CN110336032B - Preparation method of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon and application of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon in lithium-sulfur battery - Google Patents
Preparation method of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon and application of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon in lithium-sulfur battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a nanometer cobalt loaded nitrogen doped three-dimensional porous carbon and application thereof in a lithium-sulfur battery. According to the preparation method provided by the invention, the precursor is prepared by taking cobalt salt as a source, 2-methylimidazole as a carbon source and a nitrogen source and an inorganic nanosphere as a template through a stirring and solvent evaporation method, so that the yield of the precursor is close to 100%, the yield of the final product, namely the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon can be effectively improved, and the preparation method is favorable for large-scale production and preparation; the three-dimensional porous carbon prepared by the preparation method can be applied to lithium-sulfur batteries, and the sulfur capacity and the electrochemical performance of the lithium-sulfur batteries are effectively improved.
Description
Technical Field
The invention relates to a nano carbon material and the technical field of preparation thereof, in particular to a preparation method of a nano cobalt-loaded nitrogen-doped three-dimensional porous carbon and application thereof in a lithium-sulfur battery.
Background
The lithium-sulfur battery has the advantages of high theoretical specific capacity (1672mAh/g), high energy density (2600Wh/kg), abundant elemental sulfur resource, low price, environmental friendliness and the like, and is considered as the next-generation high-energy-density secondary power source with the greatest development prospect. However, the following problems of the lithium-sulfur battery restrict the performance of the lithium-sulfur battery: (1) sulfur Positive electrode poor conductivity (only 5X 10 at room temperature)-30S/cm), severely decreasesLow sulfur utilization and battery rate performance; (2) long chain polythiol lithium (Li) during discharge2SxX is 3-8) is dissolved in ether electrolyte to form a shuttle effect, so that the lower coulombic efficiency and reversible capacity are caused; (3) the large volume change of the sulfur positive electrode in the circulation process causes the structural damage of the battery.
In order to overcome the above disadvantages, one of the most common strategies is to construct a porous carbon composite sulfur positive electrode having high conductivity, strong polysulfide ion adsorption and rich pore structure. MOFs (Metal Organic Frameworks) materials have a high specific surface area, a rich microporous structure and a large number of active Metal sites, and are receiving more and more attention in the fields of gas storage, catalysis, adsorption, chemical energy, biosensing, and the like. In recent years, porous carbon hybrid materials derived from MOFs are applied to sulfur-carrying matrix materials of lithium-sulfur batteries due to the abundant microporous structure and good catalysis and adsorption effects. For example, Dong et al (DOI: 10.1039/C6EE00104A) carry out mixed reaction on a methanol solution of cobalt nitrate and a methanol solution of 2-methylimidazole to prepare a metal organic framework structure ZIF-67, then the ZIF-67 is subjected to heat treatment in a high-temperature inert atmosphere, and acid etching is carried out to obtain nano Co-N doped microporous carbon (Co-N-GC) serving as a sulfur carrier. However, the nano metal-microporous carbon obtained by simply carbonizing the MOFs has the following defects: (1) the yield in the ZIF-67 synthesis process is too low (about 20%), so that the finally obtained nano Co-N doped microporous carbon material is difficult to produce and prepare on a large scale; (2) the prepared nano Co-N doped microporous carbon material mainly has a microporous structure, lacks a mesoporous and macroporous structure, is difficult to accommodate a large amount of sulfur and buffer the volume change of a sulfur positive electrode in the charging and discharging process, and is not beneficial to preparing a high-energy-density and high-performance lithium sulfur battery. Therefore, the preparation of the MOFs-derived porous carbon hybrid material with high yield and rich in mesoporous and macroporous structures has very important significance and application value for improving the electrochemical performance of the lithium-sulfur positive electrode under high sulfur loading and realizing mass preparation.
Disclosure of Invention
The invention provides a preparation method of a nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon and application of the nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon in a lithium-sulfur battery, which are used for overcoming the defects in the prior art and realizing large-scale production and preparation of the three-dimensional porous carbon.
In order to realize the purpose, the invention provides a preparation method of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon, which comprises the following steps:
(1) adding the inorganic nanospheres into methanol for ultrasonic dispersion, then adding cobalt salt, stirring and dissolving, and then adding a 2-methylimidazole methanol solution to obtain a precursor solution;
(2) stirring the precursor solution for reaction, and then heating and stirring to evaporate the solvent to dryness to obtain a grayish purple precursor powder;
(3) putting the gray purple precursor powder in an inert reducing atmosphere for heat treatment to obtain black powder;
(4) and (3) washing the black powder in an acidic aqueous solution, filtering and drying to obtain the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon material.
In order to achieve the above object, the present invention also provides a nanocobalt-supported nitrogen-doped three-dimensional porous carbon formed by uniformly dispersing nanocobalt particles in a three-dimensional honeycomb nitrogen-doped porous carbon matrix; the size of the nano cobalt particles is 5-50 nm, and the aperture of the porous carbon is 100-500 nm.
In order to achieve the purpose, the invention also provides application of the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon in a lithium sulfur battery, and the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon/sulfur composite material is prepared by utilizing the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon; the nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon is prepared by the preparation method, and the mass fraction of sulfur in the composite material is 40-90 wt%.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the nanometer cobalt loaded nitrogen-doped three-dimensional porous carbon provided by the invention comprises the steps of firstly preparing a precursor solution containing an inorganic matter nanometer ball template, cobalt salt and 2-methylimidazole, then taking the cobalt salt and the 2-methylimidazole as a cobalt source and a carbon source, taking an inorganic matter nanometer ball as a template, preparing the precursor, then carrying out high-temperature carbonization and reduction treatment on the precursor, and finally removing the inorganic matter nanometer ball template and partial metal cobalt through acid washing to obtain the nanometer cobalt loaded nitrogen-doped three-dimensional porous carbon. According to the preparation method, low-yield ZIF-67 is not directly used as a precursor, an inorganic nanosphere is used as a template, cobalt (Co) salt is used as a cobalt source, 2-methylimidazole is used as a carbon source and a nitrogen source, the cobalt salt and the 2-methylimidazole react in a methanol solution to generate ZIF67 and wrap the ZIF67 on the surface of the inorganic nanosphere, and then a stirring evaporation solvent method is adopted to prepare the precursor, so that the yield of the precursor is close to 100%, the yield of the nitrogen-doped three-dimensional porous carbon loaded by the nano cobalt can be effectively improved, and the large-scale production and preparation are facilitated. According to the preparation method, the inorganic nanospheres are used as templates for forming mesopores (the aperture is between 2nm and 50nm) and macropores (the aperture is larger than 50nm), so that the finally prepared nano cobalt-loaded nitrogen-doped three-dimensional porous carbon not only has rich micropore (the aperture is smaller than 2nm) structures, but also has mesopore and macropore structures, part of cobalt is removed by acid cleaning to form the mesopores, so that the number of the mesopores is increased, the cobalt which is not removed by acid cleaning can improve the adsorption polysulfide performance of the material, the finally prepared material has a hierarchical porous three-dimensional network conductive carbon structure, the inorganic nanospheres can avoid the growth and agglomeration of the nano cobalt in the heat treatment sintering process, the distribution uniformity degree and the catalytic property of the nano cobalt are improved, and the sulfur loading capacity and the electrochemical performance of the lithium-sulfur battery are effectively improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
Fig. 1 is a Scanning Electron Microscope (SEM) image of the nanocobalt-loaded nitrogen-doped three-dimensional porous carbon in example 1 of the present invention;
FIG. 2 is a partially enlarged Scanning Electron Microscope (SEM) view of FIG. 1;
fig. 3 is an X-ray diffraction (XRD) pattern of the nanocobalt-supported nitrogen-doped three-dimensional porous carbon in example 1 of the present invention;
fig. 4a is a Scanning Electron Microscope (SEM) image of the nanocobalt-loaded nitrogen-doped three-dimensional porous carbon/sulfur composite in example 1 of the present invention;
fig. 4b is a Scanning Electron Microscope (SEM) image of the nanocobalt-supported nitrogen-doped microporous carbon/sulfur composite of comparative example 1;
fig. 5 is a comparison graph of charge and discharge cycle performance of a lithium-sulfur battery assembled by using the nanocobalt-supported nitrogen-doped three-dimensional porous carbon/sulfur composite material in example 1 and the nanocobalt-supported nitrogen-doped microporous carbon/sulfur composite material in comparative example 1, respectively.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The drugs/reagents used are all commercially available without specific mention.
The invention provides a preparation method of a nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon, which comprises the following steps:
(1) adding the inorganic nanospheres into methanol for ultrasonic dispersion, then adding cobalt salt, stirring and dissolving, and then adding a 2-methylimidazole methanol solution to obtain a precursor solution;
preferably, the concentration of the inorganic nanospheres in the precursor solution is 5-50 g/L; the concentration of cobalt salt in the precursor solution is 0.01-0.1 mol/L; the molar ratio of the cobalt salt to the 2-methylimidazole is 1: (0.5-10) to form ZIF67 precursor. The quantity of mesopores and macropores is controlled by controlling the adding amount of the cobalt salt and the inorganic nanospheres, and the wall thickness of the three-dimensional porous carbon in the product is controlled by controlling the proportion of the cobalt salt and the inorganic nanospheres.
Preferably, the inorganic nanospheres are SiO2、TiO2ZnO, the raw material is cheap and easy to obtain, and is easy to remove by acid washing; the particle size of the inorganic nanospheres is 50-500 nm, and the inorganic nanospheres are used as templates for forming mesopores and macropores.
Preferably, the cobalt salt is at least one of cobalt nitrate, cobalt chloride and cobalt acetate. The common cobalt salt is selected, so that the reaction is facilitated, and the raw materials are easy to obtain.
(2) Stirring the precursor solution for reaction, and then heating and stirring to evaporate the solvent to dryness to obtain a grayish purple precursor powder;
preferably, the stirring reaction temperature is 10-40 ℃, and the stirring time is 0.5-2 h. In the stirring reaction process, inorganic nanospheres are used as a template, cobalt (Co) salt is used as a cobalt source, 2-methylimidazole is used as a carbon source and a nitrogen source, and a precursor reacts in a methanol solution to generate ZIF67 which is coated on the surfaces of the inorganic nanospheres.
Preferably, the heating and stirring temperature is 70-90 ℃, the heating and stirring are carried out until the solvent is completely volatilized, the proper temperature is favorable for evaporating the solvent, and the damage to the original structure of the material is avoided.
(3) Putting the gray purple precursor powder in an inert reducing atmosphere for heat treatment to obtain black powder; carbonizing the precursor at high temperature, and reducing cobalt ions in the precursor into metal cobalt.
Preferably, the inert reducing atmosphere is Ar and H2Mixed gas of Ar and H2The volume percentage of (70-95): (5-30) reducing cobalt ions in the precursor into metallic cobalt in a reducing atmosphere; the temperature of the heat treatment is 500-1000 ℃, and the time is 0.5-10 h, so that the precursor is completely carbonized, and cobalt ions are promoted to be reduced into metal cobalt.
(4) And (3) washing the black powder in an acidic aqueous solution, filtering and drying to obtain the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon material. And removing the partially reduced metal cobalt and inorganic nanosphere templates by acid washing to form mesopores and macropores in the product.
Preferably, the acid in the acidic aqueous solution is hydrofluoric acid (HF) and hydrochloric acid (HCl) or sulfuric acid (H)2SO4) Or nitric acid (HNO)3) The mixed acid of (1); the mass fraction of the acid in the acidic aqueous solution is 5-30 wt%. Common acid reagents are selected, so that the method is easy to obtain and reduces the cost. The proper acid content is selected, so that the inorganic nanosphere template and part of metal cobalt can be effectively removed, and the cost can be saved.
The nano cobalt-loaded nitrogen-doped three-dimensional porous carbon prepared by the preparation method of the nano cobalt-loaded nitrogen-doped three-dimensional porous carbon is formed by uniformly dispersing nano cobalt particles in a three-dimensional honeycomb nitrogen-doped porous carbon matrix; the size of the nano cobalt particles is 5-50 nm, the aperture of the porous carbon is 100-500 nm, and the porous carbon can be applied to lithium-sulfur batteries.
The invention also provides the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon, which is formed by uniformly dispersing nano-cobalt particles in a three-dimensional honeycomb nitrogen-doped porous carbon matrix; the size of the nano cobalt particles is 5-50 nm, and the aperture of the porous carbon is 100-500 nm.
The invention also provides application of the nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon in a lithium-sulfur battery, and the nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon/sulfur composite material is prepared by utilizing the nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon; the nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon is prepared by the preparation method, and the mass fraction of sulfur in the composite material is 40-90 wt%.
Example 1
The embodiment provides a preparation method of a nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon, which comprises the following steps:
(1) adding 15ml of tetraethyl orthosilicate into a mixed solvent consisting of 10ml of ammonia water, 200ml of ethanol and 100ml of water under magnetic stirring, stirring for 2 hours at 30 ℃, filtering, washing and drying the obtained product to obtain silicon dioxide nanosphere powder with the particle size of about 300 nm.
(2) Taking 3.0g of white SiO obtained in step (1)2The nanosphere powder was dispersed by sonication for 2h in 100ml methanol, followed by the addition of 0.8g Co (NO)3)2After the mixture was dissolved by stirring, 100ml of a methanol solution containing 1.0g of 2-methylimidazole was added to obtain a precursor solution.
(3) Stirring the precursor solution at 30 ℃ for reaction for 1h, and then stirring at 80 ℃ to evaporate the solvent to obtain a grayish purple precursor powder;
(4) the grayish purple precursor powder is placed in a tube furnace at high purity Ar/10% H2Sintering at 900 ℃ for 2h under the atmosphere to obtain black powder;
(5) the black powder was stirred for 12 hours in a mixture of 100ml of a 10% aqueous HF solution and 100ml of a 20% aqueous HCl solution, and SiO was washed off2And filtering, washing and drying the nano-sphere template and part of metal cobalt to obtain the nano-cobalt loaded nitrogen-doped three-dimensional porous carbon material.
Fig. 1 is an SEM image of the nanocobalt-loaded nitrogen-doped three-dimensional porous carbon in example 1 of the present invention, and fig. 2 is a partially enlarged SEM image of fig. 1, and it can be seen from fig. 1 that the nanocobalt-loaded nitrogen-doped three-dimensional porous carbon has a three-dimensional honeycomb network structure, and the diameter of the honeycomb pores is about 300 nm; as can be seen from fig. 2, the nano-cobalt-supported nitrogen-doped three-dimensional porous carbon is formed by dispersing nano-cobalt in a honeycomb carbon structure, and the white particles are nano-cobalt and have a size of about 10 nm.
Fig. 3 is an XRD pattern of the nano-cobalt-supported nitrogen-doped three-dimensional porous carbon in example 1 of the present invention, and it can be seen from the XRD pattern of the nano-cobalt-supported nitrogen-doped three-dimensional porous carbon that (002) diffraction peaks of graphite and (111) and (200) diffraction peaks of metallic cobalt appear, which indicates that graphitized carbon and metallic cobalt exist in the nano-cobalt-supported nitrogen-doped three-dimensional porous carbon.
A nanometer cobalt loaded nitrogen-doped three-dimensional porous carbon material/sulfur composite material is prepared by the following steps:
0.1g of the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon material prepared in the embodiment and 0.4g of elemental sulfur powder are ground, mixed uniformly and then placed in a container filled with N2And (3) preserving the heat of the protected tubular furnace at 155 ℃ for 10h, cooling the tubular furnace, and taking out the tubular furnace to obtain the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon material/sulfur composite material. The sulfur content of the composite was 84%.
Fig. 4a is an SEM image of the nanocobalt-loaded nitrogen-doped three-dimensional porous carbon/sulfur composite in the present example; fig. 4b is an SEM image of the nanocobalt-supported nitrogen-doped microporous carbon/sulfur composite in comparative example 1. As can be seen from fig. 4a, the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon material/sulfur composite material prepared in this embodiment has a three-dimensional honeycomb carbon network structure similar to the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon, and no large-particle sulfur appears on the surface, which indicates that sulfur is uniformly infiltrated into the porous carbon material, and this is due to its abundant microporous, mesoporous, and macroporous structures; as can be seen from fig. 4b, the nano cobalt-supported nitrogen-doped microporous carbon/sulfur composite material prepared in comparative example 1 was composed of irregular particles having a particle size of 100nm to 1 μm, and large-particle sulfur was clearly present, indicating that it was difficult for sulfur to completely penetrate into the carbon skeleton due to the lack of a hierarchical pore structure.
Fig. 5 is a comparison graph of charge-discharge cycle performance of a lithium-sulfur battery assembled by respectively using the nano-cobalt-supported nitrogen-doped three-dimensional porous carbon/sulfur composite material in example 1 and the nano-cobalt-supported nitrogen-doped microporous carbon/sulfur composite material in comparative example 1, in which a is the charge-discharge cycle performance of the lithium-sulfur battery assembled by the nano-cobalt-supported nitrogen-doped three-dimensional porous carbon/sulfur composite material in example 1, and B is the charge-discharge cycle performance of the lithium-sulfur battery assembled by the nano-cobalt-supported nitrogen-doped three-dimensional porous carbon/sulfur composite material in comparative example 1. As can be seen from the figure, the nano cobalt-loaded nitrogen-doped three-dimensional porous carbon/sulfur composite material provided in this embodiment has a higher discharge capacity and a better cycle stability than the nano cobalt-loaded nitrogen-doped microporous carbon/sulfur composite material provided in comparative example 1.
Example 2
The embodiment provides a preparation method of a nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon, which comprises the following steps:
(1) adding 15ml of tetraethyl orthosilicate into a mixed solvent consisting of 5ml of ammonia water, 200ml of ethanol and 20ml of water under magnetic stirring, stirring for 2 hours at 30 ℃, filtering, washing and drying the obtained product to obtain silicon dioxide nanosphere powder with the particle size of about 100 nm.
(2) Taking 3.0g of SiO obtained in step (1)2The nanosphere powder was dispersed by sonication for 2h in 100ml methanol, followed by the addition of 0.8g Co (NO)3)2Stirring to dissolve, and adding 100ml of methanol solution containing 1.0g of 2-methylimidazole to obtain a precursor reaction solution.
(3) Stirring the precursor reaction solution obtained in the step (2) at 40 ℃ for reaction for 0.5h, and then stirring at 90 ℃ to evaporate the solvent to obtain a grayish purple precursor powder;
(4) putting the ash purple precursor powder obtained in the step (3) into a tube furnace, and putting the tube furnace in a high-purity Ar/20% H2Sintering at 1000 deg.C for 0.5h under atmosphere to obtain black powder;
(5) placing the black powder obtained in the step (4) in a mixed solution of 100ml of 5% HF aqueous solution and 100ml of 30% HCl aqueous solution, stirring for 12h, and washing off SiO2And filtering, washing and drying the nano-sphere template and part of metal cobalt to obtain the nano-cobalt loaded nitrogen-doped three-dimensional porous carbon material.
The nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon presents a three-dimensional honeycomb network structure, the diameter of a honeycomb hole is about 100nm, the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon is formed by dispersing nano-cobalt in a honeycomb carbon structure, and the size of the nano-cobalt is 5-50 nm.
A nanometer cobalt loaded nitrogen-doped three-dimensional porous carbon material/sulfur composite material is prepared by the following steps:
0.1g of the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon material prepared in the embodiment and 0.4g of elemental sulfur powder are ground, uniformly mixed and then placed in a container filled with N2And (3) preserving the heat of the protected tubular furnace at 155 ℃ for 10h, cooling the tubular furnace, and taking out the tubular furnace to obtain the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon material/sulfur composite material.
Example 3
The embodiment provides a preparation method of a nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon, which comprises the following steps:
(1) adding 5ml tetraethyl titanate into a mixed solvent consisting of 2ml ammonia water, 400ml ethanol and 5ml water under magnetic stirring, stirring for 30min at 30 ℃, then transferring the mixture into a hydrothermal kettle to react for 2h at 100 ℃, filtering, washing and drying the obtained product to obtain TiO with the particle size of about 200nm2A nanosphere powder.
(2) Taking 3.0g of white TiO obtained in the step (1)2The nanosphere powder was dispersed by ultrasonic dispersion in 100ml methanol for 2h, followed by addition of 0.8g Co (NO)3)2Stirring to dissolve, and adding 100ml of methanol solution containing 1.0g of 2-methylimidazole to obtain a precursor reaction solution.
(3) Stirring the precursor reaction solution obtained in the step (2) at 20 ℃ for reaction for 2.0h, and then stirring at 70 ℃ to evaporate the solvent to obtain a grayish purple precursor powder;
(4) putting the ash purple precursor powder obtained in the step (3) into a tube furnace, and putting the tube furnace in a high-purity Ar/15% H2Sintering at 500 ℃ for 10h in the atmosphere to obtain black powder;
(5) placing the black powder obtained in the step (4) in 100ml of 15% HF aqueous solution and 100ml of 20% HNO3Stirring the mixed solution of the aqueous solution for 12 hours, and washing off TiO2And filtering, washing and drying the nano-sphere template and part of metal cobalt to obtain the nano-cobalt loaded nitrogen-doped three-dimensional porous carbon material.
The nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon presents a three-dimensional honeycomb network structure, the diameter of a honeycomb hole is about 200nm, the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon is formed by dispersing nano-cobalt in a honeycomb carbon structure, and the size of the nano-cobalt is 5-50 nm.
A nanometer cobalt loaded nitrogen-doped three-dimensional porous carbon material/sulfur composite material is prepared by the following steps:
0.1g of the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon material prepared in the embodiment and 0.4g of elemental sulfur powder are ground, uniformly mixed and then placed in a container filled with N2And (3) preserving the heat of the protected tubular furnace at 155 ℃ for 10h, cooling the tubular furnace, and taking out the tubular furnace to obtain the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon material/sulfur composite material.
Comparative example 1
The comparative example provides a preparation method of a nanocobalt-loaded nitrogen-doped microporous carbon/sulfur nanocomposite, comprising the following steps:
(1) 0.8g of Co (NO)3)2And 1.0g of 2-methylimidazole are respectively added into 100ml of methanol and stirred for dissolution, and the two solutions are mixed under magnetic stirring to obtain a precursor reaction solution.
(2) Stirring the precursor reaction solution obtained in the step (1) at 30 ℃ for reaction for 1h, standing for reaction for 24h, filtering, washing and drying by using ethanol to obtain purple powder;
(3) putting the purple precursor powder obtained in the step (2) into a tube furnace, and putting the purple precursor powder into the tube furnace to be heated in high-purity Ar/15% H2Sintering at 900 ℃ for 2h under the atmosphere to obtain black powder;
(4) and (4) placing the black powder obtained in the step (3) in 100ml of 20% HCl aqueous solution, stirring for 12h, washing off part of metal cobalt, filtering, washing and drying to obtain the nano-cobalt-loaded nitrogen-doped microporous carbon material.
(5) 0.1g of nano-cobalt loaded nitrogen-doped microporous carbon material and 0.4g of elemental sulfur powder are ground, mixed uniformly and then placed in a container filled with N2And (3) preserving the heat of the protected tubular furnace at 155 ℃ for 10h, cooling the tubular furnace, and taking out the tubular furnace to obtain the nano cobalt-loaded nitrogen-doped microporous carbon/sulfur composite material. The sulfur content of the composite was 83%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon is characterized by comprising the following steps:
(1) adding the inorganic nanospheres into methanol for ultrasonic dispersion, then adding cobalt salt, stirring and dissolving, and then adding a 2-methylimidazole methanol solution to obtain a precursor solution; the particle size of the inorganic nanospheres is 50-500 nm;
(2) stirring the precursor solution for reaction, and then heating and stirring to evaporate the solvent to dryness to obtain a grayish purple precursor powder; in the stirring reaction, inorganic nanospheres are used as templates, cobalt salt is used as a cobalt source, 2-methylimidazole is used as a carbon source and a nitrogen source, and a precursor reacts in a methanol solution to generate ZIF67 which is coated on the surfaces of the inorganic nanospheres;
(3) putting the gray purple precursor powder in an inert reducing atmosphere for heat treatment to obtain black powder; the precursor is carbonized through the heat treatment, and cobalt ions in the precursor are reduced into metal cobalt;
(4) washing the black powder in an acidic aqueous solution, filtering and drying to obtain a nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon material; the nitrogen-doped three-dimensional porous carbon material loaded with the nano cobalt is formed by uniformly dispersing nano cobalt particles in a three-dimensional honeycomb nitrogen-doped porous carbon matrix.
2. The method for preparing the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon according to claim 1, wherein in the step (1), the concentration of the inorganic nanospheres in the precursor solution is 5-50 g/L; the concentration of cobalt salt in the precursor solution is 0.01-0.1 mol/L; the molar ratio of the cobalt salt to the 2-methylimidazole is 1: (0.5 to 10).
3. The method for preparing nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon according to claim 1 or 2, wherein the inorganic nanospheres are SiO2、TiO2、ZnO。
4. The method for preparing the nanocobalt-supported nitrogen-doped three-dimensional porous carbon according to claim 1 or 2, wherein the cobalt salt is at least one of cobalt nitrate, cobalt chloride and cobalt acetate.
5. The preparation method of the nano-cobalt-supported nitrogen-doped three-dimensional porous carbon according to claim 1, wherein in the step (2), the stirring reaction temperature is 10-40 ℃ and the reaction time is 0.5-2 h.
6. The preparation method of the nano-cobalt-supported nitrogen-doped three-dimensional porous carbon according to claim 1, wherein in the step (2), the temperature for heating and stirring is 70-90 ℃, and the stirring is carried out until the solvent is completely volatilized.
7. The method for preparing nano-cobalt-supported nitrogen-doped three-dimensional porous carbon according to claim 1, wherein in the step (3), the inert reducing atmosphere is Ar and H2Mixed gas of Ar and H2The volume percentage of (70-95): (5-30); the temperature of the heat treatment is 500-1000 ℃, and the time is 0.5-10 h.
8. The method for preparing the nanocobalt-supported nitrogen-doped three-dimensional porous carbon according to claim 1, wherein in the step (4), the acid in the acidic aqueous solution is a mixed acid of hydrofluoric acid and hydrochloric acid or sulfuric acid or nitric acid; the mass fraction of the acid in the acidic aqueous solution is 5-30 wt%.
9. The nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon is characterized by being prepared by the preparation method of any one of claims 1-8; the size of the nano cobalt particles is 5-50 nm, and the aperture of the porous carbon is 100-500 nm.
10. The application of the nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon in the lithium-sulfur battery is characterized in that the nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon is used for preparing a nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon/sulfur composite material; the nanometer cobalt-loaded nitrogen-doped three-dimensional porous carbon is prepared by the preparation method of any one of claims 1 to 8, and the mass fraction of sulfur in the composite material is 40-90 wt%.
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