CN111453712A - Hollow carbon ball with multistage pore structure and preparation method thereof - Google Patents
Hollow carbon ball with multistage pore structure and preparation method thereof Download PDFInfo
- Publication number
- CN111453712A CN111453712A CN201910052287.5A CN201910052287A CN111453712A CN 111453712 A CN111453712 A CN 111453712A CN 201910052287 A CN201910052287 A CN 201910052287A CN 111453712 A CN111453712 A CN 111453712A
- Authority
- CN
- China
- Prior art keywords
- carbon
- carbon source
- hollow
- hollow carbon
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 151
- 239000011148 porous material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 22
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 20
- 238000001694 spray drying Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- 235000002639 sodium chloride Nutrition 0.000 claims description 11
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 150000003904 phospholipids Chemical class 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000000463 material Substances 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000000635 electron micrograph Methods 0.000 description 19
- 239000003575 carbonaceous material Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000012798 spherical particle Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 241001247852 Berchemia Species 0.000 description 1
- 125000003184 C60 fullerene group Chemical group 0.000 description 1
- 235000015826 Flagellaria indica Nutrition 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
Abstract
The invention relates to a hollow carbon sphere with a hierarchical pore structure, which is of the hierarchical pore structure and simultaneously has micropores, mesopores and macropores; wherein, the aperture of the micropore is not more than 2nm, the aperture of the mesopore is distributed between 2nm and 50nm, and the aperture of the macropore is more than 50 nm; the pore volume of the micro-pores is 0.047-0.30cm3The pore volume of the contribution of the mesopores is 0.15-0.49cm3The pore volume of the macro-pores is 0.07-0.80cm3(ii) in terms of/g. The hollow carbon spheres have the particle size of 2.5-6.5 mu m, the wall thickness of 5-8nm and the specific surface area of 443.23m2(ii) in terms of/g. The invention also provides a preparation method of the material. The carbon spheres provided by the invention have the characteristics of thin wall, porosity, high specific surface area and the like, and can increaseThe application performance is enhanced. Meanwhile, the method has the advantages of simple and controllable steps, low cost, suitability for industrial production and wide application field.
Description
Technical Field
The invention relates to the field of porous carbon materials, in particular to a hollow carbon sphere with a multistage pore channel structure and a preparation method thereof.
Background
The use of carbon materials dates back to the ancient times in humans. The hollow carbon spheres have the characteristics of high electrical conductivity, good thermal stability, corrosion resistance, light weight, various molecular structures and the like, so that the hollow carbon spheres have particularly wide application in the fields of batteries, chemical engineering, machinery, electronics, aerospace, metallurgy, nuclear energy and the like. In recent years, with the discovery and development of carbon materials such as C60, carbon nanotubes, and graphene, it has been found that the microstructure, e.g., pore size, has a decisive role in the properties and applications of the material. It is generally stated that pore sizes of less than 2nm are micropores, those of more than 50nm are macropores, and those in between are mesopores. Hierarchical pore means to include both micropores, mesopores, and macropores. Besides conventional properties, the carbon material with hierarchical pores also has a macroporous structure, a short-distance diffusion path, a high specific surface area, high porosity and the like, and is beneficial to adsorption and transmission of active substances, so that the carbon material has higher application performance. On the basis of the size of the pore channel, the hollow structure can obviously increase the specific area and reduce the density, thereby being beneficial to further improving the performance.
At present, the methods for preparing the hollow carbon spheres mainly comprise a high-temperature pyrolysis method, a laser distillation method, a template method, an arc discharge method and the like. The development of a simple and efficient preparation method of the hollow carbon spheres with the multilevel pore channel structure is still one of important challenges.
In the prior art, no public report is found about a preparation method of a hollow carbon sphere with a hierarchical pore structure. Although there are some reports on the multi-level pore carbon material and the hollow carbon sphere, for example, chinese patent CN104528720A discloses a preparation method and product of the multi-level pore carbon material; CN105731419A discloses a preparation method of a rod-shaped hierarchical porous carbon material; CN103537262B discloses a preparation method of a nitrogen-doped hierarchical porous carbon material; CN104310368A discloses a preparation method of hollow carbon spheres; CN100537422C discloses a preparation method of hollow micron carbon spheres with regular size; CN104319402B discloses a preparation method of a multilayer carbon hollow sphere negative electrode material. However, these reports differ from the present invention mainly in that: 1. the carbon spheres have different structures, and the sample prepared by the method simultaneously contains a hierarchical pore structure and a hollow structure; 2. the preparation method is different, and the invention comprises a spray drying method to prepare the carbon sphere particles.
Based on the above, a carbon sphere having both hierarchical porous channels and a hollow structure and a method for preparing the same are desired. The special structure in the carbon ball makes the carbon ball have the following characteristics: the thin wall, the porosity and the high specific surface area are beneficial to the potential application of the material in the fields of energy storage, chemistry and chemical engineering, mechanical electronics and the like. In addition, the preparation method of the carbon ball provided by the invention comprises a spray drying step, and the use of the step enables the obtained carbon ball to have multilevel pore channels and hollow structures simultaneously, so that the carbon ball has the excellent performances of thin wall, porosity and high specific surface area.
Disclosure of Invention
The invention aims to provide a hollow carbon sphere with a multistage pore channel structure and a preparation method thereof. The hollow carbon sphere with the multilevel pore channel structure has the advantages of thin wall, multiple pores and high specific surface area, and the preparation method provided by the invention has the advantages of simple process flow, low cost, suitability for industrial production and wide application field.
The object of the present invention and the technical problem to be solved are achieved by the following technical means. According to the hollow carbon sphere with the multilevel pore channel structure, the hollow carbon sphere is of the multilevel pore channel structure and simultaneously has micropores, mesopores and macropores; wherein, the aperture of the micropore is not more than 2nm, the aperture of the mesopore is distributed between 2nm and 50nm, and the aperture of the macropore is more than 50 nm; the pore volume of the micro-pores is 0.047-0.30cm3The pore volume of the contribution of the mesopores is 0.15-0.49cm3The pore volume of the macro-pores is 0.07-0.80cm3/g。
The hollow carbon sphere has a particle size of 2.5-6.5 μm, a wall thickness of 5-8nm, and a specific surface area of 443.23m2/g。
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The invention provides a method for preparing hollow carbon spheres with a hierarchical pore structure, which comprises the following steps:
dissolving a carbon source in a solvent to obtain a carbon source precursor solution, wherein the concentration of the obtained carbon source precursor solution is 5-30 g/L;
step (2): adding metal salt into the carbon source precursor solution prepared in the step (1), and mixing and uniformly stirring to obtain a carbon source solution;
and (3): carrying out spray drying on the carbon source solution obtained in the step (2) at a certain temperature and a certain pressure and at a certain extrusion pump speed to obtain a dried product;
and (4): pre-oxidizing the product dried in the step (3) under a certain condition to obtain an oxidized product;
and (5): and (4) calcining the oxidized product in the step (4) under the argon atmosphere to obtain the hollow carbon sphere with the multi-stage pore channel structure.
The preparation method described above, wherein the carbon source in the step (1) is selected from one or more of graphene oxide, glucose, acetic acid, phospholipid, gelatin, fructose or lactose.
The preparation method described above, wherein the solvent in the step (1) is one or more selected from ethanol, water, methanol, ethylene glycol or acetone.
The preparation method described above, wherein the metal salt in the step (2) is selected from one or more of sodium nitrate, sodium carbonate, sodium sulfate, potassium chloride, potassium nitrate or sodium chloride.
The preparation method described above, wherein the metal salt in the step (2) is added in a weight ratio of the metal salt to the carbon source of (1-20): 1 is added.
The preparation method as described above, wherein the spray drying conditions in the step (3) are: the temperature is 150 ℃ and 300 ℃, the air pressure is 0.07-0.23bar, and the extrusion pump speed is 5-35R/min.
The preparation method as described above, wherein the pre-oxidation conditions in the step (4) are: the temperature is 100 ℃ and 290 ℃, and the time is 1-17 h.
The preparation method, wherein the calcination temperature in the step (5) is 500-1300 ℃, and the time is 3-8 h.
By the technical scheme, the invention (name) at least has the following advantages:
(1) the hollow carbon ball with the multi-stage pore channel structure has the advantages of 2.5-6.5 mu m of particle size, thin wall, thickness of only 5-8nm, high specific surface area of 443.23m2/g。
(2) The hollow carbon sphere with the hierarchical pore structure provided by the invention has the hierarchical pore structure and the mesoporous structure, wherein the hierarchical pore structure has micropores, mesopores and macropores, and the carbon material with the hierarchical pores has the conventional properties, a macroporous structure, a short-distance diffusion path, a high specific surface area, high porosity and the like, so that the adsorption and transmission of active substances are facilitated, and the hollow carbon sphere has higher application performance.
(3) The invention also provides a method for preparing the hollow carbon sphere with the hierarchical pore structure, which comprises the step of spray drying to prepare the carbon microsphere particles with the hierarchical pore structure, wherein the step of spray drying can be used for facilitating the uniform distribution of the particle size; the carbon sphere particles with the hollow structure are prepared by thermal cracking, and the whole preparation method has simple process and low cost, is suitable for industrial production and has wide application field.
In summary, the hollow carbon spheres with the hierarchical pore structure and the preparation method thereof provided by the invention provide porous carbon spheres with uniform size distribution and high specific surface area, so that the porous carbon spheres are more practical and have industrial utilization value. The hollow carbon ball has a special structure, and the contribution of the size and the pore volume of each stage of pore channel structure makes the material different from the prior art, has the characteristics of thin wall, multiple pores, high specific surface area and the like, and can enhance the application performance.
The material has the advantages and practical value, does not have similar design publication or use in similar products, is innovative, has great improvement on the preparation method or function, has great technical progress, produces good and practical effects, has multiple enhanced efficacies compared with the existing porous carbon material, is more suitable for practical use, has industrial wide utilization value, and is a novel, improved and practical new design.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
The specific preparation method and structure of the present invention are given in detail by the following examples.
Drawings
Fig. 1 is an SEM electron micrograph of a hollow carbon sphere having a hierarchical pore structure prepared in example 1 according to the present invention;
fig. 2 is an EDX elemental distribution diagram of hollow carbon spheres having a hierarchical pore structure prepared in example 1 according to the present invention;
fig. 3 is a TEM electron micrograph of a hollow carbon sphere having a hierarchical pore structure prepared in example 1 according to the present invention;
fig. 4 is a BET test graph of specific surface area of a hollow carbon sphere having a hierarchical pore structure prepared in example 1 according to the present invention;
fig. 5 is an SEM electron micrograph of a hollow carbon sphere having a hierarchical pore structure prepared in example 2 according to the present invention;
fig. 6 is an SEM electron micrograph of a hollow carbon sphere having a hierarchical pore structure prepared in example 3 according to the present invention;
fig. 7 is an SEM electron micrograph of a hollow carbon sphere having a hierarchical pore structure prepared in example 4 according to the present invention;
FIG. 8 is an SEM electron micrograph of hollow carbon spheres with a hierarchical pore structure prepared in example 5 according to the present invention;
FIG. 9 is a TEM electron micrograph of hollow carbon spheres with a hierarchical pore structure prepared in example 6 according to the present invention;
FIG. 10 is a TEM electron micrograph of hollow carbon spheres with a hierarchical pore structure prepared in example 7 according to the present invention;
fig. 11 is an SEM electron micrograph of the hollow carbon spheres having a hierarchical pore structure prepared in example 8 according to the present invention.
FIG. 12 is an SEM electron micrograph of carbon spheres prepared in comparative example 1 according to the present invention;
fig. 13 shows a hollow carbon sphere having a multi-level pore structure according to the present invention.
Detailed Description
The present invention is further illustrated by the following figures and examples, which are to be understood as merely illustrative and not restrictive. Furthermore, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings herein, and such equivalents may fall within the scope of the invention as defined in the appended claims.
Example 1
Taking 0.5g of graphene oxide to dissolve in 100ml of ethanol to prepare a carbon source precursor solution with the concentration of 5 g/L, adding 0.55g of sodium nitrate into the obtained carbon source precursor solution, mixing and uniformly stirring to obtain the carbon source solution, carrying out spray drying on the carbon source solution at the temperature of 150 ℃ and the air pressure of 0.07bar at the extrusion pump speed of 5R/min to obtain a dried product, then carrying out pre-oxidation at 100 ℃ for 10 hours, and finally calcining at 700 ℃ for 3 hours in an argon atmosphere to obtain the hollow carbon sphere with the multi-stage pore channel structure.
Fig. 1 is an SEM electron micrograph of a hollow carbon sphere having a hierarchical pore structure prepared in example 1 according to the present invention. It can be seen that the particles produced are spherical in morphology and have a size of about 3.5 microns.
Fig. 2 is an EDX elemental distribution diagram of hollow carbon spheres having a hierarchical pore structure prepared in example 1 according to the present invention. It can be seen that the carbon content reaches 95% and only a small amount of oxygen impurities are contained.
Fig. 3 is a TEM electron micrograph of the hollow carbon sphere having a hierarchical pore structure prepared in example 1 according to the present invention. As can be seen from the figure, the carbon spheres have spherical shapes, hollow structures, thin sphere walls and thickness of about 5 nm.
Fig. 4 is a BET test chart of specific surface area of the hollow carbon sphere having a hierarchical pore structure prepared in example 1 according to the present invention. It can be seen that the spherical material contains micropores smaller than 2nm, mesopores between 2nm and 50nm, and macropores larger than 50nm, i.e. a hierarchical pore structure. The pore volume contributed by micropores was 0.047-0.30cm3The pore volume of the contribution of the mesopores is 0.15-0.49cm3The pore volume of the macro-pores is 0.07-0.80cm3(ii) in terms of/g. The specific surface area is high and can reach 443.23m2/g。
Example 2
The same procedure as in example 1 was followed except that the carbon source concentration was adjusted as follows:
the preparation method comprises the steps of dissolving 3g of graphene oxide in 100ml of ethanol to prepare a carbon source precursor solution with the concentration of 30 g/L, adding 11.4g of sodium nitrate into the obtained carbon source precursor solution, mixing and uniformly stirring to obtain the carbon source solution, carrying out spray drying on the carbon source solution at the temperature of 150 ℃ and the pressure of 0.07bar at the extrusion pump speed of 5R/min to obtain a dried product, pre-oxidizing at 100 ℃ for 10 hours, and finally calcining at 700 ℃ for 3 hours in an argon atmosphere to obtain the hollow carbon ball with the multi-stage pore channel structure.
Fig. 5 is an SEM electron micrograph of the hollow carbon spheres having a hierarchical pore structure prepared in example 2 according to the present invention. It can be seen from the figure that the prepared carbon spheres have spherical particle shapes, the size of the carbon spheres is about 5 microns, and the particle size distribution is not very uniform.
Example 3
The same procedure as in example 1 was followed, except that the type of carbon source was adjusted as follows:
taking 0.5g of glucose to dissolve in 100ml of ethanol to prepare a carbon source precursor solution with the concentration of 5 g/L, adding 0.55g of sodium nitrate into the obtained carbon source precursor solution, mixing and stirring uniformly to obtain the carbon source solution, carrying out spray drying on the carbon source solution at the temperature of 150 ℃ and the pressure of 0.07bar and at the extrusion pump speed of 5R/min to obtain a dried product, then carrying out pre-oxidation at 100 ℃ for 10 hours, and finally calcining at 700 ℃ for 3 hours in an argon atmosphere to obtain the hollow carbon sphere with the multi-stage pore channel structure.
Fig. 6 is an SEM electron micrograph of the hollow carbon spheres having a hierarchical pore structure prepared in example 3 according to the present invention. It can be seen that the prepared carbon spheres have spherical particle morphology and a size of about 3 microns.
Example 4
The same procedure as in example 1 was followed, except that the kind of the solvent was adjusted as follows:
the preparation method comprises the steps of dissolving 0.5g of graphene oxide in 100ml of water to prepare a carbon source precursor solution with the concentration of 5 g/L, adding 0.55g of sodium nitrate into the obtained carbon source precursor solution, mixing and uniformly stirring to obtain the carbon source solution, carrying out spray drying on the carbon source solution at the temperature of 150 ℃ and the pressure of 0.07bar at the extrusion pump speed of 5R/min to obtain a dried product, pre-oxidizing at 100 ℃ for 10 hours, and finally calcining at 700 ℃ for 3 hours in an argon atmosphere to obtain the hollow carbon ball with the multi-stage pore channel structure.
Fig. 7 is an SEM electron micrograph of the hollow carbon spheres having a hierarchical pore structure prepared in example 4 according to the present invention. It can be seen from the figure that the prepared carbon spheres have spherical particle morphology, the size of the carbon spheres is about 2.5 microns, and the particle size is relatively uniform.
Example 5
The same procedure as in example 1 was followed, except that the mass ratio of the carbon source to the salt was adjusted as follows:
taking 0.5g of graphene oxide to dissolve in 100ml of water to prepare a carbon source precursor solution with the concentration of 5 g/L, adding 11g of sodium nitrate into the obtained carbon source precursor solution, mixing and stirring uniformly to obtain a carbon source solution, carrying out spray drying on the carbon source solution at the temperature of 150 ℃ and the pressure of 0.07bar at the extrusion pump speed of 5R/min to obtain a dried product, then carrying out pre-oxidation at 100 ℃ for 10 hours, and finally calcining at 700 ℃ for 3 hours in an argon atmosphere to obtain the hollow carbon sphere with the multistage pore structure.
Fig. 8 is an SEM electron micrograph of the hollow carbon spheres having the hierarchical pore structure prepared in example 5 according to the present invention. It can be seen that the prepared carbon spheres have spherical particle morphology and size of about 6 microns.
Example 6
The same procedure as in example 1 was followed, except that the relevant reaction conditions were adjusted as follows:
taking 0.5g of graphene oxide to dissolve in 100ml of ethanol to prepare a carbon source precursor solution with the concentration of 5 g/L, adding 0.55g of sodium nitrate into the obtained carbon source precursor solution, mixing and uniformly stirring to obtain the carbon source solution, carrying out spray drying on the carbon source solution at the temperature of 300 ℃ and the pressure of 0.07bar at the extrusion pump speed of 20R/min to obtain a dried product, then carrying out pre-oxidation at 290 ℃ for 1 hour, and finally calcining at 900 ℃ for 8 hours in an argon atmosphere to obtain the hollow carbon sphere with the hierarchical pore structure.
Fig. 9 is a TEM electron micrograph of a hollow carbon sphere having a hierarchical pore structure prepared in example 6 according to the present invention. It can be seen from the figure that the prepared carbon sphere particles are spherical in shape and have a hollow structure.
Example 7
The same procedure as in example 1 was followed, except that the relevant reaction conditions were adjusted as follows:
taking 0.5g of graphene oxide to dissolve in 100ml of ethanol to prepare a carbon source precursor solution with the concentration of 5 g/L, adding 0.55g of sodium nitrate into the obtained carbon source precursor solution, mixing and uniformly stirring to obtain the carbon source solution, carrying out spray drying on the carbon source solution at the temperature of 225 ℃ and the pressure of 0.23bar and at the extrusion pump speed of 35R/min to obtain a dried product, then carrying out pre-oxidation at 195 ℃ for 9 hours, and finally calcining at 1300 ℃ for 3 hours in an argon atmosphere to obtain the hollow carbon sphere with the multi-stage pore channel structure.
Fig. 10 is a TEM electron micrograph of a hollow carbon sphere having a hierarchical pore structure prepared in example 7 according to the present invention. The prepared carbon sphere particles are spherical in shape, have a hollow structure and have a wall thickness of about 8 nanometers.
Example 8
The same procedure as in example 1 was followed, except that the relevant reaction conditions were adjusted as follows:
taking 0.5g of graphene oxide to dissolve in 100ml of ethanol to prepare a carbon source precursor solution with the concentration of 5 g/L, adding 0.55g of sodium nitrate into the obtained carbon source precursor solution, mixing and uniformly stirring to obtain the carbon source solution, carrying out spray drying on the carbon source solution at the temperature of 150 ℃ and the air pressure of 0.15bar and at the extrusion pump speed of 5R/min to obtain a dried product, then carrying out pre-oxidation at 100 ℃ for 17 hours, and finally calcining at 1300 ℃ for 6 hours in an argon atmosphere to obtain the hollow carbon sphere with the multi-stage pore channel structure.
Fig. 11 is an SEM electron micrograph of the hollow carbon spheres having a hierarchical pore structure prepared in example 8 according to the present invention. It can be seen from the figure that the prepared carbon sphere has a spherical particle shape, and the internal structure of the carbon sphere is exposed due to the higher temperature, and the size of the carbon sphere is about 6.5 microns.
Comparative example 1
A carbon microsphere prepared by a hydrothermal carbonization method is reported in literature (Weijing, et al, functional materials, 1001, 9731(2014) and supplejack (II) -136-04), 1.5g of glucose is weighed, 60m of L deionized water is weighed and added into a beaker for dissolving, the prepared solution is transferred into a 100m L reaction kettle and put into an oven for reacting for 24 hours at 200 ℃, the oven is closed, natural cooling is carried out, products in the reaction kettle are poured out, centrifuged and ultrasonically washed for multiple times, and the products are dried at 60 ℃ to obtain the carbon sphere product.
Fig. 12 is an SEM characterization view of carbon spheres prepared in comparative example 1 according to the present invention. As can be seen, the carbon spheres are solid spheres with a uniform size distribution and a particle size of about 1.8 microns. Thus, it can be concluded from the carbon sphere structure that the methods of the prior art do not allow the preparation of the hollow hierarchical pore structure of the present invention.
In summary, the preparation method provided by the present invention includes a step of spray drying to prepare the carbon microsphere particles with a hierarchical pore structure, wherein the step of spray drying can facilitate uniform distribution of particle size; the carbon sphere particles with the hollow structure are prepared by thermal cracking, and the whole preparation method has simple process and low cost, is suitable for industrial production and has wide application field. The carbon spheres obtained by the preparation method have the particle size of 2.5-6.5 mu m, thin wall and thickness of only 5-8 nm. The pore volume of the micropore contribution is 0.047-0.30cm calculated according to the BET test result3G, pores contributed by mesoporesThe volume is 0.15-0.49cm3The pore volume of the macro-pores is 0.07-0.80cm3(ii) in terms of/g. The specific surface area is high and can reach 443.23m2(ii) in terms of/g. The carbon ball has a hierarchical pore structure and a mesoporous structure, wherein the hierarchical pore structure has micropores, mesopores and macropores, and the carbon material with the hierarchical pores has a macroporous structure, a short-distance diffusion path, a high specific surface area, high porosity and the like besides conventional properties, and is beneficial to adsorption and transmission of active substances, so that the carbon ball has higher application performance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A hollow carbon ball with a hierarchical pore structure is provided, which has micropores, mesopores and macropores; wherein, the aperture of the micropore is not more than 2nm, the aperture of the mesopore is distributed between 2nm and 50nm, and the aperture of the macropore is more than 50 nm; the pore volume of the micro-pores is 0.047-0.30cm3The pore volume of the contribution of the mesopores is 0.15-0.49cm3The pore volume of the macro-pores is 0.07-0.80cm3/g。
2. The hollow carbon sphere of claim 1, wherein the hollow carbon sphere has a particle diameter of 2.5 to 6.5 μm, a wall thickness of 5 to 8nm, and a specific surface area of 443.23m2/g。
3. A method for preparing the hollow carbon sphere having a hierarchical pore structure of claim 1 or 2, comprising the steps of:
dissolving a carbon source in a solvent to obtain a carbon source precursor solution, wherein the concentration of the obtained carbon source precursor solution is 5-30 g/L;
step (2): adding metal salt into the carbon source precursor solution prepared in the step (1), and mixing and uniformly stirring to obtain a carbon source solution;
and (3): carrying out spray drying on the carbon source solution obtained in the step (2) at a certain temperature and a certain pressure and at a certain extrusion pump speed to obtain a dried product;
and (4): pre-oxidizing the product dried in the step (3) under a certain condition to obtain an oxidized product;
and (5): and (4) calcining the oxidized product in the step (4) under the argon atmosphere to obtain the hollow carbon sphere with the multi-stage pore channel structure.
4. The preparation method according to claim 3, wherein the carbon source in the step (1) is selected from one or more of graphene oxide, glucose, acetic acid, phospholipid, gelatin, fructose or lactose.
5. The production method according to claim 3, wherein the solvent in the step (1) is selected from one or more of ethanol, water, methanol, ethylene glycol or acetone.
6. The production method according to claim 3, wherein the metal salt in the step (2) is selected from one or more of sodium nitrate, sodium carbonate, sodium sulfate, potassium chloride, potassium nitrate, or sodium chloride.
7. The production method according to any one of claims 3 to 6, wherein the metal salt in the step (2) is used in a weight ratio of the metal salt to the carbon source of (1 to 20): 1 is added.
8. The production method according to claim 3, wherein the spray-drying conditions in the step (3) are: the temperature is 150 ℃ and 300 ℃, the air pressure is 0.07-0.23bar, and the extrusion pump speed is 5-35R/min.
9. The production method according to claim 3, wherein the pre-oxidation conditions in the step (4) are: the temperature is 100 ℃ and 290 ℃, and the time is 1-17 h.
10. The preparation method according to claim 3, wherein the calcination temperature in step (5) is 500-1300 ℃ for 3-8 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910052287.5A CN111453712A (en) | 2019-01-21 | 2019-01-21 | Hollow carbon ball with multistage pore structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910052287.5A CN111453712A (en) | 2019-01-21 | 2019-01-21 | Hollow carbon ball with multistage pore structure and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111453712A true CN111453712A (en) | 2020-07-28 |
Family
ID=71675396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910052287.5A Pending CN111453712A (en) | 2019-01-21 | 2019-01-21 | Hollow carbon ball with multistage pore structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111453712A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079346A (en) * | 2020-10-09 | 2020-12-15 | 济南大学 | Metal organic framework in-situ activated hollow carbon sphere and preparation method and application thereof |
| CN114433055A (en) * | 2022-03-10 | 2022-05-06 | 苏州大学 | Carbon catalyst with highly-open hierarchical pore structure and preparation method and application thereof |
| CN114558603A (en) * | 2022-03-10 | 2022-05-31 | 苏州大学 | Nitrogen-doped hollow hierarchical pore carbon microsphere with high oxygen content and preparation method and application thereof |
| CN114832773A (en) * | 2022-03-08 | 2022-08-02 | 湖北工业大学 | Composite hollow carbon sphere ion adsorption material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4937210A (en) * | 1987-09-24 | 1990-06-26 | Ecc International Limited | Production of porous inorganic materials |
| CN105329874A (en) * | 2014-08-08 | 2016-02-17 | 中国石油化工股份有限公司 | Heteroatom-doped carbon microsphere and preparation method thereof |
| CN107275098A (en) * | 2017-06-30 | 2017-10-20 | 湖南大学 | A kind of three-dimensional hollow carbon foam electrode material with multiple dimensioned pore structure and preparation method and application |
| KR20170136147A (en) * | 2016-05-31 | 2017-12-11 | 가천대학교 산학협력단 | Method of manufacturing porous graphene and porous graphene electrode for elecrochemical device |
| CN108511204A (en) * | 2018-04-02 | 2018-09-07 | 张家港博威新能源材料研究所有限公司 | A kind of preparation method of the nitrogen co-doped Porous hollow carbosphere of oxygen |
| CN108993537A (en) * | 2018-08-03 | 2018-12-14 | 苏州大学 | A kind of carbon-based sulfonic acid microballoon in the multistage gradient hole of uniform particle diameter, preparation method and its application |
-
2019
- 2019-01-21 CN CN201910052287.5A patent/CN111453712A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4937210A (en) * | 1987-09-24 | 1990-06-26 | Ecc International Limited | Production of porous inorganic materials |
| CN105329874A (en) * | 2014-08-08 | 2016-02-17 | 中国石油化工股份有限公司 | Heteroatom-doped carbon microsphere and preparation method thereof |
| KR20170136147A (en) * | 2016-05-31 | 2017-12-11 | 가천대학교 산학협력단 | Method of manufacturing porous graphene and porous graphene electrode for elecrochemical device |
| CN107275098A (en) * | 2017-06-30 | 2017-10-20 | 湖南大学 | A kind of three-dimensional hollow carbon foam electrode material with multiple dimensioned pore structure and preparation method and application |
| CN108511204A (en) * | 2018-04-02 | 2018-09-07 | 张家港博威新能源材料研究所有限公司 | A kind of preparation method of the nitrogen co-doped Porous hollow carbosphere of oxygen |
| CN108993537A (en) * | 2018-08-03 | 2018-12-14 | 苏州大学 | A kind of carbon-based sulfonic acid microballoon in the multistage gradient hole of uniform particle diameter, preparation method and its application |
Non-Patent Citations (4)
| Title |
|---|
| MEI,RG: "Hollow reduced graphene oxide microspheres as a high-performance anode materials for Li-ion batteries", 《ELECTROCHIMICAL ACTA》 * |
| 吕路路等: "基于分子设计多孔碳球的制备研究进展", 《电子元件与材料》 * |
| 庞杰: "木质素磺酸钠基多孔炭的制备及电容性能研究", 《中国博士学位论文全文数据库》 * |
| 程锦: "超级电容器及其电极材料研究进展", 《电池工业》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079346A (en) * | 2020-10-09 | 2020-12-15 | 济南大学 | Metal organic framework in-situ activated hollow carbon sphere and preparation method and application thereof |
| CN114832773A (en) * | 2022-03-08 | 2022-08-02 | 湖北工业大学 | Composite hollow carbon sphere ion adsorption material and preparation method and application thereof |
| CN114832773B (en) * | 2022-03-08 | 2023-04-18 | 湖北工业大学 | Composite hollow carbon sphere ion adsorption material and preparation method and application thereof |
| CN114433055A (en) * | 2022-03-10 | 2022-05-06 | 苏州大学 | Carbon catalyst with highly-open hierarchical pore structure and preparation method and application thereof |
| CN114558603A (en) * | 2022-03-10 | 2022-05-31 | 苏州大学 | Nitrogen-doped hollow hierarchical pore carbon microsphere with high oxygen content and preparation method and application thereof |
| CN114433055B (en) * | 2022-03-10 | 2022-12-23 | 苏州大学 | Carbon catalyst with highly-open hierarchical pore structure and preparation method and application thereof |
| WO2023168799A1 (en) * | 2022-03-10 | 2023-09-14 | 苏州大学 | Carbon catalyst with highly open hierarchical pore structure as well as preparation method for and use of carbon catalyst |
| WO2023168800A1 (en) * | 2022-03-10 | 2023-09-14 | 苏州大学 | Nitrogen-doped hollow hierarchically-porous carbon microsphere with high oxygen content, and preparation method therefor and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Revitalizing carbon supercapacitor electrodes with hierarchical porous structures | |
| Eftekhari et al. | Ordered mesoporous carbon and its applications for electrochemical energy storage and conversion | |
| Peng et al. | Programmable synthesis of radially gradient-structured mesoporous carbon nanospheres with tunable core-shell architectures | |
| Weng et al. | Template-free synthesis of metal oxide hollow micro-/nanospheres via Ostwald ripening for lithium-ion batteries | |
| CN111453712A (en) | Hollow carbon ball with multistage pore structure and preparation method thereof | |
| Zhu et al. | Hard-template synthesis of three-dimensional interconnected carbon networks: rational design, hybridization and energy-related applications | |
| Qiu et al. | High performance asymmetric supercapacitors with ultrahigh energy density based on hierarchical carbon nanotubes@ NiO core–shell nanosheets and defect-introduced graphene sheets with hole structure | |
| JP6198810B2 (en) | Carbon material for catalyst support | |
| Wei et al. | Controllable synthesis of mesoporous carbon nanospheres and Fe–N/carbon nanospheres as efficient oxygen reduction electrocatalysts | |
| Zhao et al. | A universal method to fabricating porous carbon for Li-O2 battery | |
| WO2020150855A1 (en) | Hollow carbon sphere with multi-stage pore structure and preparation method therefor | |
| JP7153005B2 (en) | MESOPOROUS CARBON, METHOD FOR MANUFACTURING SAME, AND POLYMER FUEL CELL | |
| CN111293301B (en) | Soft and hard carbon composite porous negative electrode material for sodium ion battery and preparation method thereof | |
| CN108346782B (en) | Porous copper oxide microsphere/multilayer graphene composite material and preparation method thereof | |
| CN110729480A (en) | Nitrogen-doped porous hollow carbon sphere and preparation method and application thereof | |
| Liu et al. | Mesoporous carbon with large pores as anode for Na-ion batteries | |
| Liu et al. | N-doped microporous carbon hollow spheres with precisely controlled architectures for supercapacitor | |
| JP2014240330A (en) | Method for preparing graphene spherical hollow body, graphene spherical hollow body, graphene spherical hollow body integrated electrode, and graphene spherical hollow body integrated capacitor | |
| Yu et al. | Sculpturing solid polymer spheres into internal gridded hollow carbon spheres under controlled pyrolysis micro-environment | |
| Bulbula et al. | Hierarchically porous graphene for batteries and supercapacitors | |
| Zhang et al. | Scalable synthesis of porous silicon/carbon microspheres as improved anode materials for Li-ion batteries | |
| Wang et al. | Fabrication and activation of carbon nanotube foam and its application in energy storage | |
| Zhao et al. | Facile synthesis of hierarchically porous carbons and their application as a catalyst support for methanol oxidation | |
| Lv et al. | Potassium chloride-catalyzed growth of porous carbon nanotubes for high-performance supercapacitors | |
| CN111153403B (en) | Alginate-based porous carbon and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200728 |
|
| RJ01 | Rejection of invention patent application after publication |