CN112209364A - Hierarchical pore structure nano carbon material and preparation method and application thereof - Google Patents
Hierarchical pore structure nano carbon material and preparation method and application thereof Download PDFInfo
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention provides a nano carbon material with a hierarchical pore structure, and a preparation method and application thereof. The preparation method comprises the following steps: 1,2,4, 5-pyromellitic dianhydride and hydrazine are used as monomers, a polymer is obtained through stepwise polymerization, the polymer is subjected to intramolecular cyclization induced self-assembly to obtain an hourglass-shaped polymer assembly, and the assembly is used as a precursor and carbonized in an inert atmosphere to obtain the hierarchical pore structure carbon material; the preparation method can be realized by a one-pot method, has simple and convenient preparation steps, mild conditions and short preparation period, and can be used for mass preparation. The unique internal penetrating network structure and the hierarchical pore structure of the nano carbon material with the hierarchical pore structure are beneficial to electron and substance transmission, have excellent adsorption performance and electricity storage capacity, and can be used as an adsorption material and an electrode material of a lithium ion capacitor.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a hierarchical pore structure nano carbon material, a preparation method of the hierarchical pore structure nano carbon material and application of the hierarchical pore structure nano carbon material.
Background
With global warming, the production and storage of energy has become a focus of attention in today's society. To meet the increasing energy demand of human society, in 2050 the electricity demand of human beings was 14TW, which is equivalent to twice of today, and the fossil fuels consumed for the production of this electricity are equivalent to 10 per year10Ton of petroleum. However, the conventional energy is increasingly exhausted and causes serious environmental pollution, so that the development of renewable clean energy is urgently needed. Among the energy sources, electric energy is considered as one of the most potential clean energy sources, but the storage and carrying of the electric energy requires a carrier, and the development of an electric energy storage system is crucial.
In various electric energy carriers such as lithium ion batteries, super capacitors and solar batteries, the lithium ion capacitor is used as a novel energy storage device, has the advantages of high power density, high electrostatic capacity and long cycle life, and is expected to be widely applied to the fields of new energy automobiles, solar energy, wind energy and the like. The activated carbon is an ideal positive electrode material of the lithium ion capacitor, and carbon nanotubes, graphene, carbon nanospheres and the like are widely applied to the lithium ion capacitor. However, these materials often have a mesoporous or microporous structure, and the high power density of the lithium ion capacitor cannot be fully exerted in the charging and discharging process. The multi-level pore structure can promote the ion transmission and the electron transmission rate in the charge and discharge process of the lithium ion capacitor, thereby obviously improving the energy density and the power density of the lithium ion capacitor.
At present, the preparation of carbon materials with hierarchical pore structures still faces a serious challenge, and especially for the control of the size of the hierarchical pores, it is difficult to obtain the hierarchical pore structures with micropores, small mesopores and large mesopores.
Disclosure of Invention
In order to solve the problems in the prior art, the present invention aims to provide a nano carbon material with a hierarchical pore structure, a preparation method thereof and an application thereof. The preparation method of the nano carbon material with the hierarchical pore structure is simple and convenient in steps, environment-friendly and capable of being prepared in large scale.
In order to achieve the purpose, the invention adopts the following technical scheme:
the hierarchical pore structure carbon nanomaterial is characterized in that the hierarchical pore structure carbon nanomaterial is composed of carbon nanosheets, or the hierarchical pore structure carbon nanomaterial has a hierarchical pore structure with micropores, small mesopores and large mesopores.
A method for preparing a hierarchical pore structure nano carbon material comprises the following steps: carbonizing an hourglass-shaped polymer assembly serving as a precursor in an inert atmosphere to obtain a hierarchical pore structure carbon material; the hourglass-shaped polymer assembly is obtained by self-assembly of a polymer through intramolecular cyclization induction, wherein the polymer is an alternating copolymer of 1,2,4, 5-pyromellitic dianhydride and hydrazine, contains a large number of benzene rings, and has a regular structure.
The preparation method of the hourglass-shaped polymer assembly comprises the following steps: dissolving a polymer in dimethylformamide at a concentration of 50.0-150.0 mg/mL, carrying out heat treatment on the polymer solution, carrying out intramolecular cyclization induced self-assembly to obtain an hourglass-shaped polymer assembly dispersion liquid, cooling, centrifuging, and carrying out vacuum drying to obtain hourglass-shaped polymer assembly powder.
In the above method for preparing the hourglass-shaped polymer assembly, the heat treatment temperature is 153 ℃ and the heat treatment time is 10-60 minutes.
In the preparation method of the hierarchical pore structure carbon material, the inert gas can be one or more of nitrogen, hydrogen and ammonia; the calcining temperature can be 700-1200 ℃; the hourglass-shaped polymer assembly is composed of fusiform nano sheets.
The hierarchical pore structure carbon material can be applied as an adsorbing material or an electrode material of a lithium ion capacitor.
Due to the adoption of the scheme, the invention has the beneficial effects that:
the carbon material with the hierarchical pore structure is composed of carbon nano sheets, and the carbon nano sheets are connected with each other in the inner part and mutually penetrate, so that the carbon material with the hierarchical pore structure with micropores, small mesopores and large mesopores is beneficial to effective transmission of electrons and substances, and the electrochemical energy storage performance can be obviously improved.
Secondly, the preparation steps of the hierarchical pore structure carbon material are simple and convenient, and the hierarchical pore structure carbon material can be prepared in large scale. After the polymerization is finished, the solution of the polymer is directly subjected to heat treatment for intramolecular cyclization induced self-assembly, and can be obtained in a single solvent by a one-pot method without a dialysis process. The hourglass-shaped polymer assembly can be obtained after centrifugal drying, the carbon material with the hierarchical pore structure can be obtained after carbonization in inert atmosphere, the preparation steps are simple and convenient, the period is short, and mass preparation can be realized.
Thirdly, the polymer is an alternating copolymer of 1,2,4, 5-pyromellitic dianhydride and hydrazine, and due to the regular structure and the aromatic structure of the polymer, the multi-level pore structure nano carbon material obtained after carbonization has a highly graphitized structure and has very good conductive capability and energy storage capability. In addition, the hierarchical pore structure of micropores, small mesopores and large mesopores of the hierarchical pore structure nano carbon material is beneficial to the effective transmission of electrons and substances, and can be used as an active electrode material of a lithium ion capacitor.
Fourthly, the carbon material with the hierarchical pore structure is obtained by directly carbonizing the hourglass-shaped polymer assembly, has a controllable hierarchical pore structure, and has three pore structures, namely a micropore structure, a mesopore structure and a macropore structure. The hierarchical pore structure enables the hierarchical pore structure carbon material to have excellent adsorption performance, and therefore the hierarchical pore structure carbon material can be used as a high-efficiency adsorption material.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of an hourglass-shaped polymer assembly according to a first embodiment of the present invention.
FIG. 2 is a Transmission Electron Microscope (TEM) image of a carbon material having a hierarchical pore structure in a first example of the present invention.
FIG. 3 is a pore structure distribution diagram of the multi-stage pore structure carbon material according to the first embodiment of the present invention.
FIG. 4 is a graph showing the adsorption performance of the carbon material having a hierarchical pore structure according to the first embodiment of the present invention.
FIG. 5 is a graph showing electrochemical performance of the carbon material with a hierarchical pore structure according to the first embodiment of the present invention.
Detailed Description
The invention provides a preparation method of a hierarchical pore structure nano carbon material and an application of the hierarchical pore structure nano carbon material.
< carbon Material having hierarchical pore Structure >
The nano carbon material with the hierarchical pore structure is composed of carbon nano sheets, a penetrating three-dimensional network is formed inside the nano carbon material, and the nano carbon material is provided with the hierarchical pore structure with micropores, small mesopores and large mesopores.
< method for producing carbon Material having hierarchical pore Structure >
The preparation method of the hierarchical pore structure carbon material comprises the following steps: and taking the hourglass-shaped polymer assembly as a precursor, and carbonizing in an inert atmosphere to obtain the carbon material with the hierarchical pore structure.
The hourglass-shaped polymer assembly is formed by self-assembly of polymers through intramolecular cyclization induction. The polymer is an alternating copolymer of 1,2,4, 5-pyromellitic dianhydride and hydrazine, contains a large number of benzene rings, and has a regular structure.
The preparation method of the hourglass-shaped polymer assembly comprises the following steps: dissolving a polymer in Dimethylformamide (DMF) at a concentration of 50.0-150.0 mg/mL, carrying out heat treatment under a stirring condition, obtaining an hourglass-shaped polymer assembly dispersion liquid through intramolecular cyclization induced self-assembly, cooling the hourglass-shaped polymer assembly dispersion liquid, centrifuging, and carrying out vacuum drying to obtain the hourglass-shaped polymer assembly, wherein the hourglass-shaped polymer assembly is composed of shuttle-shaped nanosheets. In the method, the polymer is induced to self-assemble by adopting a direct heat treatment method, so that the solid content of an assembly can be obviously improved, and the method has the condition of large-scale preparation.
In the above method for preparing the hourglass-shaped polymer assembly, the heat treatment temperature is 153 ℃ and the heat treatment time is 10 to 60 minutes, preferably 10 minutes.
In the preparation method of the hierarchical pore structure carbon material, the inert gas may be one or more of nitrogen, hydrogen and ammonia. The temperature of carbonization and calcination is 700-1200 ℃.
< application of hierarchical porous carbon Material >
1. The hierarchical pore structure carbon material of the present invention can be used as an adsorbing material.
The carbon material with the multilevel pore structure is obtained by taking an hourglass-shaped polymer assembly as a precursor and carbonizing the hourglass-shaped polymer assembly in an inert atmosphere. The hourglass-shaped polymer assembly is formed by self-assembling an alternating copolymer of 1,2,4, 5-pyromellitic dianhydride and hydrazine. Since the hourglass-shaped polymer assembly is composed of the fusiform nanosheets, the hierarchical pore structure carbon material formed after calcination has a hierarchical pore structure and can be used as an adsorbent.
2. The hierarchical pore structure carbon material can be used as an active electrode material of a lithium ion capacitor.
The carbon material with the multilevel pore structure is obtained by taking an hourglass-shaped polymer assembly as a precursor and carbonizing the hourglass-shaped polymer assembly in an inert atmosphere. The hierarchical pore structure carbon material is composed of carbon nanosheets, has a hierarchical pore structure of micropores, small mesopores and large mesopores, and can promote the transmission rate of electrons and ions in the charging and discharging process, so that the hierarchical pore structure carbon material can be used as an active electrode material of a lithium ion capacitor, and the energy density and the power density of the lithium ion capacitor are remarkably improved.
The invention is further described below with reference to the following figures and examples.
Example one
The embodiment provides a hierarchical pore structure nano carbon material and a preparation method thereof, wherein the hierarchical pore structure nano carbon material is composed of carbon nano sheets, a penetrating three-dimensional network is formed inside the hierarchical pore structure nano carbon material, and the hierarchical pore structure comprises micropores, small mesopores and large mesopores. The preparation method comprises the following steps:
(1) preparation of hourglass-shaped polymer assemblies:
1000mg of the polymer was dissolved in Dimethylformamide (DMF) at a concentration of 50mg/mL, and the polymer solution was heated to 153 ℃ in an oil bath and kept at that temperature for 10 minutes, followed by natural cooling to room temperature to give a solution containing an hourglass-shaped polymer assembly. The solution was centrifuged and the precipitate was washed 3 times with deionized water to give an hourglass-shaped polymer assembly (in powder form) after drying in a vacuum oven for 24 hours.
(2) And preparing the hierarchical pore structure carbon material:
carbonizing the hourglass-shaped polymer assembly (in a powder form) obtained in the step (1) at 700 ℃ under the protection of nitrogen, preserving the temperature at 700 ℃ for 2 hours, and naturally cooling to room temperature to obtain the hierarchical pore structure carbon material with the hierarchical pore structure.
The resulting hourglass-shaped polymer assembly has a regular structure, as shown in fig. 1, and is clearly seen to be composed of fusiform nanoplates. Fig. 2 shows that the obtained hierarchical porous carbon material is assembled by carbon nano-sheets, and a large number of gaps are formed among the nano-sheets, but the carbon material is not a solid structure. The obtained hierarchical pore structure carbon material was subjected to pore size distribution analysis, and found to have a hierarchical pore structure including micropores of 0.98nm, small mesopores of 3.8nm and 8.3nm, and large mesopores of 16nm and 28nm, respectively, as shown in fig. 3. Fig. 4 shows the effect of adsorbing methylene blue by the hierarchical porous carbon material, and it is understood from the figure that almost all methylene blue is adsorbed by the hierarchical porous carbon material after the adsorption is completed, and therefore, the adsorbent is preferable. As shown in fig. 5, electrochemical analysis shows that the hierarchical porous structure carbon material shows high specific capacity and excellent cycling stability when used as an electrode material of a lithium ion capacitor, and thus is an ideal electrochemical energy storage material.
Example two
The embodiment provides a hierarchical pore structure nano carbon material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) preparation of hourglass-shaped polymer assemblies:
1000mg of the polymer was dissolved in Dimethylformamide (DMF) at a concentration of 100mg/mL, and the polymer solution was heated to 153 ℃ in an oil bath and kept at that temperature for 25 minutes, followed by natural cooling to room temperature to give a solution containing an hourglass-shaped polymer assembly. The solution was centrifuged and the precipitate was washed 3 times with deionized water to give an hourglass-shaped polymer assembly (in powder form) after drying in a vacuum oven for 24 hours.
(2) And preparing the hierarchical pore structure carbon material:
carbonizing the hourglass-shaped polymer assembly (in a powder form) obtained in the step (1) at 900 ℃ under the protection of nitrogen, preserving the temperature of 900 ℃ for 2 hours, and naturally cooling to room temperature to obtain the hierarchical pore structure carbon material with the hierarchical pore structure.
EXAMPLE III
The embodiment provides a hierarchical pore structure nano carbon material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) preparation of hourglass-shaped polymer assemblies:
1000mg of the polymer was dissolved in Dimethylformamide (DMF) at a concentration of 125mg/mL, and the polymer solution was heated to 153 ℃ in an oil bath and kept at that temperature for 40 minutes, followed by natural cooling to room temperature to give a solution containing an hourglass-shaped polymer assembly. The solution was centrifuged and the precipitate was washed 3 times with deionized water to give an hourglass-shaped polymer assembly (in powder form) after drying in a vacuum oven for 24 hours.
(2) And preparing the hierarchical pore structure carbon material:
carbonizing the hourglass-shaped polymer assembly (in a powder form) obtained in the step (1) at 1000 ℃ under the protection of hydrogen, preserving the temperature at 1000 ℃ for 2 hours, and naturally cooling to room temperature to obtain the hierarchical pore structure carbon material with the hierarchical pore structure.
Example four
The embodiment provides a hierarchical pore structure nano carbon material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) preparation of hourglass-shaped polymer assemblies:
1000mg of the polymer was dissolved in Dimethylformamide (DMF) at a concentration of 150mg/mL, and the polymer solution was heated to 153 ℃ in an oil bath and maintained at that temperature for 60 minutes, followed by natural cooling to room temperature to give a solution containing an hourglass-shaped polymer assembly. The solution was centrifuged and the precipitate was washed 3 times with deionized water to give an hourglass-shaped polymer assembly (in powder form) after drying in a vacuum oven for 24 hours.
(2) And preparing the hierarchical pore structure carbon material:
carbonizing the hourglass-shaped polymer assembly (in a powder form) obtained in the step (1) at 1200 ℃ under the protection of ammonia gas, preserving the heat at 1200 ℃ for 2 hours, and naturally cooling to room temperature to obtain the hierarchical pore structure carbon material with the hierarchical pore structure.
In summary, the method for preparing the carbon material with the hierarchical pore structure of the present invention uses the hourglass-shaped polymer assembly as a precursor, specifically, obtains an hourglass-shaped polymer assembly dispersion liquid through intramolecular cyclization induced self-assembly after the heat treatment of the polymer in DMF, and obtains the hourglass-shaped polymer assembly (in powder form) after centrifugation, washing and vacuum drying. And carbonizing the hourglass-shaped polymer assembly serving as a precursor in an inert atmosphere to prepare the multistage pore structure carbon material. In the preparation method, the hourglass-shaped polymer assembly is composed of the shuttle-shaped nanosheets (figure 1), so that the structure of the hourglass-shaped polymer assembly is reserved after carbonization, and the obtained hierarchical pore structure carbon material is composed of the carbon nanosheets and has a hierarchical pore structure. The preparation method has the advantages of simple steps, simple operation and low raw material cost, and can be used for preparing a large amount of the carbon material with the hierarchical pore structure. The obtained carbon material with the hierarchical pore structure has the hierarchical pore structure, can efficiently adsorb pollutants in sewage, and is an ideal adsorbing material. In addition, the hierarchical pore structure of the hierarchical pore structure carbon material can effectively promote the transmission of electrons and ions in the charging and discharging process, so that the energy storage capacity of the hierarchical pore structure carbon material can be obviously improved, and the hierarchical pore structure carbon material is an ideal energy storage material.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A nano carbon material with a hierarchical pore structure is characterized in that: the nano carbon material with the hierarchical pore structure is composed of carbon nano sheets, a penetrating three-dimensional network is formed inside the nano carbon material, and the nano carbon material has a hierarchical pore structure with micropores, small mesopores and large mesopores.
2. The method for producing a hierarchical pore structure nanocarbon material according to claim 1, wherein: the hourglass-shaped polymer assembly is obtained through intramolecular cyclization induced self-assembly, and is carbonized in an inert atmosphere to obtain the nano carbon material with the multilevel pore structure, wherein the hourglass-shaped polymer assembly is obtained through intramolecular cyclization induced self-assembly of a polymer, and the polymer is an alternating copolymer of 1,2,4, 5-pyromellitic dianhydride and hydrazine, contains a large number of benzene rings and has a regular structure.
3. The method of claim 2, wherein: the hourglass-shaped polymer assembly is composed of fusiform nano sheets.
4. The method of claim 2, wherein: the preparation method of the hourglass-shaped polymer assembly comprises the following steps: dissolving the polymer in dimethylformamide at a concentration of 50.0-150.0 mg/mL, carrying out heat treatment on the polymer solution, carrying out intramolecular cyclization induced self-assembly to obtain an hourglass-shaped polymer assembly dispersion liquid, cooling the hourglass-shaped polymer assembly dispersion liquid, centrifuging, and carrying out vacuum drying to obtain hourglass-shaped polymer assembly powder.
5. The method of claim 4, wherein: the heat treatment temperature is 153 ℃, and the heat treatment time is 10-60 minutes.
6. The method of claim 2, wherein: the inert gas is one or more of nitrogen, hydrogen and ammonia; the carbonization temperature is 700-1200 ℃.
7. Use of the hierarchical pore structure carbon material according to claim 1 as an adsorbent material.
8. Use of the hierarchical pore structure carbon material according to claim 1 as an electrode material for a lithium ion capacitor.
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