CN114974938B - Preparation of Mn-Ni double single-atom modulation CN graded carbon tube electrode material - Google Patents
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Abstract
The invention discloses a preparation method of an Mn-Ni double single-atom modulation CN graded carbon tube electrode material, and belongs to the technical field of materials. The preparation method comprises the following steps: obtaining a NiO nano-sheet array by a low-temperature autodeposition method; by Mn (NO) 3 ) 2 ·6H 2 The activity of metal ions in the polar solution of O carries out nanoparticle modification on the NiO nano-sheet array to obtain the Mn-NiO nano-sheet array, and finally melamine is taken as a carbon source to obtain the Mn-Ni diatomic modulated C by a chemical vapor deposition method under the atmosphere of inert gas 3 N 4 And grading the carbon tube electrode material. The method uses Ni and Mn monoatoms as adsorption and activation sites, improves electrode materials and OH ‑ The adsorption energy and the reaction energy barrier of ions, and simultaneously, the multivalent state of Mn ions also increases the OH of the electrode material ‑ Thereby improving the energy storage performance of MnNi-INCs. And the process steps are simple, the cost is low, and the product is easy to obtain.
Description
Technical Field
The invention relates to a preparation method of an Mn-Ni double single-atom modulation CN graded carbon tube electrode material, and belongs to the technical field of materials.
Background
With the acceleration of the global carbon neutralization process, the demand for off-grid storage of energy has stimulated the development of high energy density and safe energy storage devices. Supercapacitors have higher energy density and power performance than lithium ion batteries, and are considered candidates for next generation energy storage. Low-cost and naturally abundant carbon-based nanomaterials are widely used as electrode materials for energy storage devices due to their high specific surface area and porous structure. However, low volumetric energy density, poor charge and discharge performance and slow reaction kinetics are major bottlenecks that limit the energy storage capacity of carbon-based nanomaterials.
To address these challenges, much effort has been devoted to material design and synthesis. One such example, a heteroatom doped carbon material, shows good promise due to its tunable surface function, excellent performance and strong redox activity. To date, many studies have been made, including N, P and O Co-doped carbon, manganese doped carbon microspheres, ni doped carbon nanotubes and Fe/Co/Ni doped carbon nanotubes. However, the improvement of performance based on simple recombination is still very limited due to the insufficient electroactive sites and low surface reactivity of the carbon-based nanomaterial. It is therefore important to design a novel structure to achieve high surface reactivity and to shorten the electron/ion diffusion path for the energy storage material to fully release its charge storage capacity.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of an Mn-Ni double single-atom modulation CN graded carbon tube electrode material, which provides the following scheme:
the invention provides a preparation method of an Mn-Ni double single-atom modulation CN graded carbon tube electrode material, which comprises the following steps:
(1) Ni (OAc) 2 And (NH) 4 ) 2 S 2 O 8 Dissolving in deionized water, ultrasonic vibrating and stirring to obtain light blue mixed solution, and adding NH 3 ·H 2 O is dripped into the mixed solution to be uniformly mixed to become blue solution, carbon Cloth (CC) is immersed and stood untilThe NiOOH film grows on a Carbon Cloth (CC) substrate, the Carbon Cloth (CC) is taken out, washed by deionized water, particles, which are not deposited on the carbon cloth, on the surface of the film are removed, and the NiO nano-sheet array (NiO NSs) is obtained through drying and annealing;
(2) Mn (NO) 3 ) 2 ·6H 2 O is dissolved in polar solution, and ultrasonic oscillation is carried out until Mn (NO 3 ) 2 ·6H 2 After O is completely dissolved, heating, immersing and standing the NiO nano-sheet array prepared in the step (1) after the temperature is stabilized, taking out the NiO nano-sheet array, cleaning with a polar solution, and removing redundant Mn (NO) on the surface of the NiO nano-sheet array 3 ) 2 ·6H 2 O, obtaining a core-shell lamellar array of which the MnOOH is coated on the surface of the NiO nano-sheet array, and annealing to obtain a Mn-NiO nano-sheet array (MnNi-O NSs);
(3) Heating a carbon source and the Mn-NiO nano-sheet array prepared in the step (2) in a protective gas atmosphere to obtain the Mn and Ni metal monoatomic monodispersion C 3 N 4 The surface of the graded carbon tube is the Mn-Ni diatomic modulation CN graded carbon tube electrode material (MnNi-ICNs).
Further, the Ni (OAc) 2 And (NH) 4 ) 2 S 2 O 8 The mass ratio of (2-12.8): 1, the (NH) 4 ) 2 S 2 O 8 With NH 3 ·H 2 The feed liquid ratio of O is 100mg: (100-600) mu L, the (NH) 4 ) 2 S 2 O 8 With Mn (NO) 3 ) 2 ·6H 2 The mass ratio of the O to the melamine compound is 1:1.4:5.
Further, the annealing temperatures were 500 ℃.
Further, the carbon cloth in the step (1) needs to be subjected to a pretreatment process, specifically: carbon cloth (CC, 1X 1 cm) 2 ) Ultrasonic treatment is carried out for half an hour by immersing in 3M HCl solution to remove oxide on the surface of the carbon cloth, and then immersing CC in the mixed solution (HNO 3 ∶H 2 SO 4 (v/v=3:1)), water-bathing at 80 ℃ for 3 hours to increase the hydrophilicity of the carbon cloth surface, then washing with deionized water and acetone 3 times each to remove stains on the carbon cloth surface, and drying in an oven at 45 ℃.
Further, in step (1), NH 3 ·H 2 O is added while stirring, and the dropping speed is 10 drops/min.
Further, in the step (1), the temperature of the carbon cloth which is immersed and then is kept standing is 35 ℃, and the standing time is 1h.
Further, in the step (2), the Mn (NO) 3 ) 2 ·6H 2 The ratio of O to polar solution was 0.0005mol:1mL, the temperature of the heating was 35℃and the temperature of the annealing was 500 ℃.
Further, in the step (2), the standing time is 15min.
Further, in step (2), the polar solution is acetone.
Further, in step (3), the carbon source is melamine.
Further, in the step (3), the melamine compound is located upstream of the tube furnace, the mn—nio nanoplatelet array is located in the tube furnace, and chemical vapor deposition is performed, so as to better grow carbon tubes on the surface of mnni—o NSs.
Further, in the step (3), the protective atmosphere is argon, and the volume flow is 20sccm.
Further, in the step (3), the heating rate is 5 ℃/min, the temperature is raised to 800-1000 ℃, and the temperature is kept for 4 hours.
The invention also provides a capacitor electrode material based on Mn-Ni diatomic atoms, which is prepared by the preparation method.
Monoatomic (SA) catalysts are attracting increasing attention for their excellent properties, including maximum atom utilization, unsaturated metal species, well-defined active sites and tunable electronic properties. They represent a great advantage as electrode materials in terms of energy conversion and storage. This is mainly due to the SA: (i) has an unusual electronic structure, (ii) has separate energy levels and exposes dense metal centers, (iii) has a kinetic transformation that effectively catalyzes a reaction intermediate. The invention discloses the following technical effects:
the invention aims to break through the symmetrical charge around SA siteDistribution limitation, mn-Ni double single atoms with different coordination are designed and synthesized to be mono-dispersed in C 3 N 4 A novel structure on graded carbon tubes. Pairing and coupling of different Mn/Ni monoatomic sites can correspondingly polarize the charge distribution and increase its electronic state to the fermi level, thereby increasing the adsorption capacity of the substrate/intermediate and decreasing the reaction activation energy.
The method has simple process steps and easily obtained products. Compared with the existing research cost and low energy consumption, the method has the advantages that the NiO nano-sheet array is obtained through the product of low Wen Zichen, and the Mn-NiO nano-sheet array is obtained through secondary modification of the NiO nano-sheet array by utilizing the different stabilities of different metal ions in polar solutions. The melamine is used as a carbon source, and C with evenly distributed Ni and Mn is obtained through chemical vapor deposition (the principle of high-temperature pyrolysis) 3 N 4 The energy storage performance of the electrode material is researched by taking Ni and Mn diatomic atoms as active sites, and the electrode material shows 1523.6 F.g after performance analysis -1 Is a high capacitance of (a). The energy density of the optimized asymmetric double electrode is up to 180.8 Wh.kg -1 The power density is 1152 W.kg -1 Is the best value in the super capacitor reported before. The mechanism research shows that the performance improvement is mainly based on the co-improvement of the electrode material and OH by the monodispersed Mn-Ni diatomic synergy - Adsorption energy and reaction energy barrier of ions. The technology of the invention provides a new strategy for achieving high energy storage in supercapacitors.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a preparation process of the MnNi-ICNs of the present invention;
FIG. 2 is a diagram showing the structural evolution of NiO NSs, mnNi-O NSs and MnNi-ICNs in the preparation process of the invention;
FIG. 3 is an SEM image of NiO NSs prepared in example 1 of the present invention, wherein a-b are SEM images of NiO NSs at 2000X, 4000X, 10000X and 20000X magnification, respectively;
FIG. 4 is an XRD pattern of NiO NSs prepared in example 1 of the present invention;
FIG. 5 is an SEM image of MnNi-O NSs prepared in example 1 of the present invention, wherein a-b are SEM images of MnNi-O NSs at 1000X, 7000X, 100000X and 200000X magnification, respectively;
FIG. 6 is an XRD pattern of MnNi-O NSs prepared in example 1 of the present invention;
FIG. 7 is an SEM image of MnNi-ICNs prepared in example 1 of the present invention, wherein a-b are SEM images of MnNi-ICNs at 1000X, 7000X, 100000X and 200000X magnification, respectively;
FIG. 8 is an XRD pattern of MnNi-ICNs prepared in example 1 of the present invention;
FIG. 9 is a spherical aberration diagram of MnNi-ICNs prepared in example 1 of the present invention; wherein, a is a high-angle annular dark field spectrum and each element distribution diagram of the MnNi-ICNs from left to right, b is a distribution diagram of Mn and Ni monoatoms on the surface of the MnNi-ICNs from left to right, c is an EELS energy spectrum of the MnNi-ICNs from left to right;
fig. 10 is a graph of energy storage properties of respective electrode materials.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The invention provides a preparation method of an Mn-Ni double single-atom modulation CN graded carbon tube electrode material, which comprises the following steps:
(1) Ni (OAc) 2 And (NH) 4 ) 2 S 2 O 8 Dissolving in deionized water, ultrasonic vibrating and stirring to obtain light blue mixed solution, and adding NH 3 ·H 2 O is dripped into the mixed solution to be uniformly mixed to become a blue solution, carbon Cloth (CC) is immersed and kept stand, a NiOOH film grows on a Carbon Cloth (CC) substrate, the Carbon Cloth (CC) is taken out to be washed by deionized water, particles, which are not deposited on the carbon cloth, on the surface of the film are removed, and a NiO nano-sheet array (NiO NSs) is obtained through drying and annealing;
(2) Mn (NO) 3 ) 2 ·6H 2 O is dissolved in polar solution, and ultrasonic oscillation is carried out until Mn (NO 3 ) 2 ·6H 2 Heating after O is completely dissolved, immersing the NiO nano-sheet array prepared in the step (1) into the mixture and standing the mixture after the temperature is stabilizedTaking out the NiO nano-sheet array, cleaning with a polar solution, and removing redundant Mn (NO) on the surface of the NiO nano-sheet array 3 ) 2 ·6H 2 O, obtaining a core-shell lamellar array of which the MnOOH is coated on the surface of the NiO nano-sheet array, and annealing to obtain a Mn-NiO nano-sheet array (MnNi-O NSs);
(3) Heating a carbon source and the Mn-NiO nano-sheet array prepared in the step (2) in a protective gas atmosphere to obtain the Mn and Ni metal monoatomic monodispersion C 3 N 4 The surface of the graded carbon tube is the Mn-Ni diatomic modulation CN graded carbon tube electrode material (MnNi-ICNs).
Further, the Ni (OAc) 2 And (NH) 4 ) 2 S 2 O 8 The mass ratio of (2-12.8): 1, the (NH) 4 ) 2 S 2 O 8 With NH 3 ·H 2 The feed liquid ratio of O is 100mg: (100-600) mu L, the (NH) 4 ) 2 S 2 O 8 With Mn (NO) 3 ) 2 ·6H 2 The mass ratio of the O to the melamine compound is 1:1.4:5.
Further, the annealing temperatures were 500 ℃.
Further, the carbon cloth in the step (1) needs to be subjected to a pretreatment process, specifically: carbon cloth (CC, 1X 1 cm) 2 ) Ultrasonic treatment is carried out for half an hour by immersing in 3M HCl solution to remove oxide on the surface of the carbon cloth, and then immersing CC in the mixed solution (HNO 3 ∶H 2 SO 4 (v/v=3:1)), water-bathing at 80 ℃ for 3 hours to increase the hydrophilicity of the carbon cloth surface, then washing with deionized water and acetone 3 times each to remove stains on the carbon cloth surface, and drying in an oven at 45 ℃.
Further, in step (1), NH 3 ·H 2 O is added while stirring, and the dropping speed is 10 drops/min.
Further, in the step (1), the temperature of the carbon cloth which is immersed and then is kept standing is 35 ℃, and the standing time is 1h.
Further, in the step (2), the Mn (NO) 3 ) 2 ·6H 2 The dosage ratio of O to polar solution was 0.5mol:5mL of the additionThe temperature of the heat was 35℃and the temperature of the annealing was 500 ℃.
Further, in the step (2), the standing time is 15min.
Further, in step (2), the polar solution is acetone.
Further, in step (3), the carbon source is melamine.
Further, in the step (3), the melamine compound is located upstream of the tube furnace, the mn—nio nanoplatelet array is located in the tube furnace, and chemical vapor deposition is performed, so as to better grow carbon tubes on the surface of mnni—o NSs.
Further, in the step (3), the protective atmosphere is argon, and the volume flow is 20sccm.
Further, in the step (3), the heating rate is 5 ℃/min, the temperature is raised to 800-1000 ℃, and the temperature is kept for 4 hours.
The invention also provides the Mn-Ni diatomic modulation CN graded carbon tube electrode material prepared by the preparation method.
The preparation process flow chart of the MnNi-ICNs is shown in figure 1, and the structural evolution chart of NiO NSs, mnNi-ONSs and MnNi-ICNs is shown in figure 2.
All the raw materials used in the embodiment of the invention are commercially available.
The technical scheme of the invention is further described by the following examples.
Example 1
(1) 0.64g Ni (OAc) was weighed out 2 And 100mg (NH) 4 ) 2 S 2 O 8 Dissolving in 10mL deionized water (18Ω), ultrasonic vibrating for 5min and stirring for 10min to obtain light blue mixed solution, and adding 400 μl NH 3 ·H 2 Slowly dripping O into the mixed solution at a speed of 10 drops/min while stirring, uniformly mixing to obtain a blue solution, immersing Carbon Cloth (CC) and standing at 35 ℃ for 1h, taking out the Carbon Cloth (CC), flushing with deionized water, drying at 35 ℃, and then annealing at 500 ℃ for 2h to obtain a NiO nano-sheet array (NiO NSs);
the SEM images of NiO NSs prepared in example 1 of the present invention are shown in fig. 3, where a-b are SEM images of NiO NSs at 2000×, 4000×, 10000×, and 20000× magnification, respectively, and it can be seen from fig. 3 that NiO exhibits a nanoplatelet array morphology.
FIG. 4 XRD patterns of NiO NSs prepared in example 1 of the present invention are shown in FIG. 4, and it can be seen from FIG. 4 that NiO mainly exposes the (111), (200) and (220) crystal planes.
(2) 0.14g of Mn (NO 3 ) 2 ·6H 2 O is dissolved in 5mL of polar solution (acetone), and ultrasonic oscillation is carried out for 10min until Mn (NO) 3 ) 2 ·6H 2 After O is completely dissolved, placing the mixture into a baking oven at 35 ℃ for heating for 10min, immersing the NiO nano-sheet array prepared in the step (1) and standing for 15min when the temperature of the mixed solution and the temperature of the baking oven are stable, taking out the NiO nano-sheet array, cleaning the NiO nano-sheet array by using a polar solution (acetone), and annealing the mixture at 500 ℃ for 2h to obtain a Mn-NiO nano-sheet array (MnNi-O NSs);
the SEM images of MnNi-O NSs prepared in example 1 of the present invention are shown in fig. 5, where a-b are SEM images of MnNi-O NSs at 1000×, 7000×, 100000×, and 200000× magnification, respectively, and it can be seen from fig. 5 that the surface of the NiO nanoplatelet array is coated with some nanoparticles.
The XRD pattern of the MnNi-O NSs prepared in example 1 of the present invention is shown in FIG. 6, and it can be seen from FIG. 6 that diffraction peaks of manganese oxide are not found in the NiMn-O NSs due to low mass loading rate of Mn.
(3) Placing 0.5g melamine in a 20mL magnetic boat, placing the melamine in the upstream of a tube furnace, placing the Mn-NiO nano sheet array prepared in the step (2) on the magnetic boat, placing the Mn-NiO nano sheet array in the midstream of the tube furnace, heating the Mn-NiO nano sheet array to 800 ℃ at a speed of 5 ℃/min under an Ar atmosphere of 20sccm, and keeping the temperature for 4 hours at a constant temperature to obtain the Mn and Ni metal monoatoms which are monodisperse in C 3 N 4 The surface of the graded carbon tube is Mn-Ni double single atom modulation CN graded carbon tube electrode material (MnNi-ICNs-4 h);
the SEM pictures of the MnNi-ICNs-4h prepared in example 1 of the present invention are shown in FIG. 7, wherein a-b are SEM pictures of the MnNi-ICNs-4h at 1000X, 7000X, 100000X and 200000X magnification, respectively, and it can be seen from FIG. 7 that the MnNi-ICNs-4h presents the morphology of a tube, and that there is a small white dot on the top of each carbon tube, which is mainly Ni metal.
The XRD pattern of MnNi-ICNs-4h prepared in example 1 of the invention is shown in FIG. 8, and it can be seen from FIG. 8 that the XRD pattern of MnNi-ICN-4h s mainly shows Ni, C 3 N 4 And (002) crystal plane of CC, and C 3 N 4 Partial overlap of the (002) crystal plane of CC and the peak position of CC substrate in MnNi-ICNs-4h is shifted compared to nionss. In addition, a face centered cubic (fcc) Ni crystalline phase was also found in the XRD pattern of MnNi-INCs-4h, indicating Ni metal particles and C 3 N 4 Is coexistent in MnNi-INCs material.
The spherical aberration electron microscope diagram of the MnNi-ICNs-4h prepared in the embodiment 1 of the invention is shown in fig. 9, wherein a is a high-angle annular dark field diagram and each element diagram of the MnNi-ICNs-4h from left to right, b is a diagram of Mn and Ni single atoms on the surface of the MnNi-ICNs-4h from left to right, c is an EELS energy diagram of the MnNi-ICNs-4h from left to right, and C, N, O, ni and Mn are uniformly distributed on the carbon nanotubes as can be seen from fig. 9. HAADF-STEM imaging showed that monodisperse Mn and Ni monoatoms were determined to be randomly dispersed in C 3 N 4 Grading the surface of the carbon tube. At the same time, the Electron Energy Loss Spectroscopy (EELS) graph also confirms the coexistence of Mn and Ni diatomic atoms in MnNi-INCs.
Example 2
(1) 0.32g Ni (OAc) was weighed out 2 And 100mg (NH) 4 ) 2 S 2 O 8 Dissolving in 10mL deionized water (18Ω), ultrasonic vibrating for 5min and stirring for 10min to obtain light blue mixed solution, and adding 100 μl NH 3 ·H 2 Slowly dripping O into the mixed solution at a speed of 10 drops/min while stirring, uniformly mixing to obtain a blue solution, immersing Carbon Cloth (CC) into the solution, standing for 1h at 35 ℃, taking out the Carbon Cloth (CC) to be washed by deionized water when a NiOOH film grows on a Carbon Cloth (CC) substrate, drying at 35 ℃, and then annealing at 500 ℃ for 2h to obtain a NiO nano-sheet array (NiO NSs);
(2) 0.14g of Mn (NO 3 ) 2 ·6H 2 O is dissolved in 5mL of polar solution (acetone), and ultrasonic oscillation is carried out for 10min until Mn (NO) 3 ) 2 ·6H 2 O is completely dissolvedAfter the solution is decomposed, placing the mixture into a baking oven at 35 ℃ for heating for 10min, immersing the NiO nano-sheet array prepared in the step (1) into the mixture and standing for 15min after the temperature of the mixed solution and the temperature of the baking oven are stabilized, taking out the NiO nano-sheet array, cleaning the NiO nano-sheet array by using a polar solution (acetone), and annealing the mixture at 500 ℃ for 2h to obtain a Mn-NiO nano-sheet array (MnNi-O NSs);
(3) Placing 0.5g melamine in a 20mL magnetic boat, placing the melamine in the upstream of a tube furnace, placing the Mn-NiO nano sheet array prepared in the step (2) on the magnetic boat, placing the Mn-NiO nano sheet array in the midstream of the tube furnace, heating the Mn-NiO nano sheet array to 800 ℃ at a speed of 5 ℃/min under an Ar atmosphere of 20sccm, and keeping the temperature for 1h at a constant temperature to obtain the Mn and Ni metal monoatoms which are monodisperse in C 3 N 4 The surface of the graded carbon tube is Mn-Ni diatomic modulation CN graded carbon tube electrode material (MnNi-ICNs).
Example 3
(1) 0.2g Ni (OAc) was weighed out 2 And 100mg (NH) 4 ) 2 S 2 O 8 Dissolving in 10mL deionized water (18Ω), ultrasonic vibrating for 5min and stirring for 10min to obtain light blue mixed solution, and adding 200 μl NH 3 ·H 2 Slowly dripping O into the mixed solution at a speed of 10 drops/min while stirring, uniformly mixing to obtain a blue solution, immersing Carbon Cloth (CC) into the solution, standing for 1h at 35 ℃, taking out the Carbon Cloth (CC) to be washed by deionized water when a NiOOH film grows on a Carbon Cloth (CC) substrate, drying at 35 ℃, and then annealing at 500 ℃ for 2h to obtain a NiO nano-sheet array (NiO NSs);
(2) 0.14g of Mn (NO 3 ) 2 ·6H 2 O is dissolved in 5mL of polar solution (acetone), and ultrasonic oscillation is carried out for 10min until Mn (NO) 3 ) 2 ·6H 2 After O is completely dissolved, placing the mixture into a baking oven at 35 ℃ for heating for 10min, immersing the NiO nano-sheet array prepared in the step (1) and standing for 15min when the temperature of the mixed solution and the temperature of the baking oven are stable, taking out the NiO nano-sheet array, cleaning the NiO nano-sheet array by using a polar solution (acetone), and annealing the mixture at 500 ℃ for 2h to obtain a Mn-NiO nano-sheet array (MnNi-O NSs);
(3) Placing 0.5g melamine in a 20mL magnetic boat, placing the melamine in the upstream of a tube furnace, and preparing Mn-NiO nano-sheets in the step (2)Placing the array on a magnetic boat, placing the array in the midstream of a tube furnace, heating to 800 ℃ at 5 ℃/min under the Ar atmosphere of 20sccm, and keeping the temperature for 2 hours at constant temperature to obtain the Mn and Ni metal monoatomic monodispersion in C 3 N 4 The surface of the graded carbon tube is Mn-Ni diatomic modulation CN graded carbon tube electrode material (MnNi-ICNs).
Example 4
(1) 0.74g Ni (OAc) was weighed out 2 And 100mg (NH) 4 ) 2 S 2 O 8 Dissolving in 10mL deionized water (18Ω), ultrasonic vibrating for 5min and stirring for 10min to obtain light blue mixed solution, and adding 500 μl NH 3 ·H 2 Slowly dripping O into the mixed solution at a speed of 10 drops/min while stirring, uniformly mixing to obtain a blue solution, immersing Carbon Cloth (CC) into the solution, standing for 1h at 35 ℃, taking out the Carbon Cloth (CC) to be washed by deionized water when a NiOOH film grows on a Carbon Cloth (CC) substrate, drying at 35 ℃, and then annealing at 400 ℃ for 2h to obtain a NiO nano-sheet array (NiO NSs);
(2) 0.14g of Mn (NO 3 ) 2 ·6H 2 O is dissolved in 5mL of polar solution (acetone), and ultrasonic oscillation is carried out for 10min until Mn (NO) 3 ) 2 ·6H 2 After O is completely dissolved, placing the mixture into a baking oven at 35 ℃ for heating for 10min, immersing the NiO nano-sheet array prepared in the step (1) and standing for 15min when the temperature of the mixed solution and the temperature of the baking oven are stable, taking out the NiO nano-sheet array, cleaning the NiO nano-sheet array by using a polar solution (acetone), and annealing the mixture at 500 ℃ for 2h to obtain a Mn-NiO nano-sheet array (MnNi-O NSs);
(3) Placing 0.5g melamine in a 20mL magnetic boat, placing the melamine in the upstream of a tube furnace, placing the Mn-NiO nano sheet array prepared in the step (2) on the magnetic boat, placing the Mn-NiO nano sheet array in the midstream of the tube furnace, heating the Mn-NiO nano sheet array to 800 ℃ at a speed of 5 ℃/min under an Ar atmosphere of 20sccm, and keeping the temperature for 3 hours at a constant temperature to obtain the Mn and Ni metal monoatoms which are monodisperse in C 3 N 4 The surface of the graded carbon tube is Mn-Ni diatomic modulation CN graded carbon tube electrode material (MnNi-ICNs).
Example 5
(1) 1.28g Ni (OAc) was weighed out 2 And 100mg (NH) 4 ) 2 S 2 O 8 Dissolving in 10mL deionized water (18Ω), ultrasonic vibrating for 5min and stirring for 10min to obtain light blue mixed solution, and adding 600 μl NH 3 ·H 2 Slowly dripping O into the mixed solution at a speed of 10 drops/min while stirring, uniformly mixing to obtain a blue solution, immersing Carbon Cloth (CC) into the solution and standing for 1h at 35 ℃, taking out the Carbon Cloth (CC) to be washed by deionized water when a NiOOH film grows on a Carbon Cloth (CC) substrate, drying at 35 ℃, and then annealing for 2h at 500 ℃ to obtain a NiO nano-sheet array (NiO NSs);
(2) 0.14g of Mn (NO 3 ) 2 ·6H 2 O is dissolved in 5mL of polar solution (acetone), and ultrasonic oscillation is carried out for 10min until Mn (NO) 3 ) 2 ·6H 2 After O is completely dissolved, placing the mixture into a baking oven at 35 ℃ for heating for 10min, immersing the NiO nano-sheet array prepared in the step (1) and standing for 15min when the temperature of the mixed solution and the temperature of the baking oven are stable, taking out the NiO nano-sheet array, cleaning the NiO nano-sheet array by using a polar solution (acetone), and annealing the mixture at 500 ℃ for 2h to obtain a Mn-NiO nano-sheet array (MnNi-O NSs);
(3) Placing 0.5g melamine in a 20mL magnetic boat, placing the melamine in the upstream of a tube furnace, placing the Mn-NiO nano sheet array prepared in the step (2) on the magnetic boat, placing the Mn-NiO nano sheet array in the midstream of the tube furnace, heating the Mn-NiO nano sheet array to 1000 ℃ at 5 ℃/min under an Ar atmosphere of 20sccm, and keeping the temperature for 5 hours at constant temperature to obtain the Mn and Ni metal monoatoms monodisperse in C 3 N 4 The surface of the graded carbon tube is Mn-Ni diatomic modulation CN graded carbon tube electrode material (MnNi-ICNs).
Comparative example 1
(1) 0.64g Ni (OAc) was weighed out 2 And 100mg (NH) 4 ) 2 S 2 O 8 Dissolving in 10mL deionized water (18Ω), ultrasonic vibrating for 5min and stirring for 10min to obtain light blue mixed solution, and adding 400 μl NH 3 ·H 2 Slowly dripping O into the mixed solution at a speed of 10 drops/min under stirring, mixing uniformly to obtain blue solution, immersing Carbon Cloth (CC) and standing at 35deg.C for 1 hr, taking out Carbon Cloth (CC), washing with deionized water, oven drying at 35deg.C, and annealing at 500deg.C for 2 hr to obtain NiO nanoplatelet arrays (nionss);
(2) Placing 0.5g melamine in a 20mL magnetic boat, placing the melamine in the upstream of a tube furnace, placing the NiO nano-sheet array prepared in the step (1) on the magnetic boat, placing the NiO nano-sheet array in the midstream of the tube furnace, heating to 800 ℃ at 5 ℃/min under the Ar atmosphere of 20sccm, and keeping the temperature for 4 hours at constant temperature to obtain the Ni metal monoatomic monodispersed in C 3 N 4 Graded carbon tube surface (Ni-ICNs).
Comparative example 2
The procedure was as in example 1 except that in step (3), the temperature was raised to 800℃at 5℃per minute under an Ar atmosphere of 20sccm and kept constant at this temperature for 1 hour to prepare a Mn-Ni diatomic modified CN staged carbon tube electrode material (MnNi-ICNs-1 hour).
Comparative example 3
The procedure was as in example 1 except that in step (3), the temperature was raised to 800℃at 5℃per minute under an Ar atmosphere of 20sccm and kept constant at this temperature for 2 hours, to prepare a Mn-Ni diatomic modified CN staged carbon tube electrode material (MnNi-ICNs-2 hours).
Comparative example 4
The procedure was as in example 1 except that in step (3), the temperature was raised to 800℃at 5℃per minute under an Ar atmosphere of 20sccm and kept constant at this temperature for 3 hours, to prepare a Mn-Ni diatomic modified CN staged carbon tube electrode material (MnNi-ICNs-3 h).
Comparative example 5
The procedure was as in example 1 except that in step (3), the temperature was raised to 800℃at 5℃per minute under an Ar atmosphere of 20sccm and kept constant at this temperature for 5 hours, to prepare a Mn-Ni diatomic modified CN staged carbon tube electrode material (MnNi-ICNs-5 hours).
Performance testing
The electrochemical energy storage properties of NiO NSs, mnNi-O NSs and MnNi-ICNs-4h prepared in example 1, mnNi-ICNs-1h, mnNi-ICNs-2h, mnNi-ICNs-3h and MnNi-ICNs-5h prepared in comparative example 2-5 and Ni-ICNs prepared in comparative example 1 were evaluated, all electrochemical measurements were performed on Chen Hua electrochemical workstations, the above material electrodes were tested directly on a non-adhesive CC substrate, and the above materials were tested at room temperatureAt (about 25 ℃) the electrolyte is 3mol KOH solution, the electrode of the above material is used as working electrode, and the platinum grid and calomel electrode are used as counter electrode and reference electrode respectively. Impedance spectrum measuring frequency is 1-10 5 HZ. The working electrode should be immersed in the electrolyte for 10 minutes before measurement to ensure adequate wettability and stability of the working electrode.
The specific capacitance of the electrode material is calculated according to formula (I):
in the formula (I), I ≡vdt is the area surrounded by the discharge curve in the GCD curve, m is the effective mass of the electrode, and Δv is the operating potential window of the curve.
The energy storage properties of the respective electrode materials are shown in fig. 10, and it can be seen from fig. 10 that: compared with NiO NSs, mnNi-O NSs, ni-INCs and samples prepared in comparative examples 2-5, the specific capacitance of MnNi-INCs-4h is increased by about 1.38 times, and the energy storage performance is higher.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (8)
1. The preparation method of the Mn-Ni diatomic modulation CN graded carbon tube electrode material is characterized by comprising the following steps:
(1) Ni (OAc) 2 And (NH) 4 ) 2 S 2 O 8 Dissolving in deionized water, ultrasonically oscillating and stirring to obtain a mixed solution, and then adding NH 3 ·H 2 O is dripped into the mixed solution to be uniformly mixed, carbon cloth is immersed and kept stand, the carbon cloth is taken out to be washed by deionized water, and the NiO nano-sheet array is obtained through drying and annealing;
(2) Mn (NO) 3 ) 2 ·6H 2 O is dissolved in a polar solution, heating is carried out after ultrasonic oscillation, then the NiO nano-sheet array prepared in the step (1) is immersed and kept stand, the NiO nano-sheet array is taken out, the polar solution is used for cleaning, and the Mn-NiO nano-sheet array is obtained through annealing;
(3) Heating a carbon source and the Mn-NiO nano-sheet array prepared in the step (2) in a protective gas atmosphere to obtain the Mn-Ni diatomic modulation CN graded carbon tube electrode material;
in the step (3), the carbon source is melamine.
2. The method according to claim 1, wherein the Ni (OAc) 2 And (NH) 4 ) 2 S 2 O 8 The mass ratio of (2-12.8): 1, the (NH) 4 ) 2 S 2 O 8 With NH 3 ·H 2 The feed liquid ratio of O is 100mg: (100-600) mu L of the (NH) 4 ) 2 S 2 O 8 With Mn (NO) 3 ) 2 ·6H 2 The mass ratio of the O to the melamine compound is 1:1.4:5.
3. the method of claim 1, wherein the annealing is performed at a temperature of 500 ℃.
4. The method according to claim 1, wherein in the step (1), the carbon cloth is immersed and then left to stand at a temperature of 35 ℃.
5. The method according to claim 1, wherein in the step (2), the Mn (NO 3 ) 2 ·6H 2 The ratio of O to polar solution was 0.0005mol:1mL, the temperature of the heating was 35℃and the temperature of the annealing was 500 ℃.
6. The method of claim 1, wherein in step (2), the polar solution is acetone.
7. The method according to claim 1, wherein in the step (3), the heating rate is 5 ℃/min, the temperature is raised to 800 ℃, and the temperature is kept for 4 hours.
8. An Mn-Ni diatomic modulation CN graded carbon tube electrode material prepared by the preparation method of any one of claims 1-7.
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