CN106430146B - Preparation method of nitrogen-manganese co-doped hierarchical pore carbon material - Google Patents

Preparation method of nitrogen-manganese co-doped hierarchical pore carbon material Download PDF

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CN106430146B
CN106430146B CN201611032059.4A CN201611032059A CN106430146B CN 106430146 B CN106430146 B CN 106430146B CN 201611032059 A CN201611032059 A CN 201611032059A CN 106430146 B CN106430146 B CN 106430146B
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CN106430146A (en
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刘玉荣
胡荣
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Chongqing University of Arts and Sciences
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Abstract

The invention discloses a preparation method of a nitrogen-manganese co-doped hierarchical pore carbon material, which comprises the following steps: (1) preparation of oligomeric phenolic resin: dissolving phenol and formaldehyde in an alkali solution, and heating and stirring to obtain the aqueous solution; (2) preparing a nitrogen-manganese co-doped hierarchical porous carbon block material: adding template agents P123 and F127 and a nitrogen-containing compound into the low-polymer phenolic resin prepared in the step (1), stirring for 2-4 h at 65-75 ℃, cooling to room temperature, adding manganese salt, continuing stirring for 0.5-3 h at 65-75 ℃, transferring the obtained solution into a hydrothermal kettle for hydrothermal reaction, filtering out the block material, cleaning, drying, roasting for 1.5-5 h at 550-800 ℃ under the protection of inert gas, and cooling to room temperature to obtain the nitrogen and manganous oxide co-doped hierarchical pore carbon block material. The prepared carbon material has high specific capacity, good rate capacity, low electrolyte transmission resistance and excellent cycling stability.

Description

Preparation method of nitrogen-manganese co-doped hierarchical pore carbon material
Technical Field
The invention relates to a preparation technology of a novel carbon material, and particularly relates to a preparation method of a nitrogen-manganese co-doped hierarchical pore carbon material.
Background
The super capacitor is a novel green energy storage device, has the advantages of high charging and discharging speed, high efficiency, long cycle life, wide use temperature range, high safety, no pollution to the environment and the like, and has very wide application prospect in the aspects of fuel cell vehicles, hybrid electric vehicles, buses, low-temperature starting of vehicles, solar system power storage devices, high-power rapid charging power supplies and the like. The electrode material is a key factor in determining the performance of the supercapacitor. The porous carbon material has the advantages of low price, good electrochemical stability, large specific surface area and pore capacity and the like, and is a preferred electrode material of the super capacitor. However, porous carbon materials of a single pore size suffer from several disadvantages. For example, the micro-porous carbon material has poor electrolyte wettability on the inner surface due to the limitation condition of small pore diameter, the available specific surface area is small, the transport resistance of electrolyte ions in the micro-pores is large, and the specific capacitance of the micro-pores is seriously attenuated under the condition of high power density. With a mesoporous carbon material, the specific surface area is not large enough, since small mesopores are embedded in large particles, ion diffusion must take a long distance, and the internal pore structure is hardly fully utilized. Macroporous carbon has an extremely small specific surface area, resulting in poor capacitive performance. In summary, the microporous carbon, mesoporous carbon, and macroporous carbon have certain limitations when used as an electrode material of a supercapacitor.
The hierarchical porous carbon is a material with two or more pore systems of macropore (d is more than 50nm), mesopore (2nm < d <50nm) and micropore (d <2 nm). The unique pore structure of the hierarchical porous carbon is very suitable for being used as an electrode material of a super capacitor, wherein the macroporous structure plays a role of an ion buffer pool and is beneficial to high-power discharge; the mesoporous structure ensures the rapid infiltration and transmission of the electrolyte, thereby improving the specific power; the micropores can provide larger specific surface area and pore volume, thereby leading the material to obtain larger specific capacity. Therefore, compared with the traditional single-pore system carbon material, the application advantage of the hierarchical-pore carbon material in the super capacitor is very obvious.
Nitrogen doping is another effective way to improve the electrochemical performance of carbon electrode materials. The carbon electrode material has the advantages that the conductivity and the capacity of storing charges in unit area of the carbon electrode material can be improved by doping nitrogen elements while the ordered structure of the porous carbon material is kept, and the equivalent series resistance of the electrode is reduced, so that the surface utilization rate of the material is effectively improved, and the specific capacity and the power characteristic of the electrode material are improved to a new height. In addition, nitrogen-containing functional groups can also create pseudocapacitive effects. The nitrogen-doped carbon material is mainly prepared by two methods of post-treatment and in-situ synthesis. The post-treatment adopts nitrogen-containing gas such as ammonia gas and the like to modify the surface of the pre-synthesized carbon material under the high-temperature condition, or nitrogen-containing organic groups are grafted on the surface of the material. The post-treatment method generally has more complex steps and less nitrogen doping amount, and simultaneously, nitrogen only modifies the surface of the material, and the bulk property of the carbon material is not changed. In situ synthesis methods generally involve introducing a nitrogen source during the synthesis of the carbon material or using a carbon source that itself contains nitrogen, which nitrogen atoms are incorporated into the carbon material during carbonization of the carbon precursor. The in-situ doping method can realize uniform doping, nitrogen atoms can enter the inside of the crystal lattice, the nitrogen content can be increased, the structure and the property of the carbon material body are changed, and the doping amount is controllable. Most importantly, the in-situ doping method has simple steps and omits the post-treatment step.
The introduction of the metal oxide into the carbon material system can lead the composite electrode material to generate highly reversible redox reaction in the charge-discharge process, generate great pseudocapacitance and be an effective way for further improving the electrochemical performance of the carbon material. For MnO2、NiO、Co3O4The metal oxides have been studied more and MnO and carbon matrix have been studied moreThe research on the preparation of the electrode material of the super capacitor by line compounding is very rare. Research (Q.Y.Liao, N.Li, H.Cui, C.X.Wang.Vertically-aligned graphene @ MnO nanosheets as binder-free high-performance electrochemical devices. J.Mater.chem.A,2013,1:13715-2Theoretical specific capacity (1110F/g).
In addition, the morphology of the porous carbon material has important influence on the structure, the characteristics and the electrochemical performance of the porous carbon material. The macro morphology of the synthesized hierarchical porous carbon material generally takes particles and powder as main materials, and the particles or powder has the defects of easy falling, difficult recovery, dust pollution and the like, so that the application of the particles or powder in the super capacitor is limited. In contrast, the carbon block material has an integral structure and a controllable pore structure, and is more suitable for application in the field of supercapacitors.
Although nitrogen-doped porous carbon materials or multi-level porous carbon materials have wide application prospects in the field of supercapacitors, the following problems still exist in the research on the aspect: (1) the preparation of nitrogen-doped carbon materials at present usually adopts expensive raw material reagents and toxic nitrogen sources, such as pyrrole and NH3Or HCN and the like, and the problems of high production cost, poor safety, environmental pollution and the like generally exist; (2) the steps for preparing the nitrogen-doped porous carbon material are complicated, the time is long, and the industrial production is not facilitated; (3) at present, most of researches on nitrogen-doped carbon materials focus on researches on nitrogen-doped activated carbon or nitrogen-doped mesoporous carbon materials, and the researches on nitrogen-doped hierarchical porous carbon materials are rare; (4) although nitrogen-doped carbon materials and multi-level pore carbon electrode materials are researched, researches for designing high-performance supercapacitor electrode materials by combining nitrogen-doped modification and pore structure optimization are rarely reported; (5) the researched nitrogen-doped carbon material for the super capacitor is mostly in a particle or powder shape, and the research on the use of a block material as an electrode material of the super capacitor is very little; (6) the nitrogen content of nitrogen-doped carbon materials used as electrode materials of the super capacitor is generally low, and in order to fully exert the advantages of nitrogen doping, the nitrogen content needs to be further increased; (7) will be provided withThe research of designing the high-performance super capacitor by combining nitrogen doping, metal oxide doping, pore structure, morphology design and the like is rarely reported.
Disclosure of Invention
The invention aims to provide a method for preparing a nitrogen-manganese co-doped hierarchical pore carbon material with high specific capacity, good rate capacity, low electrolyte transmission resistance and excellent cycle stability, aiming at the problems of complicated preparation steps and time consumption, expensive template agent, high toxicity of raw material reagents, low nitrogen content and the like of the conventional nitrogen-doped carbon material.
The technical scheme for realizing the purpose of the invention is as follows: a preparation method of a nitrogen-manganese co-doped hierarchical pore carbon material comprises the following steps:
(1) preparation of oligomeric phenolic resin: dissolving phenol and formaldehyde in an alkali solution, and heating and stirring to obtain the aqueous solution;
(2) preparing a nitrogen-manganese co-doped hierarchical porous carbon block material: adding template agents P123 and F127 and a nitrogen-containing compound into the low-polymer phenolic resin prepared in the step (1), stirring for 2-4 h at 65-75 ℃, cooling to room temperature, adding manganese salt, continuing stirring for 0.5-3 h at 65-75 ℃, transferring the obtained solution into a hydrothermal kettle for hydrothermal reaction, filtering out the block material, cleaning, drying, roasting for 1.5-5 h at 550-800 ℃ under the protection of inert gas, and cooling to room temperature to obtain the nitrogen and manganous oxide co-doped hierarchical pore carbon block material.
In the above technical solution, the nitrogen-containing compound is melamine, dicyanodiamine or urea.
In the technical scheme, the manganese salt is manganese chloride, manganese nitrate or manganese acetate.
The mass ratio of the phenol to the P123 to the F127 to the nitrogen-containing compound to the manganese salt is 1: 0.6-0.9: 1.1-1.5: 0.05-0.5: 0.05-0.4, and the dosage of the formaldehyde solution is 2.5-4.5 ml of a formaldehyde solution with the concentration of 37-40% used for every 1g of phenol.
The alkali solution is sodium hydroxide solution.
The dosage of the alkali solution is 4-6 ml of sodium hydroxide solution with the concentration of 0.5M used for every 1g of phenol.
In the technical scheme, the heating temperature in the step (1) is 65-75 ℃, and the stirring time is 0.4-0.7 h.
And (3) the inert gas in the step (2) is nitrogen or argon.
In the technical scheme, the hydrothermal reaction temperature in the step (2) is 100-130 ℃, and the reaction time is 10-18 h.
And (3) cleaning the block material in the step (2), and drying the block material at 50-80 ℃ for 6-24 hours in vacuum.
The invention has the beneficial effects that:
1. common nitrogen-containing compounds such as melamine, dicyanodiamine, urea and the like are used as nitrogen sources, and nitrogen elements are introduced into the carbon material matrix through an in-situ doping method, the in-situ doping method is simple in steps, the post-treatment step is omitted, the nitrogen elements can be uniformly doped in the carbon matrix, and nitrogen atoms can enter the inside of crystal lattices, so that the structure and the properties of the carbon material matrix are changed.
2. The selected raw materials are cheap and easily available chemical raw materials, expensive and toxic raw material reagents are not adopted, and the method has the advantages of low process cost, no environmental pollution and the like.
3. The preparation method is a synthesis method which takes water as a solvent in a special sealed reaction container, and compared with other preparation methods, the hydrothermal method has the advantages of simple operation, mild conditions, easy control of reaction process, controllable material structure and performance, wide raw material selection range, high carbon yield and the like. Moreover, the hydrothermal method adopted by the invention is simple and feasible, the process is controllable, complex experimental equipment and complicated experimental steps are not needed, and the industrial large-scale production is easy to carry out.
4. The prepared nitrogen and manganous oxide codoped hierarchical porous carbon block material is in a regular cylinder shape, has excellent structural stability, high nitrogen content and manganese content and large specific surface area, and can be used as an electrode material of a high-performance super capacitor.
5. The prepared nitrogen and manganous oxide codoped hierarchical pore carbon block material has a hierarchical pore structure of micropore-mesopore-macropore, wherein the micropore can increase the specific surface area of the material, improve the utilization rate of the specific surface and increase the double electric layer capacitance of the material; the mesopores can provide a low-resistance channel for electrolyte ions to enter the electrode material; the large pores can store a large amount of electrolyte ions, and provide a short diffusion distance for the electrolyte to enter the inner surface of the material.
6. The prepared electrode material has high nitrogen content, and the introduction of nitrogen atoms not only increases hydrophilic polar active points in the material, improves the wettability of electrolyte to the material, but also can improve the charge storage capacity of the material. In addition, the nitrogen-containing functional group can also generate a Faraday pseudo-capacitance effect, so that the super-capacitance performance of the carbon electrode material is improved.
7. The prepared electrode material adopts a modified porous carbon material doped with nitrogen and manganous oxide together, wherein MnO has a theoretical specific capacity up to 1350F/g, and the advantages of heteroatom and metal oxide doping can be simultaneously utilized, so that the comprehensive performance of the porous carbon material is effectively improved.
8. When the prepared nitrogen and manganous oxide co-doped hierarchical porous carbon block material is used as an electrode material of a super capacitor, the material has high specific capacitance, good rate performance, low transmission resistance and excellent circulation stability, and has great application potential in the field of super capacitors.
Drawings
FIG. 1 is a macroscopic image of the nitrogen and manganous oxide co-doped hierarchical porous carbon bulk (N-MnO-HPCM) material obtained in example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the N-MnO-HPCM material obtained in example 1.
FIG. 3 is Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM) images of the N-MnO-HPCM material obtained in example 1, wherein a is a TEM image and b is an HRTEM image.
FIG. 4 is a nitrogen adsorption and desorption isotherm and a pore size distribution curve of the N-MnO-HPCM material obtained in example 1, wherein a is the nitrogen adsorption and desorption isotherm and b is the pore size distribution curve.
FIG. 5 is a graph of Cyclic Voltammetry (CV) results of electrochemical measurements of the N-MnO-HPCM material obtained in example 1.
FIG. 6 is a graph of the constant current charge and discharge (GCD) results of electrochemical testing of the N-MnO-HPCM material obtained in example 1.
FIG. 7 is a graph of the cycling stability at a current density of 1A/g for the N-MnO-HPCM material obtained in example 1. FIG. 8 is a Nyquist plot for the N-MnO-HPCM material obtained in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1: preparation of nitrogen-manganese co-doped hierarchical porous carbon material
The method comprises the following steps:
(1) preparation of oligomeric phenolic resin Resol
Adding 1.0g of phenol and 2.5mL of 40% formaldehyde solution into 4mL of 0.5M NaOH solution, and stirring at 65 ℃ for 0.7h to obtain the oligomeric phenolic resin Resol.
(2) Preparation of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
0.6g P123 (EO)20PO70EO20)，1.1g F127(EO106PO70EO106) 0.05g of melamine was added to the above-mentioned oligomeric phenol resin Resol, stirred at 65 ℃ for 4 hours, cooled to room temperature, and then 0.05g of MnCl was added2·4H2And O, continuously stirring for 3h at 65 ℃, transferring the obtained solution into a hydrothermal kettle, carrying out hydrothermal treatment for 18h at 100 ℃, filtering the obtained block material, repeatedly cleaning the block material by using distilled water, carrying out vacuum drying for 24h at 50 ℃, then transferring the block material into a tubular furnace, roasting for 1.5h at 800 ℃ under the protection of nitrogen gas, and cooling to room temperature to obtain the nitrogen and manganous oxide co-doped hierarchical pore carbon block (N-MnO-HPCM) material.
(3) Electrochemical performance test of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
A three-electrode system and 6M KOH solution are adopted as electrolyte, and Cyclic Voltammetry (CV), constant current charge and discharge (GCD) tests and Electrochemical Impedance (EIS) tests are carried out on an electrochemical workstation. The working electrode was prepared by mixing 90 wt% of the previously prepared active material (N-MnO-HPCM material) and 10 wt% of polyvinylidene fluoride (PVDF) in N-methylpyrrolidone (NMP). 5mg of the above material was coated onto a 1cm by 1cm nickel foam current collector and dried at 60 ℃ for 12 h. The cyclic voltammetry test potential window was from-0.9V to 0V, and the scan rate was from 1mV/s to 50 mV/s. Constant current charge and discharge test current density is from 1A/g to 5A/g. Electrochemical impedance testing frequencies ranged from 100KHz to 10 mHz. The specific capacitance is calculated from the GCD curve.
(4) Performance test and discussion of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
The macroscopic image of the N-MnO-HPCM material obtained by the hydrothermal method is shown in figure 1, and the N-MnO-HPCM material is in a regular cylindrical shape, has no crack phenomenon and shows good structural stability. FIG. 2 is a Scanning Electron Microscope (SEM) image of the N-MnO-HPCM material, and it can be seen from the image that the N-MnO-HPCM material has a three-dimensional macroporous structure which is communicated with each other, the size of the macropores is 0.5-2 μm, the three-dimensional macroporous structure which is communicated with each other can fully play a role of an ion buffer pool, the distance of ion diffusion can be shortened, and a continuous channel is provided for the rapid transmission of electrolyte ions.
FIG. 3 is a Transmission Electron Microscope (TEM) and High Resolution Transmission Electron Microscope (HRTEM) image of the N-MnO-HPCM material. It can be seen from the figure that the MnO nanoparticles are uniformly distributed in the carbon matrix with an average size of 6 nm. The carbon matrix can stabilize the MnO nano structure, improve the conductivity of MnO and facilitate electron transfer in the charge and discharge process. The MnO nanoparticles have lattice sizes of 0.256nm and 0.223nm, corresponding to the (111) and (200) crystal planes of MnO. Moreover, a large number of microporous structures can be observed in the carbon matrix, which not only provides a high specific surface area, but also provides a rapid transport channel for electrolyte ions, thereby enabling the material to have good supercapacitive performance.
FIG. 4 is a nitrogen desorption isotherm and pore size distribution curve of the N-MnO-HPCM material. In the low-pressure region (P/P0)<0.01) rapidly increasing nitrogen adsorption indicates the presence of a large number of microporous structures; in the medium-pressure region (0.4)<P/P0<0.8) a hysteresis loop showing a significant type IV adsorption isotherm, indicating the presence of a mesoporous structure. The BET specific surface area of the obtained N-MnO-HPCM material is 606m2Per g, pore volume of 0.33cm3(ii) in terms of/g. The pore size distribution curve also indicates that micropores and mesoporous structures exist simultaneously, wherein the micropore structures are generated by pyrolysis of a phenolic resin matrix, and the mesoporous structures are mainly generated by thermal decomposition of the template agents F127 and P123. By integrating SEM, TEM and nitrogen adsorption and desorption test results, the prepared N-MnO-HPCM material is proved to have a microporous-mesoporous-macroporous multilevel pore structure, and the three pore structures act synergistically in the charging and discharging processes, so that excellent electrochemical performance is shown.
The nitrogen content in the N-MnO-HPCM material was 3.21 wt% as measured by elemental analysis and the manganese content in the N-MnO-HPCM material was 3.36 wt% as measured by induced plasma atomic emission Spectroscopy (ICP-AES). The nitrogen doping and the introduction of MnO can obviously improve the super-capacitance performance of the carbon electrode material.
FIG. 5 is a Cyclic Voltammetry (CV) curve of the N-MnO-HPCM material, the CV curve showing an approximately rectangular shape over the range of voltages measured, illustrating the ideal double layer capacitance performance of the N-MnO-HPCM material. The obvious hump phenomenon exists in a CV curve, and is mainly the pseudocapacitance generated by nitrogen-containing functional groups in a carbon matrix and MnO nano particles. FIG. 6 is a GCD curve of the N-MnO-HPCM material showing a substantially symmetrical triangular shape, indicating that the N-MnO-HPCM material has ideal supercapacitive properties. The specific capacitance of the N-MnO-HPCM material at the current density of 1A/g is 261.7F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 2A/g is 244.4F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 3A/g is 233.3F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 5A/g is 194.4F/g, and when the current density is increased, the attenuation amplitude of the specific capacitance is smaller, which shows that the N-MnO-HPCM material has good rate capacity, mainly due to the shortened diffusion path of electrolyte ions provided by the multi-level pore structure of the N-MnO-HPCM material, and the diffusion resistance is greatly reduced. The specific capacity retention after 2000 cycles at a current density of 1A/g was 96.1%, as shown in FIG. 7.
The transmission resistance condition of the N-MnO-HPCM material is researched by adopting electrochemical impedance spectroscopy, the Nyquist curve is shown in figure 8, and the inset is the Nyquist curve of the N-MnO-HPCM material in a high-frequency region. The semi-circle has an intercept on the horizontal axis of equivalent series resistance (Rs) of 0.34 Ω, representing the sum of the resistance from the electrolyte and the interior of the active material, and the contact resistance between the active material and the current collector, which is relatively small, indicating that the supercapacitor has good rate capacity or power density. The diameter of the semicircle corresponds to the charge transfer resistance at the electrode-electrolyte interface, which is 0.14 Ω, indicating that the N-MnO-HPCM material has a lower charge transfer resistance and higher conductivity. The Nyquist curve is in a shape close to a straight line in a low-frequency region, shows ideal capacitance behavior and lower ion diffusion resistance, which is mainly attributed to the hierarchical pore structure thereof, promotes rapid diffusion of electrolyte ions, and shortens the diffusion distance of the electrolyte ions in the charging and discharging processes. Example 2: preparation of nitrogen-manganese co-doped hierarchical porous carbon material
The method comprises the following steps:
(1) preparation of oligomeric phenolic resin Resol
1.0g of phenol and 4.5mL of 37% formaldehyde solution are added into 6mL of 0.5M NaOH solution and stirred for 0.4h at 75 ℃ to obtain the oligomeric phenolic resin Resol.
(2) Preparation of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
Adding 0.90g P123, 1.5g F127, 0.20g dicyandiamide into the above-mentioned oligomeric phenolic resin Resol, stirring at 75 deg.C for 2h, cooling to room temperature, adding 0.12g MnCl2·4H2And O, continuously stirring for 0.5h at 75 ℃, transferring the obtained solution into a hydrothermal kettle, carrying out hydrothermal treatment for 10h at 130 ℃, filtering the obtained block material, repeatedly cleaning the block material by using distilled water, carrying out vacuum drying for 6h at 80 ℃, then transferring the block material into a tubular furnace, roasting for 5h at 550 ℃ under the protection of nitrogen gas, and cooling to room temperature to obtain the nitrogen and manganous oxide co-doped hierarchical pore carbon block (N-MnO-HPCM) material.
(3) Electrochemical performance test of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
A three-electrode system and 6M KOH solution are adopted as electrolyte, and Cyclic Voltammetry (CV), constant current charge and discharge (GCD) tests and Electrochemical Impedance (EIS) tests are carried out on an electrochemical workstation. The working electrode was prepared by mixing 90 wt% of the previously prepared active material (N-MnO-HPCM material) and 10 wt% of polyvinylidene fluoride (PVDF) in NMP. 5mg of the above material was coated on a 1cm by 1cm nickel foam current collector and dried at 70 ℃ for 10 h. The cyclic voltammetry test potential window was from-0.9V to 0V, and the scan rate was from 1mV/s to 50 mV/s. Constant current charge and discharge test current density is from 1A/g to 5A/g. Electrochemical impedance testing frequencies ranged from 100KHz to 10 mHz. The specific capacitance is calculated from the GCD curve.
(4) Performance test and discussion of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
The nitrogen and manganous oxide co-doped hierarchical porous carbon block material obtained in the embodiment has a hierarchical porous structure of micropore-mesopore-macropore, the macropore size is 0.5-2 mu m, the average mesopore size is 3.88nm, the micropore size is about 1nm, and the BET specific surface area is 763m2Per g, pore volume of 0.49cm3(ii) in terms of/g. The nitrogen content in the N-MnO-HPCM material was 4.78 wt% as measured by elemental analysis and the manganese content in the N-MnO-HPCM material was 2.75 wt% as measured by ICP-AES.
The specific capacitance of the N-MnO-HPCM material at the current density of 1A/g is 274.3F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 2A/g is 257F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 3A/g is 245.9F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 5A/g is 227F/g, and when the current density is increased, the attenuation amplitude of the specific capacitance is smaller, which indicates that the N-MnO-HPCM material has good rate capacity. The specific capacity retention after 2000 cycles at a current density of 1A/g was 96.3%. The equivalent series resistance of the N-MnO-HPCM material is 0.30 omega and the charge transfer resistance of the electrode-electrolyte interface is 0.12 omega. The good electrochemical performance of the N-MnO-HPCM material is mainly attributed to the hierarchical pore structure, so that the diffusion resistance is greatly reduced, the rapid diffusion of electrolyte ions is promoted, and the diffusion distance of the electrolyte ions in the charging and discharging processes is shortened; in addition, the nitrogen doping and the manganese doping also greatly improve the super-capacitance performance of the carbon electrode material.
Example 3: preparation of nitrogen-manganese co-doped hierarchical porous carbon material
The method comprises the following steps:
(1) preparation of oligomeric phenolic resin Resol
Adding 1.0g of phenol and 3.5mL of 39% formaldehyde solution into 5mL of 0.5M NaOH solution, and stirring at 65 ℃ for 0.7h to obtain the oligomeric phenolic resin Resol.
(2) Preparation of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
Adding 0.85g P123, 1.15g F127, 0.5g urea into the above oligomeric phenol formaldehyde resin, stirring at 70 deg.C for 3h, cooling to room temperature, adding 0.4g MnCl2·4H2And O, continuously stirring for 2h at 70 ℃, transferring the obtained solution into a hydrothermal kettle, carrying out hydrothermal treatment for 15h at 120 ℃, filtering the obtained block material, repeatedly cleaning the block material by using distilled water, carrying out vacuum drying for 15h at 60 ℃, then transferring the block material into a tubular furnace, roasting for 4h at 700 ℃ under the protection of nitrogen gas, and cooling to room temperature to obtain the nitrogen and manganous oxide co-doped hierarchical pore carbon block (N-MnO-HPCM) material.
(3) Test of electrochemical performance of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
A three-electrode system and 6M KOH solution are adopted as electrolyte, and Cyclic Voltammetry (CV), constant current charge and discharge (GCD) tests and Electrochemical Impedance (EIS) tests are carried out on an electrochemical workstation. The working electrode was prepared by mixing 90 wt% of the previously prepared active material (N-MnO-HPCM material) and 10 wt% of polyvinylidene fluoride (PVDF) in NMP. 5mg of the above material was coated onto a 1cm by 1cm nickel foam current collector and dried at 60 ℃ for 12 h. The cyclic voltammetry test potential window was from-0.9V to 0V, and the scan rate was from 1mV/s to 50 mV/s. Constant current charge and discharge test current density is from 1A/g to 5A/g. Electrochemical impedance testing frequencies ranged from 100KHz to 10 mHz. The specific capacitance is calculated from the GCD curve.
(4) Performance test and discussion of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
The nitrogen and manganous oxide co-doped hierarchical porous carbon block material obtained in the embodiment has a hierarchical pore structure of micropore-mesopore-macropore, the macropore size is 0.5-2 mu m, the average mesopore size is 3.79nm, the micropore size is about 1nm, and the BET specific surface area is 749m2Per g, pore volume of 0.46cm3(ii) in terms of/g. The nitrogen content in the N-MnO-HPCM material was 4.55 wt% as measured by elemental analysis, and the nitrogen content in the N-MnO-HPCM material was measured by ICP-AESThe manganese content was 2.91 wt%.
The specific capacitance of the N-MnO-HPCM material at the current density of 1A/g is 270.9F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 2A/g is 253.6F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 3A/g is 242.5F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 5A/g is 223.6F/g, and when the current density is increased, the attenuation amplitude of the specific capacitance is smaller, which indicates that the N-MnO-HPCM material has good rate capacity. The specific capacity retention after 2000 cycles at a current density of 1A/g was 95.8%. The equivalent series resistance of the N-MnO-HPCM material is 0.31 omega and the charge transfer resistance of the electrode-electrolyte interface is 0.13 omega. The good electrochemical performance of the N-MnO-HPCM material is mainly attributed to the hierarchical pore structure, so that the diffusion resistance is greatly reduced, the rapid diffusion of electrolyte ions is promoted, and the diffusion distance of the electrolyte ions in the charging and discharging processes is shortened; in addition, the nitrogen doping and the manganese doping also greatly improve the super-capacitance performance of the carbon electrode material.
Example 4: preparation of nitrogen-manganese co-doped hierarchical porous carbon material
The method comprises the following steps:
(1) preparation of oligomeric phenolic resin Resol
Adding 1.0g of phenol and 4.0mL of 37% formaldehyde solution into 5mL of 0.5M NaOH solution, and stirring at 70 ℃ for 0.6h to obtain the oligomeric phenolic resin Resol.
(2) Preparation of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
0.75g P123, 1.25g F127, 0.15g melamine was added to the above oligomeric phenol resin Resol, stirred at 70 ℃ for 3h, cooled to room temperature, and then 0.23g Mn (NO) was added3)2·4H2And O, continuously stirring for 2h at 70 ℃, transferring the obtained solution into a hydrothermal kettle, carrying out hydrothermal treatment for 18h at 100 ℃, filtering the obtained block material, repeatedly cleaning the block material by using distilled water, carrying out vacuum drying for 20h at 50 ℃, then transferring the block material into a tubular furnace, roasting for 3h at 700 ℃ under the protection of nitrogen gas, and cooling to room temperature to obtain the nitrogen and manganous oxide co-doped hierarchical pore carbon block (N-MnO-HPCM) material.
(3) Test of electrochemical performance of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
A three-electrode system and 6M KOH solution are adopted as electrolyte, and Cyclic Voltammetry (CV), constant current charge and discharge (GCD) tests and Electrochemical Impedance (EIS) tests are carried out on an electrochemical workstation. The working electrode was prepared by mixing 90 wt% of the previously prepared active material (N-MnO-HPCM material) and 10 wt% of polyvinylidene fluoride (PVDF) in NMP. 5mg of the above material was coated onto a 1cm by 1cm nickel foam current collector and dried at 60 ℃ for 12 h. The cyclic voltammetry test potential window was from-0.9V to 0V, and the scan rate was from 1mV/s to 50 mV/s. Constant current charge and discharge test current density is from 1A/g to 5A/g. Electrochemical impedance testing frequencies ranged from 100KHz to 10 mHz. The specific capacitance is calculated from the GCD curve.
(4) Performance test and discussion of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
The nitrogen and manganous oxide co-doped hierarchical porous carbon block material obtained in the embodiment has a hierarchical pore structure of micropore-mesopore-macropore, the macropore size is 0.5-2 mu m, the average mesopore size is 4.10nm, the micropore size is about 1nm, and the BET specific surface area is 799m2Per g, pore volume of 0.53cm3(ii) in terms of/g. The nitrogen content in the N-MnO-HPCM material was 4.54 wt% as measured by elemental analysis and the manganese content in the N-MnO-HPCM material was 3.22 wt% as measured by ICP-AES.
The specific capacitance of the N-MnO-HPCM material at the current density of 1A/g is 282.2F/g, the specific capacitance at the current density of 2A/g is 264.9F/g, the specific capacitance at the current density of 3A/g is 253.8F/g, the specific capacitance at the current density of 5A/g is 234.9F/g, and when the current density is increased, the specific capacitance attenuation amplitude is smaller, which indicates that the N-MnO-HPCM material has good rate capacity. The specific capacity retention after 2000 cycles at a current density of 1A/g was 96.6%. The equivalent series resistance of the N-MnO-HPCM material is 0.28 omega and the charge transfer resistance of the electrode-electrolyte interface is 0.11 omega. The good electrochemical performance of the N-MnO-HPCM material is mainly attributed to the hierarchical pore structure, so that the diffusion resistance is greatly reduced, the rapid diffusion of electrolyte ions is promoted, and the diffusion distance of the electrolyte ions in the charging and discharging processes is shortened; in addition, the nitrogen doping and the manganese doping also greatly improve the super-capacitance performance of the carbon electrode material.
Example 5: preparation of nitrogen-manganese co-doped hierarchical porous carbon material
The method comprises the following steps:
(1) preparation of oligomeric phenolic resin Resol
Adding 1.0g of phenol and 3.5mL of 40% formaldehyde solution into 5mL of 0.5M NaOH solution, and stirring at 70 ℃ for 0.5h to obtain the oligomeric phenolic resin Resol.
(2) Preparation of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
0.75g P123, 1.25g F127, 0.15g of melamine was added to the above oligomeric phenol resin Resol, stirred at 70 ℃ for 3h, cooled to room temperature, and then 0.20g of Mn (CH)3COO)2·4H2And O, continuously stirring for 1h at 70 ℃, transferring the obtained solution into a hydrothermal kettle, carrying out hydrothermal treatment for 18h at 100 ℃, filtering the obtained block material, repeatedly cleaning the block material by using distilled water, carrying out vacuum drying for 15h at 60 ℃, then transferring the block material into a tubular furnace, roasting for 3h at 700 ℃ under the protection of nitrogen gas, and cooling to room temperature to obtain the nitrogen and manganous oxide co-doped hierarchical pore carbon block (N-MnO-HPCM) material.
(3) Electrochemical performance test of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
A three-electrode system and 6M KOH solution are adopted as electrolyte, and Cyclic Voltammetry (CV), constant current charge and discharge (GCD) tests and Electrochemical Impedance (EIS) tests are carried out on an electrochemical workstation. The working electrode was prepared by mixing 90 wt% of the previously prepared active material (N-MnO-HPCM material) and 10 wt% of polyvinylidene fluoride (PVDF) in NMP. 5mg of the above material was coated onto a 1cm by 1cm nickel foam current collector and dried at 50 ℃ for 20 h. The cyclic voltammetry test potential window was from-0.9V to 0V, and the scan rate was from 1mV/s to 50 mV/s. Constant current charge and discharge test current density is from 1A/g to 5A/g. Electrochemical impedance testing frequencies ranged from 100KHz to 10 mHz. The specific capacitance is calculated from the GCD curve.
(4) Performance test and discussion of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
Nitrogen and manganous oxide codoped from this exampleThe hierarchical porous carbon block material has a hierarchical porous structure of micropore-mesopore-macropore, the macropore size is 0.5-2 mu m, the average mesopore size is 3.96nm, the micropore size is about 1nm, and the BET specific surface area is 783m2Per g, pore volume of 0.48cm3(ii) in terms of/g. The nitrogen content in the N-MnO-HPCM material was 4.41 wt% as measured by elemental analysis and the manganese content in the N-MnO-HPCM material was 3.33 wt% as measured by ICP-AES.
The specific capacitance of the N-MnO-HPCM material at the current density of 1A/g is 276.6F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 2A/g is 259.6F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 3A/g is 248.7F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 5A/g is 230.2F/g, and when the current density is increased, the specific capacitance attenuation amplitude is smaller, which indicates that the N-MnO-HPCM material has good rate capacity. The specific capacity retention after 2000 cycles at a current density of 1A/g was 95.7%. The equivalent series resistance of the N-MnO-HPCM material is 0.31 omega and the charge transfer resistance of the electrode-electrolyte interface is 0.13 omega. The good electrochemical performance of the N-MnO-HPCM material is mainly attributed to the hierarchical pore structure, so that the diffusion resistance is greatly reduced, the rapid diffusion of electrolyte ions is promoted, and the diffusion distance of the electrolyte ions in the charging and discharging processes is shortened; in addition, the nitrogen doping and the manganese doping also greatly improve the super-capacitance performance of the carbon electrode material.
Example 6: preparation of nitrogen-manganese co-doped hierarchical porous carbon material
The method comprises the following steps:
(1) preparation of oligomeric phenolic resin Resol
Adding 1.0g of phenol and 3.5mL of 37% formaldehyde solution into 5mL of 0.5M NaOH solution, and stirring at 70 ℃ for 0.5h to obtain the oligomeric phenolic resin Resol.
(2) Preparation of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
0.75g P123, 1.25g F127, 0.20g of melamine are added to the above-mentioned oligomeric phenol-formaldehyde resin Resol, stirred at 70 ℃ for 3h, cooled to room temperature, and then 0.18g of MnCl is added2·4H2O, continuing stirring for 1h at 70 ℃, transferring the obtained solution into a hydrothermal kettle, performing hydrothermal for 18h at 100 ℃, and filtering the obtained block materialAnd (3) repeatedly cleaning the material with distilled water, drying the material in vacuum at 60 ℃ for 15h, then transferring the material into a tubular furnace, roasting the material at 700 ℃ for 3h under the protection of nitrogen gas, and cooling the material to room temperature to obtain the nitrogen and manganous oxide co-doped hierarchical pore carbon block (N-MnO-HPCM) material.
(3) Electrochemical performance test of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
A three-electrode system and 6M KOH solution are adopted as electrolyte, and Cyclic Voltammetry (CV), constant current charge and discharge (GCD) tests and Electrochemical Impedance (EIS) tests are carried out on an electrochemical workstation. The working electrode was prepared by mixing 90 wt% of the previously prepared active material (N-MnO-HPCM material) and 10 wt% of polyvinylidene fluoride (PVDF) in NMP. 5mg of the above material was coated onto a 1cm by 1cm nickel foam current collector and dried at 60 ℃ for 12 h. The cyclic voltammetry test potential window was from-0.9V to 0V, and the scan rate was from 1mV/s to 50 mV/s. Constant current charge and discharge test current density is from 1A/g to 5A/g. Electrochemical impedance testing frequencies ranged from 100KHz to 10 mHz. The specific capacitance is calculated from the GCD curve.
(4) Performance test and discussion of nitrogen and manganous oxide co-doped hierarchical porous carbon block material
The nitrogen and manganous oxide co-doped hierarchical porous carbon block material obtained in the embodiment has a hierarchical pore structure of micropore-mesopore-macropore, the macropore size is 0.5-2 mu m, the average mesopore size is 4.14nm, the micropore size is about 1nm, and the BET specific surface area is 806m2Per g, pore volume of 0.55cm3(ii) in terms of/g. The nitrogen content in the N-MnO-HPCM material was 5.22 wt% as measured by elemental analysis and the manganese content in the N-MnO-HPCM material was 3.29 wt% as measured by ICP-AES.
The specific capacitance of the N-MnO-HPCM material at the current density of 1A/g is 301.7F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 2A/g is 283.2F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 3A/g is 271.3F/g, the specific capacitance of the N-MnO-HPCM material at the current density of 5A/g is 251.1F/g, and when the current density is increased, the specific capacitance attenuation amplitude is smaller, which indicates that the N-MnO-HPCM material has good rate capacity. The specific capacity retention after 2000 cycles at a current density of 1A/g was 97.2%. The equivalent series resistance of the N-MnO-HPCM material is 0.25 omega and the charge transfer resistance of the electrode-electrolyte interface is 0.10 omega. The good electrochemical performance of the N-MnO-HPCM material is mainly attributed to the hierarchical pore structure, so that the diffusion resistance is greatly reduced, the rapid diffusion of electrolyte ions is promoted, and the diffusion distance of the electrolyte ions in the charging and discharging processes is shortened; in addition, the nitrogen doping and the manganese doping also greatly improve the super-capacitance performance of the carbon electrode material.

Claims (2)

1. A preparation method of a nitrogen-manganese co-doped hierarchical pore carbon material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of oligomeric phenolic resin: dissolving phenol and formaldehyde in an aqueous alkali, and heating and stirring to obtain the aqueous alkali, wherein the aqueous alkali is a sodium hydroxide solution, the using amount of the aqueous alkali is 4-6 mL of 0.5M sodium hydroxide solution used for every 1g of phenol, the heating temperature is 65-75 ℃, and the stirring time is 0.4-0.7 h;
(2) preparing a nitrogen-manganese co-doped hierarchical porous carbon block material: adding template agents P123 and F127 and a nitrogen-containing compound into the low-polymer phenolic resin prepared in the step (1), stirring for 2-4 h at 65-75 ℃, cooling to room temperature, adding manganese salt, continuing to stir for 0.5-3 h at 65-75 ℃, transferring the obtained solution into a hydrothermal kettle for hydrothermal reaction at 100-130 ℃ for 10-18 h, filtering out the block material, cleaning, drying in vacuum at 50-80 ℃ for 6-24 h, roasting at 550-800 ℃ for 1.5-5 h under the protection of inert gas, and cooling to room temperature to obtain the nitrogen and manganous oxide co-doped hierarchical porous carbon block material; the nitrogen-containing compound is melamine, dicyanodiamine or urea; the manganese salt is manganese chloride, manganese nitrate or manganese acetate;
the mass ratio of the phenol to the P123 to the F127 to the nitrogen-containing compound to the manganese salt is 1: 0.6-0.9: 1.1-1.5: 0.05-0.5: 0.05-0.4 in sequence, and the dosage of the formaldehyde solution is 2.5-4.5 ml of formaldehyde solution with the concentration of 37-40% used for every 1g of phenol;
prepared nitrogen and manganous oxide co-doped hierarchical porous carbon block material has the multilevel of micropore-mesopore-macropore
Pore structure.
2. The preparation method of the nitrogen-manganese co-doped hierarchical porous carbon material according to claim 1, characterized in that: and (3) in the step (2), the inert gas is nitrogen or argon.
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