CN111153398B - 3D bubble network structure carbon microsphere and preparation method thereof - Google Patents
3D bubble network structure carbon microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of material preparation, and relates to a 3D bubble network structure carbon microsphere and a preparation method thereof. The invention provides a preparation method of carbon microspheres with 3D bubble network structures on the basis of fully utilizing the high-temperature catalytic graphitization effect of cobalt on carbon, wherein a cobalt source and a carbon source are introduced, a hydrothermal process is adjusted to obtain precursor microspheres, and the precursor microspheres are obtained through high-temperature calcination and acid etching processes, so that the carbon microspheres have novel 3D bubble network structures, are various in pore structures, have higher specific surface area and good porosity, can be used as excellent carbon carrier materials, and can slow down the influence of volume effect on the performance of battery materials; in addition, the carbon microsphere has a double-component heterostructure of amorphous carbon and onion carbon, can form interface polarization loss and a conductive network structure, is favorable for promoting the rapid attenuation of electromagnetic wave energy, and has wide application prospects in the field of electromagnetic wave absorption.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a 3D bubble network structure carbon microsphere and a preparation method thereof.
Background
The carbon material has the advantages of low density, low price, simple preparation process and adjustable structure, is widely applied, and has various forms, such as carbon fiber, carbon nano tube, graphene, amorphous carbon and the like, and the carbon material is widely applied in the fields of catalysis, energy storage, biosensing, drug loading, electromagnetic wave absorption and the like due to the various forms, high conductivity and large specific surface area.
The porous carbon is a novel derivative material of a carbon material, has high specific surface area and various pore structures, can provide an expansion space for a lithium battery electrode material, and slows down the crushing and falling of an active material; in addition, porous carbon can also be used as a three-dimensional porous current collector to load metal lithium, and a patent (201910785543.1) provides a preparation method of a three-dimensional porous carbon loaded flaky molybdenum disulfide current collector for a lithium metal negative electrode, wherein a porous structure provides enough lithium storage space, the growth of lithium dendrites is inhibited, and the porous carbon has a high specific surface area and can effectively reduce the local current density of the electrode, so that the deposition of lithium metal is more uniform, the coulombic efficiency and the cycle life of the lithium metal negative electrode are effectively improved, and therefore, the porous carbon has an important function as a carrier material of a lithium battery.
At present, the preparation method of porous carbon comprises an activation method and a template method, wherein the activation method is to mix a carbon precursor with KOH and ZnCl2、K2CO3After mixing inorganic salt, high-temp. treatment, its activation process mainly includes opening and closing hole, enlarging original gap,The method can obtain the carbon material with certain porosity, but the formed pores are large in number, the reaction process is complex, and the pore structure is uncontrollable. In practical application, the hierarchical porous carbon containing macropores, mesopores and micropores is more widely applied. Wang et al prepared a hierarchical porous carbon material and found that pores of different sizes could exert different effects and could bring the performance of the carbon material to a very good level (Angew Chem Int Edit, 2009, 48, 1525-. In recent years, attention is paid to a method for preparing hierarchical porous carbon by a sugar blowing method, a 3D graphene bubble grid special structure is prepared by gas flow, the structure contains rich macropores and mesopores, and the bubble grid has interconnectivity, is favorable for rapid mass transfer of catalytic reaction, and is a catalyst carrier material with great potential. The sugar blowing method has harsh reaction conditions and complex process, and currently only stays in a laboratory stage, so that the method which is simple and easy to operate and has a wide application range is adopted to obtain the porous carbon material with the bubble network structure, and the method becomes an important problem to be solved in the field of carbon materials.
Disclosure of Invention
The invention aims to solve the problems of single carbon component, non-adjustable conductivity characteristic and single pore structure in a carbon carrier, and provides a carbon microsphere with a 3D bubble network structure and a preparation method thereof on the basis of fully utilizing the high-temperature catalytic graphitization effect of cobalt on carbon.
The technical scheme of the invention is realized as follows:
a preparation method of a 3D bubble network structure carbon microsphere comprises the following steps:
(1) preparing a mixed solution of glycerol and alcohol as a solvent according to a certain proportion, adding cobalt salt, glucose and a surfactant, stirring for 25-35min to obtain a clarified reaction solution, transferring the clarified reaction solution into a high-pressure reaction kettle, and reacting at 220 ℃ for 3-8h to obtain a reaction product;
(2) cooling the reaction product prepared in the step (1) to room temperature, respectively and fully washing the reaction product with deionized water and ethanol to obtain precipitates, and performing vacuum drying at 40 ℃ to obtain precursor microspheres;
(3) placing the precursor microspheres obtained in the step (2) in a high-temperature tube furnace with atmosphere protection for high-temperature calcination to obtain cobalt/carbon microspheres;
(4) and (4) placing the cobalt/carbon microspheres obtained in the step (3) in an acid solution, stirring for 24 hours to remove metal cobalt particles, repeating the process of removing the metal cobalt particles for 3-5 times, and washing and drying the mixture obtained by filtering to obtain the carbon microspheres with the 3D bubble network structure.
The volume ratio of the glycerol to the alcohol in the step (1) is (1-6): (10-30); every 110-360 mL of solvent is added with 0.1-1 g of cobalt salt, 1-10 g of glucose and 1-10 g of surfactant.
The alcohol is one or a mixed solution of isopropanol, ethanol and glycol; the cobalt salt is Co (NO)3)2·6H2O、CoSO4·7H2O、CoCl2·6H2O、Co(CH3COO)2·4H2One or more mixtures of O; the surfactant is one or more of polyethylene glycol, polyvinylpyrrolidone, sodium dodecyl benzene sulfonate, triethanolamine and sodium lauryl sulfate.
The conditions of high-temperature calcination in the step (3) are that the heating rate is 1 ℃/min, the calcination temperature is 400-.
The calcining atmosphere is nitrogen and hydrogen which are uniformly mixed according to the proportion of (95-97) to (3-5).
And (3) in the step (4), the acidic solution is one or more of hydrochloric acid, sulfuric acid and nitric acid, and the concentration is 1-10 mol/L.
The carbon microsphere with the 3D bubble network structure has a 3D bubble network structure and a two-component heterostructure of amorphous carbon and onion carbon, so that an interface polarization and 3D conductive network structure is formed, the conductivity characteristic is adjustable, and the heterostructure is favorably formed.
The invention has the following beneficial effects:
the invention provides a preparation method of carbon microspheres with 3D bubble network structures on the basis of fully utilizing the high-temperature catalytic graphitization effect of cobalt on carbon, wherein a cobalt source and a carbon source are introduced, a hydrothermal process is adjusted to obtain precursor microspheres, and the precursor microspheres are obtained through high-temperature calcination and acid etching processes, so that the carbon microspheres have novel 3D bubble network structures, are various in pore structures, have higher specific surface areas and good porosity, can be used as excellent carbon carrier materials, and can slow down the influence of volume effect on the performance of battery materials; in addition, the carbon microsphere has a double-component heterostructure of amorphous carbon and onion carbon, can form interface polarization loss and a conductive network structure, is favorable for promoting the rapid attenuation of electromagnetic wave energy, and has wide application prospects in the field of electromagnetic wave absorption.
The obtained carbon microsphere has a 3D bubble network structure, is different from the traditional porous carbon, has various pore structures and variable pore volumes, has higher specific surface area and good porosity, and can provide a proper load space for an active material, for example, the material can be used as a silicon cathode material carrier of a lithium ion battery, reserve an expansion space for silicon particles, and reduce the influence of volume effect on the performance of the battery material; the material can also be used as a drug carrier, and drugs and carbon microspheres form a vesicle structure, so that the effective transportation of the drugs is ensured.
The carbon microspheres obtained by the method have tunable conductivity, and the carbon component is very sensitive to the calcining temperature, so that the method for adjusting the conductivity of the carbon microspheres by using the high-temperature annealing temperature is a simple and effective operation method, and can meet the conductivity requirements of carbon materials in different fields.
The carbon microsphere provided by the invention has a double-component heterostructure, a heterogeneous interface formed by the onion carbon and the amorphous carbon can provide a powerful interface polarization and attenuation loss path for electromagnetic wave attenuation, and meanwhile, the intricate bubble structure can also serve as a coupling circuit, generates induced current under the action of an electromagnetic field and quickly attenuates in a conductive network of carbon, so that the 3D bubble network heterostructure has a wide application prospect in the field of electromagnetic wave absorption.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an XRD pattern of 3D bubble network structure carbon microspheres.
Fig. 2 is an SEM photograph of the precursor microspheres.
Fig. 3 is a TEM photograph of the 3D bubble network structure carbon microsphere.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method and application of the carbon microsphere with the 3D bubble network structure provided by the embodiment are carried out according to the following steps:
firstly, preparing precursor microspheres: the precursor microsphere is obtained by a hydrothermal method. 28 mL of glycerol, 140 mL of isopropanol were mixed well with stirring, followed by the addition of 0.38 g of Co (NO)3)2·6H2Stirring O, 1.9 g of glucose and 3 g of polyvinylpyrrolidone for 30 min to obtain pink clear reaction liquid, and transferring the reaction liquid to a high-pressure reaction kettle to react for 6 h at 180 ℃. And after the reaction is cooled to room temperature, fully washing the obtained precipitate with deionized water and ethanol, and drying in a vacuum drying oven at 40 ℃ for later use to obtain the precursor microsphere.
Secondly, preparing the carbon microspheres with the 3D bubble network structure: placing the precursor microspheres in a high-temperature tube furnace with atmosphere protection for high-temperature calcination, wherein the heating rate is 1 ℃/min, the heat preservation time is 5 h, the calcination temperature is 600 ℃, and the calcination atmosphere is nitrogen/hydrogen mixed gas (V)N2:VH2=97:3) to obtain cobalt/carbon microspheres. Placing the cobalt/carbon microspheres in 1 mol/L HCl solution, stirring for 24h to remove goldThe process is repeated for 4 times to ensure that the metal cobalt is completely removed, and the mixture is washed and dried to obtain the carbon microsphere with the 3D bubble network structure.
FIG. 1 is an XRD (X-ray diffraction) diagram of a carbon microsphere with a 3D bubble network structure, wherein a wide diffraction peak of 23.5 degrees to 23.5 degrees in the diagram proves that the carbon material is mainly in an amorphous state, and a weak diffraction peak of 44 degrees to shows that microcrystalline graphite, namely onion carbon, is formed in a high-temperature calcination process.
FIG. 2 is an SEM photograph of the precursor microsphere, and it can be seen from the figure that the diameter of the precursor microsphere is about 400 nm, the surface is smooth, and the distribution is uniform.
Fig. 3 is a TEM photograph of a 3D bubble network structure carbon microsphere, which is relatively rough in surface and has an obvious porous structure after pretreatment processes such as high-temperature calcination, acid etching and the like, and the yellow frame in the drawing is an obvious bubble structure, and a plurality of bubble structures are connected by carbon components to form a network structure, so that a 3D bubble network structure is formed, and the pore structure is diverse and the pore volume is variable.
Example 2
The preparation method and application of the carbon microsphere with the 3D bubble network structure provided by the embodiment are carried out according to the following steps:
firstly, preparing precursor microspheres: the precursor microsphere is obtained by a hydrothermal method. 10 mL of glycerol and 300 mL of ethanol were mixed with stirring, and then 1 g of CoSO was added4·7H2Stirring O, 1 g of glucose and 10 g of polyethylene glycol for 30 min to obtain pink clear reaction liquid, and transferring the reaction liquid to a high-pressure reaction kettle to react for 8h at 220 ℃. And after the reaction is cooled to room temperature, fully washing the obtained precipitate with deionized water and ethanol, and drying in a vacuum drying oven at 40 ℃ for later use to obtain the precursor microsphere.
Secondly, preparing the carbon microspheres with the 3D bubble network structure: placing the precursor microspheres in a high-temperature tube furnace with atmosphere protection for high-temperature calcination, wherein the heating rate is 1 ℃/min, the heat preservation time is 5 h, the calcination temperature is 400 ℃, and the calcination atmosphere is nitrogen/hydrogen mixed gas (V)N2:VH2=95:5) to obtain cobalt/carbon microspheres. Placing the cobalt/carbon microspheres in 10 mol/L sulfuric acid solution, stirring for 24h to remove metallic cobalt particles, repeating the process for 3 times to ensure that the metallic cobalt is completely removed, and mixingAnd washing and drying the compound to obtain the 3D bubble network structure carbon microsphere.
Example 3
The preparation method and application of the carbon microsphere with the 3D bubble network structure provided by the embodiment are carried out according to the following steps:
firstly, preparing precursor microspheres: the precursor microsphere is obtained by a hydrothermal method. 60 mL of glycerol and 100 mL of ethylene glycol were mixed with stirring and homogenized, followed by the addition of 0.1 g of CoCl2·6H2Stirring O, 10 g of glucose and 1 g of polyethylene glycol for 30 min to obtain pink clear reaction liquid, and transferring the reaction liquid to a high-pressure reaction kettle to react for 3 h at 100 ℃. And after the reaction is cooled to room temperature, fully washing the obtained precipitate with deionized water and ethanol, and drying in a vacuum drying oven at 40 ℃ for later use to obtain the precursor microsphere.
Secondly, preparing the carbon microspheres with the 3D bubble network structure: placing the precursor microspheres in a high-temperature tube furnace with atmosphere protection for high-temperature calcination, wherein the heating rate is 1 ℃/min, the heat preservation time is 5 h, the calcination temperature is 500 ℃, and the calcination atmosphere is nitrogen/hydrogen mixed gas (V)N2:VH2=96:4) to obtain cobalt/carbon microspheres. And (3) placing the cobalt/carbon microspheres in 5 mol/L nitric acid solution, stirring for 24h to remove metal cobalt particles, repeating the process for 5 times to ensure that the metal cobalt is completely removed, washing and drying the mixture to obtain the carbon microspheres with the 3D bubble network structure.
Example 4
The preparation method and application of the carbon microsphere with the 3D bubble network structure provided by the embodiment are carried out according to the following steps:
firstly, preparing precursor microspheres: the precursor microsphere is obtained by a hydrothermal method. 60 mL of glycerol and 100 mL of ethylene glycol were mixed with stirring and homogenized, followed by the addition of 0.1 g of CoCl2·6H2O、0.1 g Co(CH3COO)2·4H2Stirring O10 g, glucose and 1 g polyethylene glycol for 30 min to obtain pink clear reaction liquid, and transferring the reaction liquid to a high-pressure reaction kettle to react for 3 h at 100 ℃. And after the reaction is cooled to room temperature, fully washing the obtained precipitate with deionized water and ethanol, and drying in a vacuum drying oven at 40 ℃ for later use to obtain the precursor microsphere.
Secondly, preparing the carbon microspheres with the 3D bubble network structure: placing the precursor microspheres in a high-temperature tube furnace with atmosphere protection for high-temperature calcination, wherein the heating rate is 1 ℃/min, the heat preservation time is 5 h, the calcination temperature is 500 ℃, and the calcination atmosphere is nitrogen/hydrogen mixed gas (V)N2:VH2=96:4) to obtain cobalt/carbon microspheres. And (3) placing the cobalt/carbon microspheres in a 7 mol/L nitric acid solution, stirring for 24h to remove metal cobalt particles, repeating the process for 5 times to ensure that the metal cobalt is completely removed, washing and drying the mixture to obtain the carbon microspheres with the 3D bubble network structure.
Example 5
The preparation method and application of the carbon microsphere with the 3D bubble network structure provided by the embodiment are carried out according to the following steps:
firstly, preparing precursor microspheres: the precursor microsphere is obtained by a hydrothermal method. 28 mL of glycerol, 50 mL of isopropanol, and 140 mL of isopropanol were mixed well with stirring, followed by the addition of 0.38 g of Co (NO)3)2·6H2O, 1.9 g of glucose and 3 g of sodium dodecyl benzene sulfonate are stirred for 30 min to obtain pink clear reaction liquid, and the reaction liquid is transferred to a high-pressure reaction kettle to react for 6 h at 180 ℃. And after the reaction is cooled to room temperature, fully washing the obtained precipitate with deionized water and ethanol, and drying in a vacuum drying oven at 40 ℃ for later use to obtain the precursor microsphere.
Secondly, preparing the carbon microspheres with the 3D bubble network structure: placing the precursor microspheres in a high-temperature tube furnace with atmosphere protection for high-temperature calcination, wherein the heating rate is 1 ℃/min, the heat preservation time is 5 h, the calcination temperature is 600 ℃, and the calcination atmosphere is nitrogen/hydrogen mixed gas (V)N2:VH2=97:3) to obtain cobalt/carbon microspheres. And (3) placing the cobalt/carbon microspheres in 6 mol/L HCl solution, stirring for 24h to remove metal cobalt particles, repeating the process for 4 times to ensure that the metal cobalt is completely removed, washing and drying the mixture to obtain the 3D bubble network structure carbon microspheres.
Example 6
The preparation method and application of the carbon microsphere with the 3D bubble network structure provided by the embodiment are carried out according to the following steps:
firstly, preparing precursor microspheres: the precursor microsphere is obtained by a hydrothermal method. Mixing 28 mL of glycerol and 50 mL of isopropanol, 140 mL of isopropanol were mixed well with stirring, followed by the addition of 0.38 g of Co (NO)3)2·6H2Stirring O, 1.9 g of glucose, 3 g of polyvinylpyrrolidone and 2 g of polyethylene glycol for 30 min to obtain pink clear reaction liquid, and transferring the reaction liquid to a high-pressure reaction kettle to react for 6 h at 180 ℃. And after the reaction is cooled to room temperature, fully washing the obtained precipitate with deionized water and ethanol, and drying in a vacuum drying oven at 40 ℃ for later use to obtain the precursor microsphere.
Secondly, preparing the carbon microspheres with the 3D bubble network structure: placing the precursor microspheres in a high-temperature tube furnace with atmosphere protection for high-temperature calcination, wherein the heating rate is 1 ℃/min, the heat preservation time is 5 h, the calcination temperature is 650 ℃, and the calcination atmosphere is nitrogen/hydrogen mixed gas (V)N2:VH2=97:3) to obtain cobalt/carbon microspheres. And (3) placing the cobalt/carbon microspheres in 3 mol/L HCl solution, stirring for 24h to remove metal cobalt particles, repeating the process for 3 times to ensure that the metal cobalt is completely removed, washing and drying the mixture to obtain the 3D bubble network structure carbon microspheres.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A preparation method of a 3D bubble network structure carbon microsphere is characterized by comprising the following steps:
(1) preparing a mixed solution of glycerol and alcohol as a solvent according to a certain proportion, adding cobalt salt, glucose and a surfactant, stirring for 25-35min to obtain a clarified reaction solution, transferring the clarified reaction solution into a high-pressure reaction kettle, and reacting at 220 ℃ for 3-8h to obtain a reaction product; the surfactant is one or more of polyethylene glycol, polyvinylpyrrolidone, sodium dodecyl benzene sulfonate, triethanolamine and sodium lauryl sulfate;
(2) cooling the reaction product prepared in the step (1) to room temperature, respectively and fully washing the reaction product with deionized water and ethanol to obtain precipitates, and performing vacuum drying at 40 ℃ to obtain precursor microspheres;
(3) placing the precursor microspheres obtained in the step (2) in a high-temperature tube furnace with atmosphere protection for high-temperature calcination to obtain cobalt/carbon microspheres; the calcining atmosphere is nitrogen and hydrogen which are uniformly mixed according to the proportion of (95-97) to (3-5);
(4) placing the cobalt/carbon microspheres obtained in the step (3) in an acid solution, stirring for 24 hours to remove metal cobalt particles, repeating the process of removing the metal cobalt particles for 3-5 times, and washing and drying the mixture obtained by filtering to obtain the carbon microspheres with the 3D bubble network structure; the acid solution is one or more of hydrochloric acid, sulfuric acid and nitric acid, and the concentration is 1-10 mol/L.
2. The method for preparing the carbon microsphere with the 3D bubble network structure according to claim 1, wherein the method comprises the following steps: the volume ratio of the glycerol to the alcohol in the step (1) is (1-6): (10-30); every 110-360 mL of solvent is added with 0.1-1 g of cobalt salt, 1-10 g of glucose and 1-10 g of surfactant.
3. The method for preparing the carbon microsphere with the 3D bubble network structure according to claim 2, wherein the method comprises the following steps: the alcohol is one or a mixed solution of isopropanol, ethanol and glycol; the cobalt salt is Co (NO)3)2·6H2O、CoSO4·7H2O、CoCl2·6H2O、Co(CH3COO)2·4H2One or more mixtures of O.
4. The method for preparing the carbon microsphere with the 3D bubble network structure according to claim 1, wherein the method comprises the following steps: the conditions of high-temperature calcination in the step (3) are that the heating rate is 1 ℃/min, the calcination temperature is 400-.
5. A3D bubble network structure carbon microsphere prepared by the method of any one of claims 1 to 4, characterized in that: the carbon microsphere with the 3D bubble network structure has a 3D bubble network structure and a two-component heterostructure of amorphous carbon and onion carbon, so that an interface polarization and 3D conductive network structure is formed, the conductivity characteristic is adjustable, and the heterostructure is favorably formed.
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