CN116544373A - Nitrogen doped carbon nano rod and NiCo 2 S 4 Method for preparing nanocrystalline composite and application thereof - Google Patents
Nitrogen doped carbon nano rod and NiCo 2 S 4 Method for preparing nanocrystalline composite and application thereof Download PDFInfo
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- 229910003266 NiCo Inorganic materials 0.000 title claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002073 nanorod Substances 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 42
- 239000002159 nanocrystal Substances 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 18
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 28
- 239000007772 electrode material Substances 0.000 abstract description 18
- 239000012621 metal-organic framework Substances 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000007773 negative electrode material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 239000010439 graphite Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 238000004729 solvothermal method Methods 0.000 description 2
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- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a nitrogen-doped carbon nano rod and NiCo 2 S 4 A preparation method and application of a nanocrystal compound relate to the field of lithium ion battery anode materials, and nitrogen-doped carbon nanorods and NiCo are synthesized through MOFs (metal-organic frameworks) derivative strategies 2 S 4 The carbon matrix in the invention can increase the stability of the material and improve the conductivity of the material; interconnected voids, which can provide free space to mitigate volume expansion and increase the contact area of the material with the electrolyte; doping of nitrogen atoms can improve the conductivity of the electrode material and increase the active sites of the material, thereby changing the electricity of the electrode materialChemical property, the nitrogen doped carbon nano rod and NiCo prepared by the invention 2 S 4 The nano crystal composite material has simple and efficient process, safety and easy implementation, short synthesis period and hopeful popularization and industrialized production. The nitrogen-doped carbon nano rod and NiCo obtained by the invention 2 S 4 When the nano crystal composite material is used as a negative electrode material of a lithium ion battery, the nano crystal composite material has high specific capacity and good cycle stability.
Description
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to a nitrogen-doped carbon nano rod and NiCo 2 S 4 A method for preparing a nanocrystal composition and application thereof.
Background
With the continuous development of modern society and economy, continuous exploitation and unreasonable use of various fossil fuels cause serious resource shortage and environmental pollution. Therefore, there is an urgent need to find a green clean energy source that can replace fossil fuel with high efficiency, no pollution, renewable and capable of being recycled, thereby effectively protecting the ecological environment. Therefore, there is a need to convert green energy into electric energy in various ways and store it by using energy storage technology, thereby improving the utilization rate of renewable energy, and thus development of an energy storage device having a high capacity has been attracting attention. Among the numerous secondary batteries, lithium Ion Batteries (LIBs) are considered as one of the most promising energy storage devices because of their advantages of long cycle life, high energy density, high power density, environmental friendliness, no memory effect, and the like. The energy storage of Lithium Ion Batteries (LIBs) is essentially the storage of ions by the electrode material, and thus the storage capacity of the electrode material for ions directly determines the capacity of the battery. Therefore, in order to meet the increasing living demands of people, further research and development of battery anode materials with high specific capacity, long cycle life and good rate performance are necessary.
Graphite is commonly used as a commercial negative electrode material for Lithium Ion Batteries (LIBs), but has a relatively low theoretical capacity (372 mAhg -1 ) The growing demands of the rapidly evolving Lithium Ion Battery (LIBs) market cannot be met. In recent years, metal sulfides are often used as anode materials of lithium ion batteries, and binary transition metal sulfides are used as anode materials of lithium ion batteries, can combine functions of two transition metal sulfides to generate a synergistic effect, however, the transition metal sulfides are easy to aggregate and expand in volume in a charging and discharging process, so that capacity attenuation is serious and conductivity is poor when the lithium ion batteries are used as anode materialsThe cycling stability is always poor, which severely hampers their use as negative electrode materials for lithium ion batteries. Currently, one of the effective strategies to solve the above problems is to compound transition metal sulfides with carbon, wherein the carbon matrix not only effectively relieves the volume expansion, but also greatly improves the conductivity of the entire electrode. In recent years, researchers have been trying to design metal-organic framework Materials (MOFs) as templates for the preparation of metal sulfide nanoparticles embedded in porous carbon materials, where organic ligands decompose during carbonization to release a large number of gas molecules (e.g., H 2 O、CO 2 、NO 2 ) The synthesized material always exhibits a porous structure, and furthermore, the in situ generated carbon matrix may limit further growth of transition metal sulfides during synthesis, for example: zhang et al reported an RGO-NiCo 2 S 4 It is 500mAg -1 When having 903mAhg -1 And excellent cycling stability (newj.chem., 2018,42,1467-1476). In addition, heteroatom doping (e.g., N, S, P, etc.) in carbon matrices has been demonstrated to improve the ion storage properties of electrode materials, which can also be obtained in situ by carbonizing MOFs materials containing heteroatom ligands, e.g., mai et al prepared nitrogen doped carbon coated metal sulfides using MOFs as templates and exhibited good lithium storage properties (NanoEnergy, 2019,64,103899). However, the currently reported synthesis of porous sulfide and heteroatom doped carbon composite materials is often of a carbon cladding structure, and the process is relatively complex, the cost is expensive, and the commercialization popularization is not facilitated, so that the nitrogen doped carbon nanorod and NiCo need to be provided 2 S 4 A method for preparing a nanocrystal composition and its use solve the above problems.
Disclosure of Invention
In order to solve the technical problems, the invention provides the following technical scheme:
nitrogen doped carbon nano rod and NiCo 2 S 4 A method of preparing a nanocrystal composition comprising the steps of:
s1, adding 0.43g of nickel chloride, 0.83g of cobalt chloride and 0.9g of nitrilotriacetic acid into 30ml of isopropanol, and magnetically stirring for 20min;
s2, adding 10mL of deionized water and magnetically stirring for 30min to form a mixture A;
s3, transferring the mixture A into a 50ml polytetrafluoroethylene lining reaction kettle, sealing the reaction kettle completely, and keeping the reaction kettle at 180 ℃ for 6 hours until the reaction is complete;
s4, after the reaction kettle is completely cooled, opening the reaction kettle, centrifugally collecting a precursor, washing the precursor with ethanol for 3 times, and then drying the precursor in an oven at 60 ℃ for 12 hours to obtain a precursor Ni-Co-NTA;
s5, mixing the precursor Ni-Co-NTA and sulfur powder according to the mass ratio of 1:2, grinding uniformly to form a mixture B, and mixing the mixture B in N 2 Heating to 600 ℃ at a heating rate of 5 ℃/min in the atmosphere, and maintaining the temperature for 2 hours to form the nitrogen-doped carbon nano rod and NiCo 2 S 4 Nanocrystalline composite material.
The invention also discloses an application of the nitrogen-doped carbon nano rod and NiCo 2 S 4 The nano crystal compound is used for preparing the lithium ion battery cathode electrode plate.
The preparation method of the lithium ion battery negative electrode plate comprises the steps of adding N-methyl-2-pyrrolidone into a nitrogen-doped carbon nano rod and NiCo in a mass ratio of 8:1:1 2 S 4 And grinding the mixture C into slurry in a slurry state in the mixture C of the nano crystal composite powder, the binder PVDF and the acetylene black, uniformly coating the slurry on a current collector copper foil, drying the current collector copper foil for 12 hours at the temperature of 80 ℃ in vacuum, and preparing a wafer with the diameter of 14mm to obtain the lithium ion battery negative electrode plate.
The invention also discloses a lithium ion battery prepared by applying the lithium ion battery negative electrode plate.
The invention has the beneficial effects that:
1. the nitrogen doped carbon nano rod and NiCo are synthesized by MOFs derivative strategy 2 S 4 Nanocrystalline composite material (denoted NiCo 2 S 4 @ N-C). First, ni is used 2+ /Co 2+ Is a metal ion, and the nitrilotriacetic acid is an organic ligand, and a solvothermal method is adopted to synthesize the Ni-Co-NTA precursor. Next, it will obtainMixing MOFs of (2) with sulfur powder in a ratio of 1:2, and adding the mixture into N 2 Medium carbonization to form NiCo 2 S 4 N-C nanorods. In the calcination process of the precursor, the ligand can generate a nitrogen doped carbon matrix in situ, thereby avoiding NiCo in situ 2 S 4 Further growth of nanoparticles imparts NiCo 2 S 4 The @ N-C stable structure, while the MOFs precursor also releases gaseous molecules (e.g., CO 2 、H 2 O、NO 2 ) Resulting in a final product having many interconnected voids, which can provide free space to mitigate volume expansion and increase the contact area of the material with the electrolyte. In addition, the ligand contains a large amount of N element, which is favorable for in-situ N doping of the product, and the doping of nitrogen atoms can improve the conductivity of the electrode material and increase the active sites of the material, thereby changing the electrochemical performance of the electrode material. The carbon matrix can increase the stability of the material and improve the conductivity of the material; interconnected voids, which can provide free space to mitigate volume expansion and increase the contact area of the material with the electrolyte; the doping of nitrogen atoms can improve the conductivity of the electrode material and increase the active sites of the material, thereby changing the electrochemical performance of the electrode material.
2. The nitrogen-doped carbon nano rod and NiCo prepared by the invention 2 S 4 The nano crystal composite material has simple and efficient process, safety and easy implementation, short synthesis period and hopeful popularization and industrialized production.
3. The nitrogen-doped carbon nano rod and NiCo obtained by the invention 2 S 4 When the nano crystal composite material is used as a negative electrode material of a lithium ion battery, the nano crystal composite material has high specific capacity and good cycle stability. NiCo 2 S 4 When N-C is applied to a lithium ion battery cathode material, under the condition that the current density is 100mA/g, after 200 times of circulation of a lithium ion half battery, niCo 2 S 4 The discharge capacity of @ N-C is maintained at 1543mAh/g; after the current density is 1A/g and the cycle is 1000 times, the discharge capacity can still be kept at 893mAh/g, which shows that the lithium ion battery has excellent cycle performance, shows the potential of the lithium ion battery as a negative electrode material, and is expected to be applied to the field of rapid charge and discharge.
Drawings
FIG. 1 shows a nitrogen-doped carbon nanorod and NiCo 2 S 4 Schematic of the preparation of nanocrystal complexes.
FIG. 2 (a) is a Scanning Electron Microscope (SEM) photograph of a precursor prepared according to the present invention; fig. 2 (b) is a Transmission Electron Microscope (TEM) photograph of the precursor.
FIGS. 3 (a-c) are NiCo respectively 2 S 4 @N-C、CoS 2 Scanning Electron Microscope (SEM) photographs of @ N-C and NiS @ N-C.
FIGS. 4 (a-c) are NiCo respectively 2 S 4 @N-C、CoS 2 Transmission Electron Microscope (TEM) photographs of @ N-C and NiS @ N-C.
Fig. 5 is a thermogravimetric analysis (TGA) diagram of a precursor.
FIG. 6 is NiCo 2 S 4 XRD pattern of @ N-C nanorods.
FIG. 7 is NiCo 2 S 4 Raman spectra of @ N-C nanorods.
FIG. 8 is NiCo 2 S 4 XPS full spectrum of @ N-C nanorods.
FIG. 9 is NiCo 2 S 4 N of the @ N-C nanorods 2 Adsorption-desorption isotherms.
FIG. 10 shows a lithium ion half-cell after 200 cycles at a current density of 100mA/g
FIG. 11 shows NiCo 2 S 4 And @ N-C is used as an electrode material, and after 1000 times of circulation under the current density of 1A/g, the discharge capacity can still be kept at 893mAh/g.
FIG. 12 shows NiCo 2 S 4 N-C as electrode material, when the current density is gradually increased from 100 to 200, 400, 600, 800 and 1000mAg -1 When NiCo 2 S 4 The specific capacity of @ N-C was reduced from 1432 to 1129, 1001, 910, 826 and 786mAhg, respectively -1 。
Detailed Description
The invention is further described in connection with the following detailed description, in order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the invention easy to understand.
Nitrogen doped carbon nano rod and NiCo 2 S 4 A method of preparing a nanocrystal composition (see the schematic representation of the preparation of fig. 1), comprising the steps of:
s1, adding 0.43g of nickel chloride, 0.83g of cobalt chloride and 0.9g of nitrilotriacetic acid into 30ml of isopropanol, and magnetically stirring for 20min;
s2, adding 10mL of deionized water and magnetically stirring for 30min to form a mixture A;
s3, transferring the mixture A into a 50ml polytetrafluoroethylene lining reaction kettle, sealing the reaction kettle completely, and keeping the reaction kettle at 180 ℃ for 6 hours until the reaction is complete;
s4, after the reaction kettle is completely cooled, opening the reaction kettle, centrifugally collecting a precursor, washing the precursor with ethanol for 3 times, and then drying the precursor in an oven at 60 ℃ for 12 hours to obtain a precursor Ni-Co-NTA; FIG. 2 (a) is a Scanning Electron Microscope (SEM) photograph of a precursor prepared according to the present invention, from which it can be seen that the precursor is a nanowire having a length of about ten microns and a uniform morphology; fig. 2 (b) is a Transmission Electron Microscope (TEM) photograph of the precursor, and it can be clearly seen from the photograph that the diameter of the precursor is about several hundred nanometers.
S5, mixing the precursor Ni-Co-NTA and sulfur powder according to the mass ratio of 1:2, grinding uniformly to form a mixture B, and mixing the mixture B in N 2 Heating to 600 ℃ at a heating rate of 5 ℃/min in the atmosphere, and maintaining the temperature for 2 hours to form the nitrogen-doped carbon nano rod and NiCo 2 S 4 Nanocrystalline composite material (NiCo 2 S 4 @N-C)。
To show nitrogen doped carbon nano-rod and NiCo 2 S 4 Nanocrystalline composite material (NiCo 2 S 4 Performance superiority @ N-C), which was demonstrated in comparison with two other materials by passing NiCl in step S1 above 2 And CoCl 2 The mass of the mixture is respectively adjusted to 1.2g, thus the precursors Ni-NTA and Co-NTA can be obtained, and then the nitrogen-doped carbon nano rod and NiS nano crystal composite material (NiS@N-C) and the nitrogen-doped carbon nano rod and CoS can be obtained according to the step S5 2 Nanocrystalline composite material (CoS 2 @N-C)。
FIGS. 3 (a-c) are NiCo respectively 2 S 4 @N-C、CoS 2 Scanning Electron Microscope (SEM) photographs of @ N-C and NiS @ N-C, from which NiCo can be seen 2 S 4 @N-C、CoS 2 The @ N-C and NiS @ N-C inherit the rod-like morphology of the precursor.
FIGS. 4 (a-c) are NiCo respectively 2 S 4 @N-C、CoS 2 Transmission Electron Microscope (TEM) photographs of @ N-C and NiS @ N-C, from FIG. 4 (a), niCo 2 S 4 N-C is made of rich NiCo 2 S 4 Nanoparticle composition, radius of about 5nm, and release gaseous molecules (CO during calcination of the precursor 2 ，NH 3 Etc.), resulting in NiCo 2 S 4 The @ N-C nanorods have a number of interconnected voids, which can provide free space to reduce volume expansion and increase the contact area of the material with the electrolyte; from FIG. 4 (b, c), it can be seen that CoS 2 Intermediate CoS of @ N-C and NiS @ N-C 2 And the particle size of the NiS is large and maldistributed.
FIG. 5 is a thermogravimetric analysis (TGA) of the precursor, tested for Ni-Co-NTA in N 2 The thermal behavior at a temperature rise rate of 10 ℃ per minute from room temperature to 800 ℃. The mass loss of 2.83wt% below 242 ℃ can be attributed to evaporation of absorbed water and other gaseous molecules. When the temperature is raised to 498 ℃, the weight loss is about 64.42wt%, which can be attributed to the decomposition of Ni-Co-NTA.
In FIG. 6, niCo 2 S 4 XRD patterns of @ N-C nanorods, diffraction peaks at 16.28 °, 26,74 °, 31.48 °, 38.19 °, 47.25 °, 50.30 °, and 55.13 ° correspond to the (111), (220), (311), (400), (422), (511), and (440) crystal planes of a standard PDF card NiCo2S4@N-C (JCPF No. 43-1447).
FIG. 7 is NiCo 2 S 4 The raman spectrum of the @ N-C nanorods further characterizes defects in the material. About 491.65cm -1 And 662.53cm -1 The peaks at these correspond to Ni-S and Co-S stretching vibrations, further indicating NiCo 2 S 4 Successful synthesis of @ N-C nanorods. In addition, at about 1350cm -1 And 1569cm -1 There are two characteristic peaks corresponding to defect-related D-band and graphite-related G-band, respectively, with an ID/IG intensity ratio calculated to be 1.12, indicating NiCo 2 S 4 The @ N-C nanorods have a high level of defects. It is noted that doping of the N atoms may provide more defects, increasing the conductivity of the electrode material and thus changing the electrochemical properties of the electrode material.
FIG. 8 shows NiCo 2 S 4 XPS full spectrum of @ N-C nanorods, from which NiCo can be seen 2 S 4 The @ N-C material is composed of Ni, co, S, C and N elements, further illustrating NiCo 2 S 4 Successful synthesis of @ N-C nanorods, and no other impurity elements.
FIG. 9 is NiCo 2 S 4 N of the @ N-C nanorods 2 Adsorption-desorption isotherms, study NiCo 2 S 4 The specific surface area and pore structure of @ N-C. NiCo as shown in the figure 2 S 4 Brunauer-Emmett-Teller (BET) specific surface area at N-C of 11.33m 2 g -1 . Pore size distribution curve shows NiCo 2 S 4 The average pore size of @ N-C was 6.53nm.
The invention also discloses an application of the nitrogen-doped carbon nano rod and NiCo 2 S 4 The nano crystal compound is used for preparing the lithium ion battery cathode electrode plate.
The preparation method of the lithium ion battery negative electrode plate comprises the steps of adding N-methyl-2-pyrrolidone into a nitrogen-doped carbon nano rod and NiCo in a mass ratio of 8:1:1 2 S 4 And grinding the mixture C into slurry in a slurry state in the mixture C of the nano crystal composite powder, the binder PVDF and the acetylene black, uniformly coating the slurry on a current collector copper foil, drying the current collector copper foil for 12 hours at the temperature of 80 ℃ in vacuum, and preparing a wafer with the diameter of 14mm to obtain the lithium ion battery negative electrode plate. The invention also discloses a lithium ion battery prepared by applying the lithium ion battery negative electrode plate.
NiCo 2 S 4 Lithium storage properties of @ N-C materials were tested using CR2032 coin half cells assembled in an argon filled glove box (H 2 O<1ppm，O 2 <1 ppm). The electrode plate of the lithium ion battery cathode electrode plate obtained in the previous paragraph is taken as the positive electrode, and a round metal lithium plate with the diameter of 14mm is taken as the negative electrodeThe electrode (the material prepared by the invention is used as a negative electrode sheet of a lithium ion battery, and the voltage in a full battery is lower than that of a positive electrode, so the material is a negative electrode, a half battery is prepared in the performance test, a metal lithium sheet is used as a reference electrode, the electrode voltage prepared by coating the prepared material on a copper foil is higher than that of the metal lithium sheet, so the electrode sheet prepared in the half battery is a positive electrode, the metal lithium sheet is a negative electrode), the lithium ion battery is used as a diaphragm by using a Celgard2400 polypropylene film, and the electrolyte is 1M LiPF in a mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) (volume ratio is 1:1) 6 . Electrode capacity and cycling stability were evaluated by a constant current discharge/charge method using newware CT3008W with a voltage range of 0.01-3.0V. For NiCo on electrochemical workstation (CHI 760E) 2 S 4 The @ N-C electrode was subjected to Cyclic Voltammetry (CV) and electrochemical impedance spectroscopy. The voltage range is 0-3V.
Measurement results:
as shown in FIG. 10, at a current density of 100mA/g, after 200 cycles of the lithium ion half cell, niCo 2 S 4 @N-C、CoS 2 The discharge capacities of @ N-C and NiS @ N-C are respectively maintained at 1543, 987 and 830mAh/g; in addition, niCo was found 2 S 4 The specific capacities of @ N-C, niS @ N-C and CoS2@ N-C slowly increased after the 10 th cycle, which can be attributed to activation of the electrode material during the cycle; at the same time, niCo 2 S 4 Coulomb Efficiency (CE) of @ N-C remained above 99.68% after 100 cycles, indicating NiCo 2 S 4 The @ N-C has good cycle stability when used as a cathode material of a lithium ion half battery.
As shown in FIG. 11, niCo 2 S 4 After 1000 times of circulation under the current density of 1A/g, the discharge capacity can still be kept at 893mAh/g by taking @ N-C as an electrode material, which shows that the material has excellent circulation performance. Rate performance is also an important parameter in measuring cell stability.
As shown in FIG. 12, niCo 2 S 4 N-C as electrode material, when the current density is gradually increased from 100 to 200, 400, 600, 800 and 1000mAg -1 When NiCo 2 S 4 The specific capacities of @ N-C were respectively reduced from 1432 to 1129,1001. 910, 826 and 786mAhg -1 . When the current density is reduced from 1000 to 100mAg again -1 When the discharge capacity was kept at 1559mAhg -1 Indicating NiCo 2 S 4 N-C has good reversibility to LIBs, and furthermore, niCo 2 S 4 The multiplying power performance of @ N-C is superior to CoS 2 @N-C and NiS@N-C.
The invention synthesizes the nitrogen doped carbon nano rod and NiCo through MOFs derivative strategy 2 S 4 Nanocrystalline composite material (denoted NiCo 2 S 4 @ N-C). First, ni is used 2+ /Co 2+ Is a metal ion, and the nitrilotriacetic acid is an organic ligand, and a solvothermal method is adopted to synthesize the Ni-Co-NTA precursor. Next, the obtained MOFs were mixed with sulfur powder in a ratio of 1:2, and were mixed in N 2 Medium carbonization to form NiCo 2 S 4 N-C nanorods. In the calcination process of the precursor, the ligand can generate a nitrogen doped carbon matrix in situ, thereby avoiding NiCo in situ 2 S 4 Further growth of nanoparticles imparts NiCo 2 S 4 The @ N-C stable structure, while the MOFs precursor also releases gaseous molecules (e.g., CO 2 、H 2 O、NO 2 ) Resulting in a final product having many interconnected voids, which can provide free space to mitigate volume expansion and increase the contact area of the material with the electrolyte. In addition, the ligand contains a large amount of N element, which is favorable for in-situ N doping of the product, and the doping of nitrogen atoms can improve the conductivity of the electrode material and increase the active sites of the material, thereby changing the electrochemical performance of the electrode material.
The nitrogen-doped carbon nano rod and NiCo prepared by the invention 2 S 4 The nano crystal composite material has simple and efficient process, safety and easy implementation, short synthesis period and hopeful popularization and industrialized production.
The carbon matrix can increase the stability of the material and improve the conductivity of the material; interconnected voids, which can provide free space to mitigate volume expansion and increase the contact area of the material with the electrolyte; the doping of nitrogen atoms can improve the conductivity of the electrode material and increase the active sites of the material, thereby changing the electrochemistry of the electrode materialPerformance. The nitrogen-doped carbon nano rod and NiCo obtained by the invention 2 S 4 When the nano crystal composite material is used as a negative electrode material of a lithium ion battery, the nano crystal composite material has high specific capacity and good cycle stability. NiCo 2 S 4 When N-C is applied to a lithium ion battery cathode material, under the condition that the current density is 100mA/g, after 200 times of circulation of a lithium ion half battery, niCo 2 S 4 The discharge capacity of @ N-C is maintained at 1543mAh/g; after the current density is 1A/g and the cycle is 1000 times, the discharge capacity can still be kept at 893mAh/g, which shows that the lithium ion battery has excellent cycle performance, shows the potential of the lithium ion battery as a negative electrode material, and is expected to be applied to the field of rapid charge and discharge.
It will be appreciated by those skilled in the art that the present invention can be carried out in other embodiments without departing from the spirit or essential characteristics thereof. Accordingly, the above disclosed embodiments are illustrative in all respects, and not exclusive. All changes that come within the scope of the invention or equivalents thereto are intended to be embraced therein.
Claims (4)
1. Nitrogen doped carbon nano rod and NiCo 2 S 4 A method of preparing a nanocrystal composition comprising the steps of:
s1, adding 0.43g of nickel chloride, 0.83g of cobalt chloride and 0.9g of nitrilotriacetic acid into 30ml of isopropanol, and magnetically stirring for 20min;
s2, adding 10mL of deionized water and magnetically stirring for 30min to form a mixture A;
s3, transferring the mixture A into a 50ml polytetrafluoroethylene lining reaction kettle, sealing the reaction kettle completely, and keeping the reaction kettle at 180 ℃ for 6 hours until the reaction is complete;
s4, after the reaction kettle is completely cooled, opening the reaction kettle, centrifugally collecting a precursor, washing the precursor with ethanol for 3 times, and then drying the precursor in an oven at 60 ℃ for 12 hours to obtain a precursor Ni-Co-NTA;
s5, mixing the precursor Ni-Co-NTA and sulfur powder according to the mass ratio of 1:2, grinding uniformly to form a mixture B, and mixing the mixture B in N 2 Heating to 600 ℃ at a heating rate of 5 ℃/min in the atmosphere, and maintaining the temperature for 2 hours to form the nitrogen-doped carbon nano rod and NiCo 2 S 4 Nanocrystalline composite material.
2. Nitrogen doped carbon nano rod and NiCo 2 S 4 Use of a nanocrystal composition characterized by: use of a nitrogen-doped carbon nanorod according to claim 1 with NiCo 2 S 4 The nano crystal compound is used for preparing the lithium ion battery cathode electrode plate.
3. A nitrogen-doped carbon nanorod and NiCo according to claim 2 2 S 4 Use of a nanocrystal composition characterized by: the preparation method of the lithium ion battery negative electrode plate comprises the steps of adding N-methyl-2-pyrrolidone into a nitrogen-doped carbon nano rod and NiCo in a mass ratio of 8:1:1 2 S 4 And grinding the mixture C into slurry in a slurry state in the mixture C of the nano crystal composite powder, the binder PVDF and the acetylene black, uniformly coating the slurry on a current collector copper foil, drying the current collector copper foil in a vacuum oven at 80 ℃ for 12 hours, and preparing a wafer with the diameter of 14mm to obtain the lithium ion battery negative electrode plate.
4. Nitrogen doped carbon nano rod and NiCo 2 S 4 Use of a nanocrystal composition characterized by: a lithium ion battery using the lithium ion battery negative electrode sheet of claim 2 or 3.
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| CN117463373B (en) * | 2023-12-27 | 2024-04-05 | 山东海化集团有限公司 | Porous hollow tubular CoS 2 /NiS 2 Rapid preparation method and application of heterojunction |
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