CN110112401B - Preparation method and application of nitrogen-doped porous carbon @ niobium nitride or niobium carbide core-shell structure - Google Patents
Preparation method and application of nitrogen-doped porous carbon @ niobium nitride or niobium carbide core-shell structure Download PDFInfo
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Abstract
The invention discloses a preparation method of a nitrogen-doped porous carbon @ niobium nitride core-shell structure, which comprises the following steps of: dispersing ZIF-8 powder in ethanol to form suspension A; dissolving niobium oxalate hydrate in deionized water to form a solution C; slowly adding the solution C into the suspension A, placing the suspension A into a water bath kettle for stirring, then centrifugally separating a product, washing the product with ethanol, and then placing the product into an oven for drying to obtain a ZIF-8@ Nb core-shell structure; and annealing the ZIF-8@ Nb core-shell structure powder under the protection of argon to obtain a product. On one hand, the product realizes that metal ions and a specific MOF material form a core-shell composite structure, and then the porous carbon core-shell composite structure is obtained through high-temperature calcination treatment, so that the structural characteristics of the MOF material, such as large specific surface area, high porosity and modifiability, are fully exerted. On the other hand, because of the load of niobium nitride, the advantages of high conductivity and high theoretical specific capacity of the transition metal nitride/carbide are exerted, the synergistic effect of the transition metal nitride/carbide and the theoretical specific capacity is fully exerted, and the lithium ion storage performance of the material is greatly improved.
Description
Technical Field
The invention relates to the technical field of micro-nano composite material synthesis, in particular to a preparation method of a nitrogen-doped porous carbon @ niobium nitride or niobium carbide core-shell structure by using a zeolite imidazole ester framework (ZIFs) as a precursor and combining with argon annealing treatment by adopting a cation exchange method, and the preparation method is applied to a cathode material of a high-performance lithium ion battery.
Background
With the development of modern technologies and the improvement of living standards, the demand of people for small-sized movable electric energy storage devices is rapidly increasing. The lithium ion battery has the advantages of high energy density, low self-discharge rate, high working voltage, environmental friendliness and the like, and is greatly concerned. The development of the novel lithium ion battery cathode material has great significance for improving the performance of the lithium ion battery.
The Metal Organic Frameworks (MOFs) are a novel porous crystal material and are formed by coordination of organic ligands and metal ions, and the MOFs has the advantages of high porosity, large specific surface area, multiple types, strong functionality, small crystal density, strong adjustability of framework size and pore size, and attracts wide attention. After the Zeolite Imidazolate Frameworks (ZIFs) are used as a branch of the MOF and subjected to high-temperature calcination treatment, the porous carbon material with nitrogen-doped high specific surface area can be obtained and used as a lithium ion battery cathode material, the volume expansion in the lithium ion intercalation process can be effectively relieved, impurity atom doping brings a large number of crystal defects, and more active sites are increased. Transition metal nitrides and carbides are electrode materials with high conductivity and high specific capacity which are newly developed in recent years, and the nitrides and the carbides can show more excellent rate capability and rapid charge and discharge performance compared with transition metal oxides. Transition metal nitrides have higher mass capacity and tap density, and exhibit greater volumetric energy density than carbon electrode materials. Therefore, the ZIF-8 and the ZIF-67 are used as templates and compounded with Nb metal ions, the nitrogen-doped porous nitrogen @ niobium nitride and nitrogen-doped porous carbon @ niobium carbide core-shell structures are prepared by a simple cation exchange method and a high-temperature annealing treatment and acid pickling strategy, the synergistic effect of the nitrogen-doped porous nitrogen @ niobium nitride and the nitrogen-doped porous carbon @ niobium carbide core-shell structures is fully exerted, and the nitrogen-doped porous nitrogen @ niobium nitride and the nitrogen-doped porous carbon @ niobium carbide core-shell structures are applied to a lithium ion battery system and have.
Disclosure of Invention
The invention aims to: the preparation method and the application of the nitrogen-doped porous carbon @ niobium nitride or niobium carbide core-shell structure are provided, and the purpose is to improve the electrochemical performance of the core-shell structure used for the lithium ion battery cathode electrode material. 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 a nitrogen-doped porous carbon @ niobium nitride core-shell structure comprises the following steps:
(1) dispersing ZIF-8 powder in ethanol to form a suspension A with uniform concentration;
(2) dissolving niobium oxalate hydrate in deionized water to form a solution C;
(3) slowly adding the solution C into the suspension A, placing the suspension A into a water bath kettle for stirring, then centrifugally separating a product, washing the product with ethanol, and then placing the product into an oven for drying to obtain a ZIF-8@ Nb core-shell structure;
(4) and annealing the ZIF-8@ Nb core-shell structure powder under the protection of argon to obtain the nitrogen-doped porous carbon @ niobium nitride core-shell composite structure.
Preferably, the concentration of the suspension A is 2.67g L-1The concentration of the solution C is 2.15g L-1And the volume ratio of the suspension A to the solution C is 3: 1.
Preferably, the temperature in the water bath kettle in the step (3) is 24-26 ℃, and the stirring time is 4-6 min; the washing times of the ethanol are 2-4 times; the drying temperature in the oven is 75-85 ℃.
Preferably, the annealing temperature in the step (4) is 750-850 ℃, and the holding time is 2-3 h.
Further, the prepared nitrogen-doped porous carbon @ niobium nitride core-shell structure can be used as a negative electrode material of a high-performance lithium ion battery.
A preparation method of a nitrogen-doped porous carbon @ niobium carbide core-shell structure comprises the following steps:
(1) dispersing ZIF-67 powder in ethanol to form a suspension B with uniform concentration;
(2) dissolving niobium oxalate hydrate in deionized water to form a solution C;
(3) slowly adding the solution C into the suspension B, placing the suspension B into a water bath kettle, stirring, centrifugally separating a product, washing the product with ethanol, and placing the product into an oven to be dried to obtain a ZIF-67@ Nb core-shell structure;
(4) annealing the ZIF-67@ Nb core-shell structure under the protection of argon to obtain a Co @ nitrogen doped porous carbon @ niobium carbide composite material;
(5) placing the Co @ nitrogen-doped porous carbon @ niobium carbide composite material in a nitric acid solution, stirring in a water bath kettle for reaction, centrifugally separating a product, washing with ethanol, and drying in an oven to obtain the nitrogen-doped porous carbon @ niobium carbide core-shell structure.
Preferably, the concentration of the suspension B is 2.67g L-1The concentration of the solution C is 2.15g L-1The volume ratio of the suspension B to the solution C is 3: 1; the temperature in the water bath kettle in the step (3) is 24-26 ℃, and the stirring time is 4-6 min; the washing times of the ethanol are 2-4 times; the drying temperature in the oven is 75-85 ℃.
Preferably, the annealing temperature in the step (4) is 750-850 ℃, and the holding time is 2-3 h.
Preferably, the volume ratio of the concentrated nitric acid to the water in the nitric acid solution in the step (5) is 1:2, the water bath temperature is 75-85 ℃, and the water bath time is 23-25 h; the drying temperature in the oven is 75-85 ℃.
Further, the prepared nitrogen-doped porous carbon @ niobium carbide core-shell structure can be used as a negative electrode material of a high-performance lithium ion battery.
Compared with the prior art, the invention has the beneficial technical effects that:
1. according to the nitrogen-doped porous carbon @ niobium nitride or niobium carbide core-shell structure prepared by the method, on one hand, the metal ions and the specific MOF material form a core-shell composite structure, and then the porous carbon core-shell composite structure is obtained through high-temperature calcination treatment, so that the structural characteristics of the MOF material, such as large specific surface area, high porosity and repairability, are fully exerted. On the other hand, because of the load of the (nitrogen) niobium carbide, the advantages of high conductivity and high theoretical specific capacity of the transition metal nitride/carbide are exerted, the synergistic effect of the two is fully exerted, and the lithium ion storage performance of the material is greatly improved. In addition, the doping of nitrogen atoms in the porous carbon provides a large number of crystal defects, more active sites are added, the electrochemical performance of the porous carbon is further improved, and a new method is provided for preparing the nitrogen-doped porous carbon, niobium nitride and niobium carbide composite material;
2. the preparation method is simple and easy to operate, safe, pollution-free and low in cost.
Drawings
FIG. 1 is an FESEM photograph of ZIF-8 and ZIF-67 prepared in example 1.
FIG. 2 is a FESEM and TEM image of the ZIF-8@ Nb core-shell structure prepared in example 2.
Fig. 3 is a FESEM and TEM image of the nitrogen doped porous carbon @ niobium nitride core-shell structure prepared in example 2.
FIG. 4 is a FESEM and TEM image of the ZIF-67@ Nb core-shell structure prepared in example 3.
Fig. 5 is FESEM and TEM images of nitrogen doped porous carbon @ niobium carbide core-shell structures prepared in example 3.
Fig. 6 is an XRD pattern of nitrogen-doped porous carbon @ niobium nitride prepared in example 2 and nitrogen-doped porous carbon @ niobium carbide prepared in example 3.
FIG. 7 is a graph of the electrochemical performance of the ZIF-8 derived nitrogen-doped porous carbon and nitrogen-doped porous carbon @ niobium nitride core-shell structures tested in example 5.
FIG. 8 is a graph of the electrochemical performance of the ZIF-67 derived nitrogen-doped porous carbon and nitrogen-doped porous carbon @ niobium carbide core-shell structures tested in example 5.
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 ZIF-8 and ZIF-67 powders.
(1) Dissolving 1.97g of dimethylimidazole in 30ml of deionized water to form a solution D, dissolving 0.527g of zinc acetate dihydrate in 6ml of deionized water to form a solution E, dissolving 0.598g of cobalt acetate tetrahydrate in 6ml of deionized water to form a solution F, pouring the solution E into the solution D, and standing at room temperature for 24 hours; pouring the solution F into the solution D, and carrying out the same treatment;
(2) and (3) respectively performing centrifugal separation on the products, washing the products with ethanol, and drying the products in an oven at 80 ℃ to obtain ZIF-8 and ZIF-67 powder.
FIG. 1 is a FESEM image of ZIF-8 and ZIF-67 prepared in this example, showing that the particle size is about 1-2 microns.
Example 2, preparation of a ZIF-8@ Nb core-shell structure and a nitrogen-doped porous carbon @ niobium nitride core-shell structure.
(1) 80mg of ZIF-8 was dispersed in 30ml of ethanol to prepare a suspension A, 21.5mg of niobium oxalate hydrate was dissolved in 10ml of deionized water to prepare a solution C, and the solution C was added dropwise to the suspension A and stirred in a 25 ℃ water bath for 5 minutes.
(2) And (3) centrifugally separating the product, washing the product with ethanol, and drying the product in an oven at 80 ℃ to obtain the ZIF-8@ Nb core-shell structure.
(3) And (3) carrying out argon annealing at 800 ℃ on the ZIF-8@ Nb core-shell structure to obtain the nitrogen-doped porous carbon @ niobium nitride core-shell structure.
FIG. 2 is a FESEM and TEM image of a doped ZIF-8@ Nb core-shell structure prepared in this example; fig. 3 is a FESEM image and a TEM image of the core-shell structure of nitrogen-doped porous carbon @ niobium nitride prepared in this example. It was found that the surface of the original particles was rough, forming a core-shell structure.
Example 3, preparation of a ZIF-67@ Nb core-shell structure and a nitrogen-doped porous carbon @ niobium carbide core-shell structure.
(1) 80mg of ZIF-67 was dispersed in 30ml of ethanol to prepare a suspension B, 21.5mg of niobium oxalate hydrate was dissolved in 10ml of deionized water to prepare a solution C, and the solution C was added dropwise to the suspension B and stirred in a 25 ℃ water bath for 5 minutes. And (3) centrifugally separating the product, washing the product with ethanol, and drying the product in an oven at 80 ℃ to obtain the ZIF-67@ Nb core-shell structure.
(2) And (3) carrying out argon annealing at 800 ℃ on the ZIF-67@ Nb core-shell structure to obtain the Co @ nitrogen doped porous carbon @ niobium carbide composite material.
(3) Placing the Co @ nitrogen-doped porous carbon @ niobium carbide composite material in a nitric acid solution (concentrated nitric acid: water is 1: 2), and stirring and reacting for 24 hours in a water bath kettle at the temperature of 80 ℃; and (3) centrifugally separating the product, washing the product with ethanol, and drying the product in an oven at 80 ℃ to obtain the nitrogen-doped porous carbon @ niobium carbide core-shell structure.
FIG. 4 is a FESEM and TEM image of a ZIF-67@ Nb core-shell structure prepared in this example. Fig. 5 is FESEM and TEM images of nitrogen-doped porous carbon @ niobium carbide core-shell structures prepared in this example. Fig. 6 is an XRD pattern of nitrogen-doped porous carbon @ niobium carbide prepared in this example and nitrogen-doped porous carbon @ niobium nitride prepared in example 2. The carbon peak and the diffraction peaks of niobium nitride and niobium nitride can be seen, and it is noted that the carbon peak in the nitrogen-doped porous carbon @ niobium nitride is at about 22 °, and the carbon is amorphous. And the carbon peak in the nitrogen-doped porous carbon @ niobium carbide is about 27 degrees, and the peak shape is sharp, which shows that the crystallinity of carbon is good, and the carbon is benefited from the catalytic action of Co.
Example 4 preparation of ZIF-8 derived nitrogen doped porous carbon and ZIF-67 derived nitrogen doped porous carbon.
(1) Carrying out argon annealing on the prepared ZIF-8 powder at 800 ℃ to obtain a nitrogen-doped porous carbon material derived from ZIF-8;
(2) and (3) carrying out argon annealing at 800 ℃ on the prepared ZIF-67 powder to obtain the Co @ nitrogen doped porous carbon composite material. And then placing the mixture into a nitric acid solution (concentrated nitric acid: water is 1: 2), and stirring the mixture in a water bath kettle at the temperature of 80 ℃ to react for 24 hours to obtain the nitrogen-doped porous carbon material derived from the ZIF-67.
Example 5 performance testing of nitrogen-doped porous carbon derived from ZIF-8, nitrogen-doped porous carbon derived from ZIF-67, nitrogen-doped porous carbon @ niobium nitride core-shell structure and nitrogen-doped porous carbon @ niobium carbide core-shell material.
(1) Respectively and uniformly mixing the nitrogen-doped porous carbon @ niobium nitride core-shell structure and the nitrogen-doped porous carbon @ niobium carbide core-shell structure with conductive carbon black and PVDF according to the mass ratio of 8:1:1, dissolving the mixture 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 Li+/Li。
(3) And performing the same treatment on the nitrogen-doped porous carbon derived from the ZIF-8 and the nitrogen-doped porous carbon material derived from the ZIF-67, and performing battery assembly and electrochemical performance test to form a control experiment.
FIG. 7 is a graph of the electrochemical performance of the ZIF-8 derived nitrogen-doped porous carbon and nitrogen-doped porous carbon @ niobium nitride core-shell structures tested in this example. It can be seen that the initial capacity of the ZIF-8 derived nitrogen-doped porous carbon is only 475 mAh g-1The nitrogen-doped porous carbon @ niobium nitride core-shell structure shows better performance, and the initial capacity is 571 mAh g-1. FIG. 8 is a graph of the electrochemical performance of the ZIF-67 derived nitrogen-doped porous carbon and nitrogen-doped porous carbon @ niobium carbide core-shell structures tested in this example. It can be seen that the initial capacity of the ZIF-67 derived nitrogen-doped porous carbon is 579 mAh g-1And the initial capacity of the nitrogen-doped porous carbon @ niobium carbide core-shell structure is 747 mAh g-1. The improvement of the performance of the two materials is benefited by the fact that the niobium nitride and the niobium carbide form a unique core-shell structure on the surface of the porous carbon, and the synergistic effect of the carbon, the niobium nitride and the niobium carbide is fully exerted.
The above examples are typical examples of the present invention, and are not intended to limit the present invention, for example, the amount of niobium oxalate hydrate, reaction time, water bath temperature, 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 (5)
1. A preparation method of a nitrogen-doped porous carbon @ niobium nitride core-shell structure is characterized by comprising the following steps: the method comprises the following steps:
(1) dispersing ZIF-8 powder in ethanol to form a suspension A with uniform concentration;
(2) dissolving niobium oxalate hydrate in deionized water to form a solution C;
(3) slowly adding the solution C into the suspension A, placing the suspension A into a water bath kettle for stirring, then centrifugally separating a product, washing the product with ethanol, and then placing the product into an oven for drying to obtain a ZIF-8@ Nb core-shell structure;
(4) annealing the ZIF-8@ Nb core-shell structure powder under the protection of argon to obtain a nitrogen-doped porous carbon @ niobium nitride core-shell composite structure;
wherein, the temperature in the water bath kettle in the step (3) is 24-26 ℃, and the stirring time is 4-6 min; the washing times of the ethanol are 2-4 times; the drying temperature in the oven is 75-85 ℃;
in the step (4), the annealing temperature is 750-;
the concentration of the suspension A is 2.67g L-1The concentration of the solution C is 2.15g L-1And the volume ratio of the suspension A to the solution C is 3: 1.
2. Use of a nitrogen-doped porous carbon @ niobium nitride core-shell structure, prepared according to any one of claims 1, characterized in that: can be used as the cathode material of lithium ion battery.
3. A preparation method of a nitrogen-doped porous carbon @ niobium carbide core-shell structure is characterized by comprising the following steps: the method comprises the following steps:
(1) dispersing ZIF-67 powder in ethanol to form a suspension B with uniform concentration;
(2) dissolving niobium oxalate hydrate in deionized water to form a solution C;
(3) slowly adding the solution C into the suspension B, placing the suspension B into a water bath kettle, stirring, centrifugally separating a product, washing the product with ethanol, and placing the product into an oven to be dried to obtain a ZIF-67@ Nb core-shell structure;
(4) annealing the ZIF-67@ Nb core-shell structure under the protection of argon to obtain a Co @ nitrogen doped porous carbon @ niobium carbide composite material;
(5) placing the Co @ nitrogen-doped porous carbon @ niobium carbide composite material in a nitric acid solution, stirring in a water bath kettle for reaction, centrifugally separating a product, washing with ethanol, and drying in an oven to obtain a nitrogen-doped porous carbon @ niobium carbide core-shell structure;
the concentration of the suspension B is 2.67gL-1The concentration of the solution C is 2.15g L-1The volume ratio of the suspension B to the solution C is 3: 1; the temperature in the water bath kettle in the step (3) is 24-26 ℃, and the stirring time is 4-6 min; the washing times of the ethanol are 2-4 times; the drying temperature in the oven is 75-85 ℃;
in the step (4), the annealing temperature is 750-;
in the step (5), the volume ratio of the concentrated nitric acid to the water in the nitric acid solution is 1:2, the water bath temperature is 75-85 ℃, and the water bath time is 23-25 h.
4. The preparation method of the nitrogen-doped porous carbon @ niobium carbide core-shell structure according to claim 3, characterized in that: the drying temperature in the oven in the step (5) is 75-85 ℃.
5. Use of a nitrogen-doped porous carbon @ niobium carbide core-shell structure, prepared according to any one of claims 3-4, characterized in that: can be used as the cathode material of lithium ion battery.
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