CN114974938A - Preparation of Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material - Google Patents
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Abstract
The invention discloses a preparation method of a Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material, belonging 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 Performing nano-particle modification on the NiO nano-sheet array by the activity of metal ions in the polar solution of O to obtain an Mn-NiO nano-sheet array, and finally obtaining Mn-Ni double-monoatomic-modulated C by using melamine as a carbon source in an inert gas atmosphere through a chemical vapor deposition method 3 N 4 Grading the carbon tube electrode material. The method takes Ni and Mn single atoms as adsorption and activation sites to improve electrode materials and OH ‑ The adsorption energy and the reaction energy barrier of ions, and meanwhile, the multi-valence state of Mn ions also increases the OH of the electrode material ‑ Thereby improving the energy storage performance of the 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 a Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material, belonging to the technical field of materials.
Background
With the acceleration of global carbon neutralization processes, the need 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 of energy storage devices due to their high specific surface area and porous structure. However, low volume energy density, poor charge-discharge performance and slow reaction kinetics are major bottlenecks that restrict the energy storage capacity of carbon-based nano materials.
To address these challenges, a great deal of effort is devoted to material design and synthesis. One such example, heteroatom-doped carbon materials, show promise due to their tunable surface function, excellent performance, and strong redox activity. Many studies have been made to date, including N, P and O Co-doped carbon, manganese doped carbon microspheres, Ni doped carbon nanotubes, and Fe/Co/Ni doped carbon nanotubes. However, due to insufficient electroactive sites and low surface reactivity of carbon-based nanomaterials, the performance improvement based on simple recombination is still very limited. Therefore, designing a novel structure to achieve high surface reactivity and shorten the electron/ion diffusion path is of great significance to 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 a Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material, and the invention provides the following scheme:
the invention provides a preparation method of a Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material, which comprises the following steps:
(1) mixing Ni (OAc) 2 And (NH) 4 ) 2 S 2 O 8 Dissolving in deionized water, ultrasonically oscillating and stirring to obtain light blue mixed solution, and then adding NH 3 ·H 2 Dripping O into the mixed solution, uniformly mixing to obtain a blue solution, immersing and standing the Carbon Cloth (CC), taking out the Carbon Cloth (CC) after a NiOOH film grows on the Carbon Cloth (CC) substrate, washing the Carbon Cloth (CC) with deionized water, removing particles which are not deposited on the carbon cloth on the surface of the film, drying and annealing to obtain a NiO nano sheet array (NiO NSs);
(2) adding Mn (NO) 3 ) 2 ·6H 2 Dissolving O in polar solution, and treating Mn (NO) by ultrasonic oscillation 3 ) 2 ·6H 2 Heating after O is completely dissolved, immersing the NiO nano-sheet array prepared in the step (1) after the temperature is stable, standing, 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 flaky array with MnOOH coated on the surface of the NiO nanosheet array, and annealing to obtain a Mn-NiO nanosheet array (MnNi-O NSs);
(3) heating a carbon source and the Mn-NiO nanosheet array prepared in the step (2) in a protective gas atmosphere to obtain Mn and Ni metal monoatomic solution which is monodisperse in C 3 N 4 And grading the surface of the carbon tube to obtain the Mn-Ni double-monoatomic modulation CN grading 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 And NH 3 ·H 2 The feed-liquid ratio of O is 100 mg: (100-600) μ L of said (NH) 4 ) 2 S 2 O 8 With Mn (NO) 3 ) 2 ·6H 2 The mass ratio of O to the melamine compound is 1:1.4: 5.
Further, the annealing temperature is 500 ℃.
Further, the carbon cloth in the step (1) needs to be subjected to a pretreatment process, which specifically comprises the following steps: mixing carbon cloth (CC, 1 × 1 cm) 2 ) Immersing in 3M HCl solution for half an hour of ultrasound to remove oxides on the surface of the carbon cloth, and immersing CC in the mixed solution (HNO) 3 ∶H 2 SO 4 (v/v ═ 3: 1)), water bath for 3h at 80 ℃ to increase the hydrophilicity of the carbon cloth surface, then washing 3 times with deionized water and acetone respectively, removing stains on the carbon cloth surface, and drying in an oven at 45 ℃.
Further, in the step (1), NH 3 ·H 2 The adding process of O is dripping while stirring, and the dripping speed is 10 drops/min.
Further, in the step (1), the temperature of the carbon cloth after being immersed and then kept stand is 35 ℃, and the standing time is 1 h.
Further, in the step (2), the Mn (NO) 3 ) 2 ·6H 2 The dosage ratio of O to the polar solution is 0.0005 mol: 1mL, the heating temperature is 35 ℃, and the annealing temperature is 500 ℃.
Further, in the step (2), the standing time is 15 min.
Further, in the step (2), the polar solution is acetone.
Further, in the step (3), the carbon source is melamine.
Further, in the step (3), the melamine compound is positioned upstream of the tube furnace, and the Mn-NiO nano sheet array is positioned in the middle of the tube furnace, and chemical vapor deposition is carried out, so that the carbon tube can be better grown on the surface of MnNi-O NSs.
Further, in the step (3), the protective atmosphere is argon, and the volume flow rate is 20 sccm.
Further, in the step (3), the heating rate is 5 ℃/min, the temperature is increased to 800-1000 ℃, and the temperature is kept for 4 h.
The invention also provides a capacitor electrode material based on the Mn-Ni double monoatomic layer prepared by the preparation method.
Monatomic (SA) catalysts are attracting increasing attention for their excellent performance, including maximum atom utilization, unsaturated metal species, defined active sites, and tunable electronic properties. They represent great advantages as electrode materials in energy conversion and storage. This is mainly due to SA: (i) has an extraordinary electronic structure, (ii) has discrete energy levels and exposes dense metal centers, and (iii) has a kinetic transition that effectively catalyzes reaction intermediates. The invention discloses the following technical effects:
in order to break the limitation of symmetrical charge distribution around the SA locus, the invention designs and synthesizes Mn-Ni double monoatomic groups with different coordination and monodispersion in C 3 N 4 Novel structures 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 reducing the reaction activation energy.
The method has simple process steps and easily obtained products. Compared with the current research, the method has low cost and low energy consumption, and the Mn-NiO nano sheet array is obtained by performing secondary modification on the NiO nano sheet array by utilizing different stability of different metal ions in a polar solution. Using melamine as a carbon source, and obtaining C with uniformly distributed Ni and Mn through chemical vapor deposition (high-temperature pyrolysis principle) 3 N 4 The graded carbon tube uses Ni and Mn double monoatomic atoms as active sites to research the energy storage performance of the electrode material, and the electrode material shows 1523.6F g after performance analysis -1 High capacitance of (2). The energy density of the optimized asymmetric double electrode is as high as 180.8 Wh-kg -1 The power density is 1152 W.kg -1 Is the best value in the supercapacitor reported previously. Mechanism research shows that the performance is improved based on the synergy of monodisperse Mn-Ni double monoatomic atoms to improve the electrode material and OH - The adsorption energy and reaction energy barrier of the ions. The technique of the present invention provides a new strategy for achieving high energy storage in a supercapacitor.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a flow chart of the preparation process of MnNi-ICNs of the invention;
FIG. 2 is a diagram showing the structure evolution of NiO NSs, MnNi-O NSs and MnNi-ICNs during the preparation process of the present invention;
FIG. 3 is an SEM image of NiO NSs prepared in example 1 of the present invention, wherein a-b are SEM spectra at 2000X, 4000X, 10000X and 20000X magnifications of NiO NSs, respectively;
FIG. 4 is an XRD pattern of NiO NSs prepared in example 1 of the present invention;
FIG. 5 is an SEM photograph of MnNi-O NSs prepared in example 1 of the present invention, wherein a-b are SEM spectra at 1000, 7000, 100000 and 200000 Xmagnification of MnNi-O NSs, respectively;
FIG. 6 is an XRD pattern of MnNi-O NSs prepared in example 1 of the present invention;
FIG. 7 is an SEM photograph of MnNi-ICNs prepared in example 1 of the present invention, wherein a-b are SEM spectra at 1000, 7000, 100000 and 200000 Xmagnification of MnNi-ICNs, respectively;
FIG. 8 is an XRD pattern of MnNi-ICNs prepared in example 1 of the present invention;
FIG. 9 is a schematic view of a spherical aberration electron microscope of MnNi-ICNs prepared in example 1 of the present invention; wherein a is a high-angle annular dark field map and each element distribution map of the MnNi-ICNs from left to right respectively, b is a distribution map of Mn and Ni single atoms on the surfaces of the MnNi-ICNs from left to right respectively, and c is an energy spectrum map of EELS of the MnNi-ICNs from left to right respectively;
fig. 10 is a graph of the energy storage performance of each electrode material.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description 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. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, 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 herein 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 present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
The invention provides a preparation method of a Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material, which comprises the following steps:
(1) mixing Ni (OAc) 2 And (NH) 4 ) 2 S 2 O 8 Dissolving in deionized water, ultrasonically oscillating and stirring to obtain light blue mixed solution, and then adding NH 3 ·H 2 Dripping O into the mixed solution, uniformly mixing to obtain a blue solution, immersing and standing the Carbon Cloth (CC), taking out the Carbon Cloth (CC) after a NiOOH film grows on the Carbon Cloth (CC) substrate, washing the Carbon Cloth (CC) with deionized water, removing particles which are not deposited on the carbon cloth on the surface of the film, drying and annealing to obtain a NiO nano sheet array (NiO NSs);
(2) adding Mn (NO) 3 ) 2 ·6H 2 Dissolving O in polar solution, and treating Mn (NO) by ultrasonic oscillation 3 ) 2 ·6H 2 Heating after O is completely dissolved, immersing the NiO nano-sheet array prepared in the step (1) after the temperature is stable, standing, 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 flaky array with MnOOH coated on the surface of the NiO nanosheet array, and annealing to obtain a Mn-NiO nanosheet array (MnNi-O NSs);
(3) heating a carbon source and the Mn-NiO nanosheet array prepared in the step (2) in a protective gas atmosphere to obtain Mn and Ni metal monoatomic solution which is monodisperse in C 3 N 4 And grading the surface of the carbon tube to obtain the Mn-Ni double-monoatomic modulation CN grading 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 And NH 3 ·H 2 The feed-liquid ratio of O is 100 mg: (100-600) μ L of said (NH) 4 ) 2 S 2 O 8 With Mn (NO) 3 ) 2 ·6H 2 The mass ratio of O to the melamine compound is 1:1.4: 5.
Further, the annealing temperature is 500 ℃.
Further, the carbon cloth in the step (1) needs to be subjected to a pretreatment process, which specifically comprises the following steps: mixing carbon cloth (CC, 1 × 1 cm) 2 ) Immersing in 3M HCl solution for half an hour of ultrasound to remove oxides on the surface of the carbon cloth, and immersing CC in the mixed solution (HNO) 3 ∶H 2 SO 4 (v/v 3: 1)), water-bath at 80 deg.C for 3h to increase hydrophilicity of the carbon cloth surface, and then deionized waterAnd washing with acetone for 3 times respectively, removing stains on the surface of the carbon cloth, and drying in an oven at 45 ℃.
Further, in the step (1), NH 3 ·H 2 The adding process of O is dripping while stirring, and the dripping speed is 10 drops/min.
Further, in the step (1), the temperature of the carbon cloth after being immersed is 35 ℃, and the standing time is 1 h.
Further, in the step (2), the Mn (NO) 3 ) 2 ·6H 2 The dosage ratio of O to the polar solution is 0.5 mol: 5mL, the heating temperature is 35 ℃, and the annealing temperature is 500 ℃.
Further, in the step (2), the standing time is 15 min.
Further, in the step (2), the polar solution is acetone.
Further, in the step (3), the carbon source is melamine.
Further, in the step (3), the melamine compound is positioned upstream of the tube furnace, and the Mn-NiO nano sheet array is positioned in the middle of the tube furnace, and chemical vapor deposition is carried out, so that the carbon tube can be better grown on the surface of MnNi-O NSs.
Further, in the step (3), the protective atmosphere is argon, and the volume flow rate is 20 sccm.
Further, in the step (3), the heating rate is 5 ℃/min, the temperature is increased to 800-1000 ℃, and the temperature is kept for 4 h.
The invention also provides the Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material prepared by the preparation method.
The flow chart of the preparation process of the MnNi-ICNs is shown in figure 1, and the structure evolution charts of NiO NSs, MnNi-ONSs and MnNi-ICNs are shown in figure 2.
The raw materials used in the examples of the present invention were all commercially available.
The technical solution of the present invention is further illustrated by the following examples.
Example 1
(1) 0.64g of Ni (OAc) was weighed 2 And 100mg (NH) 4 ) 2 S 2 O 8 Dissolving in 10mL of deionized water (18 omega), ultrasonically shaking for 5min and stirring for 10min to obtain a light blue mixed solution, and adding 400 mu L of NH 3 ·H 2 Slowly dripping O into the mixed solution at the speed of 10 drops/min while stirring, uniformly mixing to obtain a blue solution, immersing the Carbon Cloth (CC) into the blue solution, standing the Carbon Cloth (CC) for 1h at the temperature of 35 ℃, taking out the Carbon Cloth (CC), washing the Carbon Cloth (CC) with deionized water, drying the Carbon Cloth (CC) at the temperature of 35 ℃, and annealing the Carbon Cloth (CC) for 2h at the temperature of 500 ℃ to obtain a NiO nanosheet array (NiO NSs);
an SEM image of NiO NSs prepared in the embodiment 1 of the invention is shown in figure 3, wherein a-b are SEM images of the NiO NSs under 2000 x, 4000 x, 10000 x and 20000 x magnification respectively, and NiO can be seen to be in a nano sheet array shape in figure 3.
FIG. 4 is a XRD pattern of NiO NSs prepared in example 1 of the present invention shown in FIG. 4, and it can be seen from FIG. 4 that NiO mainly exposes the (111), (200) and (220) crystallographic planes.
(2) 0.14g of Mn (NO) 3 ) 2 ·6H 2 Dissolving O in 5mL polar solution (acetone), and ultrasonically shaking for 10min until Mn (NO) is obtained 3 ) 2 ·6H 2 After O is completely dissolved, putting the mixture into an oven at 35 ℃ for heating for 10min, immersing the NiO nanosheet array prepared in the step (1) and standing for 15min after the temperature of the mixed solution and the temperature of the oven are stabilized, taking out the NiO nanosheet array, cleaning the NiO nanosheet array by using polar solution (acetone), and annealing for 2h at 500 ℃ to obtain a Mn-NiO nanosheet array (MnNi-O NSs);
the SEM image of MnNi-O NSs prepared in the embodiment 1 of the invention is shown in figure 5, wherein a-b are SEM images of the MnNi-O NSs under the magnifications of 1000X, 7000X, 100000X and 200000X respectively, and figure 5 shows that some nano particles are coated outside the surface of the NiO nano sheet array.
The XRD pattern of 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 no diffraction peak of manganese oxide is found in NiMn-O NSs due to the low mass loading rate of Mn.
(3) Placing 0.5g of melamine in a 20mL magnetic boat, placing the melamine in the upstream of a tube furnace, placing the Mn-NiO nanosheet array prepared in the step (2) on the magnetic boat, and placing the Mn-NiO nanosheet array in a tubeIn the midstream of the furnace, the temperature is raised to 800 ℃ at the speed of 5 ℃/min under the Ar atmosphere of 20sccm, and the temperature is kept constant for 4 hours, thus obtaining the Mn and Ni metal monoatomic dispersion in C 3 N 4 Grading the surface of the carbon tube, namely obtaining the Mn-Ni double monoatomic modulation CN grading carbon tube electrode material (MnNi-ICNs-4 h);
the SEM picture of MnNi-ICNs-4h prepared in example 1 of the invention is shown in figure 7, wherein a-b are SEM pictures of the MnNi-ICNs-4h under the magnification of 1000X, 7000X, 100000X and 200000X respectively, and as can be seen from figure 7, the MnNi-ICNs-4h presents the appearance of the tube, and a small white spot exists at 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 figure 8, and the XRD pattern of MnNi-ICN-4h s mainly shows Ni and C in figure 8 3 N 4 And (002) crystal plane of CC, and C 3 N 4 Partially overlaps with the (002) crystal plane of CC, and the peak position of the CC substrate in MnNi-ICNs-4h is shifted compared with NiO NSs. In addition, a face centered cubic (fcc) Ni crystal phase was also found in the XRD pattern of MnNi-INCs-4h, and the results showed Ni metal particles and C 3 N 4 Coexisting in MnNi-INCs materials.
The spherical aberration electron microscope picture of MnNi-ICNs-4h prepared in the embodiment 1 of the invention is shown in figure 9, wherein a is a high-angle annular dark field picture and each element distribution picture of MnNi-ICNs-4h from left to right, b is a distribution picture of Mn and Ni single atoms on the surface of the MnNi-ICNs-4h from left to right, c is an energy spectrum picture of EELS of the MnNi-ICNs-4h from left to right, and C, N, O, Ni and Mn are uniformly distributed on the carbon nano tube as can be seen from figure 9. HAADF-STEM imaging showed that monodisperse Mn and Ni monoatomic atoms were determined to be randomly dispersed in C 3 N 4 Grading the surface of the carbon tube. Meanwhile, the Electron Energy Loss Spectroscopy (EELS) diagram also confirms the coexistence of Mn and Ni double single atoms in MnNi-INCs.
Example 2
(1) 0.32g of Ni (OAc) was weighed 2 And 100mg (NH) 4 ) 2 S 2 O 8 Dissolving in 10mL of deionized water (18 Ω), ultrasonically shaking for 5min and stirring for 10min to obtain light blue mixed solution, and thenAdding 100 mu L of NH 3 ·H 2 Slowly dripping O into the mixed solution at the speed of 10 drops/min while stirring, uniformly mixing to obtain a blue solution, immersing the Carbon Cloth (CC) into the blue solution, standing the Carbon Cloth (CC) for 1h at the temperature of 35 ℃, taking out the Carbon Cloth (CC) to be washed by deionized water after a NiOOH film grows on the Carbon Cloth (CC) substrate, drying the Carbon Cloth (CC) at the temperature of 35 ℃, and then annealing the Carbon Cloth (CC) for 2h at the temperature of 500 ℃ to obtain a NiO nano sheet array (NiO NSs);
(2) 0.14g of Mn (NO) 3 ) 2 ·6H 2 Dissolving O in 5mL polar solution (acetone), and ultrasonically shaking for 10min until Mn (NO) is obtained 3 ) 2 ·6H 2 After O is completely dissolved, putting the mixture into an oven at 35 ℃ for heating for 10min, immersing the NiO nanosheet array prepared in the step (1) and standing for 15min after the temperature of the mixed solution and the temperature of the oven are stabilized, taking out the NiO nanosheet array, cleaning the NiO nanosheet array by using polar solution (acetone), and annealing for 2h at 500 ℃ to obtain a Mn-NiO nanosheet array (MnNi-O NSs);
(3) placing 0.5g of melamine in a 20mL magnetic boat, placing the melamine at the upstream of a tubular furnace, placing the Mn-NiO nanosheet array prepared in the step (2) on the magnetic boat, placing the magnetic boat at the midstream of the tubular furnace, heating to 800 ℃ at the speed of 5 ℃/min under the Ar atmosphere of 20sccm, and keeping the temperature for 1h at the constant temperature to obtain the Mn and Ni metal monoatomic dispersion in C 3 N 4 The surface of the graded carbon tube is the Mn-Ni double monoatomic modulation CN graded carbon tube electrode material (MnNi-ICNs).
Example 3
(1) 0.2g of Ni (OAc) is weighed 2 And 100mg (NH) 4 ) 2 S 2 O 8 Dissolving in 10mL of deionized water (18 omega), ultrasonically shaking for 5min and stirring for 10min to obtain a light blue mixed solution, and adding 200. mu.L of NH 3 ·H 2 Slowly dripping O into the mixed solution at the speed of 10 drops/min while stirring, uniformly mixing to obtain a blue solution, immersing the Carbon Cloth (CC) into the blue solution, standing the Carbon Cloth (CC) for 1h at the temperature of 35 ℃, taking out the Carbon Cloth (CC) to be washed by deionized water after a NiOOH film grows on the Carbon Cloth (CC) substrate, drying the Carbon Cloth (CC) at the temperature of 35 ℃, and then annealing the Carbon Cloth (CC) for 2h at the temperature of 500 ℃ to obtain a NiO nano sheet array (NiO NSs);
(2) 0.14g of Mn (NO) 3 ) 2 ·6H 2 Dissolving O in 5mL polar solution (acetone), and ultrasonically shaking for 10min until Mn (NO) is obtained 3 ) 2 ·6H 2 After O is completely dissolved, putting the mixture into an oven at 35 ℃ for heating for 10min, immersing the NiO nanosheet array prepared in the step (1) and standing for 15min after the temperature of the mixed solution and the temperature of the oven are stabilized, taking out the NiO nanosheet array, cleaning the NiO nanosheet array by using polar solution (acetone), and annealing for 2h at 500 ℃ to obtain a Mn-NiO nanosheet array (MnNi-O NSs);
(3) placing 0.5g of melamine in a 20mL magnetic boat, placing the melamine at the upstream of a tubular furnace, placing the Mn-NiO nanosheet array prepared in the step (2) on the magnetic boat, placing the magnetic boat at the midstream of the tubular furnace, heating to 800 ℃ at the speed of 5 ℃/min under the Ar atmosphere of 20sccm, and keeping the temperature for 2 hours at the constant temperature to obtain the Mn and Ni metal monoatomic dispersion in C 3 N 4 The surface of the graded carbon tube is the Mn-Ni double monoatomic modulation CN graded carbon tube electrode material (MnNi-ICNs).
Example 4
(1) 0.74g of Ni (OAc) was weighed 2 And 100mg (NH) 4 ) 2 S 2 O 8 Dissolving in 10mL of deionized water (18 omega), ultrasonically shaking for 5min and stirring for 10min to obtain a light blue mixed solution, and adding 500. mu.L of NH 3 ·H 2 Slowly dripping O into the mixed solution at the speed of 10 drops/min while stirring, uniformly mixing to obtain a blue solution, immersing the Carbon Cloth (CC) into the blue solution, standing the Carbon Cloth (CC) for 1h at the temperature of 35 ℃, taking out the Carbon Cloth (CC) to be washed by deionized water after a NiOOH film grows on the Carbon Cloth (CC) substrate, drying the Carbon Cloth (CC) at the temperature of 35 ℃, and then annealing the Carbon Cloth (CC) for 2h at the temperature of 400 ℃ to obtain a NiO nanosheet array (NiO NSs);
(2) 0.14g of Mn (NO) 3 ) 2 ·6H 2 Dissolving O in 5mL polar solution (acetone), and ultrasonically shaking for 10min until Mn (NO) is obtained 3 ) 2 ·6H 2 After O is completely dissolved, putting the mixture into an oven at 35 ℃ for heating for 10min, immersing the NiO nanosheet array prepared in the step (1) and standing for 15min after the temperature of the mixed solution and the temperature of the oven are stabilized, taking out the NiO nanosheet array, cleaning the NiO nanosheet array by using polar solution (acetone), and annealing for 2h at 500 ℃ to obtain a Mn-NiO nanosheet array (MnNi-O NSs);
(3) placing 0.5g of melamine in a 20mL magnetic boat, placing the melamine at the upstream of a tubular furnace, placing the Mn-NiO nanosheet array prepared in the step (2) on the magnetic boat, placing the magnetic boat at the midstream of the tubular furnace, heating to 800 ℃ at the speed of 5 ℃/min under the Ar atmosphere of 20sccm, and keeping the temperature for 3 hours at the constant temperature to obtain the Mn and Ni metal monoatomic dispersion in C 3 N 4 The surface of the graded carbon tube is the Mn-Ni double monoatomic modulation CN graded carbon tube electrode material (MnNi-ICNs).
Example 5
(1) 1.28g of Ni (OAc) are weighed 2 And 100mg (NH) 4 ) 2 S 2 O 8 Dissolving in 10mL of deionized water (18 omega), ultrasonically shaking for 5min and stirring for 10min to obtain a light blue mixed solution, and adding 600 mu L of NH 3 ·H 2 Slowly dripping O into the mixed solution at the speed of 10 drops/min while stirring, uniformly mixing to obtain a blue solution, immersing the Carbon Cloth (CC) into the blue solution, standing the Carbon Cloth (CC) for 1h at the temperature of 35 ℃, taking out the Carbon Cloth (CC) to be washed by deionized water after a NiOOH film grows on the Carbon Cloth (CC) substrate, drying the Carbon Cloth (CC) at the temperature of 35 ℃, and then annealing the Carbon Cloth (CC) for 2h at the temperature of 500 ℃ to obtain a NiO nanosheet array (NiO NSs);
(2) 0.14g of Mn (NO) 3 ) 2 ·6H 2 Dissolving O in 5mL polar solution (acetone), and ultrasonically vibrating for 10min until Mn (NO) is obtained 3 ) 2 ·6H 2 After O is completely dissolved, putting the mixture into an oven at 35 ℃ for heating for 10min, immersing the NiO nanosheet array prepared in the step (1) and standing for 15min after the temperature of the mixed solution and the temperature of the oven are stabilized, taking out the NiO nanosheet array, cleaning the NiO nanosheet array by using polar solution (acetone), and annealing for 2h at 500 ℃ to obtain a Mn-NiO nanosheet array (MnNi-O NSs);
(3) placing 0.5g of melamine in a 20mL magnetic boat, placing the melamine at the upstream of a tubular furnace, placing the Mn-NiO nanosheet array prepared in the step (2) on the magnetic boat, placing the magnetic boat at the midstream of the tubular furnace, heating to 1000 ℃ at the speed of 5 ℃/min under the Ar atmosphere of 20sccm, and keeping the temperature for 5 hours at the constant temperature to obtain the Mn and Ni metal monoatomic dispersion in C 3 N 4 The surface of the graded carbon tube is the Mn-Ni double monoatomic modulation CN graded carbon tube electrode material (MnNi-ICNs).
Comparative example 1
(1) 0.64g of Ni (OAc) was weighed 2 And 100mg (NH) 4 ) 2 S 2 O 8 Dissolving in 10mL of deionized water (18 omega), ultrasonically shaking for 5min and stirring for 10min to obtain a light blue mixed solution, and adding 400 mu L of NH 3 ·H 2 Slowly dripping O into the mixed solution at the speed of 10 drops/min while stirring, uniformly mixing to obtain a blue solution, immersing the Carbon Cloth (CC) into the blue solution, standing the Carbon Cloth (CC) for 1h at the temperature of 35 ℃, taking out the Carbon Cloth (CC), washing the Carbon Cloth (CC) with deionized water, drying the Carbon Cloth (CC) at the temperature of 35 ℃, and annealing the Carbon Cloth (CC) for 2h at the temperature of 500 ℃ to obtain a NiO nanosheet array (NiO NSs);
(2) placing 0.5g of melamine in a 20mL magnetic boat, placing the melamine at the upstream of a tubular furnace, placing the NiO nanosheet array prepared in the step (1) on the magnetic boat, placing the NiO nanosheet array at the midstream of the tubular furnace, heating to 800 ℃ at the speed of 5 ℃/min under the Ar atmosphere of 20sccm, and keeping the temperature for 4 hours at the constant temperature to obtain the Ni metal monoatomic solution which is monodisperse in C 3 N 4 Grading the surface of the carbon tubes (Ni-ICNs).
Comparative example 2
The difference from example 1 is that in step (3), the temperature is raised to 800 ℃ at a rate of 5 ℃/min under an Ar atmosphere of 20sccm, and the temperature is kept constant for 1h, so as to prepare the Mn-Ni double-monoatomic-modulation CN graded carbon tube electrode material (MnNi-ICNs-1 h).
Comparative example 3
The difference is that in step (3), the temperature is raised to 800 ℃ at 5 ℃/min under the Ar atmosphere of 20sccm, and the temperature is kept constant for 2h, so as to prepare the Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material (MnNi-ICNs-2 h).
Comparative example 4
The difference from example 1 is that in step (3), the temperature is raised to 800 ℃ at a rate of 5 ℃/min under an Ar atmosphere of 20sccm, and the temperature is kept constant for 3h, so as to prepare the Mn-Ni diatomic monoatomic modulation CN graded carbon tube electrode material (MnNi-ICNs-3 h).
Comparative example 5
The difference is that in the step (3), the temperature is raised to 800 ℃ at 5 ℃/min under the Ar atmosphere of 20sccm, and the temperature is kept constant for 5h, so as to prepare the Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material (MnNi-ICNs-5 h).
Performance testing
Evaluating the electrochemical energy storage performance of the NiO NSs, the MnNi-O NSs and the MnNi-ICNs-4h prepared in the example 1, the MnNi-ICNs-1h, the MnNi-ICNs-2h, the MnNi-ICNs-3h and the MnNi-ICNs-5h prepared in the comparative examples 2 to 5 and the Ni-ICNs prepared in the comparative example 1, wherein all electrochemical measurements are carried out on a Chenghua electrochemical workstation, the material electrodes are directly tested on a non-glue CC substrate, at the normal temperature (about 25 ℃), 3mol KOH solution is adopted as electrolyte, the material electrodes are respectively used as working electrodes, and a platinum grid and a calomel electrode are respectively used as a counter electrode and a reference electrode. The measurement frequency of the impedance spectrum is 1-10 5 HZ. The working electrode should be soaked in the electrolyte for 10 minutes before measurement to ensure sufficient wettability and stability of the working electrode.
The specific capacitance of the electrode material is calculated according to formula (I):
in formula (I), I ═ Vdt is the area enclosed by the discharge curve in the GCD curve, m is the effective mass of the electrode, and Δ V is the operating potential window of the curve.
The energy storage performance of each electrode material is 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 according to comparative examples 2-5, the specific capacitance of MnNi-INCs-4h is increased by about 1.38 times, and the high-energy storage performance is achieved.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. A preparation method of a Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material is characterized by comprising the following steps:
(1) mixing Ni (OAc) 2 And (NH) 4 ) 2 S 2 O 8 Dissolving in deionized water, ultrasonic oscillating and stirring to obtain mixed solution, and then adding NH 3 ·H 2 Dripping O into the mixed solution, uniformly mixing, immersing and standing the carbon cloth, taking out the carbon cloth, washing with deionized water, drying and annealing to obtain a NiO nano sheet array;
(2) adding Mn (NO) 3 ) 2 ·6H 2 Dissolving O in a polar solution, heating after ultrasonic oscillation, immersing and standing the NiO nano sheet array prepared in the step (1), taking out the NiO nano sheet array, cleaning with the polar solution, and annealing to obtain an Mn-NiO nano sheet array;
(3) and (3) heating a carbon source and the Mn-NiO nanosheet array prepared in the step (2) in a protective gas atmosphere to obtain the Mn-Ni double-monoatomic modulation CN graded carbon tube electrode material.
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 And NH 3 ·H 2 The feed-liquid ratio of O is 100 mg: (100-600) μ L of said (NH) 4 ) 2 S 2 O 8 With Mn (NO) 3 ) 2 ·6H 2 The mass ratio of O to the melamine compound is 1:1.4: 5.
3. the method according to claim 1, wherein the annealing temperature is 500 ℃.
4. The production method according to claim 1, wherein in the step (1), the temperature at which the carbon cloth is left standing after being immersed is 35 ℃.
5. The method of claim 1, wherein the step of(2) In (1), the Mn (NO) 3 ) 2 ·6H 2 The dosage ratio of O to the polar solution is 0.0005 mol: 1mL, the heating temperature is 35 ℃, and the annealing temperature is 500 ℃.
6. The method according to claim 1, wherein in the step (2), the polar solution is acetone.
7. The method according to claim 1, wherein in the step (3), the carbon source is melamine.
8. The preparation method according to claim 1, wherein in the step (3), the heating rate is 5 ℃/min, the temperature is increased to 800 ℃, and the temperature is maintained for 4 h.
9. An Mn-Ni double-monoatomic modulated CN graded carbon tube electrode material prepared by the preparation method of any one of claims 1 to 8.
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