CN114361411A - Graphene-coated layered double hydroxide derivative composite material and preparation method and application thereof - Google Patents
Graphene-coated layered double hydroxide derivative composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 150000004679 hydroxides Chemical class 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000002159 nanocrystal Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 8
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 5
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 5
- 229910015667 MoO4 Inorganic materials 0.000 description 4
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000011684 sodium molybdate Substances 0.000 description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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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
- H01M4/366—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/58—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a graphene-coated layered double hydroxide derivative composite material and a preparation method and application thereof, wherein the method comprises the following steps: (1) dispersing a cobalt source in methanol, adding an accelerant, stirring, aging, washing and drying to obtain a ZIF-67 nanocrystal; (2) mixing ZIF-67 nanocrystals with a molybdenum source, centrifuging to obtain a solid, dispersing the obtained solid in water, reacting, washing and drying to obtain a CoMo LDH polyhedral material; (3) mixing a graphene oxide aqueous solution with the obtained CoMo LDH polyhedral material, and then carrying out hydrothermal treatment, washing and drying to obtain a CoMo LDH @ GO polyhedral material; (4) and calcining the obtained CoMo LDH @ GO polyhedral material to obtain the target product. The composite material has the advantages of excellent electrochemical performance, high reversible capacity, good cycle stability and high rate performance, is expected to be used in the field of lithium ion batteries, has a simple preparation method, and is convenient for industrial production.
Description
Technical Field
The invention belongs to the technical field of material science and electrochemistry, and relates to a graphene-coated layered double hydroxide derivative composite material, and a preparation method and application thereof.
Background
Lithium ion batteries have been widely used as power sources for portable electronic products, electric vehicles, power storage in power grids, and the like due to their high energy density (which can provide more energy) and environmental protection properties. The ever-increasing demand for high performance electronic devices has driven further innovation in Lithium Ion Batteries (LIBs) in terms of higher energy/power density, longer cycle performance, and lower cost. However, the conventional graphite anode material has a low theoretical capacity (372mAh g)-1) And cannot meet these requirements.
It is highly desirable to rationally design electrode materials with high reversible capacity and long cycle life. Great efforts are made to explore various high-capacity anode and cathode materials such as tin oxide, cobalt oxide, zinc oxide, and the like. However, the practical application of these materials is greatly hindered by their poor cycling performance or low capacity due to their poor conductivity, severe aggregation, and large volume expansion during lithium insertion/extraction.
To overcome these obstacles, hybrids of inorganic materials with carbon nanotubes or graphene have been proposed, which can significantly improve the efficiency of charge transfer by shortening the lithium ion diffusion length and enhancing the electrical conductivity. Constructing a three-dimensional (3D) structure with good macroporous channels provides an ideal solution for effectively enhancing the electrochemical performance of the electrode. However, most previously reported 3D macroporous LIB electrodes have irregular porosity, which inevitably leads to electrode polarization and a large loss of intrinsic capacity at high charge/discharge rates.
Disclosure of Invention
The invention aims to provide a graphene-coated layered double hydroxide derivative composite material, and a preparation method and application thereof, so as to overcome the defects of low reversible capacity of an electrode material or large loss of inherent capacity at a high charge/discharge rate and the like in the prior art.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of a graphene-coated double hydroxide derivative composite material, which comprises the following steps:
(1) dispersing a cobalt source in methanol, adding an accelerant, stirring, aging, washing and drying to obtain a ZIF-67 nanocrystal;
(2) mixing ZIF-67 nanocrystals with a molybdenum source, centrifuging to obtain a solid, dispersing the obtained solid in water, reacting, washing and drying to obtain a CoMo LDH polyhedral material;
(3) mixing a graphene oxide aqueous solution with the obtained CoMo LDH polyhedral material, and then carrying out hydrothermal treatment, washing and drying to obtain a CoMo LDH @ GO polyhedral material;
(4) and calcining the obtained CoMo LDH @ GO polyhedral material to obtain the target product.
Further, in the step (1), the cobalt source is cobalt nitrate hexahydrate, and the accelerator is a methanol solution of 2-methylimidazole.
Furthermore, the mass volume ratio of the 2-methylimidazole to the methanol in the methanol solution of the 2-methylimidazole is (0.3-0.4) g: 90ml, the ratio of the addition amounts of cobalt nitrate hexahydrate, methanol and a methanol solution of 2-methylimidazole is (0.2-0.4) g: (30-50) ml: 90 ml.
Further, in the step (1), the stirring time is 2 hours, the aging time is 24 hours, and the aging temperature is 25 ℃.
Further, in the step (1), the drying temperature is 60 ℃.
Further, in the step (1), washing is performed using methanol.
Further, in the step (2), the molybdenum source is an ethanol solution of sodium molybdate dihydrate.
Furthermore, the mass-volume ratio of the sodium molybdate dihydrate to the ethanol solution of the sodium molybdate dihydrate is 100 mg: 30ml, wherein the adding amount ratio of the ZIF-67 nano crystal, the ethanol solution of sodium molybdate dihydrate and water is (30-60) mg: 30 ml: 25 ml.
Further, Na is used2MoO4And chemically etching the obtained ZIF-67 nano crystal to obtain the CoMo LDH polyhedral material.
Further, in the step (2), the reaction temperature is 85 ℃ and the reaction time is 12 min.
Further, in the step (2), the drying temperature is 60 ℃.
Further, in the step (2), washing is performed using ethanol.
Further, in the step (3), the concentration of the graphene oxide aqueous solution is 0.34mg/ml, and the mass ratio of the graphene oxide to the CoMo LDH polyhedral material is 1: (1-2).
Further, in the step (3), the hydrothermal temperature is 120 ℃ and the hydrothermal time is 12 h.
Further, in the step (3), the drying temperature is 60 ℃.
Further, in the step (3), washing is performed using deionized water.
Further, in the step (4), calcining is carried out in the nitrogen atmosphere, the calcining temperature is 350 ℃, the calcining time is 2 hours, and the heating rate is 5 ℃ per minute-1。
The second technical scheme of the invention provides a graphene-coated double hydroxide derivative composite material (CoO/Co)2Mo3O8@ RGO composite) prepared by the above-described preparation method.
Further, CoO/Co2Mo3O8The @ RGO composite has a hollow structure.
Further, CoO/Co2Mo3O8The @ RGO composite material is a graphene-based metal oxide mesoporous organic hybrid material.
The third technical scheme of the invention provides application of the composite material, and the composite material can be used in the field of lithium ion batteries.
CoO/Co prepared by using button type half cell pair2Mo3O8The @ RGO composite material was electrochemically tested, the testing process comprising the following steps:
s1 taking CoO/Co2Mo3O8The @ RGO composite material, the carbon black and the polyvinylidene fluoride are dispersed in a solvent, then coated on a copper foil, and dried to obtain a negative electrode material;
and S2, taking a lithium sheet as a counter electrode, taking the obtained negative electrode material as a working electrode, and carrying out electrochemical test by using a button type half cell.
Further, in step S1, the CoO/Co2Mo3O8The mass ratio of the @ RGO composite material to the carbon black to the polyvinylidene fluoride is 8: 1:1.
further, in step S1, the solvent is N-methyl-2-pyrrolidone (NMP).
Further, in step S1, vacuum drying is performed at 80 ℃.
The graphene-based macroporous structure can provide a 3D interconnection path for electron transmission and promote the diffusion of electrolyte in an electrode network, so that the graphene is used as a support, the metal nano-frame is hybridized by the graphene to form a package, then heat treatment is carried out in a nitrogen environment to enhance the conductivity of the material, and finally the hollow CoO/Co/carbon nanotube is obtained2Mo3O8@ RGO composite material, which exhibits excellent electrochemical properties.
According to the invention, by utilizing the characteristic of positive and negative electric attraction, a CoMo LDH polyhedral material prepared from ZIF-67 nanocrystals and graphene oxide are self-assembled to form a wrapped organic hybrid, and then a cross-linked conductive network formed by a hollow metal oxide framework and a graphene wrapping layer is obtained by calcining, so that a more effective channel can be provided for ion transmission, and the reversible capacity and the rate capability of the composite material for a lithium ion battery are improved.
Co (NO) used in the invention3)2·6H2O is taken as a precursor, 2-methylimidazole (2-MIM) is taken as an accelerating agent, and the mixture is incubated in methanol at 25 ℃ for 24 hours to synthesize ZIF-67 polyhedron with the average diameter of 900 nm. Then using Na2MoO4·2H2O chemical etching of ZIF-67 particles in 85 deg.C water for 12min, during which MoO4 2-Promoting ZIF-67 hydrolysis to release Co from surface to center by protonating organic linker (2-MIM)2+Ion, Co2+Ions and OH in solution-And MoO4 2-And coupling to finally generate a hollow polyhedron formed by the CoMo LDH nano sheets which are connected with each other. The Graphene Oxide (GO) with negative charges and the CoMo LDH polyhedron with positive charges form a hollow CoMo LDH @ GO hierarchical structure through electrostatic self-assembly, so that the capacitance of the structure is greatly increased. Then calcining for 2h at 350 ℃ in a nitrogen atmosphere to enhance the conductivity of the structure, reducing the calcined GO into graphene (RGO), and finally converting CoMo LDH @ GO into CoO/Co2Mo3O8@RGO。
The synthesis of ZIF-67 in the invention needs to be kept stand and aged for 24h at 25 ℃ to fully react and obtain a stable product. The ZIF-67 etch process is heavily dependent on reaction time and temperature, and high temperatures promote etch kinetics and accelerate the conversion of ZIF-67 to LDH. Adding Na at 85 deg.C2MoO4·2H2After O, the color of the ZIF-67 dispersion gradually changed from violet to blue, forming a yolk-shell structure at 8 min. As the reaction proceeded, ZIF-67 particles were completely converted to hollow polyhedrons assembled from layers of CoMo LDH nanosheets in 12 minutes, being green in color. Meanwhile, the addition amount of the ZIF-67 is controlled to be within the limit range of the invention as much as possible, and is not too high or too low, otherwise, the problems of uneven appearance and the like are caused.
Compared with the prior art, the invention has the following advantages:
(1) CoO/Co of the invention2Mo3O8The @ RGO composite material has excellent electrochemical performance, high reversible capacity, good energy density, good cycle stability, good conductivity and high rate performance, and is expected to be used in the field of lithium ion batteries;
(2) the raw materials required by the preparation process are easy to obtain, designability is realized, and the cost is low;
(3) the composite material is prepared by a solvent method, and the preparation process is simple and easy to operate and is convenient for industrial production;
(4) according to the invention, the CoMo LDH polyhedral material and graphene oxide are reacted through hydrothermal reaction, the reaction temperature is 120 ℃, the reaction time is 12h, and compared with other methods, the method has the advantages of short reaction time, simple equipment, environmental protection and sustainability.
Drawings
FIG. 1 is a TEM image of an assembled hollow polyhedron of CoMo LDH nanosheets of example 1;
FIG. 2 is CoO/Co example 12Mo3O8Scanning Electron Microscope (SEM) images of @ RGO composites;
FIG. 3 is CoO/Co example 12Mo3O8@ RGO composite Material at 100 mA.g-1Reversible capacity under charge-discharge current of (1);
FIG. 4 is CoO/Co example 12Mo3O8@ RGO composite switching the current density back to 100mA g at cycle 90-1Capacity that can be maintained afterwards.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, all the conventional commercially available raw materials or conventional processing techniques in the art are indicated.
Example 1:
preparation of graphene coated CoO/Co2Mo3O8@ RGO composite:
(1) 0.33 g of Co (NO)3)2·6H2O was dissolved in 45 ml of methanol, and 90ml of a methanol solution containing 0.37 g of 2-methylimidazole was rapidly added thereto;
(2) stirring the mixture for 2 hours and aging at 25 ℃ for 24 hours, collecting the purple product by centrifugation, washing several times with methanol, and drying overnight at 60 ℃ to obtain ZIF-67 nanocrystals;
(3) dispersing 30.0 mg of ZIF-67 nanocrystals in a dispersion containing 100.0 mg of Na2MoO4·2H2O in 30ml ethanol solution, stirring for 10 minutes, and carrying out ultrasonic treatment for 1 minute;
(4) the product was collected by centrifugation and redispersed in 25ml of water. The reaction vessel was then held at 85 ℃ for 12 minutes until the purple color disappeared. Centrifuging again to obtain green precipitate, washing with ethanol for three times, and drying at 60 ℃ overnight to obtain a CoMo LDH polyhedral material;
(5) taking 1.30ml of 6.93mg/ml graphene oxide aqueous solution, adding 25ml of water into the graphene oxide aqueous solution to prepare 0.34mg/ml graphene oxide aqueous solution;
(6) the diluted graphene oxide aqueous solution and the CoMo LDH polyhedral material were directly mixed together and kept under stirring for 10 minutes. The mass ratio of the graphene oxide to the CoMo LDH polyhedral material is controlled to be 1: 1;
(7) the mixture was then hydrothermally treated at 120 ℃ for 12 hours. Centrifuge for 10 minutes and the pellet is washed three times with deionized water. Thereafter, the solid precipitate was collected and dried overnight at 60 ℃ to obtain a comosldh @ GO polyhedral material. Then annealing the CoMo LDH @ GO polyhedral material at 350 ℃ for 2 hours (5 ℃ C. min) under flowing nitrogen-1) To produce hollow CoO/Co2Mo3O8@ RGO composite.
(8) The obtained CoO/Co2Mo3O8@ RGO composite was thoroughly ground, mixed with carbon black (Super-P), polyvinylidene fluoride (PVDF) in a weight ratio of 8: 1:1, N-methyl-2-pyrrolidone (NMP) as a solvent, and grinding the material for 30 minutes to form a slurry.The negative electrode was prepared by coating on a pure copper foil (99.6%) uniformly by a coating method and dried overnight under vacuum at 80 c, and electrochemical test was performed using a button type half cell using a pure lithium sheet as a counter electrode. Fig. 1 is a TEM image of a CoMo LDH nanosheet assembled hollow polyhedron of the present embodiment, and it can be observed from fig. 1 that a CoMo LDH hollow polyhedron with an average diameter of 900nm is obtained by the present embodiment, and after proper etching, the CoMo LDH hollow polyhedron has a large morphological specific surface area, non-overlapping layered structures, abundant open channels, and excellent properties such as capacitance and conductivity, and is suitable for constructing other high-performance materials. From the Scanning Electron Microscope (SEM) image of fig. 2, it can be known that the two-dimensional nanosheet of the layered double hydroxide derivative with positive charges, which is effectively wrapped by the graphene, is processed into a three-dimensional hollow frame; the cycle performance diagram and the rate performance diagram are respectively shown in FIGS. 3 and 4, and as can be seen from FIG. 3, the negative electrode material prepared by the invention has high reversible capacity at 100mA · g-1The capacity of the battery can reach 242mAh g under charging and discharging current-1(ii) a As can be seen from FIG. 4, the current density was switched back to 100mA g at the 90 th cycle-1Then, 211.5mAh g was maintained-1The capacity of the graphene coated CoO/Co prepared by the method indicates that the novel electrode has excellent structural stability and rate capability, so that the graphene coated CoO/Co prepared by the method has the advantages of high stability, high yield and high stability2Mo3O8The @ RGO composite material has potential application prospects in the field of lithium ion batteries.
Example 2:
preparation of graphene coated CoO/Co2Mo3O8@ RGO composite:
(1) 0.33 g of Co (NO)3)2·6H2O was dissolved in 45 ml of methanol, and 90ml of a methanol solution containing 0.37 g of 2-methylimidazole was rapidly added thereto;
(2) stirring the mixture for 2 hours and aging at 25 ℃ for 24 hours, collecting the purple product by centrifugation, washing several times with methanol, and drying overnight at 60 ℃ to obtain ZIF-67 nanocrystals;
(3) dispersing 45.0 mg of ZIF-67 nanocrystals in a medium containing 100.0 mg of Na2MoO4·2H2Of OAdding 30ml of ethanol solution, stirring for 10 minutes, and carrying out ultrasonic treatment for 1 minute;
(4) the product was collected by centrifugation and redispersed in 25ml of water. The reaction vessel was then held at 85 ℃ for 12 minutes until the purple color disappeared. Centrifuging again to obtain green precipitate, washing with ethanol for three times, and drying at 60 ℃ overnight to obtain a CoMo LDH polyhedral material;
(5) taking 1.30ml of 6.93mg/ml graphene oxide aqueous solution, adding 25ml of water into the graphene oxide aqueous solution to prepare 0.34mg/ml graphene oxide aqueous solution;
(6) the diluted graphene oxide aqueous solution and the CoMo LDH polyhedral material were directly mixed together and kept under stirring for 10 minutes. The mass ratio of the graphene oxide to the CoMo LDH polyhedral material is controlled to be 1: 1.5;
(7) the mixture was then hydrothermally treated at 120 ℃ for 12 hours. Centrifuge for 10 minutes and the pellet is washed three times with deionized water. Thereafter, the solid precipitate was collected and dried overnight at 60 ℃ to obtain a comosldh @ GO polyhedral material. Then annealing the CoMo LDH @ GO polyhedral material at 350 ℃ for 2 hours (5 ℃ C. min) under flowing nitrogen-1) To produce hollow CoO/Co2Mo3O8@ RGO composite.
Example 3:
preparation of graphene coated CoO/Co2Mo3O8@ RGO composite:
(1) 0.33 g of Co (NO)3)2·6H2O was dissolved in 45 ml of methanol, and 90ml of a methanol solution containing 0.37 g of 2-methylimidazole was rapidly added thereto;
(2) stirring the mixture for 2 hours and aging at 25 ℃ for 24 hours, collecting the purple product by centrifugation, washing several times with methanol, and drying overnight at 60 ℃ to obtain ZIF-67 nanocrystals;
(3) dispersing 60.0 mg of ZIF-67 nanocrystals in a medium containing 100.0 mg of Na2MoO4·2H2O in 30ml ethanol solution, stirring for 10 minutes, and carrying out ultrasonic treatment for 1 minute;
(4) the product was collected by centrifugation and redispersed in 25ml of water. The reaction vessel was then held at 85 ℃ for 12 minutes until the purple color disappeared. Centrifuging again to obtain green precipitate, washing with ethanol for three times, and drying at 60 ℃ overnight to obtain a CoMo LDH polyhedral material;
(5) taking 1.30ml of 6.93mg/ml graphene oxide aqueous solution, adding 25ml of water into the graphene oxide aqueous solution to prepare 0.34mg/ml graphene oxide aqueous solution;
(6) the diluted graphene oxide aqueous solution and the CoMo LDH polyhedral material were directly mixed together and kept under stirring for 10 minutes. The mass ratio of the graphene oxide to the CoMo LDH polyhedral material is controlled to be 1: 2;
(7) the mixture was then hydrothermally treated at 120 ℃ for 12 hours. Centrifuge for 10 minutes and the pellet is washed three times with deionized water. Thereafter, the solid precipitate was collected and dried overnight at 60 ℃ to obtain a comosldh @ GO polyhedral material. Then annealing the CoMo LDH @ GO polyhedral material at 350 ℃ for 2 hours (5 ℃ C. min) under flowing nitrogen-1) To produce hollow CoO/Co2Mo3O8@ RGO composite.
Example 4:
compared with example 1, most of the same except that in this example, 90ml of a methanol solution containing 0.37 g of 2-methylimidazole was changed to 90ml of a methanol solution containing 0.3 g of 2-methylimidazole.
Example 5:
compared with example 1, most of the same except that in this example, 90ml of a methanol solution containing 0.37 g of 2-methylimidazole was changed to 90ml of a methanol solution containing 0.4 g of 2-methylimidazole.
Example 6:
compared to example 1, most of them are the same except that in this example, 0.33 g Co (NO) is used3)2·6H2Changing the O dissolved in 45 ml of methanol to 0.2 g of Co (NO)3)2·6H2O was dissolved in 30ml of methanol.
Example 7:
compared to example 1, most of them are the same except that in this example, 0.33 g Co (NO) is used3)2·6H2Changing the O dissolved in 45 ml of methanol to 0.4 g of Co (NO)3)2·6H2O was dissolved in 50 ml of methanol.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a graphene-coated layered double hydroxide derivative composite material is characterized by comprising the following steps:
(1) dispersing a cobalt source in methanol, adding an accelerant, stirring, aging, washing and drying to obtain a ZIF-67 nanocrystal;
(2) mixing ZIF-67 nanocrystals with a molybdenum source, centrifuging to obtain a solid, dispersing the obtained solid in water, reacting, washing and drying to obtain a CoMo LDH polyhedral material;
(3) mixing a graphene oxide aqueous solution with the obtained CoMo LDH polyhedral material, and then carrying out hydrothermal treatment, washing and drying to obtain a CoMo LDH @ GO polyhedral material;
(4) and calcining the obtained CoMo LDH @ GO polyhedral material to obtain the target product.
2. The preparation method of the graphene-coated layered double hydroxide derivative composite material according to claim 1, wherein in the step (1), the cobalt source is cobalt nitrate hexahydrate, and the accelerator is a methanol solution of 2-methylimidazole;
the mass-volume ratio of 2-methylimidazole to methanol in the methanol solution of 2-methylimidazole is (0.3-0.4) g: 90ml, the ratio of the addition amounts of cobalt nitrate hexahydrate, methanol and a methanol solution of 2-methylimidazole is (0.2-0.4) g: (30-50) ml: 90 ml.
3. The preparation method of the graphene-coated layered double hydroxide derivative composite material according to claim 1, wherein in the step (1), the stirring time is 2 hours, the aging time is 24 hours, and the aging temperature is 25 ℃.
4. The method for preparing the graphene-coated layered double hydroxide derivative composite material according to claim 1, wherein in the step (2), the molybdenum source is an ethanol solution of sodium molybdate dihydrate;
the mass-volume ratio of the sodium molybdate dihydrate to the ethanol in the ethanol solution of the sodium molybdate dihydrate is 100 mg: 30ml, wherein the adding amount ratio of the ZIF-67 nano crystal, the ethanol solution of sodium molybdate dihydrate and water is (30-60) mg: 30 ml: 25 ml.
5. The method for preparing the graphene-coated layered double hydroxide derivative composite material according to claim 1, wherein in the step (2), the reaction temperature is 85 ℃ and the reaction time is 12 min.
6. The method for preparing a graphene-coated layered double hydroxide derivative composite material according to claim 1, wherein in the step (3), the concentration of the graphene oxide aqueous solution is 0.34mg/ml, and the mass ratio of the graphene oxide to the CoMo LDH polyhedral material is 1: (1-2).
7. The preparation method of the graphene-coated layered double hydroxide derivative composite material according to claim 1, wherein in the step (3), the hydrothermal temperature is 120 ℃ and the hydrothermal time is 12 hours.
8. The method for preparing the graphene-coated layered double hydroxide derivative composite material according to claim 1, wherein in the step (4), the calcination is performed in a nitrogen atmosphere, the calcination temperature is 350 ℃, the calcination time is 2h,the heating rate is 5 ℃ min-1。
9. A graphene-coated layered double hydroxide derivative composite material, which is prepared by the preparation method according to any one of claims 1 to 8.
10. The application of the graphene-coated layered double hydroxide derivative composite material according to claim 9, wherein the composite material is used in the field of lithium ion batteries.
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