CN116805715A - Nonaqueous electrolyte, lithium ion battery and application of amine compound containing double bonds - Google Patents
Nonaqueous electrolyte, lithium ion battery and application of amine compound containing double bonds Download PDFInfo
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- CN116805715A CN116805715A CN202311075047.XA CN202311075047A CN116805715A CN 116805715 A CN116805715 A CN 116805715A CN 202311075047 A CN202311075047 A CN 202311075047A CN 116805715 A CN116805715 A CN 116805715A
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- carbonate
- nonaqueous electrolyte
- lithium ion
- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- -1 amine compound Chemical class 0.000 title claims abstract description 27
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 58
- 239000013538 functional additive Substances 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229910013870 LiPF 6 Inorganic materials 0.000 claims abstract description 5
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims abstract description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims abstract description 4
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims abstract description 4
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims abstract description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 23
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 9
- 150000005678 chain carbonates Chemical class 0.000 claims description 7
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims 3
- 239000003660 carbonate based solvent Substances 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 abstract description 8
- 150000003624 transition metals Chemical class 0.000 abstract description 8
- 238000004090 dissolution Methods 0.000 abstract description 5
- 238000006864 oxidative decomposition reaction Methods 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 3
- LWCXZSDKANNOAR-UHFFFAOYSA-N 4-[(2,4-diaminopteridin-6-yl)methyl-methylamino]benzoic acid Chemical compound C=1N=C2N=C(N)N=C(N)C2=NC=1CN(C)C1=CC=C(C(O)=O)C=C1 LWCXZSDKANNOAR-UHFFFAOYSA-N 0.000 description 14
- 239000000654 additive Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 230000005611 electricity Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910013872 LiPF Inorganic materials 0.000 description 5
- 101150058243 Lipf gene Proteins 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011325 microbead Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- MDQRDWAGHRLBPA-UHFFFAOYSA-N fluoroamine Chemical class FN MDQRDWAGHRLBPA-UHFFFAOYSA-N 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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
-
- 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
- H01M10/42—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
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a nonaqueous electrolyte, a lithium ion battery and application of an amine compound containing double bonds in the nonaqueous electrolyte of the lithium ion battery. The nonaqueous electrolyte comprises electrolyte lithium salt, an organic solvent and a functional additive, wherein the functional additive is N-allyl-N-methyl-2-propylene-1-amine shown in a formula I. The electrolyte lithium salt comprises LiPF 6 、LiBF 4 、LiAsF 6 、LiN(SO 2 CF 3 ) 2 、LiN(SO2C2F 5 ) 2 、LiC(SO 2 C 2 F 3 ) 2 、LiC(SO 2 C 2 F 5 ) 2 And LiN (SO) 2 F) 2 One or more of the following. The ratio of the amount of the functional additive to the amount of the nonaqueous electrolyte is 0.5-2wt%. The invention is thatThe provided functional additive can remove water and hydrofluoric acid in the electrolyte, prolong the storage and service life of the electrolyte, and meanwhile, the nonaqueous electrolyte containing the functional additive can inhibit oxidative decomposition reaction of the electrolyte in the circulation process, reduce transition metal dissolution in the circulation process of the anode material and prolong the cycle life of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of electrolyte, in particular to a non-aqueous electrolyte, a lithium ion battery and an amine compound containing double bonds.
Background
The current new energy automobile industry is vigorously developed, so that the requirements on the lithium ion power battery as a core component of the new energy automobile are higher and higher. The pursuit of the lithium ion battery on energy density and safety performance makes the high nickel trend of the lithium battery anode material obvious. The high nickel material itself is sensitive to moisture and has a higher surface activity, which presents a great challenge for adapting to the performance of high performance electrolytes. The water and acidity in the electrolyte of a lithium ion battery are important indicators for controlling the quality of the electrolyte, and the water in the electrolyte causes the hydrolysis and acidity increase of lithium salt, which directly affects the capacity, cycle life and safety performance of the battery. Thus, strict control of the moisture and acidity of the electrolyte is required during both production, storage and use of the electrolyte.
In the prior art, when the high-performance electrolyte strictly controls the moisture and the acidity in the electrolyte, various functional additives are usually matched by adding a water/acid additive, so that the circulation performance and the safety performance of the electrolyte are improved while the moisture and the acidity are reduced. In the current lithium ion battery, the water/acid additive mainly takes amine or silazane compounds as main components, but the additive has single function, and usually affects the circulation performance of electrolyte, and the water/acid additive needs to be matched with various functional additives for use, but the various additives also affect the performance of each additive mutually, and meanwhile, the production cost is increased.
Accordingly, improvements are needed in the art.
Disclosure of Invention
In the prior art, the water/acid additive mainly takes amine or silazane compounds as main components, but the additive has single function and can generally influence the circulation performance of electrolyte, and the additive needs to be matched with various functional additives for use, but the various additives can mutually influence the respective performance, and meanwhile, the production cost is increased, so the invention provides the nonaqueous electrolyte containing the double bond amine compounds, the lithium ion battery and the application thereof in solving the problems.
In order to achieve the above object, in a first aspect, the present invention provides a nonaqueous electrolyte solution, which comprises an electrolyte lithium salt, an organic solvent and a functional additive, wherein the functional additive is N-allyl-N-methyl-2-propylene-1-amine shown in formula I, and the structural formula I is as follows:
formula I.
In one implementation, the electrolyte lithium salt includes LiPF 6 、LiBF 4 、LiAsF 6 、LiN(SO 2 CF 3 ) 2 、LiN(SO2C2F 5 ) 2 、LiC(SO 2 C 2 F 3 ) 2 、LiC(SO 2 C 2 F 5 ) 2 And LiN (SO) 2 F) 2 One or more of the following.
In one implementation, the ratio of the amount of the functional additive to the amount of the nonaqueous electrolyte is 0.5-2 wt%.
In one implementation, the organic solvent is a carbonate solvent, which includes a chain carbonate and/or a cyclic carbonate.
In one implementation, the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate; the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate and fluoroethylene carbonate.
In a second aspect, the present invention also provides a lithium ion battery, which includes a positive electrode sheet and a negative electrode sheet, and a separator and an electrolyte disposed between the positive electrode sheet and the negative electrode sheet, where the electrolyte is the nonaqueous electrolyte of any one of the above.
In a third aspect, the invention also provides an application of the double bond-containing amine compound in nonaqueous electrolyte of lithium ion batteries, wherein the double bond-containing amine compound is N-allyl-N-methyl-2-propylene-1-amine shown in a formula I, and the structural formula I is as follows:
formula I.
The beneficial effects are that: according to the non-aqueous electrolyte, the lithium ion battery and the amine compound containing double bonds, provided by the invention, the functional additive containing the amine compound containing double bonds is added, namely double bonds are introduced into amine molecules, so that the functional additive can remove water and hydrofluoric acid, the storage life and the service life of the electrolyte are prolonged, meanwhile, the oxidative decomposition reaction of the electrolyte in the circulation process is inhibited, the transition metal dissolution in the circulation process of the positive electrode material is reduced, and the cycle life of the lithium ion battery is prolonged.
Drawings
FIG. 1 is a photograph showing the appearance of a hydrolysis experiment of a nonaqueous electrolyte solution provided by the invention;
FIG. 2 is a schematic diagram showing the change of the capacity retention rate of the power on cycle of the lithium ion battery provided by the invention;
FIG. 3 is a schematic diagram showing the change of the direct current discharge resistance of the power down cycle of the lithium ion battery provided by the invention;
fig. 4 is a graph showing the comparison of the content of the negative electrode transition metal after recycling of the lithium ion battery provided by the invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Furthermore, the descriptions of the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., described below mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily for the same embodiment or example. The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
The invention provides a non-aqueous electrolyte which comprises electrolyte lithium salt, an organic solvent and a functional additive, wherein the functional additive is an amine compound containing double bonds shown in a formula I, and specifically is N-allyl-N-methyl-2-propylene-1-amine shown in the formula I, and the structural formula I is as follows:
formula I.
Specifically, the compound N-allyl-N-methyl-2-propen-1-amine, in this example represented by DAMPA, is a lithium salt of the electrolyte comprising LiPF 6 、LiBF 4 、LiAsF 6 、LiN(SO 2 CF 3 ) 2 、LiN(SO2C2F 5 ) 2 、LiC(SO 2 C 2 F 3 ) 2 、LiC(SO 2 C 2 F 5 ) 2 And LiN (SO) 2 F) 2 One or more of the following. The ratio of the amount of the functional additive to the amount of the nonaqueous electrolyte is 0.5-2wt%.
The organic solvent is a carbonate solvent, and the carbonate solvent comprises chain carbonate and/or cyclic carbonate. The chain carbonate is selected from one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethylmethyl carbonate (EMC); the cyclic carbonate is selected from one or more of Ethylene Carbonate (EC), propylene carbonate and fluoroethylene carbonate. The cyclic carbonate has higher dielectric constant, but has high self viscosity, while the DEC, DMC and EMC in the chain carbonate have lower viscosity and low dielectric constant, so that the requirements of high dielectric constant and low viscosity of the solvent are met, and the solvent adopts an EC/EMC mixed solvent.
The invention also provides a lithium ion battery, which comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are arranged between the positive pole piece and the negative pole piece, and the electrolyte is the electrolyte containing the double bond amine compound. The active material of the positive electrode is LiNi x Co y Mn z L (1-x-y-z) O 2 Wherein L is Al, sr, mg, ti, ca, zr, zn, si or Fe, 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. The active material of the positive electrode is LiCo x L (1-x) O 2 Wherein L is Al, sr, mg, ti, ca, zr, zn, si or Fe,0<x is less than or equal to 1. The active material of the negative electrode is artificial graphite, natural graphite or SiO k And the k of the silicon-carbon composite material compounded with graphite is less than or equal to 2. These substances, alone or in combination, are used in the present invention, which preferably selects Mesophase Carbon Microbeads (MCMBs).
The invention also provides application of the double bond amine compound in nonaqueous electrolyte of lithium ion batteries, which is characterized in that the double bond amine compound is N-allyl-N-methyl-2-propylene-1-amine shown in a formula I, and the structural formula I is as follows:
formula I.
In the specific embodiment of the invention, the positive electrode of the lithium ion battery is composed of nickel, cobalt and manganese materials according to different dosage proportions, and comprises NMC111 type, NMC523 type, NMC622 type, NMC811 type and the like, wherein the specific embodiment of the invention adopts 622 type and 811 type; the negative electrode was a button cell of Mesophase Carbon Microbeads (MCMB) and the separator was Celgard 2320.
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1: carbonic acid is added intoMixing vinyl Ester (EC) and methyl ethyl carbonate (EMC) according to a mass ratio EC: emc=3:7, and adding lithium hexafluorophosphate (LiPF 6 ) The lithium salt concentration of the electrolyte is made to be 1.2mol/L, and DAMPA accounting for 0.5wt% relative to the total mass of the electrolyte is added, wherein the positive electrode of the buckling electricity is NMC811 type, and the negative electrode of the buckling electricity is MCMB.
Example 2: mixing Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC) according to a mass ratio EC: emc=3:7, and adding lithium hexafluorophosphate (LiPF) 6 ) The lithium salt concentration of the electrolyte is made to be 1.2mol/L, and DAMPA accounting for 1.0wt% relative to the total mass of the electrolyte is added, wherein the positive electrode of the buckling electricity is NMC811 type, and the negative electrode of the buckling electricity is MCMB.
Example 3: mixing Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC) according to a mass ratio EC: emc=3:7, and adding lithium hexafluorophosphate (LiPF) 6 ) The lithium salt concentration of the electrolyte is made to be 1.2mol/L, and DAMPA accounting for 2.0wt% relative to the total mass of the electrolyte is added, wherein the positive electrode of the buckling electricity is NMC811 type, and the negative electrode of the buckling electricity is MCMB.
Example 4: mixing Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC) according to a mass ratio EC: emc=4:6, and adding lithium hexafluorophosphate (LiPF) 6 ) The lithium salt concentration of the electrolyte is made to be 1.2mol/L, and DAMPA which is 1.0wt% relative to the total mass of the electrolyte is added, wherein the positive electrode of the buckling electrode is NMC622 type, and the negative electrode of the buckling electrode is MCMB.
Comparative example 1: mixing Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC) according to a mass ratio EC: emc=3:7, and adding lithium hexafluorophosphate (LiPF) 6 ) The lithium salt concentration of the electrolyte is made to be 1.2mol/L, and DAMPA accounting for 0.5wt% relative to the total mass of the electrolyte is added, wherein the positive electrode of the buckling electricity is NMC811 type, and the negative electrode of the buckling electricity is MCMB.
Comparative example 2: mixing Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC) according to a mass ratio EC: emc=4:6, and adding lithium hexafluorophosphate (LiPF) 6 ) The lithium salt concentration of the electrolyte is made to be 1.2mol/L, and DAMPA accounting for 0.5wt% relative to the total mass of the electrolyte is added, wherein the positive electrode of the buckling electrode is NMC622 type, and the negative electrode of the buckling electrode is MCMB.
Experiments were performed below on the above examples and comparative examples to verify their performance.
Experiment 1 hydrolysis experiment
In an argon atmosphere glove box, 2mL of each of the formulated electrolytes was added to a 4mL transparent glass sample bottle and transferred to a fume hood. After 100 μl of deionized water was added to each sample bottle, the sample bottles were sealed and photographed by regular observation.
Referring specifically to fig. 1, fig. 1 is a photo of a hydrolysis experiment of a nonaqueous electrolyte provided by the present invention. Comparative example 1 lithium hexafluorophosphate in the electrolyte was hydrolyzed to generate a lithium salt with low solubility and a highly corrosive hydrofluoric acid due to the addition of water, the lithium salt with low solubility became turbid, and the highly corrosive hydrofluoric acid corroded the glass sample bottle. The electrolyte of example 1 remains clear liquid after being placed for one month, has no obvious corrosion to a glass sample bottle, shows good water removal and acid inhibition functions of DAMPA, shows that amine compounds can be combined with hydrofluoric acid existing in the electrolyte to generate fluoroammonium salt, achieves the purpose of removing free hydrofluoric acid, and meanwhile, the property of Lewis base can enable lithium hexafluorophosphate to be stabilized, inhibit hydrolysis of lithium hexafluorophosphate and prolong the storage life of the electrolyte.
Experiment 2, electric-buckling electrochemistry
Electricity-buckling electrochemical performance experiment: and respectively adding the prepared various lithium ion battery electrolytes into a button battery with a ternary material anode, a medium-phase carbon microsphere (MCMB) cathode and Celgard2320 diaphragm, wherein the rated capacity of the battery is about 3mAh, and testing the cycle performance of the battery. The battery is placed in an incubator with a constant temperature of 30 ℃, is charged to 4.35V at a constant current and constant voltage with a current of 0.1C, has a cut-off current of 0.05C, is discharged to 3.0V at a constant current of 0.1C, and circulates for 4 circles. The 5 th round starts to charge to 4.35V with a constant current and constant voltage of 0.5C, and the 0.5C discharges to 3.0V with a constant current, and the cycle is circulated to 104 rounds, the discharge specific capacity of the 5 th round is taken as the initial discharge specific capacity, and the capacity retention rate is calculated as follows:
n-th cycle capacity retention (%) = (n-th cycle specific capacity/5-th cycle specific capacity) ×100%
Referring to fig. 2 and fig. 3, fig. 2 is a schematic diagram of a change in a retention rate of a power cycle capacitance of a lithium ion battery according to the present invention, and fig. 3 is a schematic diagram of a change in a power cycle dc discharge resistance of the lithium ion battery according to the present invention. It can be seen from comparative example 1 and examples 1 to 3 that the addition of an appropriate amount of DAMPA can improve the cycle performance of the battery, with 1wt% being the optimum ratio. From comparative example 2 and example 4, it can be seen that the DAMPA can be used for electrolyte systems (EC/EMC, 4/6) and positive electrode material systems (NMC 622) in different ratios, which also improve the cycle performance of the electrolyte, indicating the broad applicability of DAMPA. The dc resistance during the power cycling increases, typically due to oxidative decomposition of the electrolyte during the cycling. By recording the change of the buckling circulation direct current discharge resistance, it can be inferred that DAMPA can form an effective passivation film on the surface of the positive electrode in the formation process, and can inhibit the oxidative decomposition of the electrolyte in the circulation process, thereby prolonging the cycle life of the battery.
Experiment 3, negative electrode detection transition metal dissolution experiment after recovery cycle
Referring to fig. 4, fig. 4 is a graph showing the content of transition metal in the negative electrode after recycling of the lithium ion battery according to the present invention. The recovered and recycled anode material was used in ICP-AES analysis, and from the results, it was found that the anode recovered from the battery using the electrolyte containing DAMPA detected less transition metal content, indicating that DAMPA was able to suppress transition metal dissolution of the cathode material during the cycle, proving that the use of additives was able to increase the cycle life of the battery.
In summary, according to the nonaqueous electrolyte, the lithium ion battery and the amine compound containing double bonds, provided by the invention, in application, the functional additive of the amine compound containing double bonds is added, namely double bonds are introduced into amine molecules, so that the functional additive can remove hydrofluoric acid, the storage and service life of the electrolyte are prolonged, meanwhile, the oxidative decomposition reaction of the electrolyte in the circulation process is inhibited, the dissolution of transition metal in the circulation process of the positive electrode material is reduced, and the cycle life of the lithium ion battery is prolonged.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes using the descriptions and drawings of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the invention.
Claims (7)
1. The nonaqueous electrolyte is characterized by comprising electrolyte lithium salt, an organic solvent and a functional additive, wherein the functional additive is N-allyl-N-methyl-2-propylene-1-amine shown in a formula I, and the structural formula I is as follows:
formula I.
2. The nonaqueous electrolytic solution according to claim 1, wherein the electrolyte lithium salt comprises LiPF 6 、LiBF 4 、LiAsF 6 、LiN(SO 2 CF 3 ) 2 、LiN(SO2C2F 5 ) 2 、LiC(SO 2 C 2 F 3 ) 2 、LiC(SO 2 C 2 F 5 ) 2 And LiN (SO) 2 F) 2 One or more of the following.
3. The nonaqueous electrolyte according to claim 1, wherein a ratio of an amount of the functional additive to an amount of the nonaqueous electrolyte is 0.5 to 2wt%.
4. The nonaqueous electrolytic solution according to claim 1, wherein the organic solvent is a carbonate-based solvent including a chain carbonate and/or a cyclic carbonate.
5. The nonaqueous electrolytic solution according to claim 4, wherein the chain carbonate is one or more selected from the group consisting of dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate; the cyclic carbonate is selected from one or more of ethylene carbonate, propylene carbonate and fluoroethylene carbonate.
6. A lithium ion battery, comprising a positive electrode plate, a negative electrode plate, a diaphragm arranged between the positive electrode plate and the negative electrode plate, and an electrolyte, wherein the electrolyte is the nonaqueous electrolyte according to any one of claims 1 to 5.
7. The application of the double bond amine compound in the nonaqueous electrolyte of the lithium ion battery is characterized in that the double bond amine compound is N-allyl-N-methyl-2-propylene-1-amine shown in a formula I, and the structural formula I is as follows:
formula I.
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