CN111613787A - Titanium dioxide coated carbon-cobaltosic oxide composite material, preparation method and application thereof - Google Patents
Titanium dioxide coated carbon-cobaltosic oxide composite material, preparation method and application thereof Download PDFInfo
- Publication number
- CN111613787A CN111613787A CN202010477895.3A CN202010477895A CN111613787A CN 111613787 A CN111613787 A CN 111613787A CN 202010477895 A CN202010477895 A CN 202010477895A CN 111613787 A CN111613787 A CN 111613787A
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- zif
- cobaltosic oxide
- titanium dioxide
- composite material
- carbon
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 154
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000011257 shell material Substances 0.000 claims abstract description 18
- 239000011258 core-shell material Substances 0.000 claims abstract description 13
- 210000002969 egg yolk Anatomy 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 27
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000013601 eggs Nutrition 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 15
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 9
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- 238000003917 TEM image Methods 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
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- 150000004706 metal oxides Chemical class 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
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- 238000011282 treatment Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
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- -1 enamel Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
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- 238000001338 self-assembly Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 241001481789 Rupicapra Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 239000012300 argon atmosphere Substances 0.000 description 1
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- 239000003990 capacitor Substances 0.000 description 1
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- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a titanium dioxide coated carbon-cobaltosic oxide composite material, a preparation method and application thereof, wherein the composite material has a yolk shell structure, yellow is a carbon-cobaltosic oxide core-shell material, egg is a titanium dioxide material, the carbon-cobaltosic oxide core-shell material has a core of cobaltosic oxide and a shell of a carbon layer which is coated outside the cobaltosic oxide after ZIF-67 high-temperature carbonization. The preparation method is simple, the operation is simple, the prepared composite material has the characteristics of uniform size, controllable appearance, good conductivity and the like, and the composite material shows excellent electrochemical performance in electrochemical aspects such as lithium ion batteries, electrocatalysis, supercapacitors and the like.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to TiO with a yolk shell structure2@C-Co3O4Composite material, preparation method and application.
Background
Metal-Organic Frameworks (MOFs), which are Organic-inorganic hybrid materials with intramolecular pores formed by self-assembly of Organic ligands and Metal ions or clusters through coordination bonds. As a novel porous material developed in recent years, MOFs have many advantages such as large specific surface area, high porosity, and various types, and different types of MOFs have been prepared in the past years, and have important applications in the fields of hydrogen storage, gas adsorption and separation, sensors, drug release, catalytic reactions, and the like. Zeolite-like framework materials (ZIFs) are novel zeolite-like materials with a regular microporous network structure, which are formed by self-assembly of inorganic metal ions and nitrogen-containing polydentate organic ligands through coordination, and are porous crystal materials. In which organic imidazolate is cross-linked to a transition metal to form a tetrahedral framework. In recent years, a variety of methods have been developed to synthesize ZIFs of different sizes, morphologies, and compositions, such as microfluidics, xerogel methods, electrospray, mechanochemical formulations, sonochemical reactions, electrochemical synthesis, and the like. ZIF-67 is a special ZIF material and is formed by reacting cobalt nitrate hexahydrate with dimethyl imidazole, and due to the special properties and structural characteristics of the ZIF-67 material, researchers have conducted treatments under different conditions in recent years, so that the ZIF-67 material has excellent properties in the aspects of batteries, supercapacitors, electrocatalysis and the like.
Titanium dioxide is a white solid or powdered amphoteric oxide, also called titanium dioxide, chemical formula TiO2The molecular weight is 79.9, the melting point is 1830-1850 ℃, and the boiling point is 2500-3000 ℃. There are three variants of titanium dioxide that exist in nature: rutile is a tetragonal crystal; anatase is a tetragonal crystal; brookite is an orthorhombic crystal. The titanium dioxide has the advantages of low cost, good chemical stability, large specific surface area, high photocatalytic efficiency, no secondary pollution and the like, is a material with wide application and great potential, is widely applied to paint, paper, rubber, plastic, enamel, glass, cosmetics, printing ink, watercolor and oil color pigments, and can also be used in the wide fields of metallurgy, radio, ceramics, welding electrodes, electrochemistry and the like.
However, since the zeolite-like framework material is easy to collapse under high-temperature calcination, the conventional calcination method cannot maintain the conventional morphology of the ZIF material, so that a surface carbon layer and a metal oxide are easy to separate after the ZIF material is subjected to high temperature, and the carbon material cannot protect the metal oxide. Titanium dioxide, while providing good capacity in energy storage systems, particularly lithium batteries, has been plagued by poor conductivity and volume expansion during charging and discharging.
In recent years, with the intensive research on new materials by researchers, more and more multifunctional composite materials emerge, and the composite materials of various metal oxides are always the research objects of universities and factories. Bimetallic metal oxides have great potential in electrochemical applications.
Disclosure of Invention
The invention aims to provide titanium dioxide coated carbon-cobaltosic oxide (TiO) with low preparation cost, simple equipment requirement, uniform appearance and good conductivity2@C-Co3O4) Composite materials and methods for making the same.
The invention achieves the purposeThe technical scheme is as follows: a titanium dioxide coated carbon-cobaltosic oxide composite material has a yolk shell structure, wherein yellow is carbon-cobaltosic oxide (C-Co)3O4) The eggs are titanium dioxide materials.
Preferably, the carbon-cobaltosic oxide core-shell material has a cobaltosic oxide core and a ZIF-67 shell which is a carbon layer coated outside the cobaltosic oxide after high-temperature carbonization.
A preparation method of a titanium dioxide coated carbon-cobaltosic oxide composite material comprises the following steps:
1) uniformly dispersing ZIF-67 in a mixed solution of absolute ethyl alcohol and acetonitrile, adding a certain amount of Cetyl Trimethyl Ammonium Bromide (CTAB) and a small amount of ammonia water, and stirring for 30min to obtain a solution 1;
2) adding tetrabutyl titanate (TBT) into a mixed solution of absolute ethyl alcohol and acetonitrile, and then violently stirring to obtain a solution 2;
3) rapidly adding the solution 2 into the solution 1, stirring vigorously for a period of time, adding a small amount of ammonia water again, slowing down the stirring speed, continuously stirring for a period of time, centrifuging the mixture, washing, and drying in vacuum to obtain titanium dioxide coated ZIF-67 (TiO)2@ ZIF-67) composite material;
4) calcining the material obtained in the step 3) at high temperature under the protection of argon to obtain titanium dioxide coated carbon-cobaltosic oxide (TiO)2@C-Co3O4) A composite material.
Preferably, in the step 1), the volume ratio of the absolute ethyl alcohol to the acetonitrile is 2:1, the concentration of the ZIF-67 is 2-5mg/mL when the ZIF-67 is dispersed in a mixed solution of the ethyl alcohol and the acetonitrile, the mass ratio of the ZIF-67 to the hexadecyl trimethyl ammonium bromide is 2:1, and a small amount of ammonia water is added to adjust the pH value to be 8-9.
Preferably, in the step 2), the volume ratio of the absolute ethyl alcohol to the acetonitrile is 1:1, and the volume ratio of the TBT to the mixed solution of the absolute ethyl alcohol and the acetonitrile is 1: 40.
Preferably, in the step 3), the vigorous stirring time is 20-30 min, a small amount of ammonia water is added to adjust the pH value to 8-9, and the slow stirring time is 10-12 h.
Preferably, the mass ratio of ZIF-67 to tetrabutyl titanate is 1: 5.
Preferably, in step 4), the calcination is performed at a high temperature of 700-800 ℃ for 3-5 hours.
The invention also discloses the TiO2@C-Co3O4The composite material is applied to lithium ion batteries, electrocatalysis and supercapacitors.
Compared with the prior art, the process has the advantages that: the preparation method is simple, the operation is simple and convenient, the raw materials are easy to obtain, and the cost is lower. Prepared TiO2@C-Co3O4The composite material has uniform appearance, good conductivity, higher specific surface area and large pore volume, and can accelerate the shuttling of lithium ions on one hand, and C-Co formed after the ZIF-67 is carbonized3O4Not only increased material conductivity, still provided electron transmission channel, unique titanium dioxide protective layer plays the supporting role, makes the difficult collapse of material. On the other hand due to TiO2And Co3O4The catalyst has rich catalytic active centers, good chemical stability and high specific capacitance. Therefore, the material has good prospects in the aspects of lithium ion batteries, supercapacitors, electrocatalysis and the like.
Drawings
FIG. 1 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of ZIF-67 prepared using the present invention.
FIG. 2 shows a ZIF-67 (TiO) coated spherical titanium dioxide with a core-shell structure prepared by the present invention2@ ZIF-67) scanning Electron micrograph (a) and Transmission Electron micrograph (b) of the composite material.
FIG. 3 shows a preparation of a titanium dioxide coated carbon-cobaltosic oxide (TiO) with a yolk shell structure according to the present invention2@C-Co3O4) Scanning electron micrographs (a) and transmission electron micrographs (b) of the composite.
FIG. 4 shows ZIF-67, TiO compounds prepared by the present invention2@ ZIF-67 and TiO2@C-Co3O4X-ray diffraction pattern of (a).
FIG. 5 shows TiO prepared by the present invention2@ ZIF-67 and TiO2@C-Co3O4The impedance diagram of the lithium ion battery cathode material with the model number CR2032 is taken.
FIG. 6 shows TiO prepared by the present invention2@C-Co3O4Linear Sweep Voltammetry (LSV) curves measured as electrode materials in electrocatalytic Oxygen Evolution (OER).
FIG. 7 shows TiO prepared by the present invention2@C-Co3O4Constant current charge-discharge curve measured as electrode material in a supercapacitor.
FIG. 8 shows TiO prepared by the present invention2@C-Co3O4The charge-discharge curve is measured in a CR2032 button cell as the negative electrode material of the lithium ion battery.
Detailed Description
The invention is further elucidated with reference to the figures and embodiments.
The invention relates to a preparation method of a titanium dioxide coated carbon-cobaltosic oxide composite material, which is characterized in that amorphous titanium dioxide coated MOF material is carbonized at high temperature to form rutile type titanium dioxide coated carbon-cobaltosic oxide (TiO) with a yolk shell structure2@C-Co3O4) A composite material comprising the steps of:
1) ZIF-67 was prepared.
Respectively dissolving cobalt nitrate and dimethyl imidazole in a methanol solution, pouring the methanol solution of dimethyl imidazole into the methanol solution of cobalt nitrate, violently stirring for 24 hours, and drying to obtain the ZIF-67 with uniform morphology.
2) Preparation of spherical titanium dioxide-coated ZIF-67 (TiO) with core-shell structure2@ ZIF-67) composite material.
Uniformly dispersing the dried ZIF-67 in a mixed solution of absolute ethyl alcohol and acetonitrile, adding a certain amount of Cetyl Trimethyl Ammonium Bromide (CTAB) and a small amount of ammonia water, and stirring for about 30 min. Taking a test tube, adding a certain amount of absolute ethyl alcohol and acetonitrile in an anhydrous environment, stirring to uniformly mix, adding tetrabutyl titanate (TBT), and then violently stirring to obtain a yellow transparent solution. Dissolving yellow transparent solutionQuickly adding the solution into a beaker containing ZIF-67, vigorously stirring for a period of time, adding a small amount of ammonia water again, slowing down the stirring speed, continuously stirring for a period of time, centrifuging the mixture, washing, and vacuum drying to obtain solid titanium dioxide coated ZIF-67 (TiO)2@ ZIF-67) composite material.
3) Preparation of titanium dioxide-coated carbon-cobaltosic oxide (TiO) with yolk shell structure2@C-Co3O4) A composite material.
Adding TiO into the mixture2The @ ZIF-67 composite material is moved into a tubular furnace and calcined at high temperature under the protection of argon to obtain titanium dioxide coated carbon-cobaltosic oxide (TiO)2@C-Co3O4) A composite material.
The invention also discloses the TiO2@C-Co3O4A method for producing a composite material, comprising the steps of 1) to 3) described above.
In the step 1) of the method, the amount of cobalt nitrate is 2mmol, the amount of dimethyl imidazole is 8mmol, the cobalt nitrate and the dimethyl imidazole are respectively dissolved in 50mL of methanol solution, the methanol solution of dimethyl imidazole with 8mmol is poured into the methanol solution of cobalt nitrate with 2mmol, and the mixture is vigorously stirred for 24 hours, at this time, 100mL of methanol provides enough reaction environment for the formation of ZIF-67, so that the generated ZIF-67 cannot be agglomerated due to too little methanol in the reaction environment, and the cobalt nitrate and the dimethyl imidazole completely react under the environment. If the amount of methanol is continuously increased, it will result in a waste of methanol. Under the condition, the ZIF-67 has high yield (about 110 mg), uniform size and uniform appearance.
In the step 2) of the method, the dried ZIF-67 with the concentration of about 100mg is uniformly dispersed in a mixed solution of 30mL of anhydrous ethanol and 15mL of acetonitrile (TBT has a particularly high hydrolysis rate, so that the ethanol needs to be treated by anhydrous sodium sulfate in order to prevent the reaction from being damaged by excessive water in the ethanol). CTAB is 50mg, on one hand, the addition of CTAB can increase the dispersity of ZIF-67 in a mixed solution and reduce the agglomeration degree of a final reaction product, on the other hand, TBT can generate orthotitanic acid and metatitanic acid in the hydrolysis process, and the addition of CTAB can increase counter cations on the surface of ZIF-67,the TiO finally generated after hydrolyzing orthotitanic acid and metatitanic acid2A protective layer is more easily formed on the surface of ZIF-67. To create an alkaline environment and to provide a small water source to slowly hydrolyze the TBT, 0.5mL of ammonia was added. In another test tube, 10mL of absolute ethyl alcohol and 10mL of acetonitrile are added and stirred to be uniformly mixed, in order to prevent the titanium dioxide layer from being too thick and increasing the insulation property of the material, and prevent the generated titanium dioxide from being too much and forming balls independently, and the generated titanium dioxide cannot well coat ZIF-67 and cannot form a titanium dioxide protective layer due to too little TBT, a large number of experiments show that the addition of 0.5mL of tetrabutyl titanate (TBT) is most suitable, and a yellow transparent solution is obtained by vigorous stirring. And quickly adding the yellow transparent solution into a mixed solution containing ZIF-67, and stirring for about 20min to ensure that titanium dioxide generated by the slow hydrolysis of TBT generates a protective layer on the surface of the ZIF-67. Thereafter, 0.5mL of aqueous ammonia was added, and the reaction was terminated after stirring for 12 hours to complete hydrolysis of TBT. Since TBT hydrolyzes very rapidly, the reaction is completed in a glove box during the reaction to avoid water-borne influences in the air. Centrifuging the reaction product, washing the reaction product for 2 to 3 times by acetonitrile, and drying to obtain spherical TiO with a core-shell structure and uniform appearance2@ ZIF-67 composite (in this case titanium dioxide is amorphous titanium dioxide).
In the step 3) of the method, the conditions of high-temperature calcination are as follows: under the protection of argon, the temperature of the tube furnace is raised to 750 ℃ at the rate of 3 ℃/min and is kept for 3 hours. Under the condition, the titanium dioxide is changed into a rutile type with a tetragonal crystal at high temperature, the smooth surface of the titanium dioxide is rough due to the change of the crystal form of the titanium dioxide at high temperature, and the volume of the titanium dioxide is slightly expanded at high temperature. While ZIF-67 is carbonized at high temperature (crystal structure of ZIF-67 is changed and crystal form collapses at high temperature) to generate carbon film and cobaltosic oxide (C-Co)3O4) Resulting in a change in the microstructure of the original MOF and a reduction in volume, thereby forming a TiO yolk shell structure with a unique protective layer of titanium dioxide2@C-Co3O4A composite material.
To avoid environmental pollutionWater, etc. cause the TBT to hydrolyze too fast to destroy the material, and the reaction environment must be anhydrous and protected with a protective gas (therefore we chose to carry out the reaction in a glove box under a high purity argon atmosphere). In order to react to obtain TiO with uniform appearance, good structure and good conductivity2@C-Co3O4The amounts of the composite material, the reaction reagent and the medicine must be strictly reacted according to the charge ratio described in the above steps.
Example 1
1) Preparation of ZIF-67
Taking a beaker with the measuring range of 150mL, adding 2mmol of cobalt nitrate (about 580-585 mg) and 50mL of methanol into the beaker, and stirring to completely dissolve the cobalt nitrate in the methanol solution for later use; in addition, a centrifuge tube with a measuring range of 50mL is taken, 50mL of methanol and 8mmol of dimethylimidazole (about 650-660 mg) are added, and ultrasonic treatment is carried out for about 10min, so that the dimethylimidazole is completely dissolved in the methanol solution. The methanolic dimethylimidazole solution in the centrifuge tube was then quickly poured into a beaker containing methanolic cobalt nitrate, vigorously stirred for 24 hours, the purple mixture was centrifuged, washed 2-3 times with methanol, and dried to yield a purple ZIF-67 solid with a yield of about 110 mg.
2) Preparation of spherical titanium dioxide-coated ZIF-67 (TiO) with core-shell structure2@ ZIF-67) composite material.
All of the tests were carried out in a glove box which was anhydrous and provided with a protective atmosphere. Firstly, 100mg of ZIF-67 solid is weighed and dissolved in a mixed solution of 30mL of anhydrous ethanol (commercial ethanol contains a small amount of water, which can damage subsequent experiments, and therefore a certain amount of anhydrous sodium sulfate needs to be added for drying treatment) and 15mL of acetonitrile, and after the ZIF-67 is uniformly dispersed, about 50mg of CTAB and 0.5mL of ammonia water are added, and the mixture is continuously stirred for later use. Then taking a 50mL centrifuge tube, adding 0.5mL tetrabutyl titanate (TBT) into the centrifuge tube to uniformly disperse the tetrabutyl titanate in 10mL absolute ethyl alcohol and 10mL acetonitrile, quickly adding the tetrabutyl titanate into the mixed solution containing ZIF-67 to stir for about 20min after the tetrabutyl titanate becomes yellow transparent solution, then dropwise adding 0.5mL ammonia water into the reaction system again, stirring for about 12 hours under a closed state, and finishing when the purple solid becomes light purpleAnd (4) reacting. Centrifuging the reaction product, washing the reaction product for 2 to 3 times by acetonitrile, and drying to obtain spherical TiO with a core-shell structure and uniform appearance2@ ZIF-67 composite material.
3) Preparation of titanium dioxide-coated carbon-cobaltosic oxide (TiO) with yolk shell structure2@C-Co3O4) A composite material.
The prepared TiO is mixed2@ ZIF-67 composite material was transferred to a tube furnace and heated to 750 ℃ under argon shielding at a rate of 3 ℃/min and held for 3 hours. After the high-temperature reaction is finished, obtaining black brown solid powder TiO2@C-Co3O4A composite material.
4) Preparation of electrode material in electrocatalytic oxygen evolution.
First, Al with a particle size of 50nm is used2O3The aqueous solution of (polishing powder) was buffed on a chamois leather to make the surface of a glassy carbon electrode (GC electrode) smooth and clean. And then ultrasonically washing the substrate in deionized water and absolute ethyl alcohol for 5-10min, and naturally airing the substrate at room temperature to obtain a clean GC electrode. Then 4mg of TiO are weighed2@C-Co3O4The composite material is prepared by adding 1000 microliters of a mixture of water and ethanol at a ratio of 2:1 and 120 microliters of a 5wt% Nafion mixture, and ultrasonically mixing the mixture uniformly. And finally, measuring 5 microliters of solution by using a liquid transfer gun, dropwise adding the solution to the center of the glassy carbon electrode, and naturally airing at room temperature to test on an electrochemical workstation.
5) And preparing an electrode material in the super capacitor.
Adding TiO into the mixture2@C-Co3O4The composite material and acetylene black or super P are ground according to the weight ratio of 80: 15, 5mL of isopropanol is added after the composite material and the acetylene black or super P are uniformly ground, the grinding is continued, and then a drop of Polytetrafluoroethylene (PTFE) emulsion is added into the mixture to form mixed slurry. The slurry was applied to a previously prepared nickel foam over an area of about 1cm2And flattening the sample by using a tablet press after the sample is dried. The experimental conditions are as follows: the three-electrode system comprises a working electrode, a counter electrode, a reference electrode and a three-electrode system, wherein the working electrode is foamed nickel coated with active substances, the counter electrode is a platinum electrode, and the reference electrode is an Hg/HgO electrode or 3M KOH
The aqueous solution was used as an electrolyte and the test was performed on an electrochemical workstation.
6) Preparation of electrode materials in lithium ion batteries and battery assembly.
Weighing the above TiO2@C-Co3O4Grinding the composite material (60 mg) and the conductive agent carbon black (30 mg) in a mortar uniformly, adding a binder (the binder is PVDF and is added by about 10 mg), mixing uniformly, coating on a copper foil, and drying in a vacuum drying oven; after drying, the pieces were cut with a slitter, the mass of each piece was weighed and recorded, and then assembled into a cell model CR2032 in a glove box, and further tested for performance on an electrochemical workstation and a cell test system.
FIG. 1 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of ZIF-67 prepared using the present invention. From scanning and transmission images, the ZIF-67 prepared by the invention has uniform particle size, uniform appearance and smooth surface.
FIG. 2 shows a ZIF-67 (TiO) coated spherical titanium dioxide with a core-shell structure prepared by the present invention2@ ZIF-67) scanning Electron micrograph (a) and Transmission Electron micrograph (b) of the composite material. From the scanned image, TiO can be seen2@ ZIF-67 is a spherical structure with a smooth surface, because TBT is hydrolyzed into amorphous silica which is uniformly coated on the surface of bulk ZIF-67, the bulk ZIF-67 structure under the microscopic level disappears. The transmission diagram shows that the inner core of the composite material is blocky ZIF-67, the outer layer is a smooth silica protective layer, and the silica is tightly attached to the surface of the ZIF-67, so that the composite material with the core-shell structure is formed.
FIG. 3 shows a preparation of a titanium dioxide coated carbon-cobaltosic oxide (TiO) with a yolk shell structure according to the present invention2@C-Co3O4) Scanning electron micrographs (a) and transmission electron micrographs (b) of the composite. After the high-temperature calcination at 750 ℃, the smooth amorphous titanium dioxide can be gradually changed into rough rutile type titanium dioxide, and the titanium dioxide has high strength, and the high temperature can not greatly change the appearance, so that the scanning electron microscope picture can show that the composite material still maintains the composite materialSpherical structure with TiO2@ ZIF-67 except that the smooth surface becomes rough. It is obvious from the transmission electron microscope picture that a larger space is formed between the titanium dioxide shell and the inner core, which is probably because the ZIF-67 is changed into a mixture of carbon and cobaltosic oxide under high-temperature calcination, the appearance is changed, the ZIF-67 structure is collapsed, the volume is reduced, and the volume is not changed greatly with the temperature because the strength of the titanium dioxide shell is higher, but the TiO with the yolk shell structure with rough appearance is formed2@C-Co3O4A composite material.
FIG. 4 shows ZIF-67, TiO compounds prepared by the present invention2@ ZIF-67 and TiO2@C-Co3O4X-ray diffraction pattern of (a). Due to TiO2@ ZIF-67 titanium dioxide is amorphous titanium dioxide, so TiO is in XRD2@ ZIF-67 showed only the characteristic peak of ZIF-67. After high-temperature treatment, in TiO2@C-Co3O4The characteristic peak of medium ZIF-67 disappears and instead the characteristic peaks of titanium dioxide appear at diffraction angles of 28 ° and 55 °, indicating that the amorphous titanium dioxide forms rutile titanium dioxide after the high temperature reaction. A typical Co appears at a diffraction angle of about 36 DEG3O4And a carbon peak appears at about 76 degrees, which indicates that the high-temperature carbonization of the ZIF-67 forms C and Co3O4. Therefore, the composite material is a carbon-cobaltosic oxide composite material coated by titanium dioxide under high-temperature reaction.
FIG. 5 shows TiO prepared by the present invention2@ ZIF-67 and TiO2@C-Co3O4The impedance diagram of the lithium ion battery cathode material with the model number CR2032 is taken. The TiO is evident from the impedance diagram2@C-Co3O4The impedance of the material as the lithium battery cathode material is far less than that of TiO2@ ZIF-67, since in TiO2In @ ZIF-67, both ZIF-67 and titanium dioxide are poor conductive substances. And TiO 22@ ZIF-67 high-temperature calcining, ZIF-67 carbonizing to form C-Co3O4The existence of carbon improves the conductivity of the composite material and accelerates electron transfer, compared with TiO with a core-shell structure2@ZIF67, electrolyte more easily penetrates TiO with hollow yolk shell structure2@C-Co3O4The composite material is more suitable for electrochemical research.
FIG. 6 shows TiO prepared by the present invention2@C-Co3O4Linear Sweep Voltammetry (LSV) curves measured as electrode materials in electrocatalytic Oxygen Evolution (OER). Judging whether the OER activity of a material is good or bad, and the key point is that the current is 10mA cm-2The corresponding voltage, TiO is obviously seen in the LSV curve2@C-Co3O4When used as an electrode material, the current is 10mA cm-2When the voltage is 1.629V, good OER activity is shown.
FIG. 7 shows TiO prepared by the present invention2@C-Co3O4Constant current charge-discharge curve measured as electrode material in a supercapacitor. The shape of the curve indicates TiO2@C-Co3O4Is a pseudocapacitance based on redox reactions. At a current density of 0.5A/g, TiO2@C-Co3O4Has a specific capacitance of about 154Fg-1. Good reaction kinetics are shown, which is likely related to the particular nanostructure the material possesses.
FIG. 8 shows TiO prepared by the present invention2@C-Co3O4The charge-discharge curve is measured in a CR2032 button cell as the negative electrode material of the lithium ion battery. TiO 22@C-Co3O4The lithium ion battery cathode material shows excellent electrochemical performance, and 700 mAhg is obtained after the lithium ion battery cathode material is cycled for 300 circles under the current density of 500 mA/g-1The specific capacity and the coulombic efficiency are about 100 percent. From the figure, the initial specific capacity of the material is only 480mAhg-1On the other hand, the specific capacity gradually increases with the increase in the number of cycles, which may be due to C-Co3O4The pulverization process increases the specific surface of the composite material, makes full use of the active substances, and prevents the C-Co from being generated because the titanium dioxide has higher strength and plays a role of a protective layer3O4Excessive losses lead to reduced battery life; on the other hand, theThe material shows good battery performance related to the structure of the material, the rough titanium dioxide surface can promote the wettability of electrolyte to the material, a unique electron transmission channel is provided, and the yolk shell structure adapts to the volume expansion of titanium dioxide and cobaltosic oxide in the charge and discharge processes, so that the material shows good electrochemical performance.
The above examples are further illustrative of the present invention and are not intended to limit the scope of the present invention. Various modifications and changes may be made in the parameters of the present embodiment without departing from the entire technical scope of the present invention.
Claims (10)
1. The titanium dioxide-coated carbon-cobaltosic oxide composite material is characterized by having a yolk shell structure, wherein yellow is a carbon-cobaltosic oxide core-shell material, and eggs are titanium dioxide materials.
2. The titanium dioxide-coated carbon-cobaltosic oxide composite material as claimed in claim 1, wherein the carbon-cobaltosic oxide core-shell material comprises cobaltosic oxide as a core, and the shell is a carbon layer coated outside the cobaltosic oxide after ZIF-67 high-temperature carbonization.
3. A method for preparing the titania-coated carbon-cobaltosic oxide composite material according to claim 1 or 2, comprising the steps of:
1) uniformly dispersing ZIF-67 in a mixed solution of absolute ethyl alcohol and acetonitrile, adding a certain amount of hexadecyl trimethyl ammonium bromide and ammonia water, and stirring for 30min to obtain a solution 1;
2) adding tetrabutyl titanate into a mixed solution of absolute ethyl alcohol and acetonitrile, and then violently stirring to obtain a solution 2;
3) rapidly adding the solution 2 into the solution 1, stirring vigorously for a period of time, then adding a small amount of ammonia water again, slowing down the stirring speed, continuously stirring for a period of time, centrifuging the mixture, washing, and drying in vacuum;
4) and 3) calcining the material obtained in the step 3) at high temperature under the protection of argon to obtain the composite material.
4. The method of claim 3, wherein in step 1), the volume ratio of the absolute ethanol to the acetonitrile is 2:1, the mass ratio of the ZIF-67 to the cetyltrimethylammonium bromide is 2:1, and ammonia is added to adjust the pH value to 8-9.
5. The method of claim 3, wherein the concentration of ZIF-67 in step 1) is 2 to 5mg/mL when ZIF-67 is dispersed in a mixed solution of ethanol and acetonitrile.
6. The method according to claim 3, wherein in the step 2), the volume ratio of the absolute ethanol to the acetonitrile is 1:1, and the volume ratio of the tetrabutyl titanate to the mixed solution of the absolute ethanol and the acetonitrile is 1: 40.
7. The method as claimed in claim 3, wherein in the step 3), the vigorous stirring time is 20-30 min, a small amount of ammonia water is added to adjust the pH value to 8-9, and the slow stirring time is 10-12 h.
8. The method of claim 3, wherein the mass ratio of ZIF-67 to tetrabutyl titanate is 1: 5.
9. The method as claimed in claim 3, wherein the calcination is performed at a high temperature of 700 ℃ and 800 ℃ for 3-5 hours in the step 4).
10. Use of the titania-coated carbon-cobaltosic oxide composite of claim 1 or 2 in lithium ion batteries, electrocatalysis and supercapacitors.
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