CN111196603B - Preparation method of amino phenolic resin based pyrrole nitrogen doped carbon electrode material - Google Patents

Preparation method of amino phenolic resin based pyrrole nitrogen doped carbon electrode material Download PDF

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CN111196603B
CN111196603B CN202010088986.8A CN202010088986A CN111196603B CN 111196603 B CN111196603 B CN 111196603B CN 202010088986 A CN202010088986 A CN 202010088986A CN 111196603 B CN111196603 B CN 111196603B
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CN111196603A (en
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郭万春
田克松
杨薇
王君妍
曹玲
王海燕
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Yanshan University
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
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    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C01B32/348—Metallic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a preparation method of an amino phenolic resin based pyrrole nitrogen doped carbon electrode material, which comprises the following specific steps: A. preparing 3-aminophenol-3-halophenol-formaldehyde resin; B. low-temperature carbonization of 3-aminophenol-3-halophenol-formaldehyde resin; C. the method realizes the doping of a single pyrrole nitrogen configuration in a carbon material through low-temperature heat treatment, improves the utilization efficiency of nitrogen-doped active sites in pseudo-capacitance reaction, simultaneously reduces the energy consumption in the preparation of nitrogen-doped carbon materials, and when the material is applied as a super capacitor electrode material, the amino phenol-formaldehyde resin based pyrrole nitrogen-doped carbon electrode material shows high capacity, typical pseudo-capacitance characteristics, good rate performance and high cycle stability characteristics.

Description

Preparation method of amino phenolic resin based pyrrole nitrogen doped carbon electrode material
Technical Field
The invention relates to a preparation method of an amino phenolic resin based pyrrole nitrogen doped carbon electrode material, belonging to the technical field of electrochemical super capacitors.
Background
Super capacitor has received extensive attention in the industry as a kind of novel energy storage device because characteristics such as its high power density and long-life. The electrode material is a key factor influencing the capacity of the super capacitor, and the structure and the interface characteristics of the electrode material play a vital role in enhancing the capacitance performances such as specific capacity, cycling stability, rate capability and the like. Electrode materials can be generally classified into three types, carbon materials, conductive polymers and metal oxides. Among them, carbon materials are currently the most promising electrode materials due to their diverse forms of existence, good conductivity, light weight, fast charge and discharge, good stability, low cost, and ready availability. However, pure carbon materials can only exhibit an electric double layer capacitance determined by a specific surface area, and the capacity thereof still remains to be improved (Science, 2013, 341, 534-537). In recent years, heteroatom doping, particularly nitrogen doping, can provide pseudo-capacitance active sites for carbon materials, and can effectively improve the specific capacity of the carbon materials, so that the development of nitrogen-doped carbon materials becomes a research hotspot in the field of supercapacitors (Advanced Science, 2017, 4, 1600408).
For carbon Materials, the nitrogen atom doping method is generally divided into in-situ doping and post-doping (Advanced Functional Materials, 2013, 23, 2322-2328; Nano Lett, 2011, 11, 2472-2477), wherein the in-situ doping method generally means that nitrogen atoms are introduced into a carbon skeleton in a carbonization process by using small molecules, polymers or biomass Materials containing nitrogen elements, so as to obtain the nitrogen-doped carbon material (Advanced Materials, 2018, 1804394) with stable chemical structure, uniform doping sites and controllable doping amount. The nitrogen-doped form mainly comprises three configurations of pyridine nitrogen, pyrrole nitrogen and graphite nitrogen, wherein the pyridine nitrogen and the pyrrole nitrogen can provide capacity as pseudocapacitance sites (Science, 2015, 350, 1508-1513). However, in the prior art, in order to improve the conductivity of the nitrogen-doped carbon material, the higher carbonization temperature often causes incomplete conversion of pyrrole nitrogen and pyridine nitrogen to graphite nitrogen (Electrochimica Acta, 2016, 205, 132-. Therefore, the development of single pyrrole nitrogen, single pyridine nitrogen or pyridine nitrogen and pyrrole nitrogen co-doped high-capacity carbon materials becomes the research focus and research difficulty of the current carbon electrode material. In order to solve the problem, an amino phenolic resin based pyrrole nitrogen doped carbon material and a preparation method thereof are provided.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of an amino phenolic resin based pyrrole nitrogen doped carbon electrode material, synthesize a single pyrrole nitrogen doped carbon material with pseudocapacitance activity completely, improve the utilization efficiency of nitrogen doped active sites in pseudocapacitance reaction, and develop the amino phenolic resin based pyrrole nitrogen doped carbon electrode material with high specific capacity and long cycle stability.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of an amino phenolic resin based pyrrole nitrogen doped carbon electrode material comprises the steps of stirring 3-halophenol, 3-aminophenol and hexamethylenetetramine at normal temperature, polymerizing by a hydrothermal method to obtain halogenated phenolic resin, washing and drying, carbonizing at low temperature, activating at low temperature by potassium hydroxide, washing by a hydrochloric acid solution, washing and drying.
The technical scheme of the invention is further improved as follows: the method comprises the following steps:
A. dissolving 3-aminophenol, 3-halophenol and hexamethylenetetramine in 80 mL of distilled water according to a certain proportion to form a mixed solution, stirring for a period of time at room temperature, transferring the mixed solution to a 100 mL reaction kettle, carrying out hydrothermal reaction to obtain a solid sample I, naturally cooling to room temperature, washing the solid sample I with water until the pH value is =7, and drying to obtain a 3-aminophenol-3-halophenol-formaldehyde resin microsphere sample;
B. heating the 3-aminophenol-3-halogenated phenol-formaldehyde resin microspheres obtained in the step A from room temperature in a nitrogen atmosphere, carrying out heat treatment for a period of time, and then naturally cooling to room temperature to collect a second sample;
C. and D, grinding and uniformly mixing the sample II obtained in the step B and an activating agent KOH according to a certain proportion, then heating from room temperature in a nitrogen atmosphere, carrying out an activation reaction to obtain a solid sample III, naturally cooling to room temperature, washing the solid sample with a three-purpose hydrochloric acid solution and water to pH =7, and drying to obtain the amino phenolic resin based pyrrole nitrogen doped carbon electrode material.
The technical scheme of the invention is further improved as follows: in the step A, the mass ratio of the 3-aminophenol to the 3-halophenol is 1/1-1/7, the mass ratio of the sum of the 3-aminophenol and the 3-halophenol to the hexamethylenetetramine is 2/1, and the concentration of the hexamethylenetetramine in the mixed solution is 8.5-9.5 multiplied by 10-3 mol L-1And stirring for 1-1.5 hours at room temperature, wherein the 3-halogenated phenol is 3-fluorophenol, 3-chlorophenol or 3-bromophenol.
The technical scheme of the invention is further improved as follows: the concentration of the hexamethylenetetramine in the mixed solution in the step A is 8.92 multiplied by 10-3 mol L-1The mixture was stirred at room temperature for 1 hour.
The technical scheme of the invention is further improved as follows: the hydrothermal reaction temperature in the step A is 150-170% oC, the hydrothermal time is 3.5-4.5 hours.
The technical scheme of the invention is further improved as follows: the hydrothermal reaction temperature in the step A is 160 DEGoAnd C, the hydrothermal time is 4 hours.
The technical scheme of the invention is further improved as follows: the heat treatment temperature in the step B is 450-520 DEGoC, the heat treatment time is 4-5 hours.
The technical scheme of the invention is further improved as follows: the heat treatment temperature in the step B is 500oAnd C, the heat treatment time is 4 hours.
The technical scheme of the invention is further improved as follows: the mass ratio of the sample II to the activating agent KOH in the step C is 1/6, and the activation reaction temperature is 450-520oAnd C, activating for 8 hours.
The technical scheme of the invention is further improved as follows: the activation reaction temperature in the step C is 500oC。
Due to the adoption of the technical scheme, the invention has the technical progress that:
according to the invention, fluorine and nitrogen functional groups are introduced in the phenolic resin synthesis process, the fluorine functional groups are easy to remove in the low-temperature heat treatment process, adjacent benzene rings are covalently bonded to form a carbon material with a large conjugated structure, a carbon skeleton is rearranged in the alkali activation process to form a single pyrrole nitrogen doped carbon material, the obtained amino phenolic resin based pyrrole nitrogen doped carbon electrode material has certain conductivity, and a microporous structure and a single pyrrole nitrogen doped form are adopted, so that the high pseudocapacitance performance is shown, the carbonization and activation of the amino phenolic resin under the low-temperature condition are realized, a large number of single pyrrole nitrogen functional groups are reserved, the nitrogen doped utilization rate is improved, and the high capacity is shown.
Drawings
FIG. 1 is a Raman spectrum of an amino phenol-formaldehyde resin-based pyrrole nitrogen-doped carbon electrode material in example 1 of the invention;
FIG. 2 is a nitrogen adsorption/desorption curve and a pore size distribution spectrogram of an amino phenolic resin-based pyrrole nitrogen-doped carbon electrode material in example 1 of the present invention;
FIG. 3 is an N1 s X ray photoelectron spectroscopy (XPS) spectrum of an aminophenol-based pyrrole nitrogen-doped carbon electrode material in example 1 of the present invention;
FIG. 4 is a constant current charging and discharging curve of a three-electrode system assembled by amino phenolic resin based pyrrole nitrogen doped carbon electrode material in 1 mol/L sulfuric acid solution in example 1 of the present invention;
FIG. 5 is a cyclic voltammogram of a three-electrode system assembled from an aminophenol-based pyrrole nitrogen-doped carbon electrode material in 1 mol/L sulfuric acid solution according to example 1 of the present invention;
FIG. 6 is a graph showing the cycle stability of a three-electrode system assembled from an aminophenol-based pyrrole nitrogen-doped carbon electrode material in example 1 of the present invention under a current density condition of 10A/g in a 1 mol/L sulfuric acid solution;
FIG. 7 is an N1 s X ray photoelectron spectroscopy (XPS) spectrum of an aminophenol-based pyrrole nitrogen-doped carbon electrode material in example 2 of the present invention;
FIG. 8 is an N1 s X ray photoelectron spectroscopy (XPS) spectrum of an aminophenol-based pyrrole nitrogen-doped carbon electrode material in example 3 of the present invention;
FIG. 9 is an N1 s X ray photoelectron spectroscopy (XPS) spectrum of an aminophenol-based pyrrole nitrogen-doped carbon electrode material in example 4 of the present invention;
FIG. 10 is an N1 s X ray photoelectron spectroscopy (XPS) spectrum of an aminophenol-based pyrrole nitrogen-doped carbon electrode material of example 5 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples:
a preparation method of an amino phenolic resin based pyrrole nitrogen doped carbon electrode material comprises the steps of stirring 3-halophenol, 3-aminophenol and hexamethylenetetramine at normal temperature, polymerizing by a hydrothermal method to obtain halogenated phenolic resin, washing and drying, carbonizing at low temperature, activating at low temperature by potassium hydroxide, washing by a hydrochloric acid solution, washing and drying.
The method comprises the following specific steps:
A. dissolving 3-aminophenol, 3-halophenol and hexamethylenetetramine in 80 mL of distilled water according to a certain proportion to form a mixed solution, stirring for a period of time at room temperature, transferring the mixed solution to a 100 mL reaction kettle, carrying out hydrothermal reaction to obtain a solid sample I, naturally cooling to room temperature, washing the solid sample I with water until the pH value is =7, and drying to obtain a 3-aminophenol-3-halophenol-formaldehyde resin microsphere sample;
B. heating the 3-aminophenol-3-halogenated phenol-formaldehyde resin microspheres obtained in the step A from room temperature in a nitrogen atmosphere, carrying out heat treatment for a period of time, and then naturally cooling to room temperature to collect a second sample;
C. and D, grinding and uniformly mixing the sample II obtained in the step B and an activating agent KOH according to a certain proportion, then heating from room temperature in a nitrogen atmosphere, carrying out an activation reaction to obtain a solid sample III, naturally cooling to room temperature, washing the solid sample with a three-purpose hydrochloric acid solution and water to pH =7, and drying to obtain the amino phenolic resin based pyrrole nitrogen doped carbon electrode material.
Wherein the mass ratio of the 3-aminophenol to the 3-halophenol in the step A is 1/1-1/7, the mass ratio of the sum of the 3-aminophenol and the 3-halophenol to the hexamethylenetetramine is 2/1, and the concentration of the hexamethylenetetramine in the mixed solution is 8.5-9.5 × 10-3 mol L-1Preferably 8.92X 10-3 mol L-1And stirring the mixture at room temperature for 1 to 1.5 hours, preferably for 1 hour, wherein the 3-halogenated phenol is 3-fluorophenol, 3-chlorophenol or 3-bromophenol. The hydrothermal reaction temperature is 150-170 DEG oC, preferably 160oAnd C, the hydrothermal time is 3.5-4.5 hours, preferably 4 hours.
The heat treatment temperature in the step B is 450-520 DEGoC, preferably 500oAnd C, the heat treatment time is 4-5 hours, preferably 4 hours.
In the step C, the mass ratio of the sample II to the activating agent KOH is 1/6, and the activation reaction temperature is 450-520oC, preferably 500oAnd C, activating for 8 hours.
Example 1
A. 0.1 g of 3-aminophenol, 0.1 g of 3-fluorophenol and 0.1 g of hexamethylenetetramine were dissolved in 80 mL of distilled water, and stirred at room temperature for 1 hour until the solid sample was completely dissolved. This solution was then transferred to a 100 mL reaction kettle at 160%oAnd (3) reacting for 4 hours under the condition of C, naturally cooling to room temperature, washing the product to pH =7 with water, and drying to obtain a 3-aminophenol-3-fluorophenol-formaldehyde resin microsphere sample.
B. Heating the 3-aminophenol-3-fluorophenol-formaldehyde resin microsphere sample obtained in the step A from room temperature to 500 ℃ in a nitrogen atmosphereoAnd C, keeping the temperature for 4 hours. And naturally cooling to room temperature and collecting a sample.
C. Grinding and uniformly mixing the sample obtained in the step B and an activating agent KOH according to the mass ratio of 1/6, and then heating the mixture from room temperature to 500 ℃ in a nitrogen atmosphereoAnd C, keeping the temperature for 8 hours. And naturally cooling to room temperature, washing the solid sample to pH =7 by using a hydrochloric acid solution and water, and drying to obtain the amino phenolic resin based pyrrole nitrogen doped carbon electrode material.
The Raman spectrum of the amino phenolic resin based pyrrole nitrogen doped carbon electrode material prepared in the example is shown in figure 1 and is at 1353 cm and 1593 cm-1And each absorption peak is respectively corresponding to a D band and a G band of the carbon material, which shows that the amino phenolic resin finally realizes carbonization.
The results of the low-temperature nitrogen adsorption/desorption experiment of the amino phenol resin-based pyrrole nitrogen-doped carbon electrode material prepared in this example are shown in fig. 2, and the specific surface area is 450 cm2 g-1The pore size of the micropores is centered at 0.6 nm.
Fig. 3 shows an N1 s X ray photoelectron spectroscopy spectrum (XPS) of the amino phenol resin-based pyrrole nitrogen-doped carbon electrode material prepared in this example, which indicates that the nitrogen-doped configuration is a single pyrrole state and the content reaches 4.22 at.%.
The constant current charge and discharge test result of the amino phenolic resin based pyrrole nitrogen doped carbon electrode material prepared in the embodiment in a 1 mol/L sulfuric acid solution is shown in fig. 4, and when the current density is 1A/g, the specific capacitance is 618F/g; when the current density is 20A/g, the specific capacitance is 447F/g respectively, and high capacity and good rate performance are shown.
Cyclic voltammetry tests are performed on the amino phenol resin-based pyrrole nitrogen-doped carbon electrode material prepared in the embodiment in a 1 mol/L sulfuric acid solution, and the results are shown in fig. 5, and under different scanning rates, an obvious symmetric redox peak exists in a cyclic voltammetry curve, so that the amino phenol resin-based pyrrole nitrogen-doped carbon electrode material has good pseudocapacitance behavior and electrochemical reversibility.
The constant-current charge-discharge cycle test of the amino phenolic resin based pyrrole nitrogen doped carbon electrode material prepared in the embodiment in 1 mol/L sulfuric acid solution shows that the capacity retention rate is 100% after the current density is 10A/g and the charge-discharge is performed 30000 times, and the good cycle stability is shown as the result shown in FIG. 6.
Example 2
A. 0.05 g of 3-aminophenol, 0.15 g of 3-fluorophenol and 0.1 g of hexamethylenetetramine were dissolved in 80 mL of distilled water, and stirred at room temperature for 1 hour until the solid sample was completely dissolved. This solution was then transferred to a 100 mL reaction kettle at 160%oAnd (3) reacting for 4 hours under the condition of C, naturally cooling to room temperature, washing the product to pH =7 with water, and drying to obtain a 3-aminophenol-3-fluorophenol-formaldehyde resin microsphere sample.
B. Heating the 3-aminophenol-3-fluorophenol-formaldehyde resin microsphere sample obtained in the step A from room temperature to 500 ℃ in a nitrogen atmosphereoAnd C, keeping the temperature for 4 hours. And naturally cooling to room temperature and collecting a sample.
C. Grinding and uniformly mixing the sample obtained in the step B and an activating agent KOH according to the mass ratio of 1/6, and then heating the mixture from room temperature to 500 ℃ in a nitrogen atmosphereoAnd C, keeping the temperature for 8 hours. And naturally cooling to room temperature, washing the solid sample by using a hydrochloric acid solution, washing the solid sample by using water until the pH is =7, and drying to obtain the amino phenolic resin based pyrrole nitrogen doped carbon electrode material.
Fig. 7 shows an N1 s X ray photoelectron spectroscopy spectrum (XPS) of the amino phenol resin-based pyrrole nitrogen-doped carbon electrode material prepared in this example, which indicates that the nitrogen-doped configuration is a single pyrrole state and the content reaches 3.07 at.%.
Constant-current charge and discharge tests are carried out on the amino phenolic resin based pyrrole nitrogen doped carbon electrode material prepared in the embodiment in a 1 mol/L sulfuric acid solution, and when the current density is 1A/g, the specific capacitance is 472F/g; when the current density is 20A/g, the specific capacitance is 329F/g respectively, and high capacity and good rate performance are shown.
Example 3
A. 0.025 g of 3-aminophenol, 0.175 g of 3-fluorophenol and 0.1 g of hexamethylenetetramine were dissolved in 80 mL of distilled water, and stirred at room temperature for 1 hour until the solid sample was completely dissolved. This solution was then transferred to a 100 mL reaction kettle at 160%oAnd (3) reacting for 4 hours under the condition of C, naturally cooling to room temperature, washing the product to pH =7 with water, and drying to obtain a 3-aminophenol-3-fluorophenol-formaldehyde resin microsphere sample.
B. Heating the 3-aminophenol-3-fluorophenol-formaldehyde resin microsphere sample obtained in the step A from room temperature to 500 ℃ in a nitrogen atmosphereoAnd C, keeping the temperature for 4 hours. And naturally cooling to room temperature and collecting a sample.
C. Grinding and uniformly mixing the sample obtained in the step B and an activating agent KOH according to the mass ratio of 1/6, and then heating the mixture from room temperature to 500 ℃ in a nitrogen atmosphereoAnd C, keeping the temperature for 8 hours. And naturally cooling to room temperature, washing the solid sample by using a hydrochloric acid solution, washing the solid sample by using water until the pH is =7, and drying to obtain the amino phenolic resin based pyrrole nitrogen doped carbon electrode material.
Fig. 8 shows an N1 s X ray photoelectron spectroscopy spectrum (XPS) of the amino phenol resin-based pyrrole nitrogen-doped carbon electrode material prepared in this example, which indicates that the nitrogen-doped configuration is a single pyrrole state and the content reaches 1.51 at.%.
Constant-current charge-discharge test is carried out on the amino phenolic resin based pyrrole nitrogen doped carbon electrode material prepared in the embodiment in 1 mol/L sulfuric acid solution, and when the current density is 1A/g, the specific capacitance is 437F/g; when the current density is 20A/g, the specific capacitance is 388F/g respectively, and high capacity and good rate performance are shown.
Example 4
A. 0.1 g of 3-aminophenol, 0.1 g of 3-chlorophenol and 0.1 g of hexamethylenetetramine were dissolved in 80 mL of distilled water at room temperatureThe solid sample was stirred for 1 hour until completely dissolved. This solution was then transferred to a 100 mL reaction kettle at 160%oAnd C, reacting for 4 hours, naturally cooling to room temperature, washing the product with water to pH =7, and drying to obtain a 3-aminophenol-3-chlorophenol-formaldehyde resin microsphere sample.
B. Heating the 3-aminophenol-3-chlorophenol-formaldehyde resin microsphere sample obtained in the step A from room temperature to 500 ℃ in a nitrogen atmosphereoAnd C, keeping the temperature for 4 hours. And naturally cooling to room temperature and collecting a sample.
C. Grinding and uniformly mixing the sample obtained in the step B and an activating agent KOH according to the mass ratio of 1:6, and then heating the mixture from room temperature to 500 ℃ in a nitrogen atmosphereoAnd C, keeping the temperature for 8 hours. And naturally cooling to room temperature, washing the solid sample by using a hydrochloric acid solution, washing the solid sample by using water until the pH is =7, and drying to obtain the amino phenolic resin based pyrrole nitrogen doped carbon electrode material.
Fig. 9 shows an N1 s X ray photoelectron spectroscopy spectrum (XPS) of the amino phenol resin-based pyrrole nitrogen-doped carbon electrode material prepared in this example, which indicates that the nitrogen-doped configuration is a single pyrrole state and the content reaches 2.29 at.%.
Example 5
A. 0.1 g of 3-aminophenol, 0.1 g of 3-bromophenol, and 0.1 g of hexamethylenetetramine were dissolved in 80 mL of distilled water, and stirred at room temperature for 1 hour until the solid sample was completely dissolved. This solution was then transferred to a 100 mL reaction kettle at 160%oAnd C, reacting for 4 hours, naturally cooling to room temperature, washing the product with water until the product is neutral, and drying to obtain a 3-aminophenol-3-bromophenol-formaldehyde resin microsphere sample.
B. Heating the 3-aminophenol-3-bromophenol-formaldehyde resin microsphere sample obtained in the step A from room temperature to 500 ℃ in a nitrogen atmosphereoAnd C, keeping the temperature for 4 hours. And naturally cooling to room temperature and collecting a sample.
C. Grinding and uniformly mixing the sample obtained in the step B and an activating agent KOH according to the mass ratio of 1:6, and then heating the mixture from room temperature to 500 ℃ in a nitrogen atmosphereoAnd C, keeping the temperature for 8 hours. Naturally cooling to room temperature, washing the solid sample with hydrochloric acid solution, and drying to obtain the amino phenolic resinThe lipid-based pyrrole nitrogen is doped with the carbon electrode material.
Fig. 10 shows an N1 s X ray photoelectron spectroscopy spectrum (XPS) of the amino phenol resin-based pyrrole nitrogen-doped carbon electrode material prepared in this example, which indicates that the nitrogen-doped configuration is a single pyrrole state and the content reaches 3.71 at.%.

Claims (7)

1. The preparation method of the amino phenolic resin based pyrrole nitrogen doped carbon electrode material is characterized by comprising the following steps: stirring 3-halophenol, 3-aminophenol and hexamethylenetetramine at normal temperature, polymerizing by a hydrothermal method to obtain halogenated phenolic resin, washing and drying, carbonizing at low temperature, activating potassium hydroxide at low temperature, washing with a hydrochloric acid solution, and washing and drying to obtain the halogenated phenolic resin;
the method comprises the following steps:
A. dissolving 3-aminophenol, 3-halophenol and hexamethylenetetramine in 80 mL of distilled water according to a certain proportion to form a mixed solution, stirring for a period of time at room temperature, transferring the mixed solution to a 100 mL reaction kettle, carrying out hydrothermal reaction to obtain a solid sample I, naturally cooling to room temperature, washing the solid sample I with water until the pH value is =7, and drying to obtain a 3-aminophenol-3-halophenol-formaldehyde resin microsphere sample;
B. heating the 3-aminophenol-3-halogenated phenol-formaldehyde resin microspheres obtained in the step A from room temperature in a nitrogen atmosphere, carrying out heat treatment for a period of time, and then naturally cooling to room temperature to collect a second sample;
C. grinding and uniformly mixing the sample II obtained in the step B and an activating agent KOH according to a certain proportion, then heating from room temperature in a nitrogen atmosphere, carrying out an activation reaction to obtain a solid sample III, naturally cooling to room temperature, washing the solid sample with a three-purpose hydrochloric acid solution and water to pH =7, and drying to obtain the amino phenolic resin based pyrrole nitrogen doped carbon electrode material;
wherein the heat treatment temperature in the step B is 450-520 ℃, and the heat treatment time is 4-5 hours;
and C, in the step C, the mass ratio of the sample II to the activating agent KOH is 1/6, the activation reaction temperature is 450-520 ℃, and the activation time is 8 hours.
2. The preparation method of the amino phenolic resin based pyrrole nitrogen doped carbon electrode material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step A, the mass ratio of the 3-aminophenol to the 3-halophenol is 1/1-1/7, the mass ratio of the sum of the 3-aminophenol and the 3-halophenol to the hexamethylenetetramine is 2/1, and the concentration of the hexamethylenetetramine in the mixed solution is 8.5-9.5 multiplied by 10-3mol L-1And stirring for 1-1.5 hours at room temperature, wherein the 3-halogenated phenol is 3-fluorophenol, 3-chlorophenol or 3-bromophenol.
3. The preparation method of the amino phenolic resin based pyrrole nitrogen doped carbon electrode material as claimed in claim 2, wherein the preparation method comprises the following steps: the concentration of the hexamethylenetetramine in the mixed solution in the step A is 8.92 multiplied by 10-3 mol L-1The mixture was stirred at room temperature for 1 hour.
4. The preparation method of the amino phenolic resin based pyrrole nitrogen doped carbon electrode material as claimed in claim 1, wherein the preparation method comprises the following steps: the hydrothermal reaction temperature in the step A is 150-170 ℃, and the hydrothermal time is 3.5-4.5 hours.
5. The preparation method of the amino phenolic resin based pyrrole nitrogen doped carbon electrode material as claimed in claim 4, wherein the preparation method comprises the following steps: the hydrothermal reaction temperature in the step A is 160 ℃, and the hydrothermal time is 4 hours.
6. The preparation method of the amino phenolic resin based pyrrole nitrogen doped carbon electrode material as claimed in claim 1, wherein the preparation method comprises the following steps: and the heat treatment temperature in the step B is 500 ℃, and the heat treatment time is 4 hours.
7. The preparation method of the amino phenolic resin based pyrrole nitrogen doped carbon electrode material as claimed in claim 1, wherein the preparation method comprises the following steps: the activation reaction temperature in the step C is 500 ℃.
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