CN111916737A - Preparation method and application of porous carbon with one-dimensional core-shell structure - Google Patents
Preparation method and application of porous carbon with one-dimensional core-shell structure Download PDFInfo
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- CN111916737A CN111916737A CN202010802031.4A CN202010802031A CN111916737A CN 111916737 A CN111916737 A CN 111916737A CN 202010802031 A CN202010802031 A CN 202010802031A CN 111916737 A CN111916737 A CN 111916737A
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- 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
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- H—ELECTRICITY
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- 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
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- 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 of a one-dimensional core-shell structure porous carbon, which comprises the following steps: dissolving 2-methylimidazole powder in methanol, adding Co-MOF-74 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-MOF-74@ ZIF-8 one-dimensional core-shell structure; and (3) annealing the Co-MOF-74@ ZIF-8 one-dimensional core-shell structure under the protection of argon, and then pickling with nitric acid to obtain a product. The one-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.
Description
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 one-dimensional core-shell structure, which is obtained by taking Metal Organic Frameworks (MOFs) as precursors and combining argon annealing treatment.
Background
Metal Organic Frameworks (MOFs) are a novel class of porous crystalline materials, and are formed by matching organic ligands and inorganic metal ions (metal clusters). While MOFs have become an area of rapid development and have attracted considerable attention from researchers over the last two decades, as a class of branches of coordination polymers, a great advantage of MOFs is that their structures can be designed, varying from ligand to ligand, and metal center, depending on the application of the researchers. The key structural features of MOFs are their porosity and high specific surface area. The catalyst has excellent performance in the fields of catalysis, energy storage and conversion, gas adsorption and separation and the like. As a multifunctional material, the material for synthesizing the MOFs can enable the raw material with lower cost to have low frame density and high thermal stability, and the advantages enable the MOFs to become a candidate material of an energy material. The one-dimensional core-shell structure porous carbon prepared by the invention fully exerts the advantages of two MOF material derived porous carbons, has the conductivity of graphitized carbon and the high specific surface area of the porous carbon, and contributes to higher specific capacity. The method further enriches the types of MOF structural materials, expands the application field of MOFs materials, provides more alternative electrode active materials for high-efficiency electrochemical energy storage application, and has great practical utilization value.
Disclosure of Invention
The invention aims to: provides a preparation method of a porous carbon with a one-dimensional core-shell structure, and aims to develop an electrode material applied to a high-performance sodium-ion battery. The material has simple preparation method, low cost and wide application prospect.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of porous carbon with a one-dimensional core-shell structure comprises the following steps:
(1) dissolving 2-methylimidazole powder in methanol, adding Co-MOF-74 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-MOF-74@ ZIF-8 one-dimensional core-shell structure;
(4) annealing the Co-MOF-74@ ZIF-8 one-dimensional core-shell structure under the protection of argon to obtain a one-dimensional core-shell structure porous carbon material;
(5) and (3) placing the one-dimensional core-shell structure porous carbon material in a nitric acid solution, stirring and reacting in a water bath, then centrifugally separating a product, washing with ethanol, and drying in an oven to obtain the pure one-dimensional core-shell structure porous carbon.
Preferably, in the step (1), the concentration of 2-methylimidazole in the suspension A is 1.49mol L-1The concentration of Co-MOF-74 was 6.66g L-1The room temperature is 25 ℃;
preferably, in step (2), the concentration of solution B is 0.55mol L-1；
Preferably, in the step (3), the room temperature is 25 ℃, and the stirring time is 30 min; 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 step (5), the temperature of the oven is 75-85 ℃.
Furthermore, the prepared one-dimensional core-shell structure porous carbon can be used as a negative electrode material of a high-performance sodium ion battery.
Compared with the prior art, the invention has the beneficial technical effects that:
1. the one-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, the porous carbon outside has high specific surface area, and nitrogen is doped on the surface of the one-dimensional material, so that the performance requirements of large specific surface area, high conductivity and the like required by efficient energy storage can be met, and the electrochemical performance of the porous carbon is further improved.
2. The method provides an available way for the controllable preparation of the MOF @ MOF core-shell structure, enriches the types of MOF structural materials, expands the application of MOF materials, and provides more alternative electrode active materials for efficient electrochemical energy storage application.
3. The surface of the one-dimensional material is convex, and nucleation growth on the surface is generally difficult, but the preparation method of the invention solves the problem, and the preparation method is simple and easy to operate, safe and pollution-free, and low in cost.
Drawings
FIG. 1 is a FESEM image of Co-MOF-74 prepared in example 1.
FIG. 2 is a FESEM and TEM image of the one-dimensional core-shell structure of Co-MOF-74@ ZIF-8 prepared in example 2.
Fig. 3 is a FESEM image and a TEM image of the one-dimensional core-shell structure porous carbon prepared in example 2.
FIG. 4 is an XRD pattern of Co-MOF-74 prepared in example 1 and an XRD pattern of the one-dimensional core-shell structure of Co-MOF-74@ ZIF-8 prepared in example 2.
Fig. 5 is an electrochemical performance diagram of the one-dimensional core-shell porous carbon prepared in example 3.
Detailed Description
For the convenience of understanding of those skilled in the art, the present invention will be described with reference to the accompanying drawings and examples.
Example 1 preparation of Co-MOF-74 powder
(1) Adding 0.4g of 2, 5-dihydroxyterephthalic acid to 90ml of deionized water to form a solution A; dissolving 1.0g of cobalt acetate tetrahydrate in 10ml of deionized water to obtain a solution B; slowly adding the solution B into the solution A after the solution A is continuously stirred and heated to boiling, and continuously stirring and reacting for 40min under the state;
(2) and (3) centrifugally separating the product, washing the product with ethanol, and drying the product in an oven at 80 ℃ to obtain Co-MOF-74 powder.
FIG. 1 is a FESEM image of Co-MOF-74 prepared in this example, showing that the nanorods are uniformly distributed and have a smooth surface.
Example 2 preparation of Co-MOF-74@ ZIF-8 one-dimensional core-shell structure and one-dimensional core-shell structure porous carbon
(1) Dissolving 1.84g of 2-methylimidazole in 15ml of methanol, adding 0.1g of Co-MOF-74 powder to form a uniform suspension A, and stirring at room temperature; 0.83g 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 30 min;
(2) centrifugally separating the product, washing the product with ethanol, and drying the product in an oven at 80 ℃ to obtain a Co-MOF-74@ ZIF-8 one-dimensional core-shell structure;
(3) and (2) annealing the Co-MOF-74@ ZIF-8 one-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 one-dimensional core-shell structure porous carbon.
FIG. 2 is a FESEM and TEM image of the Co-MOF-74@ ZIF-8 one-dimensional core-shell structure prepared in this example. Fig. 3 is FESEM and TEM images of the one-dimensional core-shell structure porous carbon prepared in this example. It can be found that a layer of uniform particles is successfully loaded on the surface of the original nano rod, and a plurality of holes are formed after annealing. FIG. 4 is an XRD diagram of the one-dimensional core-shell structure of Co-MOF-74@ ZIF-8 prepared in this example, where the corresponding 2 θ corresponds to the peak of nanorod Co-MOF-74, respectively, and also corresponds to the position of the standard peak of ZIF-8 reported in the literature, indicating that the one-dimensional core-shell structure material was successfully prepared.
Example 3 Performance testing of one-dimensional core-shell porous carbon
(1) Uniformly mixing and dissolving the one-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, and assembling the working electrode in a glove box filled with argonAssembled into a 2032 button cell with the test voltage range of 0.01V-3V vs Na+/Na。
FIG. 5 is a performance diagram of electrochemical storage of sodium ions by the porous carbon sodium with the one-dimensional core-shell structure prepared in example 3. The sodium electrical property of the porous carbon with the one-dimensional core-shell structure is excellent.
The above examples are typical examples of the present invention, and are not intended to limit the present invention, for example, the reaction concentration, the reaction time, the water bath temperature, the annealing temperature, etc. can be further adjusted. Therefore, it is within the scope of the present invention to modify and modify the process parameters described by those skilled in the art without departing from the spirit of the invention or exceeding the scope defined by the claims.
Claims (9)
1. A preparation method of porous carbon with a one-dimensional core-shell structure is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving 2-methylimidazole powder in methanol, adding Co-MOF-74 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-MOF-74@ ZIF-8 one-dimensional core-shell structure;
(4) annealing the Co-MOF-74@ ZIF-8 one-dimensional core-shell structure under the protection of argon to obtain a one-dimensional core-shell structure porous carbon material;
(5) and (3) placing the one-dimensional core-shell structure porous carbon material in a nitric acid solution, stirring and reacting in a water bath, then centrifugally separating a product, washing with ethanol, and drying in an oven to obtain the pure one-dimensional core-shell structure porous carbon.
2. The method for preparing one-dimensional core-shell porous carbon according to claim 1, wherein in the step (1), the concentration of 2-methylimidazole in the suspension A is 1.49mol L-1At a concentration of Co-MOF-74 of6.66g L-1The room temperature was 25 ℃.
3. The method for preparing one-dimensional core-shell porous carbon according to claim 1, wherein in the step (2), the concentration of the solution B is 0.55mol L-1。
4. The preparation method of the one-dimensional core-shell porous carbon according to claim 1, wherein in the step (3), the room temperature is 25 ℃, and the stirring time is 30 min; the temperature of the oven is 75-85 ℃.
5. The method for preparing one-dimensional core-shell porous carbon according to claim 1, wherein in the step (4), the annealing temperature is 900 ℃ and the holding time is 2 hours.
6. The method for preparing one-dimensional core-shell porous carbon according to claim 1, wherein in the step (5), the volume ratio of the concentrated nitric acid to water in the nitric acid solution is 1: 2.
7. The preparation method of the one-dimensional core-shell porous carbon according to claim 1, wherein in the step (5), the water bath temperature is 75-85 ℃ and the water bath time is 23-25 h.
8. The method for preparing one-dimensional core-shell porous carbon according to claim 1, wherein in the step (5), the temperature of the oven is 75-85 ℃.
9. Application of the one-dimensional core-shell porous carbon prepared by the method according to any one of claims 1 to 8, which is characterized in that the porous carbon is used as a negative electrode material of a high-performance sodium-ion battery.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140284829A1 (en) * | 2011-10-04 | 2014-09-25 | Fundació Institut Catalá De Nanociéncia I Nanotecnologia | Method for the preparation of metal organic frameworks |
| CN105037444A (en) * | 2015-06-19 | 2015-11-11 | 哈尔滨工业大学 | Synthetic method of metal organic frameworks Co-MOF-74 |
| CN105668548A (en) * | 2016-03-29 | 2016-06-15 | 北京化工大学 | New method for customizing high-dispersion co-doping porous carbon with core-shell structure |
| CN107399729A (en) * | 2017-06-28 | 2017-11-28 | 中山大学 | A kind of bimetallic MOFs nitrogenous graphitized carbon material |
| US20180272313A1 (en) * | 2014-12-19 | 2018-09-27 | Korea Institute Of Industrial Technology | Complex of carbon structure and covalent organic framework, preparation method therefor, and use thereof |
| US20190043675A1 (en) * | 2016-02-04 | 2019-02-07 | Tpr Co., Ltd. | Core-shell composite, method for producing the same, electrode material, catalyst, electrode, secondary battery, and electric double-layer capacitor |
| CN109638304A (en) * | 2018-12-29 | 2019-04-16 | 江苏大学 | A kind of preparation method and purposes of M-MOF-74/ graphene composite cathode material |
| CN110090621A (en) * | 2019-05-16 | 2019-08-06 | 南京林业大学 | Derivative porous carbon materials of a kind of metal organic framework and the preparation method and application thereof |
| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
| CN110364712A (en) * | 2019-07-15 | 2019-10-22 | 合肥工业大学 | A kind of preparation method and applications of porous carbon@N doping porous carbon core-shell structure |
| CN110739463A (en) * | 2019-10-24 | 2020-01-31 | 南京邮电大学 | Preparation method and application of bimetal organic framework composite materials |
| CN111082050A (en) * | 2019-12-20 | 2020-04-28 | 兰州大学 | Lithium ion battery cathode material and preparation method thereof |
-
2020
- 2020-08-11 CN CN202010802031.4A patent/CN111916737B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140284829A1 (en) * | 2011-10-04 | 2014-09-25 | Fundació Institut Catalá De Nanociéncia I Nanotecnologia | Method for the preparation of metal organic frameworks |
| US20180272313A1 (en) * | 2014-12-19 | 2018-09-27 | Korea Institute Of Industrial Technology | Complex of carbon structure and covalent organic framework, preparation method therefor, and use thereof |
| CN105037444A (en) * | 2015-06-19 | 2015-11-11 | 哈尔滨工业大学 | Synthetic method of metal organic frameworks Co-MOF-74 |
| US20190043675A1 (en) * | 2016-02-04 | 2019-02-07 | Tpr Co., Ltd. | Core-shell composite, method for producing the same, electrode material, catalyst, electrode, secondary battery, and electric double-layer capacitor |
| CN105668548A (en) * | 2016-03-29 | 2016-06-15 | 北京化工大学 | New method for customizing high-dispersion co-doping porous carbon with core-shell structure |
| CN107399729A (en) * | 2017-06-28 | 2017-11-28 | 中山大学 | A kind of bimetallic MOFs nitrogenous graphitized carbon material |
| CN109638304A (en) * | 2018-12-29 | 2019-04-16 | 江苏大学 | A kind of preparation method and purposes of M-MOF-74/ graphene composite cathode material |
| CN110090621A (en) * | 2019-05-16 | 2019-08-06 | 南京林业大学 | Derivative porous carbon materials of a kind of metal organic framework and the preparation method and application thereof |
| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
| CN110364712A (en) * | 2019-07-15 | 2019-10-22 | 合肥工业大学 | A kind of preparation method and applications of porous carbon@N doping porous carbon core-shell structure |
| CN110739463A (en) * | 2019-10-24 | 2020-01-31 | 南京邮电大学 | Preparation method and application of bimetal organic framework composite materials |
| CN111082050A (en) * | 2019-12-20 | 2020-04-28 | 兰州大学 | Lithium ion battery cathode material and preparation method thereof |
Non-Patent Citations (5)
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