CN115477547A - Preparation method of graphene composite porous ceramic - Google Patents

Preparation method of graphene composite porous ceramic Download PDF

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CN115477547A
CN115477547A CN202210955211.5A CN202210955211A CN115477547A CN 115477547 A CN115477547 A CN 115477547A CN 202210955211 A CN202210955211 A CN 202210955211A CN 115477547 A CN115477547 A CN 115477547A
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graphene
porous ceramic
preparation
composite porous
graphene oxide
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葛震
陈曦
赖浩然
李际洋
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Yangtze River Delta Research Institute of UESTC Huzhou
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Yangtze River Delta Research Institute of UESTC Huzhou
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Abstract

The application discloses a preparation method of graphene composite porous ceramic, which comprises the following steps: adding graphene oxide into distilled water or an organic solvent system to prepare uniform graphene oxide dispersion liquid, adding ceramic powder, stirring to form a uniform dispersion liquid system, pouring the obtained dispersion liquid into a high-temperature reaction kettle, performing solvothermal reaction to form a self-supporting three-dimensional graphene-ceramic composite material, drying and sintering at high temperature to obtain the three-dimensional graphene composite porous ceramic material. The invention provides a novel powder forming method, and the prepared composite foam material consists of a porous ceramic framework and a three-dimensional cross-linked graphene network, and has the advantages of strong universality, adjustable porosity, improvement on the conductivity of a ceramic substrate and the like.

Description

Preparation method of graphene composite porous ceramic
The technical field is as follows:
the invention relates to the technical field of preparation of foamed ceramic materials, in particular to a preparation method of graphene composite porous ceramic.
Background art:
the foamed ceramic material has wide application in the fields of catalysis, adsorption separation, artificial bones and the like, so that researches on the preparation of the foamed ceramic and the multifunctionality of the foamed ceramic material are always valued by researchers. The currently used preparation method mainly comprises a foaming method, a template method, a sacrificial agent method and the like, but the introduced foaming agent or template needs to be removed in the material post-treatment process, so that certain pollution and waste are caused. The prepared foamed ceramic material has extremely low conductivity, which limits the application of the traditional ceramic material to a certain extent, especially in the fields of catalysis and electronic devices.
Graphene is a novel carbon nanomaterial, has excellent properties such as ultrahigh conductivity, good flexibility and high strength, and is widely applied in the fields of catalysis, lithium ion batteries, supercapacitors and the like. The three-dimensional graphene is a porous carbon foam material formed by cross-linking graphene sheet layers, not only maintains the unique excellent properties of the graphene sheet layers, but also can construct a macroscopic bulk phase material, and can be prepared based on a template method or a solvothermal self-assembly method.
The graphene oxide is a raw material for preparing the three-dimensional graphene by a solvothermal self-assembly method, has a hydrophobic aromatic ring conjugated system and a hydrophilic oxygen-containing functional group, has an amphiphilic characteristic, can be used as a two-dimensional surfactant material for effectively dispersing materials such as oil drops, carbon nanotubes and the like, and can also be used for effectively dispersing ceramic powder materials. Graphene oxide and ceramic powder are used as raw materials, and an interpenetrating network structure of three-dimensional graphene and a porous ceramic framework can be constructed through solvothermal reaction and sintering treatment.
The invention content is as follows:
the invention discloses a preparation method of graphene composite porous ceramic, wherein the foam material has an interpenetrating network structure of three-dimensional graphene and a porous ceramic skeleton, the porous ceramic skeleton enables the composite foam material to have higher strength, the three-dimensional graphene network plays a role in powder forming and excessive sintering prevention, and the porous ceramic skeleton is endowed with more functionality, such as improvement of the conductivity of a porous ceramic material.
The preparation method of the graphene composite porous ceramic comprises the following steps:
(1) Adding graphene oxide into distilled water, an organic solvent or a mixture of the distilled water and the organic solvent, and stirring to obtain a uniform graphene oxide dispersion liquid;
(2) Adding ceramic powder with the particle size of nanometer or micron into the graphene oxide dispersion liquid, and stirring to obtain uniform dispersion liquid;
(3) Adding the dispersion liquid formed by the graphene oxide and the ceramic powder into a high-temperature reaction kettle, and carrying out solvothermal reaction to obtain a three-dimensional graphene-ceramic composite material containing water and/or an organic solvent;
(4) And removing water and/or organic solvent in the composite material, and sintering at a temperature lower than the melting point of the ceramic in the composite material to obtain the three-dimensional graphene composite porous ceramic.
In one embodiment of the preparation method, the organic solvent is selected from one or a mixture of two or more of methanol, ethanol, ethylene glycol, N-propanol, isopropanol, N-butanol, isobutanol, t-butanol, N-dimethylformamide, tetrahydrofuran, and acetone in any ratio.
In one embodiment of the preparation method, the graphene oxide used for preparing the graphene oxide dispersion liquid is a single layer of graphene oxide or a few layers (2 to 10 layers) of graphene oxide, preferably a single layer of graphene oxide; the concentration of the graphene oxide in the graphene oxide dispersion liquid is 0.3mg/mL-10mg/mL, preferably 1-3mg/mL.
In one embodiment of the production method, the ceramic powder is a mixture of one or more ceramic powders such as alumina, silica, titania, zinc oxide, calcium hydroxy phosphate, and barium titanate at an arbitrary ratio. The particle size of the ceramic powder is 1nm-50 mu m.
In one embodiment of the preparation method, in the dispersion formed by the graphene oxide and the ceramic powder, the ceramic powder accounts for 50% -99.8% of the total solid mass content, and the graphene oxide accounts for 0.2% -50%, preferably 0.5% -5% of the total solid mass content.
In one embodiment of the preparation method, the solvothermal reaction temperature is 100 ℃ to 200 ℃ and the reaction time is 8h to 24h.
In one embodiment of the preparation method, the method for removing water and/or organic solvent from the composite material may use freeze drying or vacuum drying, preferably vacuum drying, at a temperature of 50-150 ℃ for 6-48h.
In one embodiment of the preparation method, the sintering process is performed in an inert atmosphere, the sintering temperature is 400-2000 ℃, and the sintering time is 1-12h, and it should be noted that the sintering temperature is lower than the melting point of the selected ceramic component in the three-dimensional graphene composite porous ceramic.
In one embodiment of the preparation method, the prepared three-dimensional graphene composite porous ceramic consists of a porous ceramic skeleton and a three-dimensional cross-linked graphene interpenetrating network, and the porosity is 10% -90%.
The preparation method and the obtained product have the following advantages and beneficial effects:
(1) The invention provides a novel powder forming process for preparing three-dimensional graphene composite porous ceramic, which is simple, avoids the use of foaming agents, pore-forming agents, templates and the like, and efficiently prepares multifunctional composite foamed ceramic materials;
(2) The three-dimensional graphene composite porous ceramic prepared by solvothermal reaction and sintering treatment has an inorganic porous ceramic framework and a three-dimensional graphene interpenetrating network structure, the porous ceramic framework enables a composite material to have higher compressive strength, and the introduction of the three-dimensional graphene plays a role in fixing ceramic powder and preventing over-sintering, and meanwhile, the porous ceramic framework is endowed with more functionality;
(3) The three-dimensional graphene composite porous ceramic prepared by the invention has the characteristic of adjustable porosity, and the porosity of the composite foam material can be adjusted in a large range by changing parameters such as the particle size of ceramic powder, sintering temperature, graphene oxide content and the like;
(4) The three-dimensional graphene composite porous ceramic prepared by the invention has good conductive performance, and the introduction of the three-dimensional graphene provides a good conductive network for a porous ceramic skeleton, so that the electrical insulation property of a ceramic substrate can be greatly improved;
(5) The method for preparing the three-dimensional graphene composite porous ceramic has good universality and has good applicability to ceramic powder materials such as aluminum oxide, silicon oxide, titanium oxide, calcium hydroxy phosphate, barium titanate and the like. The particle size of the ceramic powder used may be from a few nanometers to tens of micrometers.
Drawings
FIG. 1: scanning electron micrographs of graphene-alumina foam.
FIG. 2: optical photographs of three-dimensional graphene-alumina foams made with alumina particles of different particle size sizes.
FIG. 3: porosity of three-dimensional graphene-alumina foam materials prepared from alumina particles of different particle sizes.
FIG. 4: the porosity of the three-dimensional graphene-alumina foam material prepared at different sintering temperatures.
FIG. 5: the porosity of the three-dimensional graphene-alumina foam material prepared by adding different contents of graphene oxide is improved.
Examples
The following examples are for illustrative purposes only and are not intended to limit the scope of the present application.
Example 1:
adding 60mg of graphene oxide into 60mL of distilled water, uniformly stirring to prepare 1mg/mL of dispersion, and adding 5.94g of Al 2 O 3 The powder (particle size 0.2 μm) was mechanically stirred for 5 hours and mixed uniformly. Thereafter, the slurry was poured into a 100mL stainless steel reaction vessel with a Teflon liner and reacted at 180 ℃ for 12h. And (3) drying the self-supporting cylindrical composite material formed after the reaction at 80 ℃ for 24h in vacuum to obtain a green body material. Finally, the mixture is put under the protection condition of argon atmosphereAnd sintering at 1300 ℃ for 4h to obtain the three-dimensional graphene-alumina foam material. As shown in fig. 1, an interpenetrating network structure formed by the alumina framework and the three-dimensional graphene can be seen from a scanning electron microscope image. The obtained composite foam material has a porosity of 65.0% and a density of 1.4g/cm 3 The conductivity reaches 11.7S/m.
Three-dimensional graphene-alumina foams were prepared by the above experimental procedure using alumina (30nm, 0.2 μm,1250 mesh, 800 mesh, 600 mesh) powders of different particle size sizes, as shown in fig. 2. And changing the particle size of the raw material can adjust the porosity of the syntactic foam, as shown in fig. 3. In addition, the adjustment of the porosity of the composite material can also be realized by changing the sintering temperature and the content of the graphene oxide, as shown in fig. 4 and 5.
Example 2:
60mg of graphene oxide is added into 60mL of ethanol, the mixture is stirred uniformly to prepare 1mg/mL of dispersion, 5.94g of silicon oxide powder (the particle size is 2 microns) is added, and the mixture is stirred mechanically for 5 hours and mixed uniformly. Thereafter, the slurry was poured into a 100mL stainless steel reaction vessel with a Teflon liner and reacted at 160 ℃ for 10h. And (3) drying the self-supporting cylindrical composite material formed after the reaction at 60 ℃ for 24h in vacuum to obtain a green body material. And finally, sintering the composite material for 4 hours at 1200 ℃ under the protection of argon atmosphere to obtain the three-dimensional graphene-silicon oxide foam material. The obtained composite foam material has a porosity of 34.8% and a density of 1.4g/cm 3 The conductivity reaches 39S/m.
Example 3:
60mg of graphene oxide is added into 60mL of distilled water and stirred uniformly to prepare 1mg/mL of dispersion, 11.94g of titanium dioxide powder (the particle size is 40 nm) is added, and the mixture is stirred mechanically for 5 hours and mixed uniformly. Thereafter, the slurry was poured into a 100mL stainless steel reaction vessel with a Teflon liner and reacted at 180 ℃ for 10h. And (3) drying the self-supporting cylindrical composite material formed after the reaction at 80 ℃ in vacuum for 24 hours to obtain a green blank material. And finally, sintering the composite material for 4 hours at 1000 ℃ under the protection of argon atmosphere to obtain the three-dimensional graphene-titanium dioxide foam material. The obtained composite foam material has a porosity of 41.4% and a density of 2.5g/cm 3 。
Example 4:
60mg of graphene oxide is added into 60mL of distilled water and stirred uniformly to prepare 1mg/mL of dispersion, 2.94g of calcium hydroxyphosphate powder (the particle size is 30 nm) is added, and the mixture is stirred mechanically for 5 hours and mixed uniformly. Thereafter, the slurry was poured into a 100mL stainless steel reaction vessel with a Teflon liner and reacted at 200 ℃ for 10h. And (3) drying the self-supporting cylindrical composite material formed after the reaction at 80 ℃ for 24h in vacuum to obtain a green body material. And finally, sintering the composite material for 4 hours at 1000 ℃ under the protection of argon atmosphere to obtain the three-dimensional graphene-calcium hydroxy phosphate foam material. The obtained composite foam material has a porosity of 61.0% and a density of 1.2g/cm 3 。
The working principle of the invention is as follows: adding graphene oxide into distilled water or an organic solvent system to prepare uniform graphene oxide dispersion liquid, adding ceramic powder, stirring to form a uniform dispersion liquid system, pouring the obtained dispersion liquid into a high-temperature reaction kettle, performing solvothermal reaction to form a self-supporting three-dimensional graphene-ceramic composite material, drying and sintering at high temperature to obtain the three-dimensional graphene composite porous ceramic material.
While the invention has been described in detail by way of general illustration and specific embodiments, it will be apparent to those skilled in the art that certain modifications or improvements can be made thereto and in any combination as is required. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (9)

1. A preparation method of graphene composite porous ceramic is characterized by comprising the following specific steps:
step one, adding graphene oxide into distilled water, an organic solvent or a mixture of the distilled water and the organic solvent, and stirring to obtain a graphene oxide dispersion liquid;
secondly, adding ceramic powder with the particle size of nanometer or micron into the graphene oxide dispersion liquid, and stirring to obtain uniform dispersion liquid;
adding a dispersion liquid formed by the graphene oxide and the ceramic powder into a high-temperature reaction kettle, and carrying out solvothermal reaction to obtain a three-dimensional graphene-ceramic composite material containing water and/or an organic solvent;
and step four, removing water and/or organic solvent in the composite material obtained in the step three, and sintering at a temperature lower than the melting point of the ceramic in the composite material to obtain the three-dimensional graphene composite porous ceramic material.
2. The preparation method of the graphene composite porous ceramic according to claim 1, characterized in that: the organic solvent in the first step is selected from one or a mixture of more than two of methanol, ethanol, ethylene glycol, N-propanol, isopropanol, N-butanol, isobutanol, tert-butanol, N-dimethylformamide, tetrahydrofuran and acetone in any proportion.
3. The preparation method of the graphene composite porous ceramic according to claim 1, characterized in that: the graphene oxide in the first step is a single-layer graphene oxide or 2-10 layers of graphene oxide, and is preferably a single-layer graphene oxide; the concentration of the graphene oxide in the graphene oxide dispersion liquid obtained in the first step is 0.3mg/mL-10mg/mL, preferably 1-3mg/mL.
4. The preparation method of the graphene composite porous ceramic according to claim 1, characterized in that: the ceramic powder in the second step is one or a mixture of more than two of aluminum oxide, silicon oxide, titanium oxide, zinc oxide, calcium hydroxy phosphate and barium titanate in any proportion, and the particle size of the ceramic powder is 1nm-50 mu m.
5. The preparation method of the graphene composite porous ceramic according to claim 1, characterized in that: in the dispersion liquid formed by the graphene oxide and the ceramic powder in the second step, the ceramic powder accounts for 50-99.8% of the total solid mass content, and the graphene oxide accounts for 0.2-50% of the total solid mass content.
6. The preparation method of the graphene composite porous ceramic according to claim 1, characterized in that: in the third step, the solvothermal reaction temperature is 100-200 ℃, and the reaction time is 8-24 h.
7. The preparation method of the graphene composite porous ceramic according to claim 1, characterized in that: the method for removing the water and/or the organic solvent in the composite material in the fourth step can use freeze drying or vacuum drying, preferably vacuum drying, wherein the temperature of the vacuum drying is 50-150 ℃, and the drying time is 6-48h.
8. The preparation method of the graphene composite porous ceramic according to claim 1, characterized in that: and the sintering process in the fourth step is carried out in an inert atmosphere, the sintering temperature is 400-2000 ℃, the sintering time is 1-12h, and the sintering temperature is lower than the melting point of the ceramic component selected in the three-dimensional graphene composite porous ceramic material.
9. The preparation method of the graphene composite porous ceramic according to claim 1, characterized in that: the three-dimensional graphene composite porous ceramic material prepared in the fourth step is composed of a porous ceramic skeleton and a three-dimensional cross-linked graphene interpenetrating network, and the porosity is 10% -90%.
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