CN111916736A - Preparation method and application of porous carbon with two-dimensional core-shell structure - Google Patents

Preparation method and application of porous carbon with two-dimensional core-shell structure Download PDF

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CN111916736A
CN111916736A CN202010801249.8A CN202010801249A CN111916736A CN 111916736 A CN111916736 A CN 111916736A CN 202010801249 A CN202010801249 A CN 202010801249A CN 111916736 A CN111916736 A CN 111916736A
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dimensional core
porous carbon
shell structure
preparation
shell
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CN111916736B (en
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余东波
宋清镜
高晴亮
崔接武
秦永强
吴玉程
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Hefei University of Technology
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Hefei University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method and application of a porous carbon with a two-dimensional core-shell structure, which comprises the following steps: dissolving 2-methylimidazole powder in methanol, adding Co-TCPP powder to form a uniform suspension A, and stirring at room temperature; dissolving zinc nitrate hexahydrate in methanol to form a solution B; slowly adding the solution B into the suspension A, continuously stirring at room temperature, centrifugally separating a product, washing with ethanol, and drying in an oven to obtain a Co-TCPP @ ZIF-8 two-dimensional core-shell structure; annealing the two-dimensional core-shell structure powder under the protection of argon to obtain a two-dimensional core-shell structure porous carbon material; and (3) placing the two-dimensional core-shell structure porous carbon material in a nitric acid solution, carrying out stirring reaction in a water bath, then carrying out centrifugal separation on a product, washing the product with ethanol, and drying the product in an oven to obtain the pure two-dimensional core-shell structure porous carbon. The two-dimensional core-shell structure porous carbon prepared by the invention can be widely applied to the fields of electrochemical energy storage, separation and purification, drug sustained release and the like.

Description

Preparation method and application of porous carbon with two-dimensional core-shell structure
Technical Field
The invention relates to the technical field of micro-nano composite material synthesis, in particular to a preparation method and application of porous carbon with a two-dimensional core-shell structure.
Background
In recent years, MOFs materials formed by complexing organic ligands and inorganic metal ions (metal clusters) have been the focus of attention of researchers. One of the great advantages of MOFs is that the structure can be designed according to the application of researchers, varying from ligand to ligand and metal center. Due to its porosity and high specific surface area, it exhibits excellent properties in many fields such as catalysis, energy storage and conversion, and gas adsorption and separation. As a multifunctional material, the materials for synthesizing MOFs can make the raw materials with lower cost have low frame density and high thermal stability, and these advantages make MOFs a candidate material for energy materials. The two-dimensional core-shell structure porous carbon prepared by the invention has both the conductivity of graphitized carbon in the material and the high specific surface area of the porous carbon outside the material, and fully exerts the advantages of two MOF materials derived from the porous carbon. Enriches the types of MOF structural materials, expands the application field of MOFs materials and has great practical utilization value. The problems of poor cycle stability and poor large-current discharge capacity of the conventional two-dimensional core-shell structure porous carbon in the application of a lithium ion battery cathode material exist.
Disclosure of Invention
The invention aims to provide a preparation method and application of a porous carbon with a two-dimensional core-shell structure, which can solve the technical problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of porous carbon with a two-dimensional core-shell structure comprises the following steps:
(1) dissolving 2-methylimidazole powder in methanol, adding Co-TCPP powder to form a uniform suspension A, and stirring at room temperature;
(2) dissolving zinc nitrate hexahydrate in methanol to form a solution B;
(3) slowly adding the solution B into the suspension A, continuously stirring at room temperature, centrifugally separating a product, washing with ethanol, and drying in an oven to obtain a Co-TCPP @ ZIF-8 two-dimensional core-shell structure;
(4) annealing the two-dimensional core-shell structure powder under the protection of argon to obtain a two-dimensional core-shell structure porous carbon material;
(5) and (3) placing the two-dimensional core-shell structure porous carbon material in a nitric acid solution, carrying out stirring reaction in a water bath, then carrying out centrifugal separation on a product, washing the product with ethanol, and drying the product in an oven to obtain the pure two-dimensional core-shell structure porous carbon.
Preferably, in the step (1), the concentration of 2-methylimidazole in the suspension A is 0.19mol L-1Co-TCPP concentration of 0.12g L-1The room temperature was 25 ℃.
Preferably, in the step (2), the concentration of the solution B is 0.067mol L-1。
Preferably, in the step (3), the room temperature is 25 ℃, the stirring time is 10min, and the temperature of the oven is 75-85 ℃.
Preferably, in the step (4), the annealing temperature is 900 ℃ and the holding time is 2 hours.
Preferably, in the step (5), the volume ratio of the concentrated nitric acid to the water in the nitric acid solution is 1: 2.
Preferably, in the step (5), the water bath temperature is 75-85 ℃, and the water bath time is 23-25 h.
Preferably, in the step (5), the temperature of the oven is 75-85 ℃.
Preferably, the two-dimensional core-shell structure porous carbon prepared by the method is used for preparing a negative electrode material of a high-performance sodium-ion battery.
Compared with the prior art, the invention has the beneficial effects that:
1. the two-dimensional core-shell structure porous carbon prepared by the invention has different properties of two MOFs, graphitized carbon in the derived carbon material has high conductivity, and the porous carbon outside has high specific surface area, so that the performance requirements of large specific surface area, high conductivity and the like required by high-efficiency energy storage can be met, and the electrochemical performance of the porous carbon is further improved;
2. an available way for controllable preparation of the MOF @ MOF core-shell structure is provided, the types of MOF structure materials are enriched, the application of the MOF materials is expanded, and meanwhile, more alternative electrode active materials are provided for high-efficiency electrochemical energy storage application;
3. the two-dimensional core-shell porous carbon prepared by the invention has unique and novel structure, high specific surface area, rich pore size distribution, simple preparation method and high yield, and nitrogen is doped on the surface of the two-dimensional nanosheet;
4. the method provided by the invention has the advantages of simple synthesis conditions, easiness in operation and wide universality, and the two-dimensional core-shell structure porous carbon prepared by the method can be widely applied to the fields of electrochemical energy storage, separation and purification, drug sustained release and the like. Secondly, the two-dimensional core-shell structure porous carbon prepared by the invention solves the problems of poor cycle stability and poor large-current discharge capability of the conventional two-dimensional core-shell structure porous carbon in the application of lithium ion battery cathode materials.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a FESEM image of Co-TCPP prepared in an example of the present invention;
FIG. 2 is a FESEM image and a TEM image of a two-dimensional core-shell structure of Co-TCPP @ ZIF-8 prepared in an example of the present invention;
fig. 3 is a FESEM view and a TEM view of the two-dimensional core-shell structure porous carbon prepared in the example of the present invention;
FIG. 4 is an XRD pattern of Co-TCPP prepared in an example of the present invention and an XRD pattern of Co-TCPP @ ZIF-8 two-dimensional core-shell structure prepared in example 2;
fig. 5 is an electrochemical performance diagram of the two-dimensional core-shell structure porous carbon prepared in the embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
1. Preparation of Co-TCPP powder
(1) 4.4mg of cobalt nitrate hexahydrate, 1.56mg of 4, 4-bipyridine and 10mg of polyvinylpyrrolidone were dissolved in 4.5ml of N, N-dimethylformamide and 1.5ml of ethanol to prepare a solution C; dissolving 4mg porphin in 1.5ml N, N-dimethylformamide and 0.5ml ethanol to obtain solution D; slowly dropping the solution D into the solution C, uniformly stirring, and performing ultrasonic treatment for 25 min; then heating to 80 ℃, and continuously stirring to keep reacting for 24 hours;
(2) and (3) centrifugally separating the product, washing the product with ethanol, and drying the product in an oven at 80 ℃ to obtain Co-TCPP powder.
FIG. 1 is a FESEM image of the prepared Co-TCPP, showing that the nanosheets are uniformly distributed and the surface is relatively smooth.
2. Preparation of porous carbon with Co-TCPP @ ZIF-8 two-dimensional core-shell structure and two-dimensional core-shell structure
(1) Dissolving 0.4g of 2-methylimidazole in 25ml of methanol, then adding 3mg of Co-TCPP powder to form a uniform suspension A, and stirring at room temperature; 0.1g of zinc nitrate hexahydrate is dissolved in 5ml of methanol to form a solution B; slowly adding the solution B into the suspension A, continuously stirring at room temperature, and stirring for reaction for 10 min;
(2) centrifugally separating the product obtained in the step (1), washing the product with ethanol, and drying the product in an oven at 80 ℃ to obtain a Co-TCPP @ ZIF-8 two-dimensional core-shell structure;
(3) and (2) annealing the two-dimensional core-shell structure powder with argon at 900 ℃, pickling in a nitric acid solution, stirring for 24 hours at 80 ℃, centrifugally separating the product, washing for 3 times with ethanol, and then drying the product in an oven at 80 ℃ to obtain the two-dimensional core-shell structure porous carbon.
FIG. 2 is a FESEM and TEM image of the Co-TCPP @ ZIF-8 two-dimensional core-shell structure prepared in this example. Fig. 3 is FESEM and TEM images of the two-dimensional core-shell structure porous carbon prepared in this example. The surface of the original nano-sheet can be successfully loaded with a plurality of uniform particles to form a core-shell structure, and a plurality of holes are formed after annealing. Fig. 4 is an XRD pattern of the Co-TCPP @ ZIF-8 two-dimensional core-shell structure prepared in this example, and the angles corresponding to the peaks respectively correspond to the nanosheet Co-TCPP peaks, and also correspond to the positions of the ZIF-8 standard peaks reported in the literature, further illustrating the successful preparation of the two-dimensional core-shell structure material.
3. Performance test of two-dimensional core-shell structure porous carbon
(1) Uniformly mixing and dissolving two-dimensional core-shell structure porous carbon, conductive carbon black and PVDF in a mass ratio of 8:1:1 in 1-methyl-2-pyrrolidone (NMP) to prepare slurry, then uniformly coating the slurry on a copper foil current collector, and drying the copper foil current collector in a vacuum drying oven at 60 ℃ for 24 hours;
(2) slicing the dried copper foil current collector to prepare a working electrode, taking glass fiber as a diaphragm and electrolyte as binary electrolyte, assembling the working electrode and the electrolyte into a 2032 button cell in a glove box filled with argon, wherein the test voltage range is 0.01V-3V vs Na+/Na。
FIG. 5 is a sodium electrochemical storage sodium ion performance diagram of the prepared porous carbon with the two-dimensional core-shell structure. The sodium electrical property of the two-dimensional core-shell structure porous carbon is better.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the present invention as defined in the accompanying claims.

Claims (9)

1. A preparation method of porous carbon with a two-dimensional core-shell structure is characterized by comprising the following steps:
(1) dissolving 2-methylimidazole powder in methanol, adding Co-TCPP powder to form a uniform suspension A, and stirring at room temperature;
(2) dissolving zinc nitrate hexahydrate in methanol to form a solution B;
(3) slowly adding the solution B into the suspension A, continuously stirring at room temperature, centrifugally separating a product, washing with ethanol, and drying in an oven to obtain a Co-TCPP @ ZIF-8 two-dimensional core-shell structure;
(4) annealing the two-dimensional core-shell structure powder under the protection of argon to obtain a two-dimensional core-shell structure porous carbon material;
(5) and (3) placing the two-dimensional core-shell structure porous carbon material in a nitric acid solution, carrying out stirring reaction in a water bath, then carrying out centrifugal separation on a product, washing the product with ethanol, and drying the product in an oven to obtain the pure two-dimensional core-shell structure porous carbon.
2. The preparation method of the two-dimensional core-shell porous carbon according to claim 1, characterized in that: in the step (1), the concentration of the 2-methylimidazole in the suspension A is 0.19mol L-1Co-TCPP concentration of 0.12g L-1The room temperature was 25 ℃.
3. The preparation method of the two-dimensional core-shell porous carbon according to claim 1, characterized in that: in the step (2), the concentration of the solution B is 0.067mol L-1。
4. The preparation method of the two-dimensional core-shell porous carbon according to claim 1, characterized in that: in the step (3), the room temperature is 25 ℃, the stirring time is 10min, and the temperature of the oven is 75-85 ℃.
5. The preparation method of the two-dimensional core-shell porous carbon according to claim 1, characterized in that: in the step (4), the annealing temperature is 900 ℃, and the heat preservation time is 2 hours.
6. The preparation method of the two-dimensional core-shell porous carbon according to claim 1, characterized in that: in the step (5), the volume ratio of the concentrated nitric acid to the water in the nitric acid solution is 1: 2.
7. The preparation method of the two-dimensional core-shell porous carbon according to claim 1, characterized in that: in the step (5), the water bath temperature is 75-85 ℃, and the water bath time is 23-25 h.
8. The preparation method of the two-dimensional core-shell porous carbon according to claim 1, characterized in that: in the step (5), the temperature of the oven is 75-85 ℃.
9. The two-dimensional core-shell porous carbon prepared by the method according to any one of claims 1 to 8 is used for preparing a negative electrode material of a high-performance sodium-ion battery.
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