CN111613787B - 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 PDF

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CN111613787B
CN111613787B CN202010477895.3A CN202010477895A CN111613787B CN 111613787 B CN111613787 B CN 111613787B CN 202010477895 A CN202010477895 A CN 202010477895A CN 111613787 B CN111613787 B CN 111613787B
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acetonitrile
titanium dioxide
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stirring
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CN111613787A (en
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王�琦
杨光
朱柏燃
徐清
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Yangzhou University
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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 is a carbon layer coated outside the cobaltosic oxide after ZIF-67 high-temperature carbonization. The preparation method is simple, the operation is simple and convenient, and the prepared composite material has the characteristics of uniform size, controllable appearance, good conductivity and the like, and shows excellent electrochemical properties in the electrochemical aspects of lithium ion batteries, electrocatalysis, super capacitors and the like.

Description

Titanium dioxide coated carbon-cobaltosic oxide composite material, preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to TiO with a yolk shell structure 2 @C-Co 3 O 4 Composite 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 TiO 2 The 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: the rutile is 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 in structure under high-temperature calcination, the conventional calcination means 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 conductivity 2 @C-Co 3 O 4 ) Composite materials and methods for making the same.
The technical scheme for realizing the purpose of the invention 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) 3 O 4 ) 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) Quickly 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, and continuously stirring for a period of timeAfter a certain time, the mixture was centrifuged, washed and vacuum dried 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-Co 3 O 4 ) A composite material.
Preferably, in the step 1), the volume ratio of absolute ethyl alcohol to acetonitrile is 2.
Preferably, in the step 2), the volume ratio of the absolute ethyl alcohol to the acetonitrile is 1, and the volume ratio of the TBT to the mixed solution of the absolute ethyl alcohol and the acetonitrile is 1.
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 10-12h.
Preferably, the mass ratio of ZIF-67 to tetrabutyl titanate is 1.
Preferably, in step 4), the calcination is carried out at a high temperature of 700-800 ℃ for 3-5 hours.
The invention also discloses the TiO 2 @C-Co 3 O 4 The 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 TiO 2 @C-Co 3 O 4 The 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 carbonized 3 O 4 Not 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 TiO 2 And Co 3 O 4 The catalyst has rich catalytic active centers, good chemical stability and high specific capacitance. Thus it isThe material has good prospect in lithium ion battery, super capacitor, electric catalysis and other aspects.
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 invention 2 @ 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 invention 2 @C-Co 3 O 4 ) Scanning electron micrographs (a) and transmission electron micrographs (b) of the composite.
FIG. 4 shows ZIF-67, tiO compounds prepared by the present invention 2 @ ZIF-67 and TiO 2 @C-Co 3 O 4 X-ray diffraction pattern of (a).
FIG. 5 shows TiO prepared by the present invention 2 @ ZIF-67 and TiO 2 @C-Co 3 O 4 And (3) as an impedance diagram of the cathode material of the lithium ion battery with the model number of CR 2032.
FIG. 6 shows TiO prepared by the present invention 2 @C-Co 3 O 4 Linear Sweep Voltammetry (LSV) curves measured as electrode material in electrocatalytic Oxygen Evolution (OER).
FIG. 7 shows TiO prepared by the present invention 2 @C-Co 3 O 4 Constant current charge-discharge curve measured as electrode material in a supercapacitor.
FIG. 8 shows TiO prepared by the present invention 2 @C-Co 3 O 4 The 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 a material with a yolk shell structureRutile titanium dioxide-coated carbon-cobaltosic oxide (TiO) 2 @C-Co 3 O 4 ) 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 ZIF-67 with uniform morphology.
2) Preparation of spherical titanium dioxide-coated ZIF-67 (TiO) with core-shell structure 2 @ 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. Quickly adding the yellow transparent solution into a beaker containing ZIF-67, vigorously stirring 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 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 structure 2 @C-Co 3 O 4 ) A composite material.
Adding TiO into the mixture 2 The @ 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-Co 3 O 4 ) A composite material.
The invention also discloses the TiO 2 @C-Co 3 O 4 A 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 absolute ethyl alcohol 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 on the other hand, the addition of CTAB can increase counter cations on the surface of ZIF-67, so that TiO finally generated after the hydrolysis of orthotitanic acid and metatitanic acid 2 A 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 coat ZIF-67 well 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 in order to avoid the influence of water in the air. Centrifuging the reaction product, washing with acetonitrile for 2-3 times, and dryingDrying to obtain spherical TiO with uniform appearance and core-shell structure 2 @ 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. ZIF-67 is carbonized at high temperature (the crystal structure of ZIF-67 is changed, and the crystal form collapses at high temperature) to generate carbon film and cobaltosic oxide (C-Co) 3 O 4 ) 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 dioxide 2 @C-Co 3 O 4 A composite material.
In order to avoid the material damage caused by too fast hydrolysis of TBT due to water and other factors in the environment, the reaction environment must be anhydrous and protected by protective gas (therefore we chose to carry out the reaction in a glove box under high purity argon atmosphere). In order to react to obtain TiO with uniform appearance, good structure and good conductivity 2 @C-Co 3 O 4 The 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 a 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 dimethyl imidazole (about 650-660 mg) are added, and ultrasonic treatment is carried out for about 10min, so that the dimethyl imidazole 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 structure 2 @ ZIF-67) composite material.
All this test is carried out in a glove box which is anhydrous and which has 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. And 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 after the tetrabutyl titanate becomes a yellow transparent solution, stirring for about 20min, then dropwise adding 0.5mL ammonia water into the reaction system again, stirring for about 12h in a closed state, and finishing the reaction after the purple solid becomes light purple. 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 appearance 2 @ ZIF-67 composite material.
3) Preparation of titanium dioxide-coated carbon-cobaltosic oxide (TiO) with yolk shell structure 2 @C-Co 3 O 4 ) A composite material.
The prepared TiO is mixed 2 @ ZIF-67 composite material was transferred to a tube furnace and heated to 750 ℃ under argon shielding at a heating rate of 3 ℃/min and held for 3 hours. After the high-temperature reaction is finished, obtaining black brown solid powder TiO 2 @C-Co 3 O 4 A composite material.
4) Preparation of electrode material in electrocatalytic oxygen evolution.
First, al with a particle size of 50nm is used 2 O 3 The aqueous solution of (polishing powder) was sanded on a chamois leather to smooth and clean the surface of a glassy carbon electrode (GC electrode). 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 weighed 2 @C-Co 3 O 4 The 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 mixture 2 @C-Co 3 O 4 The 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 1cm 2 And 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 TiO 2 @C-Co 3 O 4 The composite material (60 mg) and the conductive agent carbon black (30 mg) are put in a mortar and ground uniformly, then a binder (PVDF is added, about 10mg is added) is added, after uniform mixing, the mixture is coated on a copper foil and then is dried 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 battery model CR2032 in a glove box, and the performance was further tested on an electrochemical workstation and a battery 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 invention 2 @ ZIF-67) composite materialScanning electron micrographs (a) and transmission electron micrographs (b). From the scanned image, tiO can be seen 2 @ 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 invention 2 @C-Co 3 O 4 ) Scanning electron micrographs (a) and transmission electron micrographs (b) of the composite. After high-temperature calcination at 750 ℃, smooth amorphous titanium dioxide can be gradually changed into rough rutile type titanium dioxide, and the titanium dioxide has high strength, and the appearance of the titanium dioxide is not greatly changed at high temperature, so that the composite material still keeps a spherical structure and is combined with TiO as can be seen from a scanning electron microscope picture 2 @ 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 formed 2 @C-Co 3 O 4 A composite material.
FIG. 4 shows ZIF-67, tiO compounds prepared by the present invention 2 @ ZIF-67 and TiO 2 @C-Co 3 O 4 X-ray diffraction pattern of (a). Due to TiO 2 @ ZIF-67 titanium dioxide is amorphous titanium dioxide, so TiO is in XRD 2 @ ZIF-67 showed only the characteristic peak of ZIF-67. After high-temperature treatment, in TiO 2 @C-Co 3 O 4 The characteristic peak of the medium ZIF-67 disappears, and instead, the characteristic peaks of titanium dioxide appear at diffraction angles of 28 degrees and 55 degrees, which shows that the amorphous titanium dioxide forms golden red after high-temperature reactionA stone type titanium dioxide. A typical Co appears at a diffraction angle of about 36 DEG 3 O 4 The characteristic peak of the ZIF shows a carbon peak at about 76 degrees, which indicates that the high-temperature carbonization of the ZIF-67 forms C and Co 3 O 4 . 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 invention 2 @ ZIF-67 and TiO 2 @C-Co 3 O 4 The impedance diagram of the lithium ion battery cathode material with the model number CR2032 is taken. The TiO is evident from the impedance diagram 2 @C-Co 3 O 4 The impedance of the material as the lithium battery cathode material is far less than that of TiO 2 @ ZIF-67, since in TiO 2 In @ ZIF-67, both ZIF-67 and titanium dioxide are poor conductive substances. And TiO 2 2 @ ZIF-67 high-temperature calcining, ZIF-67 carbonizing to form C-Co 3 O 4 The existence of carbon improves the conductivity of the composite material and accelerates electron transfer, compared with TiO with a core-shell structure 2 @ ZIF-67, the electrolyte more easily penetrates TiO having a hollow yolk shell structure 2 @C-Co 3 O 4 The composite material is more suitable for electrochemical research.
FIG. 6 shows TiO prepared by the present invention 2 @C-Co 3 O 4 Linear 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 -2 The corresponding voltage, tiO is obviously seen in the LSV curve 2 @C-Co 3 O 4 When used as an electrode material, the current is 10mA cm -2 When the voltage is 1.629V, good OER activity is shown.
FIG. 7 shows TiO prepared by the present invention 2 @C-Co 3 O 4 Constant current charge-discharge curve measured as electrode material in a supercapacitor. The shape of the curve indicates TiO 2 @C-Co 3 O 4 Is a pseudocapacitance based on redox reactions. At a current density of 0.5A/g, tiO 2 @C-Co 3 O 4 Has a specific capacitance of about 154Fg -1 . Showing good reaction kinetics, which is likely related to the particular nanostructure the material possesses.
FIG. 8 shows TiO prepared by the present invention 2 @C-Co 3 O 4 The charge-discharge curve is measured in a CR2032 button cell as the negative electrode material of the lithium ion battery. TiO 2 2 @C-Co 3 O 4 The 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 -1 The specific capacity and the coulombic efficiency are about 100 percent. From the figure, the initial specific capacity of the material is only 480mAhg -1 On the other hand, the specific capacity gradually increases with the increase in the number of cycles, which may be due to C-Co 3 O 4 The 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 layer 3 O 4 Excessive losses lead to reduced battery life; on the other hand, the 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 egg yolk shell structure is adapted 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 (9)

1. A titanium dioxide coated carbon-cobaltosic oxide composite material is characterized in that the volume of titanium dioxide slightly expands at high temperature, ZIF-67 is carbonized at high temperature to generate a carbon film and cobaltosic oxide, the volume of original MOF is reduced, and TiO with a yolk shell structure and a titanium dioxide protective layer is formed 2 @C-Co 3 O 4 A composite material;
the preparation method comprises the following steps:
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) Calcining the material obtained in the step 3) at high temperature under the protection of argon to obtain the composite material;
in the step 1), the volume ratio of absolute ethyl alcohol to acetonitrile is 2, the mass ratio of ZIF-67 to cetyl trimethyl ammonium bromide is 2;
wherein, in the step 1), when the ZIF-67 is dispersed in the mixed solution of ethanol and acetonitrile, the concentration of the ZIF-67 is 2-5mg/mL;
in the step 2), the volume ratio of the absolute ethyl alcohol to the acetonitrile is 1;
the mass ratio of ZIF-67 to tetrabutyl titanate is 1;
in the step 4), calcining is carried out for 3-5 hours at the high temperature of 700-800 ℃.
2. A method for preparing the titania-coated carbon-cobaltosic oxide composite material according to claim 1, 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.
3. The method of claim 2, wherein in step 1), the volume ratio of the absolute ethanol to the acetonitrile is 2, the mass ratio of the absolute ethanol to the acetonitrile is 2, ZIF-67 to the cetyltrimethylammonium bromide is 2.
4. The method of claim 2, wherein the concentration of ZIF-67 when ZIF-67 is dispersed in a mixed solution of ethanol and acetonitrile in step 1) is 2-5mg/mL.
5. The method according to claim 2, wherein in the step 2), the volume ratio of the anhydrous ethanol to the acetonitrile is 1.
6. The method as claimed in claim 2, 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 10-12h.
7. The method of claim 2, wherein the mass ratio of ZIF-67 to tetrabutyl titanate is 1.
8. The method of claim 2, wherein in step 4), the calcination is performed at a high temperature of 700-800 ℃ for 3-5 hours.
9. Use of the titania-coated carbon-cobaltosic oxide composite of claim 1 in a lithium ion battery, an electrocatalysis, or a supercapacitor.
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