles employed in the following examples are as follows:
example a 1:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding a nitrogen-containing heterocyclic compound S1 with the mass being 0.3% of the total mass of the electrolyte and an additive (vinylene carbonate with the mass fraction being 1%) into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen-containing heterocyclic compound;
(4) the electrolyte solution containing a nitrogen heterocyclic compound obtained in the present example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Example a 2:
compared with the embodiment A1, the difference is that the nitrogen heterocyclic compound S1 accounts for 0.1 percent of the total mass of the electrolyte.
Example a 3:
compared with the example A1, the difference is that the nitrogen heterocyclic compound S1 accounts for 0.5 percent of the total mass of the electrolyte.
Example a 4:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) in thatUnder the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding a nitrogen-containing heterocyclic compound S2 with the mass being 0.3% of the total mass of the electrolyte and an additive (vinylene carbonate with the mass fraction being 1%) into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen-containing heterocyclic compound;
(4) the electrolyte solution containing a nitrogen heterocyclic compound obtained in the present example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Example a 5:
compared with the embodiment A4, the difference is that the nitrogen heterocyclic compound S2 accounts for 0.1 percent of the total mass of the electrolyte.
Example a 6:
compared with the example A4, the difference is that the nitrogen heterocyclic compound S2 accounts for 0.5 percent of the total mass of the electrolyte.
Example a 7:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding a nitrogen-containing heterocyclic compound S3 with the mass being 0.3% of the total mass of the electrolyte and an additive (vinylene carbonate with the mass fraction being 1%) into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen-containing heterocyclic compound;
(4) the electrolyte solution containing a nitrogen heterocyclic compound obtained in the present example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Example A8:
compared with the embodiment A7, the difference is that the nitrogen heterocyclic compound S3 accounts for 0.1 percent of the total mass of the electrolyte.
Example a 9:
compared with the example A7, the difference is that the nitrogen heterocyclic compound S3 accounts for 0.5 percent of the total mass of the electrolyte.
Example a 10:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding a nitrogen-containing heterocyclic compound S4 with the mass being 0.3% of the total mass of the electrolyte and an additive (vinylene carbonate with the mass fraction being 1%) into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen-containing heterocyclic compound;
(4) the electrolyte solution containing a nitrogen heterocyclic compound obtained in the present example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Example a 11:
compared with the embodiment A10, the difference is that the nitrogen heterocyclic compound S4 accounts for 0.1 percent of the total mass of the electrolyte.
Example a 12:
compared with the example A10, the difference is that the nitrogen heterocyclic compound S4 accounts for 0.5 percent of the total mass of the electrolyte.
Example A13
(1) Cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding a nitrogen-containing heterocyclic compound S5 with the mass being 0.3% of the total mass of the electrolyte and an additive (vinylene carbonate with the mass fraction being 1%) into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen-containing heterocyclic compound;
(4) the electrolyte solution containing a nitrogen heterocyclic compound obtained in the present example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Example a 14:
compared with the embodiment A13, the difference is that the nitrogen heterocyclic compound S5 accounts for 0.1 percent of the total mass of the electrolyte.
Example a 15:
compared with the example A13, the difference is that the nitrogen heterocyclic compound S5 accounts for 0.5 percent of the total mass of the electrolyte.
Example a 16:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding a nitrogen-containing heterocyclic compound S6 with the mass being 0.3% of the total mass of the electrolyte and an additive (vinylene carbonate with the mass fraction being 1%) into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen-containing heterocyclic compound;
(4) the electrolyte solution containing a nitrogen heterocyclic compound obtained in the present example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Example a 17:
compared with the embodiment A16, the difference is that the nitrogen heterocyclic compound S6 accounts for 0.1 percent of the total mass of the electrolyte.
Example a 18:
compared with the example A16, the difference is that the nitrogen heterocyclic compound S6 accounts for 0.5 percent of the total mass of the electrolyte.
Example a 19:
compared with example A1, the difference is that vinylene carbonate is not contained.
Example a 20:
compared to example a1, the difference is that the cyclic carbonate solvent Ethylene Carbonate (EC) and the linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are used in the mass ratio EC: EMC: DEC ═ 1: 1: 1 and mixing.
Example a 21:
compared to example a1, with the difference that the cyclic carbonate solvent Ethylene Carbonate (EC) and the linear carbonate solvent Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) are used in the mass ratio EC: EMC: DMC 3: 5: 2 and mixing.
Example a 22:
compared with example A1, except that the mass fraction of the conductive lithium salt lithium hexafluorophosphate was changed to 12.5 wt% lithium bis (oxalato) borate, which was 12.5 wt%.
Example a 23:
compared with example A1, except that the mass fraction of the conductive lithium salt lithium hexafluorophosphate was changed to 12.5 wt% lithium bistrifluoromethylsulfonyl imide.
Example a 24:
compared with example A1, except that the mass fraction of the conductive lithium salt lithium hexafluorophosphate was changed to 12.5 wt% lithium bis (fluorosulfonyl) imide.
Example a 25:
the difference from example A1 is that the obtained nitrogen-containing heterocyclic compound-containing electrolyte was used for LiNi0.5Co0.2Mn0.3O2Graphite flexible package battery.
Example a 26:
the difference compared with example A1 is the electric potential of the nitrogen-containing heterocyclic compound obtainedApplication of the hydrolysate in LiNi0.6Co0.2Mn0.2O2Graphite flexible package battery.
Example a 27:
compared with example A1, the difference is that the obtained electrolyte containing nitrogen heterocyclic compound is used for LiMn1.5Ni0.5O4Graphite flexible package battery.
Example a 28:
the difference compared to example A1 is that the obtained electrolyte containing nitrogen heterocycles is used for XLi2MnO3(1-X)LiMO2(M ═ Co, Ni, Mn)/graphite flexible packaging battery.
Example a 29:
compared with the example A1, the difference is that the obtained electrolyte containing the nitrogen heterocyclic compound is used for LiFePO4Graphite flexible package battery.
Example a 30:
the difference compared to example A1 is that the resulting electrolyte solution containing a nitrogen heterocyclic compound was used for LiCoO2Graphite flexible package battery.
Example B1:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding a nitrogen-containing heterocyclic compound S1 with the mass being 0.3% of the total mass of the electrolyte and an additive (the mass fraction is 2% of vinyl sulfate) into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen-containing heterocyclic compound;
(4) the electrolyte solution containing a nitrogen heterocyclic compound obtained in the present example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Example B2:
compared with the embodiment B1, the difference is that the nitrogen-containing heterocyclic compound S1 accounts for 0.1 percent of the total mass of the electrolyte.
Example B3:
compared with the embodiment B1, the difference is that the nitrogen-containing heterocyclic compound S1 accounts for 0.5 percent of the total mass of the electrolyte.
Example B4:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding a nitrogen-containing heterocyclic compound S2 with the mass being 0.3% of the total mass of the electrolyte and an additive (the mass fraction is 2% of vinyl sulfate) into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen-containing heterocyclic compound;
(4) the electrolyte solution containing a nitrogen heterocyclic compound obtained in the present example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Example B5:
compared with the embodiment B4, the difference is that the nitrogen-containing heterocyclic compound S2 accounts for 0.1 percent of the total mass of the electrolyte.
Example B6:
compared with the embodiment B4, the difference is that the nitrogen-containing heterocyclic compound S2 accounts for 0.5 percent of the total mass of the electrolyte.
Example B7:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, the mass fraction is 12.5% conductive lithium salt lithium hexafluorophosphate (LiPF)6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding a nitrogen-containing heterocyclic compound S3 with the mass being 0.3% of the total mass of the electrolyte and an additive (the mass fraction is 2% of vinyl sulfate) into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen-containing heterocyclic compound;
(4) the electrolyte solution containing a nitrogen heterocyclic compound obtained in the present example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Example B8:
compared with the embodiment B7, the difference is that the nitrogen-containing heterocyclic compound S3 accounts for 0.1 percent of the total mass of the electrolyte.
Example B9:
compared with the embodiment B7, the difference is that the nitrogen-containing heterocyclic compound S3 accounts for 0.5 percent of the total mass of the electrolyte.
Example B10:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding a nitrogen-containing heterocyclic compound S4 with the mass being 0.3% of the total mass of the electrolyte and an additive (the mass fraction is 2% of vinyl sulfate) into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen-containing heterocyclic compound;
(4) the electrolyte solution containing a nitrogen heterocyclic compound obtained in the present example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Example B11:
compared with the embodiment B10, the difference is that the nitrogen-containing heterocyclic compound S4 accounts for 0.1 percent of the total mass of the electrolyte.
Example B12:
compared with the embodiment B10, the difference is that the nitrogen-containing heterocyclic compound S4 accounts for 0.5 percent of the total mass of the electrolyte.
Example B13:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding a nitrogen-containing heterocyclic compound S5 with the mass being 0.3% of the total mass of the electrolyte and an additive (the mass fraction is 2% of vinyl sulfate) into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen-containing heterocyclic compound;
(4) the electrolyte solution containing a nitrogen heterocyclic compound obtained in the present example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Example B14:
compared with the embodiment B13, the difference is that the nitrogen-containing heterocyclic compound S5 accounts for 0.1 percent of the total mass of the electrolyte.
Example B15:
compared with the embodiment B13, the difference is that the nitrogen-containing heterocyclic compound S5 accounts for 0.5 percent of the total mass of the electrolyte.
Example B16:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving in the solvent obtained in step (1)Stirring uniformly to obtain a basic electrolyte;
(3) adding a nitrogen-containing heterocyclic compound S6 with the mass being 0.3% of the total mass of the electrolyte and an additive (the mass fraction is 2% of vinyl sulfate) into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen-containing heterocyclic compound;
(4) the electrolyte solution containing a nitrogen heterocyclic compound obtained in the present example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Example B17:
compared with the embodiment B16, the difference is that the nitrogen-containing heterocyclic compound S6 accounts for 0.1 percent of the total mass of the electrolyte.
Example B18:
compared with the embodiment B16, the difference is that the nitrogen-containing heterocyclic compound S6 accounts for 0.5 percent of the total mass of the electrolyte.
Example B19:
compared with the embodiment B1, the difference is that the dosage of the vinyl sulfate accounts for 0.5 percent of the total mass of the electrolyte.
Example B20:
compared with the embodiment B1, the difference is that the dosage of the vinyl sulfate accounts for 1 percent of the total mass of the electrolyte.
Example B21:
compared with example B1, except that 2% of vinyl sulfate was replaced by 0.5% by weight of tris (trimethylsilane) phosphate.
Example B22:
compared with example B1, except that 1% by weight of tris (trisilane) phosphate was used instead of 2% by weight of vinyl sulfate.
Example B23:
compared with example B1, except that 2% of vinyl sulfate was replaced by 2% by weight of tris (trisilane) phosphate.
Example B24:
compared to example B1, except that 2% of vinyl sulfate was replaced by 0.5% by weight of tris (trimethylsilane) borate.
Example B25:
compared to example B1, except that 1% by weight of tris (trisilane) borate was used instead of 2% by weight of vinyl sulfate.
Example B26:
compared to example B1, except that 2% of vinyl sulfate was replaced by 2% by weight of tris (trisilane) borate.
Example B27:
compared to example B1, the difference is that the cyclic carbonate solvent Ethylene Carbonate (EC) and the linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are used in the mass ratio EC: EMC: DEC ═ 1: 1: 1 and mixing.
Example B28:
compared to example B1, the difference is that the cyclic carbonate solvent Ethylene Carbonate (EC) and the linear carbonate solvents Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) are used in the mass ratio EC: EMC: DEC ═ 3: 5: 2 and mixing.
Comparative example 1:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding vinylene carbonate with the mass fraction of 1% into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain electrolyte;
(4) the electrolyte obtained in this comparative example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Comparative example 2:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) adding 1-hydroxybenzotriazole with the mass being 0.3% of the total mass of the electrolyte and vinylene carbonate with the mass fraction being 1% into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing nitrogen heterocyclic compounds;
(4) the electrolyte obtained in this example was used for LiNi0.8Co0.1Mn0.1O2Graphite flexible package battery.
Comparative example 3:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) and (3) adding the vinyl sulfate with the mass fraction of 2% into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen heterocyclic compound.
Comparative example 4:
(1) cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a mass ratio EC: EMC: DEC ═ 3: 5: 2, mixing, purifying by adopting a molecular sieve, removing impurities and removing water;
(2) under the condition of room temperature, a 12.5 percent conductive lithium salt lithium hexafluorophosphate (LiPF) is added6) Dissolving the electrolyte in the solvent obtained in the step (1), and uniformly stirring to obtain a basic electrolyte;
(3) and (3) adding 1-hydroxybenzotriazole with the mass being 0.3% of the total mass of the electrolyte and vinyl sulfate with the mass fraction being 2% into the basic electrolyte obtained in the step (2), and uniformly stirring to obtain the electrolyte containing the nitrogen heterocyclic compound.
Test example 1-high temperature environment performance test:
the graphite pouch batteries prepared in examples a1 to a30, comparative example 1 and comparative example 2 were cycled at a high temperature of 45C, tested at a rate of 1C for cycle performance of charge and discharge, and tested at a high temperature of 60℃ for high temperature storage performance for 30 days.
Battery high temperature storage experiment: the batteries obtained in examples a1 to a30, comparative example 1 and comparative example 2 were subjected to a charge-discharge cycle test 5 times at a charge-discharge rate of 1C at room temperature, and finally charged to a full charge state at a rate of 1C. The 1C capacity Q, the internal cell resistance T0 and the cell thickness H0 were recorded separately. The battery in a full-charge state is stored for 30 days at 60 ℃, 1C discharge capacity Q1, battery internal resistance T1 and thickness H1 are recorded, the battery is charged and discharged for 5 weeks at room temperature at a rate of 1C, one time with the highest discharge capacity is selected and recorded as discharge capacity Q2, experimental data such as battery high-temperature storage capacity retention rate, capacity recovery rate, internal resistance change rate and the like are obtained through calculation, and the recording results are shown in tables 1 and 2.
TABLE 1 comparison of experimental results of high temperature cycle maintenance and high temperature storage capacity variation for the batteries of examples A1-A30, comparative example 1 and comparative example 2
As can be seen from Table 1: in the embodiment, after the nitrogenous heterocyclic compound (S1-S6) is added, the capacity retention rate at high temperature of 45 ℃ is obviously improved, and the capacity retention rate and the recovery rate are effectively improved after the high-temperature storage at 60 ℃ for 30 days; the performances of 0.3 percent of the nitrogenous heterocyclic compounds are equivalent to those of 0.5 percent of the nitrogenous heterocyclic compounds, and the nitrogenous heterocyclic compounds are superior to 0.1 percent of the nitrogenous heterocyclic compounds; the high-temperature cycle performance at 45 ℃ and the high-temperature storage performance at 60 ℃ of the electrolyte containing the nitrogen heterocyclic compound are obviously different from those of the electrolyte without the nitrogen heterocyclic compound and the electrolyte with 0.3 percent of 1-hydroxybenzotriazole.
TABLE 2 comparison of test results of internal resistance and thickness change at high temperature for storage of batteries of examples A1 to A30, comparative example 1 and comparative example 2
As can be seen from Table 2: in the examples, after the nitrogenous heterocyclic compound (S1-S6) is added, the expansion rate and the internal resistance of the battery are smaller than those of the comparative example 1 and the comparative example 2 after the battery is stored at the high temperature of 60 ℃ for 30 days; the addition of the nitrogenous heterocyclic compound can inhibit the gas production and the increase of the internal resistance of the battery, and the performances of 0.3 percent of the nitrogenous heterocyclic compound are equivalent to those of 0.5 percent of the nitrogenous heterocyclic compound and are better than those of 0.1 percent of the nitrogenous heterocyclic compound.
Test example 2 acidity and chromaticity test of electrolyte
The electrolytes of lithium secondary batteries prepared in examples B1 to B28, comparative example 3 and comparative example 4 were stored at normal temperature and at high temperature of 45 ℃, and the acidity and chromaticity of the electrolytes were measured for 7 days, 15 days, 30 days and 60 days, respectively; the acidity test instrument is a potentiometric titrator, the acidity test method is a triethylamine potentiometric titration method (examples B1-B20, B27 and B28) and a low-water triethylamine method (examples B21-26), and the chroma is tested by a colorimeter; the color recording results are shown in Table 3; the acidity is reported in Table 4.
TABLE 3 results of storage chromaticity test of the electrolytes prepared in examples B1 to B28, comparative example 3 and comparative example 4
As can be seen from Table 3: according to the results of normal-temperature storage and high-temperature storage at 45 ℃, in the embodiment, after the nitrogenous heterocyclic compound (S1-S6) is added, the nitrogenous heterocyclic compound can effectively inhibit the chroma rise of the electrolyte; particularly, the electrolyte can play a remarkable inhibiting role when the electrolyte contains additives such as vinyl sulfate, tri (trimethylsilyl) phosphate, tri (trimethylsilyl) borate and the like which are easy to increase the chromaticity of the electrolyte.
TABLE 4 results of storage acidity experiments for electrolytes prepared in examples B1 to B28, comparative example 3 and comparative example 4
As can be seen from Table 4: according to the results of normal-temperature storage and high-temperature storage at 45 ℃, in the embodiment, after the nitrogenous heterocyclic compound (S1-S6) is added, the nitrogenous heterocyclic compound can effectively inhibit the increase of the acidity of the electrolyte; particularly, when the electrolyte contains additives such as vinyl sulfate, tri (trimethylsilyl) phosphate and tri (trimethylsilyl) borate which easily increase the acidity of the electrolyte, the electrolyte can play a remarkable inhibiting role.
The examples presented herein are only implementations selected according to a combination of all possible examples. The appended claims should not be limited to the description of the embodiments of the invention. Where numerical ranges are used in the claims, including sub-ranges therein, variations in these ranges are also intended to be covered by the appended claims.
Claims (10)
1. The electrolyte of the nitrogen-containing heterocyclic compound comprises a solvent and a solute, and is characterized by further comprising at least one nitrogen-containing heterocyclic compound shown in the following structural general formula (1) or structural general formula (2):
wherein R represents C, S or S ═ O.
2. The electrolytic solution of a nitrogen-containing heterocyclic compound according to claim 1, characterized in that the nitrogen-containing heterocyclic compound accounts for 0.01 to 2% by mass of the total mass of the electrolytic solution.
3. The nitrogen-containing heterocyclic compound electrolyte solution according to claim 1, wherein the solvent comprises at least two non-aqueous solvents, and the non-aqueous solvents comprise ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl acetate, and propyl acetate.
4. The electrolytic solution of a nitrogen-containing heterocyclic compound according to claim 1, wherein the solute is an electrolyte lithium salt, and a concentration of the electrolyte lithium salt in the solvent is 0.8 to 1.5 mol/L.
5. The nitrogen-containing heterocyclic compound electrolytic solution according to claim 4, wherein the electrolyte lithium salt comprises at least one of lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium bis (fluorosulfonyl) imide, and lithium bis (trifluoromethylsulfonyl) imide.
6. The nitrogen-containing heterocyclic compound electrolyte solution according to claim 1, further comprising an additive, wherein the additive comprises at least one of vinyl sulfate, tris (trimethylsilyl) phosphate, tris (trimethylsilyl) borate, lithium difluorooxalato borate, vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, and 1, 3-propanesultone.
7. The electrolytic solution containing a nitrogen heterocyclic compound according to claim 6, characterized in that the additive is added in an amount of 0.5 to 5% by weight based on the total mass of the electrolytic solution.
8. A method of preparing an electrolyte solution containing nitrogen heterocycles according to any of claims 1-7, comprising the steps of:
(1) purifying the solvent to remove impurities and water;
(2) adding a solute into the solvent obtained in the step (1) at room temperature, and uniformly stirring;
(3) and adding a nitrogen-containing heterocyclic compound and an additive, and uniformly stirring to obtain the electrolyte of the nitrogen-containing heterocyclic compound.
9. The method of claim 8, wherein the step (1) of purifying to remove impurities and water is preferably performed by one or more of molecular sieves, activated carbon, calcium hydride, lithium hydride, anhydrous calcium oxide, calcium chloride, phosphorus pentoxide, alkali metals and alkaline earth metals.
10. A lithium secondary battery comprising a positive electrode tab and a negative electrode tab, characterized by further comprising the nitrogen-containing heterocyclic compound electrolyte according to any one of claims 1 to 7, wherein the positive electrode tab comprises a positive electrode active material that intercalates or deintercalates lithium ions, a conductive agent, a current collector, and a binder that binds the positive electrode active material and the conductive agent to the current collector; the negative electrode sheet includes a negative electrode active material capable of intercalating or deintercalating lithium ions, a conductive agent, a current collector, and a binder binding the negative electrode active material and the conductive agent to the current collector.
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|---|---|---|---|---|
| JP2024029747A (en) * | 2022-08-22 | 2024-03-06 | 三星エスディアイ株式会社 | Electrolyte additives, electrolytes for lithium secondary batteries containing the same, and lithium secondary batteries |
| CN118497504A (en) * | 2024-07-18 | 2024-08-16 | 新乡市中天新能源科技股份有限公司 | Method for recycling lithium battery recycling solution and waste ternary battery anode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107845831A (en) * | 2016-09-20 | 2018-03-27 | 中国科学院大连化学物理研究所 | A kind of electrolyte for lithium-sulfur cell |
| CN110085913A (en) * | 2019-05-23 | 2019-08-02 | 河南电池研究院有限公司 | It is a kind of suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material and preparation method thereof |
-
2021
- 2021-12-08 CN CN202111490505.7A patent/CN114156534A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107845831A (en) * | 2016-09-20 | 2018-03-27 | 中国科学院大连化学物理研究所 | A kind of electrolyte for lithium-sulfur cell |
| CN110085913A (en) * | 2019-05-23 | 2019-08-02 | 河南电池研究院有限公司 | It is a kind of suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2024029747A (en) * | 2022-08-22 | 2024-03-06 | 三星エスディアイ株式会社 | Electrolyte additives, electrolytes for lithium secondary batteries containing the same, and lithium secondary batteries |
| JP7664322B2 (en) | 2022-08-22 | 2025-04-17 | 三星エスディアイ株式会社 | Electrolyte additive, electrolyte for lithium secondary battery containing the same, and lithium secondary battery |
| CN118497504A (en) * | 2024-07-18 | 2024-08-16 | 新乡市中天新能源科技股份有限公司 | Method for recycling lithium battery recycling solution and waste ternary battery anode material |
| CN118497504B (en) * | 2024-07-18 | 2025-03-07 | 新乡市中天新能源科技股份有限公司 | Method for recycling lithium battery recycling solution and waste ternary battery anode material |
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