CN103937295A - Graphene-titanium diboride oxide compound and preparation method thereof - Google Patents

Abstract

The invention relates to a graphene-titanium diboride oxide composite and a preparation method thereof. Disperse graphite oxide in N,N-dimethylformamide, add aminated titanium diboride oxide, filter the reactant, wash, and dry to obtain a composite of titanium oxide diboride supported on the surface of graphene, Titanium diboride oxide has a core-shell structure in which the surface layer is titanium dioxide as an insulating layer and the core is conductor titanium diboride. The compound provided by the invention can form a microcapacitance structure with titanium diboride and graphene as electrodes and titanium dioxide as dielectric. Adding the compound to the polymer not only reduces the conductance loss caused by conductor contact, but also greatly increases the dielectric constant. At the same time, the surface of the composite contains a large number of active functional groups such as amino groups and hydroxyl groups, which provides a guarantee for modification and preparation of composite materials with good dispersibility. The preparation method of the composite has the characteristics of simple process, low cost, wide applicability and the like.

Description

A kind of graphene-titanium diboride oxide composite and preparation method thereof

technical field

The invention particularly relates to a graphene-titanium diboride oxide composite and a preparation method thereof, belonging to the technical field of inorganic nanomaterials.

Background technique

Graphene is a two-dimensional flake of honeycomb structure composed of carbon atoms arranged in ^sp2 hybridization, which has huge electron mobility, high thermal conductivity, excellent mechanical strength and large specific surface area. In recent years, graphene has attracted extensive attention due to its superior electrical, thermal, and mechanical properties, and has broad application potential in the fields of electronic devices, dielectric materials, and energy storage.

At present, the main method of preparing high dielectric materials is to introduce conductors into polymers. Graphene with excellent electrical properties is often introduced into polymer matrices as conductors to prepare high dielectric constant composite materials. However, since the high dielectric constant is obtained based on the percolation mechanism, the conductance loss of the material is relatively large near the percolation phenomenon, resulting in a high dielectric loss of the composite material.

So far, a method that can effectively reduce the dielectric loss of composite materials is to coat the conductor surface with an insulating layer. But this method often brings two side effects, one is the reduction of the dielectric constant. For example, Dang et al. (Dongrui Wang, Yaru Bao, Junwei Zha, Jun Zhao, Zhimin Dang, Guohua Hu. ACS Appl. Mater. Interfaces 2012; 4; 6273−6279) prepared polyvinyl alcohol-coated graphene/polyvinylidene fluoride Vinyl resin composites, found that in the case of the same graphene conductor content, the dielectric loss and dielectric constant of polyvinyl alcohol-graphene/polyvinylidene fluoride composites are lower than those of graphene/polyvinylidene fluoride composites corresponding value. This is because the polyvinyl alcohol covered on the graphene sheet hinders the movement of electrons on the graphene, so that the excellent electrical properties of graphene are not fully utilized. Another side effect is an increase in the percolation threshold of the composite. The high dielectric constant of conductor/polymer composites is due to the percolation effect. The presence of an insulating layer hinders the formation of a conductive network and often requires the presence of more conductors. In other words, in order to obtain a high dielectric constant, it is often necessary to add a high content of functional body, which will deteriorate the processability of the composite material, and even other properties such as mechanical properties. Therefore, how to overcome the above two side effects and develop a functional body for preparing resin-based composites with high dielectric constant, low dielectric loss and low percolation threshold is a topic with great application value.

Contents of the invention

The problem to be solved by the present invention is to overcome the deficiencies in the prior art, and to provide a graphene-titanium diboride oxide composite containing a large amount of active functional groups such as amino groups and hydroxyl groups on the surface and its preparation method. The product provided can be used for the preparation of High dielectric constant, low dielectric loss and low percolation threshold resin matrix composites.

Realize the purpose technical scheme of the present invention is to provide a kind of preparation method of graphene-oxidized titanium diboride compound, comprise the steps:

(1) By mass, disperse 10 parts of titanium diboride oxide into 50 to 60 parts of hydrogen peroxide solution with a mass fraction of 35% to 40%, and react at a temperature of 100 to 106°C for 5 to 6 hours; After the reaction is finished, through washing and suction filtration, hydroxylated titanium diboride oxide is obtained;

(2) By mass, add 10 parts of hydroxylated titanium diboride oxide prepared in step (1) to 100-120 parts of absolute ethanol, and mix to obtain a suspension; add 0.1 ~0.2 parts of γ-aminopropyltriethoxysilane, reacted at a temperature of 60~65°C for 5~6h, after the reaction was completed, suction filtered, washed, and dried to obtain aminated titanium diboride oxide;

(3) Disperse 1 part of graphite oxide in 500-600 parts of N,N-dimethylformamide by mass under stirring conditions to obtain a graphene oxide dispersion; 0.005-0.5 parts of step (2) The prepared aminated titanium diboride oxide is added to the graphene oxide dispersion and reacted at a temperature of 60 to 70°C for 12 to 24 hours; then adding 10 parts of L-ascorbic acid, The reaction is carried out under temperature conditions for 24-48 hours. After the reaction is completed, a graphene-titanium diboride oxide composite is obtained through suction filtration, washing and drying.

The graphite oxide described in the technical solution of the present invention, its preparation method comprises the steps:

(1) By mass, add 2 parts of graphite, 1 part of sodium nitrate and 46 parts of concentrated sulfuric acid with a mass concentration of 98% into the reactor for stirring and mixing, and place the reactor in an ice-water bath with a temperature of 0-4°C;

(2) Slowly add 6 parts of potassium permanganate into the reactor at a temperature of 10-15°C, and then keep stirring for 2-3 hours;

(3) Move the reactor to a water bath with a temperature of 30-40°C, and keep stirring for 30-35 minutes;

(4) After the reaction is over, slowly drop 92 parts of deionized water into the reactor, raise the temperature to 95-98°C, and keep it warm for 15-20 minutes;

(5) Add 15 parts of hydrogen peroxide with a mass concentration of 30% into the reactor, stir for 20 to 30 minutes, and then add 140 parts of deionized water to obtain a crude product; centrifuge the crude product with a mass concentration of 5% Washing with hydrochloric acid and deionized water until the pH is 6-7, and drying to obtain graphite oxide.

The preparation method of titanium diboride oxide described in the technical solution of the present invention comprises the following steps: under aerobic conditions, by mass, 1 part of titanium diboride with an average particle diameter of less than 200 nanometers is heated at 600-700 °C Oxidation treatment for 5-10 minutes under certain temperature conditions to obtain a crude product; disperse the crude product into 20-30 parts of ethanol, stir and then filter with suction and dry to obtain titanium diboride oxide.

The technical solution of the present invention also includes a graphene-titanium diboride oxide composite obtained by the above preparation method.

Compared with prior art, the beneficial effect of the present invention is:

1. The present invention loads oxidized titanium diboride on the surface of graphene, wherein oxidized titanium diboride is formed by high-temperature oxidation treatment of titanium diboride, the surface layer is insulating layer titanium dioxide, and the core is conductor titanium diboride, so it is A core-shell structure with conductor@insulation layer. This insulator-coated conductor was supported on graphene to form a composite. Since both titanium diboride and graphene are conductors, they can be used as electrodes; and the intermediate titanium dioxide is an insulating layer, which can be used as a dielectric, so that the graphene-titanium diboride oxide composite forms a microcapacitive structure. Adding the compound to the polymer not only reduces the conductance loss caused by conductor contact, but also greatly increases the dielectric constant.

2. The surface of the graphene-titanium diboride oxide composite contains a large number of active functional groups such as amino groups and hydroxyl groups, which provides a guarantee for its further modification and/or preparation of composite materials with good dispersibility.

3. The electrical properties of the composite can be adjusted by controlling the oxidation time of titanium diboride and the content of titanium diboride oxide, which has the characteristics of controllability and convenience in structure and performance.

4. The preparation method of the graphene-titanium diboride oxide composite provided by the present invention has the characteristics of simple process, low cost and wide applicability.

Description of drawings

Fig. 1 is the infrared spectrogram of oxide titanium diboride, aminated titanium oxide diboride, graphene and graphene-titanium oxide oxide composite in Example 1 of the present invention.

Fig. 2 is an X-ray diffraction diagram of oxide titanium diboride, aminated titanium oxide diboride, graphene and graphene-titanium oxide diboride composite in Example 1 of the present invention.

Fig. 3 is a scanning electron microscope image enlarged 25 thousand times of the graphene-titanium diboride oxide composite prepared in Examples 1-4 of the present invention.

Fig. 4 is an X-ray diffraction diagram of the graphene-titanium diboride oxide composite prepared in Examples 2-4 of the present invention.

Fig. 5 is a transmission scanning electron microscope image of the graphene-titanium diboride oxide composite in Example 4 of the present invention.

Fig. 6 is a graph showing the variation of the dielectric constant with frequency of the graphene/epoxy resin composite material provided in Comparative Example 1 of the present invention and the graphene-titanium diboride oxide composite/epoxy resin composite material provided in Comparative Example 2.

Fig. 7 is a plot of electrical conductivity versus frequency for the graphene/epoxy resin composite material provided in Comparative Example 1 of the present invention and the graphene-titanium diboride oxide composite/epoxy resin composite material provided in Comparative Example 2.

Fig. 8 is a graph showing the variation of capacitance with frequency for the graphene/epoxy resin composite material provided in Comparative Example 1 of the present invention and the graphene-titanium diboride oxide composite/epoxy resin composite material provided in Comparative Example 2.

Fig. 9 is a graph showing the variation of dielectric loss with frequency for the graphene/epoxy resin composite material provided in Comparative Example 1 of the present invention and the graphene-titanium diboride oxide composite/epoxy resin composite material provided in Comparative Example 2.

Fig. 10 is the conductivity-composite content curve of the graphene-titanium diboride oxide/epoxy resin composite material prepared in Comparative Example 3 at 1 Hz.

Detailed ways

The technical solutions of the present invention will be further described below in conjunction with the accompanying drawings, examples and comparative examples.

Example 1

1. Preparation of titanium diboride oxide

Under aerobic conditions, oxidize 10 g of titanium diboride with a particle size of less than 200 nanometers at 600 ° C for 10 minutes to obtain a crude product, disperse it in 200 mL of ethanol, stir it, filter it with suction, and dry it to obtain oxidized titanium diboride . The infrared spectrogram and X-ray diffraction pattern of the prepared titanium diboride oxide are shown in Figures 1 and 2, respectively.

2. Preparation of aminated titanium diboride oxide

Disperse 10g of titanium diboride oxide into 50mL of hydrogen peroxide solution with a mass fraction of 35%, and react at 100°C for 5h; after the reaction, wash, filter with suction, and dry in a vacuum oven at 60°C for 12h to obtain Hydroxylated titanium diboride oxide;

Add 10 g of hydroxylated oxidized titanium diboride to 100 mL of absolute ethanol, mix well by ultrasonic, add 0.1 g of γ-aminopropyltriethoxysilane under the protection of nitrogen, and stir at 60° C. for 5 h. After the reaction was completed, it was washed with absolute ethanol, filtered with suction, and vacuum-dried at 70° C. for 12 hours to obtain aminated titanium diboride oxide. The infrared spectrogram and X-ray diffraction pattern of the prepared aminated titanium diboride oxide are shown in Figures 1 and 2, respectively.

3. Preparation of graphite oxide

Take 2g of graphite, 1g of sodium nitrate and 46mL of 98% concentrated sulfuric acid, mix them in an ice-water bath at 0°C and stir for 30min, take 6g of potassium permanganate and slowly add them to the above mixture, keep the temperature at 10°C and stir for 2h, then place the flask Transfer to a 30°C water bath, and keep stirring for 30min. After the reaction, slowly add 92mL of deionized water dropwise, raise the temperature to 95°C, keep it warm for 15min, then add 15mL of 30% hydrogen peroxide, stir for 20min, then add 140mL of deionized water, and the obtained product is centrifuged and washed with 5% hydrochloric acid 1. Washing with deionized water until the pH is 7, and drying to obtain graphite oxide.

4. Preparation of graphene

Disperse 1g of graphite oxide in 2000mL of deionized water, ultrasonically and stir to obtain a yellow-brown clear solution, add 10g of L-ascorbic acid as a reducing agent to reduce graphene oxide to graphene, react at 80°C for 24h, and use Wash with deionized water, filter with suction, dry in a vacuum oven at 60°C for 12 hours, and grind to obtain graphene. Refer to accompanying drawings 1 and 2 for the infrared spectrum and X-ray diffraction diagrams of the prepared graphene, respectively.

5. Preparation of graphene-titanium diboride oxide composite

Weigh 1g graphite oxide and disperse in 500mL In N,N-dimethylformamide, stir and sonicate for 1 hour to obtain a graphene oxide dispersion, add 0.005g of aminated titanium diboride oxide to the graphene oxide dispersion, stir ultrasonically, and heat at 60°C React for 12 hours, then add 10g of L-ascorbic acid, raise the temperature of the reaction solution to 80°C and react for 24 hours, then filter, wash, and dry to obtain a graphene-titanium diboride oxide composite, in which titanium diboride oxide The mass is 0.01 times that of graphene. The infrared spectrogram, X-ray diffraction pattern, and scanning electron microscope image magnified 25 thousand times of the prepared graphene-titanium diboride oxide composite are shown in Figures 1, 2 and 3, respectively.

Referring to accompanying drawing 1, it is the infrared spectrogram of titanium diboride oxide, aminated titanium oxide diboride, graphene and graphene-titanium oxide diboride composite in the present embodiment. In the spectrogram of titanium dioxide boride, the absorption peak at 1380cm ^-1 is caused by the bending vibration of the hydroxyl group on the surface of titanium dioxide boride. This peak is weaker in the spectrogram of aminated oxidized titanium diboride, indicating that the ethoxy group in γ-aminopropyltriethoxysilane has condensed with the hydroxyl group on the surface of oxidized titanium diboride, that is, γ - Aminopropyltriethoxysilane is chemically bonded to the titanium diboride oxide surface. At the same time, the absorption peaks at 2853cm ^{− 1} and 2930cm ^{− 1} in the spectrogram of aminated titanium diboride oxide are attributed to the expansion and contraction of symmetrical and asymmetrical methylene groups in the structure of γ-aminopropyltriethoxysilane vibration, further demonstrating that γ-aminopropyltriethoxysilane is chemically bonded to the surface of titanium diboride oxide. From the spectrum of graphene-titanium diboride oxide, it can be seen that the characteristic peaks of C=O (1648cm ^{− 1} ), N–H and C–N (1509cm ^{− 1} ) indicate that titanium diboride oxide and graphene are connected to each other by chemical bonds.

Referring to accompanying drawing 2, it is the X-ray diffraction figure of oxide titanium diboride, aminated titanium oxide diboride, graphene and graphene-titanium oxide diboride composite in the present embodiment. It can be seen from the figure that the graphene obtained after reduction with L-ascorbic acid shows a broad diffraction peak at 24.85°. The aminated oxidized titanium diboride showed the characteristic diffraction peaks of titanium diboride and titanium dioxide, but the intensity was relatively weak, which was because γ-aminopropyltriethoxysilane was supported on the surface of oxidized titanium diboride. The diffraction peaks of the graphene-oxidized titanium diboride composite include the characteristic peaks of graphene and titanium diboride oxide; The characteristic peaks of titanium oxide and titanium dioxide are weaker, and this is because the oxide titanium diboride content on the graphene surface is less in this embodiment, only one percent of the graphene mass, so it shows very weak diffraction peaks .

Example 2

Preparation of Graphene-Titanium Diboride Oxide Composite

Weigh 1g graphite oxide and disperse in 600mL In N,N-dimethylformamide, stir and sonicate for 1 hour to obtain a graphene oxide dispersion, add 0.025g of aminated titanium diboride oxide to the graphene oxide dispersion, stir ultrasonically, and heat at 60°C React for 12 hours, then add 10g of L-ascorbic acid, raise the temperature of the reaction solution to 90°C and react for 24 hours, then filter with suction, wash, and dry to obtain a graphene-titanium diboride oxide composite, in which titanium diboride oxide The content is 0.05 times the mass of graphene. Its 25 thousand times magnified scanning electron microscope picture and X-ray diffraction picture are shown in accompanying drawings 3 and 4 respectively.

Example 3

Preparation of Graphene-Titanium Diboride Oxide Composite

Weigh 1g graphite oxide and disperse in 600mL In N,N-dimethylformamide, stir and sonicate for 1 h to obtain a graphene oxide dispersion, add 0.5 g of aminated titanium diboride oxide to the graphene oxide dispersion, ultrasonically stir, at 60 ° C React for 12 hours, then add 10g of L-ascorbic acid, raise the temperature of the reaction solution to 90°C and react for 24 hours, then filter with suction, wash, and dry to obtain a graphene-titanium diboride oxide composite, in which titanium diboride oxide The content is the same as the mass of graphene. Its 25 thousand times magnified scanning electron microscope picture and X-ray diffraction picture are shown in accompanying drawings 3 and 4 respectively.

Example 4

Preparation of Graphene-Titanium Diboride Oxide Composite

Weigh 1g graphite oxide and disperse in 600mL In N,N-dimethylformamide, stir and sonicate for 1 hour to obtain a graphene oxide dispersion, add 0.05g of aminated titanium diboride oxide to the graphene oxide dispersion, stir ultrasonically, and heat at 60°C React for 12 hours, then add 10g of L-ascorbic acid, raise the temperature of the reaction solution to 90°C and react for 24 hours, then filter with suction, wash, and dry to obtain a graphene-titanium diboride oxide composite, in which titanium diboride oxide The content is 0.1 times the mass of graphene. Its 25 thousand times magnified scanning electron microscope picture, X-ray diffraction picture and transmission scanning electron microscope picture are shown in Figures 3, 4 and 5, respectively.

Comparative example 1: the preparation of graphene/epoxy resin composite material

Add 0.75g of graphene and 100g of epoxy resin (brand E-51) into the flask, stir at 60°C and ultrasonic for 1 hour, vacuum degassing for 30min, add 4g of 2-ethyl-4-methylimidazole , continue to stir for 10 minutes to obtain a uniform mixture; pour the mixture into the mold, vacuum degassing for 30 minutes, and perform curing and heat treatment according to the processes of 80°C/2h + 100°C/2h+120°C/2h and 140°C/4h, namely A graphene/epoxy resin composite is obtained. The diagrams of dielectric constant versus frequency, conductivity versus frequency, capacitance versus frequency, and dielectric loss versus frequency are shown in Figures 6, 7, 8 and 9, respectively.

Comparative example 2: the preparation of graphene-titanium diboride oxide/epoxy resin composite

Add 0.825g of the graphene-titanium diboride oxide composite prepared in Example 4 and 100g of epoxy resin (brand E-51) into the flask, stir at 60°C and ultrasonically for 1 hour, then vacuum defoam for 30min, Add 4g of 2-ethyl-4-methylimidazole and continue to stir for 10 minutes to obtain a homogeneous mixture; pour the mixture into a mold and vacuum defoam for 30 minutes, according to 80℃/2h + 100℃/2h + 120℃/2h and 140°C/4h process for curing and heat treatment to obtain graphene-titanium diboride oxide composite/epoxy resin composite material. The diagrams of dielectric constant versus frequency, conductivity versus frequency, capacitance versus frequency, and dielectric loss versus frequency are shown in Figures 6, 7, 8 and 9, respectively.

Referring to accompanying drawing 3, it is the graphene-titanium diboride oxide compound that the embodiment of the present invention 1～4 prepares the scanning electron micrograph that enlarges 25 thousand times, can see, along with the titanium diboride oxide and graphene As the mass ratio increases, the content of titanium diboride supported on graphene also shows an increasing trend until it completely covers the graphene flakes.

Referring to accompanying drawing 4, it is the X-ray diffractogram of the graphene-titanium diboride oxide composite that the present invention embodiment 2～4 prepares. It can be seen from the figure that with the increase of the mass ratio of titanium diboride oxide to graphene, the diffraction peak intensity of graphene in the graphene-titanium diboride oxide composite at 24.85° becomes weaker and weaker, while the The diffraction peaks of titanium diboride and titanium dioxide in titanium boride are more and more obvious, indicating that the content of titanium diboride grafted on graphene is controllable, and the mass ratio of titanium diboride to graphene can be adjusted to accomplish.

Based on the analysis of the above performance data, compared with graphene, the graphene-titanium diboride oxide composite prepared by the present invention has the characteristics of controllable loading capacity of titanium diboride oxide, and titanium diboride oxide is covered on graphene The surface can hinder its agglomeration, improve the dispersion of graphene in the resin, and can be applied to the preparation of resin-based composite materials with good dispersion, and has broad application prospects.

Referring to accompanying drawing 5, it is the transmission electron microscope picture of graphene-titanium diboride oxide composite in this embodiment, it can be seen that titanium oxide diboride particles are supported on the graphene.

Referring to accompanying drawing 6, it is the variation curve of the dielectric constant of the composite material provided by Comparative Examples 1 and 2 with frequency. It can be seen from the figure that the dielectric constant of the graphene-titanium diboride oxide composite/epoxy resin composite is higher than that of the graphene/epoxy resin composite in the entire frequency range, indicating that the graphene-titanium diboride oxide composite It has obvious application prospects in the preparation of high dielectric constant materials.

Referring to accompanying drawing 7, it is the electric conductivity of the composite material that comparative examples 1 and 2 provide change curve with frequency. As can be seen from the figure, the electrical conductivity of the graphene-titanium diboride oxide composite/epoxy resin composite is lower than that of the graphene/epoxy resin composite, because the graphene surface is covered with low-conductivity TiO2O3 with high efficiency, proved that TiO2O2 loaded on graphene reduces the tunneling current between adjacent graphene, so that the graphene-TiO2O2 composite/epoxy resin has a lower conductivity.

Referring to accompanying drawing 8, it is the capacitance versus frequency variation curve of the composite materials provided by Comparative Examples 1 and 2. It can be seen from the figure that the capacitance of graphene-titanium diboride oxide composite/epoxy resin composite is higher than that of graphene/epoxy resin composite. In combination with the electrical conductivity data in Fig. 7, it can be considered that the reason why the graphene-titanium diboride oxide composite/epoxy resin composite material provided in Comparative Example 2 has a high dielectric constant is the increase in material capacitance.

Referring to accompanying drawing 9, it is the variation curve of the dielectric loss of the composite material provided by Comparative Examples 1 and 2 with frequency. The dielectric loss of the graphene/epoxy resin composite prepared in Comparative Example 1 has a strong dependence on frequency, and has a high dielectric loss at low frequencies (for example, the dielectric loss of the composite material at 100 Hz is as high as 9.3). However, the dielectric loss of the graphene-titanium diboride oxide composite/epoxy resin composite prepared in Comparative Example 2 has a weak dependence on frequency, and the dielectric loss at low frequencies is significantly reduced. This is because titanium dioxide oxide is covered on graphene, because the insulating layer of titanium dioxide isolates the mutual contact between graphene sheets, hindering the penetration of electrons between conductor graphene, resulting in graphene-diboron oxide The reduction of the dielectric loss of the titanium dioxide composite/epoxy resin composite shows that the graphene-titanium diboride oxide composite has outstanding advantages in the preparation of low dielectric loss composites.

Comparative Example 3: Preparation of series graphene-titanium diboride oxide/epoxy resin composites

With reference to the preparation steps of Comparative Example 2, graphene-titanium diboride composites whose contents were respectively 0.757%, 0.787%, 0.825%, 0.900%, 1.13%, and 1.50% of the epoxy resin mass were prepared. Titanium boride/epoxy composite. The conductivity-composite content curve at 1 Hz is shown in Figure 10. It can be seen that the percolation threshold of graphene-titanium diboride oxide/epoxy resin composite is only 0.767wt% of the resin mass, which proves that when graphene-titanium diboride oxide is used as a functional filler, it can Composite materials with high dielectric constant and low dielectric loss can be prepared.

Based on the results of accompanying drawings 6, 7, 8, 9 and 10, it can be seen that adding a small amount of graphene-titanium diboride oxide composite can significantly improve the dielectric constant of the composite material and greatly reduce the dielectric loss. It has significant advantages in terms of dielectric constant, low dielectric loss, and low percolation threshold composite materials, which are derived from the unique structure of graphene-titanium diboride oxide composites.

Example 5

Preparation of Graphene-Titanium Diboride Oxide Composite

Weigh 1g graphite oxide and disperse in 600mL In N,N-dimethylformamide, stir and sonicate for 1 h to obtain a graphene oxide dispersion, add 0.1 g of aminated titanium diboride oxide to the graphene oxide dispersion, stir ultrasonically, and heat at 60 ° C After reacting for 12 hours, 10 g of L-ascorbic acid was added, and the temperature of the reaction solution was raised to 90° C. for 24 hours. After suction filtration, washing and drying, a graphene-titanium diboride oxide composite was obtained.

Example 6

Preparation of Graphene-Titanium Diboride Oxide Composite

Weigh 1g graphite oxide and disperse in 600mL In N,N-dimethylformamide, stir and sonicate for 1h to obtain a graphene oxide dispersion, add 0.25g of aminated titanium diboride oxide to the graphene oxide dispersion, stir ultrasonically, at 60°C After reacting for 12 hours, 10 g of L-ascorbic acid was added, and the temperature of the reaction solution was raised to 90° C. for 24 hours. After suction filtration, washing and drying, a graphene-titanium diboride oxide composite was obtained.

Example 7

1. Preparation of titanium diboride oxide

Under aerobic conditions, oxidize 10 g of titanium diboride with a particle size of less than 200 nanometers at 700 ° C for 5 minutes to obtain a crude product, disperse it in 250 mL of ethanol, stir it, filter it with suction, and dry it to obtain oxidized titanium diboride .

2. Preparation of aminated titanium diboride oxide

Disperse 10g of titanium diboride oxide in 60mL of hydrogen peroxide solution with a mass fraction of 35%, and react at 100°C for 5.5h; after the reaction, wash with deionized water, filter with suction, and dry in a vacuum oven at 60°C for 12h , to obtain hydroxylated titanium diboride oxide.

Add 10 g of hydroxylated oxidized titanium diboride to 110 mL of absolute ethanol, mix well by ultrasonic, add 0.15 g of γ-aminopropyltriethoxysilane under nitrogen protection, and stir at 65°C for 5 h. After the reaction was completed, it was washed with absolute ethanol, filtered with suction, and vacuum-dried at 70° C. for 12 hours to obtain aminated titanium diboride oxide.

3. Preparation of graphite oxide

Take 2g of graphite, 1g of sodium nitrate and 46mL of 98% concentrated sulfuric acid, mix them in an ice-water bath at 4°C and stir for 30min, take 6g of potassium permanganate and slowly add them to the above mixture, control the temperature at 15°C and stir for 2.5h, then put The flask was transferred to a 35 °C water bath, and kept stirring for 35 min. After the reaction, slowly add 92mL of deionized water dropwise, raise the temperature to 98°C, keep it warm for 15min, then add 15mL of 30% hydrogen peroxide, stir for 25min, then add 140mL of deionized water, and the obtained product is centrifuged and washed with 5% hydrochloric acid 1. Washing with deionized water until the pH is 6, and drying to obtain graphite oxide.

4. Preparation of graphene-titanium diboride oxide composite

Weigh 1g graphite oxide and disperse in 600mL In N,N-dimethylformamide, stir and sonicate for 1.5h to obtain a graphene oxide dispersion, add 0.15g of aminated titanium diboride oxide to the graphene oxide dispersion, ultrasonically stir, at 70 After reacting at ℃ for 15 h, then adding 10 g of L-ascorbic acid, raising the temperature of the reaction liquid to 80 ° C and reacting for 24 h, after suction filtration, washing and drying, a graphene-titanium diboride oxide composite was obtained.

Example 8

1. Preparation of titanium diboride oxide

Under aerobic conditions, oxidize 10 g of titanium diboride with a particle size of less than 200 nanometers at 680 ° C for 6 minutes to obtain a crude product, disperse it in 280 mL of ethanol, stir it, filter it with suction, and dry it to obtain oxidized titanium diboride .

2. Preparation of aminated titanium diboride oxide

Disperse 10g of titanium diboride oxide in 50mL of hydrogen peroxide solution with a mass fraction of 40%, and react at 106°C for 5h; after the reaction, wash with deionized water, filter with suction, and dry in a vacuum oven at 60°C for 12h. Hydroxylated titanium diboride oxide is obtained.

Add 10 g of hydroxylated oxidized titanium diboride to 110 mL of absolute ethanol, mix well by ultrasonic, add 0.2 g of γ-aminopropyltriethoxysilane under nitrogen protection, and stir at 65°C for 5 h. After the reaction was completed, it was washed with absolute ethanol, filtered with suction, and vacuum-dried at 70° C. for 12 hours to obtain aminated titanium diboride oxide.

3. Preparation of graphite oxide

Take 2g of graphite, 1g of sodium nitrate and 46mL of 98% concentrated sulfuric acid, mix them in an ice-water bath at 2°C and stir for 30min, take 6g of potassium permanganate and slowly add them to the above mixture, control the temperature at 15°C and stir for 2h, then place the flask Transfer to a 38°C water bath, and keep stirring for 32min. After the reaction, slowly add 92mL of deionized water dropwise, raise the temperature to 96°C, keep it warm for 18min, then add 15mL of 30% hydrogen peroxide, stir for 20min, then add 140mL of deionized water, the obtained product is centrifuged and washed with 5% hydrochloric acid 1. Washing with deionized water until the pH is 6.5, and drying to obtain graphite oxide.

4. Preparation of graphene-titanium diboride oxide composite

Weigh 1g graphite oxide and disperse in 600mL In N,N-dimethylformamide, stir and sonicate for 1.5h to obtain a graphene oxide dispersion, add 0.2g of aminated titanium diboride oxide and place it in the graphene oxide dispersion, and stir ultrasonically at 70 After reacting at ℃ for 20 hours, 10 g of L-ascorbic acid was added, the temperature of the reaction solution was raised to 85 ℃ and reacted for 24 hours, then suction filtered, washed and dried to obtain a graphene-titanium diboride oxide composite.

Example 9

1. Preparation of titanium diboride oxide

Under aerobic conditions, oxidize 10 g of titanium diboride with a particle size of less than 200 nanometers at 700 ° C for 5 minutes to obtain a crude product, disperse it in 290 mL of ethanol, stir it, filter it with suction, and dry it to obtain oxidized titanium diboride .

2. Preparation of aminated titanium diboride oxide

Disperse 10g of titanium diboride oxide in 55mL of hydrogen peroxide solution with a mass fraction of 40%, and react at 106°C for 6h; after the reaction, wash with deionized water, filter with suction, and dry in a vacuum oven at 60°C for 12h. Hydroxylated titanium diboride oxide is obtained.

Add 10 g of hydroxylated oxidized titanium diboride to 120 mL of absolute ethanol, mix well by ultrasonic, add 0.2 g of γ-aminopropyltriethoxysilane under nitrogen protection, and stir at 60°C for 6 h. After the reaction was completed, it was washed with absolute ethanol, filtered with suction, and vacuum-dried at 70° C. for 12 hours to obtain aminated titanium diboride oxide.

3. Preparation of graphite oxide

Take 2g of graphite, 1g of sodium nitrate and 46mL of 98% concentrated sulfuric acid, mix them in an ice-water bath at 4°C and stir for 30min, take 6g of potassium permanganate and slowly add them to the above mixture, keep the temperature at 12°C and stir for 2h, then place the flask Transfer to a 38°C water bath, and keep stirring for 33min. After the reaction, slowly add 92mL of deionized water dropwise, raise the temperature to 96°C, keep it warm for 20min, then add 15mL of 30% hydrogen peroxide, stir for 30min, then add 140mL of deionized water, the obtained product is centrifuged and washed with 5% hydrochloric acid 1. Washing with deionized water until the pH is 6.5, and drying to obtain graphite oxide.

4. Preparation of graphene-titanium diboride oxide composite

Weigh 1g graphite oxide and disperse in 600mL In N,N-dimethylformamide, stir and sonicate for 1.5h to obtain a graphene oxide dispersion, add 0.3g of aminated titanium diboride oxide and place it in the graphene oxide dispersion, ultrasonically stir, at 65 After reacting at ℃ for 18 hours, then adding 10 g of L-ascorbic acid, raising the temperature of the reaction liquid to 90 ℃ and reacting for 48 hours, after suction filtration, washing and drying, a graphene-titanium diboride oxide composite was obtained.

Example 10

1. Preparation of titanium diboride oxide

Under aerobic conditions, oxidize 10 g of titanium diboride with a particle size of less than 200 nanometers at 650 ° C for 8 minutes to obtain a crude product, disperse it in 300 mL of ethanol, stir it, filter it with suction, and dry it to obtain oxidized titanium diboride .

2. Preparation of aminated titanium diboride oxide

Disperse 10g of titanium diboride oxide in 60mL of hydrogen peroxide solution with a mass fraction of 40%, and react at 106°C for 5h. After the reaction, wash with deionized water, filter with suction, and dry in a vacuum oven at 60°C for 12h. Hydroxylated titanium diboride oxide is obtained.

Add 10 g of hydroxylated oxidized titanium diboride to 120 mL of absolute ethanol, mix well by ultrasonic, add 0.2 g of γ-aminopropyltriethoxysilane under nitrogen protection, and stir at 65°C for 6 h. After the reaction was completed, it was washed with absolute ethanol, filtered with suction, and vacuum-dried at 70° C. for 12 hours to obtain aminated titanium diboride oxide.

3. Preparation of graphite oxide

Take 2g of graphite, 1g of sodium nitrate and 46mL of 98% concentrated sulfuric acid, mix them in an ice-water bath at 4°C and stir for 30min, take 6g of potassium permanganate and slowly add them to the above mixture, control the temperature at 12°C and stir for 3h, then place the flask Transfer to a 35°C water bath, and keep stirring for 35min. After the reaction, slowly add 92mL of deionized water dropwise, raise the temperature to 96°C, keep it warm for 18min, then add 15mL of 30% hydrogen peroxide, stir for 28min, then add 140mL of deionized water, and the obtained product is centrifuged and washed with 5% hydrochloric acid 1. Washing with deionized water until the pH is 7, and drying to obtain graphite oxide.

4. Preparation of graphene-titanium diboride oxide composite

Weigh 1g graphite oxide and disperse in 600mL In N,N-dimethylformamide, stir and sonicate for 1.5h to obtain a graphene oxide dispersion, add 0.4g of aminated titanium diboride oxide and place it in the graphene oxide dispersion, and stir ultrasonically at 65 After reacting at ℃ for 24 hours, 10 g of L-ascorbic acid was added, the temperature of the reaction liquid was raised to 95 ℃ and reacted for 48 hours, then filtered, washed and dried to obtain a graphene-titanium diboride oxide composite.

Claims (4)

1. a preparation method for Graphene-oxidation TiB2 mixture, is characterized in that comprising the steps:

(1) by mass, 10 parts of oxidation TiB2s are distributed in the superoxol that 50～60 parts of massfractions are 35%～40%, under the temperature condition of 100～106 DEG C, react 5～6h; After reaction finishes, through washing, suction filtration, obtains hydroxylated oxidation TiB2;

(2) by mass, hydroxylated oxidation TiB2 prepared by 10 parts of steps (1) joins in 100～120 parts of dehydrated alcohols, obtains suspension after mixing; In described suspension, add 0.1～0.2 part of γ-aminopropyl triethoxysilane, under the temperature condition of 60～65 DEG C, react 5～6h, after reaction finishes, through suction filtration, washing, dry, obtain amidized oxidation TiB2;

(3) by mass, under agitation condition, 1 part of graphite oxide is scattered in 500～600 parts of DMFs, obtains graphene oxide dispersion liquid; Amidized oxidation TiB2 prepared by 0.005～0.5 part of step (2) joins in described graphene oxide dispersion liquid, under the temperature condition of 60～70 DEG C, reacts 12～24h; Add again 10 parts of L-AAs, under the temperature condition of 80～100 DEG C, react 24～48h, after reaction finishes, through suction filtration, washing, dry, obtain a kind of Graphene-oxidation TiB2 mixture.

2. the preparation method of a kind of Graphene-oxidation TiB2 mixture according to claim 1, is characterized in that, the preparation method of described graphite oxide comprises the steps:

(1) by mass, the vitriol oil that is 98% by 2 parts of graphite, 1 part of SODIUMNITRATE and 46 parts of mass concentrations joins in reactor and is uniformly mixed, and it is in the ice-water bath of 0～4 DEG C that reactor is positioned over temperature;

(2) under the temperature condition of 10～15 DEG C, in reactor, slowly add 6 parts of potassium permanganate, then insulated and stirred 2～3h;

(3) reactor being moved to temperature is in the water-bath of 30～40 DEG C, insulated and stirred 30～35min;

(4) after reaction finishes, in reactor, slowly drip 92 parts of deionized waters, be warming up to 95～98 DEG C, insulation 15～20min;

(5) in reactor, add the hydrogen peroxide that 15 parts of mass concentrations are 30%, stir after 20～30min, add 140 parts of deionized waters, obtain crude product; By described crude product through salt acid elution centrifugal, that mass concentration is 5%, deionized water wash process to pH be 6～7, obtain graphite oxide after dry.

3. the preparation method of a kind of Graphene-oxidation TiB2 mixture according to claim 1, it is characterized in that, the preparation method of described oxidation TiB2 comprises the steps: under aerobic conditions, by mass, 1 part of median size is less than to the TiB2 of 200 nanometers, under the temperature condition of 600～700 DEG C, oxide treatment 5～10min, obtains crude product; Described crude product is distributed in 20～30 parts of ethanol, again through suction filtration, dry after stirring, obtain being oxidized TiB2.

4. one kind obtains Graphene-oxidation TiB2 mixture by preparation method claimed in claim 1.