CN111223685B - Preparation method of pyridine phenolic resin based nitrogen-doped carbon electrode material - Google Patents
Preparation method of pyridine phenolic resin based nitrogen-doped carbon electrode material Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 130
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 77
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 77
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000007772 electrode material Substances 0.000 title claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 31
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 230000004913 activation Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002077 nanosphere Substances 0.000 claims abstract description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 claims description 30
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000001994 activation Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- SJTBRFHBXDZMPS-UHFFFAOYSA-N 3-fluorophenol Chemical compound OC1=CC=CC(F)=C1 SJTBRFHBXDZMPS-UHFFFAOYSA-N 0.000 claims description 14
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 14
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- GCNTZFIIOFTKIY-UHFFFAOYSA-N 4-hydroxypyridine Chemical compound OC1=CC=NC=C1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- -1 3-fluorophenol-hydroxypyridine-formaldehyde Chemical compound 0.000 abstract 3
- 229920005989 resin Polymers 0.000 abstract 3
- 239000011347 resin Substances 0.000 abstract 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 3
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/48—Conductive polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a preparation method of a pyridine phenolic resin based nitrogen-doped carbon electrode material, which comprises the following steps: A. the method comprises the following steps of hydrothermal synthesis of 3-fluorophenol-hydroxypyridine-formaldehyde resin nanospheres, carbonization of 3-fluorophenol-hydroxypyridine-formaldehyde resin, and activation of carbonized 3-fluorophenol-hydroxypyridine-formaldehyde resin; meanwhile, the lower carbonization temperature and activation temperature enable the pyridine phenolic resin based nitrogen-doped carbon material to reserve more nitrogen-containing functional groups as pseudocapacitance active sites, and the pseudocapacitance material shows pseudocapacitance characteristics and high specific capacity when used as a supercapacitor electrode material.
Description
Technical Field
The invention relates to a preparation method of a pyridine phenolic resin based nitrogen-doped carbon electrode material, belonging to the technical field of carbon materials.
Background
As a novel energy storage device, the super capacitor is widely applied to the fields of electric automobiles, aerospace, national defense science and technology and the like which need rapid power conversion due to the advantages of high power density, high charging and discharging speed, long cycle life and the like. Electrode materials are currently the focus of research as key components of supercapacitors. Due to the advantages of good conductivity, high chemical stability, adjustable pore size, wide sources and the like, the carbon material becomes the most important electrode material of the supercapacitor. At present, carbon material precursors are mainly derived from natural raw materials and synthetic materials. The synthetic material has higher purity compared to natural raw materials containing various impurities, and the carbon material based on the synthetic material has higher chemical stability and shows longer service life. In the synthetic materials, the phenolic resin has high carbon forming rate, and the corresponding carbon material has low impurity content, excellent structural stability and aging resistance, and becomes one of the most potential electrode materials of the super capacitor.
However, the phenolic resin-based carbon material having high conductivity generally provides only an electric double layer capacitance, and the specific capacity thereof still remains to be improved. The increase of the specific capacity of the carbon material by providing pseudo-capacitance active sites for the carbon material through nitrogen atom doping becomes an important means for improving the electrode performance of the carbon material. Nitrogen atoms are doped into a carbon material structure in situ by taking nitrogen-containing phenolic resin as a precursor, so that the nitrogen elements can be uniformly distributed in the phenolic resin-based carbon material, and the key strategy for preparing the nitrogen-doped phenolic resin-based carbon material is realized. Generally, the nitrogen-doped phenolic resin-based carbon material prepared by the in-situ method at a low temperature can retain high nitrogen content to represent pseudo capacitance, but the multiplying power performance of the non-graphitizable phenolic resin is reduced due to insufficient conductivity under the low-temperature condition, so that the rapid charging and discharging capacity of the non-graphitizable phenolic resin is reduced; the nitrogen-doped phenolic resin-based carbon material prepared by the in-situ method at high temperature has higher conductivity, but the loss of nitrogen content is excessive, so that the pseudo capacitance of the material is reduced, and the total specific capacitance is further reduced. Therefore, it is still a great challenge to provide an effective strategy to develop a nitrogen-doped phenolic resin-based carbon material with good conductivity and high specific capacity.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a pyridine phenolic resin based nitrogen-doped carbon electrode material, so that the pyridine phenolic resin based carbon material shows good conductivity, and shows high rate capability, pseudo-capacitance characteristic and high specific capacity when used as a supercapacitor electrode material.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the pyridine phenolic resin based nitrogen-doped carbon electrode material comprises the steps of preparing hydroxypyridine, 3-fluorophenol and hexamethylenetetramine by a hydrothermal method to obtain pyridine phenolic resin, and then carrying out heat treatment and activation on the pyridine phenolic resin to obtain the pyridine phenolic resin based nitrogen-doped carbon material.
The technical scheme of the invention is further improved as follows: the preparation method comprises the following steps:
A. adding 3-fluorophenol, a hydroxypyridine monomer and hexamethylenetetramine into 80 mL of distilled water according to a certain proportion, completely dissolving to form a uniform solution, adding the uniform solution into a 100 mL reaction kettle, carrying out hydrothermal reaction to obtain a product I, washing the product with distilled water to pH =7, and drying under a certain condition to obtain a pyridine phenolic resin nanosphere sample;
B. putting the pyridine phenolic resin nanosphere sample in the step A into a tube furnace, and heating the sample to 500-800 ℃ from room temperature in a nitrogen atmosphereoC, carrying out heat treatment for a period of time, naturally cooling to room temperature, and collecting a product II;
C. and B, mixing the product II in the step B with potassium hydroxide according to a certain proportion, fully grinding, putting into a tubular furnace, heating from room temperature to a certain temperature in a nitrogen atmosphere for activation reaction, naturally cooling to room temperature, collecting a product III, washing the product III with a hydrochloric acid solution and distilled water in sequence until the pH value is =7, and then carrying out vacuum drying under a certain condition to obtain the pyridine phenolic resin based nitrogen-doped carbon material.
The technical scheme of the invention is further improved as follows: in the step A, the mass ratio of 3-fluorophenol to a hydroxypyridine monomer to hexamethylenetetramine is 1:0.85: 0.8-0.9, wherein the hydroxypyridine monomer is 2-hydroxypyridine, 3-hydroxypyridine or 4-hydroxypyridine, the concentration of the hydroxypyridine monomer is 0.009-0.015 mol/L, and the particle size of the pyridine phenolic resin nanosphere is 350-750 nm.
The technical scheme of the invention is further improved as follows: the mass ratio of the 3-fluorophenol to the hydroxypyridine monomer to the hexamethylenetetramine is 1:0.85:0.85, and the concentration of the hydroxypyridine monomer is 0.011 mol/L.
The technical scheme of the invention is further improved as follows: the temperature of the hydrothermal reaction in the step A is 170-190%oC, the time of the hydrothermal reaction is 23-25 hours, and the drying temperature is 50-70oAnd C, drying for 24-36 hours.
The technical scheme of the invention is further improved as follows: the temperature of the hydrothermal reaction in the step A is 180 DEGoC, the time of the hydrothermal reaction is 24 hours, and the drying temperature is 60 DEGoAnd C, drying for 24 hours. The mass ratio of the product II to the potassium hydroxide in the step C is 1: 5-7, and the temperature of the activation reaction is 500-600oC, activating for 7-9 hours, wherein the concentration of the hydrochloric acid solution is 0.5 mol/L, and the vacuum drying temperature is 110-120 DEGoAnd C, vacuum drying for 11-13 hours.
The technical scheme of the invention is further improved as follows: and the heat treatment time in the step B is 3-5 hours.
The technical scheme of the invention is further improved as follows: the heat treatment time in the step B is 4 hours.
The technical scheme of the invention is further improved as follows: the mass ratio of the product II to the potassium hydroxide in the step C is 1: 5-7, and the temperature of the activation reaction is 500-600oC, activating for 7-9 hours, wherein the concentration of the hydrochloric acid solution is 0.5 mol/L, and the vacuum drying temperature is 110-120 DEGoAnd C, vacuum drying for 11-13 hours.
The technical scheme of the invention is further improved as follows: the mass ratio of the product II to the potassium hydroxide in the step C is 1:6, and the temperature of the activation reaction is 500oC, the activation time is 8 hours, and the vacuum drying temperature is 120oAnd C, vacuum drying for 12 hours.
Due to the adoption of the technical scheme, the invention has the technical progress that:
the pyridine phenolic resin based nitrogen-doped carbon material obtained by the invention is subjected to electrochemical test, in a three-electrode system, a platinum mesh is taken as a current collector, a platinum sheet is taken as a counter electrode, a saturated calomel electrode is taken as a reference electrode, and the electrochemical test is carried out in a 1mol/L sulfuric acid solution, so that the pyridine phenolic resin based nitrogen-doped carbon material shows good electrochemical performance; introducing 3-fluorophenol into a polymerization process of hydroxypyridine and hexamethylenetetramine to generate fluoropyridine phenolic resin, wherein the fluoropyridine phenolic resin enables adjacent benzene rings to easily form a large conjugated structure by removing hydrogen fluoride micromolecules in the processes of carbonization and activation at a lower temperature, so that the pyridine phenolic resin-based carbon material shows good conductivity and shows high rate performance when used as a supercapacitor electrode material; meanwhile, the lower carbonization temperature and activation temperature enable the pyridine phenolic resin-based carbon material to reserve more nitrogen-containing functional groups as pseudocapacitance active sites, and the material shows pseudocapacitance characteristics and high specific capacity when used as a supercapacitor electrode material.
Drawings
FIG. 1 is a TEM image of a pyridine phenolic resin-based N-doped carbon electrode material prepared in example 1 of the present invention;
FIG. 2 is a cyclic voltammetry curve of a pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in example 1 of the present invention as a supercapacitor electrode at different sweep rates in a three-electrode system 1mol/L sulfuric acid solution;
FIG. 3 is a constant current charge and discharge curve of different current densities in a three-electrode system 1mol/L sulfuric acid solution by using the pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in example 1 of the present invention as a supercapacitor electrode;
FIG. 4 is the cycle life data of the pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in example 1 as a supercapacitor electrode under the condition of 10A/g current density in a three-electrode system 1mol/L sulfuric acid solution;
FIG. 5 is a TEM image of a pyridine phenolic resin-based N-doped carbon electrode material prepared in example 2 of the present invention;
FIG. 6 is a cyclic voltammetry curve of a pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in example 2 of the present invention as a supercapacitor electrode at different sweep rates in a three-electrode system 1mol/L sulfuric acid solution;
FIG. 7 is a constant current charge and discharge curve of different current densities in a three-electrode system 1mol/L sulfuric acid solution by using the pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in example 2 of the present invention as a supercapacitor electrode;
FIG. 8 is the cycle life data of the pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in example 2 of the present invention as a supercapacitor electrode under the condition of 10A/g current density in a three-electrode system 1mol/L sulfuric acid solution.
Detailed Description
The present invention will be described in further detail with reference to the following examples:
the preparation method of the pyridine phenolic resin based nitrogen-doped carbon electrode material comprises the steps of preparing hydroxypyridine, 3-fluorophenol and hexamethylenetetramine by a hydrothermal method to obtain pyridine phenolic resin, and then carrying out heat treatment and activation on the pyridine phenolic resin to obtain the pyridine phenolic resin based nitrogen-doped carbon material.
The preparation method comprises the following steps:
A. adding 3-fluorophenol, a hydroxypyridine monomer and hexamethylenetetramine into 80 mL of distilled water according to a certain proportion, completely dissolving to form a uniform solution, adding the uniform solution into a 100 mL reaction kettle, carrying out hydrothermal reaction to obtain a product I, washing the product with distilled water to pH =7, and drying under a certain condition to obtain a pyridine phenolic resin nanosphere sample;
B. putting the pyridine phenolic resin nanosphere sample in the step A into a tube furnace, and heating the sample to 500-800 ℃ from room temperature in a nitrogen atmosphereoC, carrying out heat treatment for a period of time, naturally cooling to room temperature, and collecting a product II;
C. and B, mixing the product II in the step B with potassium hydroxide according to a certain proportion, fully grinding, putting into a tubular furnace, heating from room temperature to a certain temperature in a nitrogen atmosphere for activation reaction, naturally cooling to room temperature, collecting a product III, washing the product III with a hydrochloric acid solution and distilled water in sequence until the pH value is =7, and then carrying out vacuum drying under a certain condition to obtain the pyridine phenolic resin based nitrogen-doped carbon material.
Wherein, in the step A, the mass ratio of the 3-fluorophenol to the hydroxypyridine monomer to the hexamethylenetetramine is 1:0.85: 0.8-0.9, preferably 1:0.85:0.85, the hydroxypyridine monomer is 2-hydroxypyridine, 3-hydroxypyridine or 4-hydroxypyridine, and the concentration of the hydroxypyridine monomer is 0.009~ 0.90.015 mol/L, preferably the concentration is 0.011 mol/L, and the particle diameter of the pyridine phenolic resin nanosphere is 350-750 nm. The temperature of the hydrothermal reaction is 170-190%oC, preferably at a temperature of 180 DEG CoC, the time of the hydrothermal reaction is 23-25 hours, the preferable time is 24 hours, and the drying temperature is 50-70oC, preferably drying at 60 deg.CoAnd C, drying for 24-36 hours, preferably for 24 hours.
The heat treatment time in step B is 4 hours, and the heat treatment time is preferably 4 hours. The mass ratio of the product II to the potassium hydroxide in the step C is 1: 5-7, the preferred mass ratio is 1:6, and the temperature of the activation reaction is 500-600oC, preferably the temperature of the activation reaction is 500oC, activating for 7-9 hours, preferably for 8 hours, wherein the concentration of the hydrochloric acid solution is 0.5 mol/L, and the vacuum drying temperature is 110-120 DEG CoC, preferably the vacuum drying temperature is 120 DEG CoAnd C, vacuum drying for 11-13 hours, preferably for 12 hours.
Example 1
A. Adding 3-fluorophenol, a hydroxypyridine monomer and hexamethylenetetramine into 80 mL of distilled water according to the mass ratio of 1:0.85:0.85 to be completely dissolved to form a uniform solution, wherein the concentration of the hydroxypyridine monomer in the uniform solution is 0.011 mol/L, then adding the mixture into a 100 mL reaction kettle, and reacting in a 180 mL reaction kettleoHydrothermal reaction for 24 hours under C, the product was washed with distilled water to pH =7 at 60oDrying for 24 hours to obtain a sample of the pyridine phenolic resin nanosphere;
B. putting the pyridine phenolic resin nanosphere sample in the step A into a tube furnace, and heating the sample from room temperature to 800 ℃ in a nitrogen atmosphereoC, performing heat treatment for 4 hours, naturally cooling to room temperature, and collecting a product II;
C. weighing the product II obtained in the step B and potassium hydroxide according to the mass ratio of 1:6, grinding, fully mixing, putting into a tube furnace, and heating to 500 ℃ from room temperature in a nitrogen atmosphereoC, activating for 8 hours, naturally cooling to room temperature, and collecting a product III. The collected product was washed with three-way 0.5 mol/L hydrochloric acid solution and distilled water in order to pH =7, and then at 120oC after vacuum drying for 12 hoursAnd obtaining the pyridine phenolic resin based nitrogen-doped carbon material.
Fig. 1 is a transmission electron micrograph of the pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in this example. The figure shows that the nitrogen-doped carbon material is of a spherical structure, and the particle size is 350-750 nm.
Fig. 2 is a cyclic voltammetry curve of the pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in this example as a supercapacitor electrode in a three-electrode system 1mol/L sulfuric acid solution, and symmetric redox peaks show obvious pseudocapacitance characteristics and electrochemical reversibility.
Fig. 3 is a constant current charge and discharge curve of the pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in the embodiment as a supercapacitor electrode in a 1mol/L sulfuric acid solution of a three-electrode system, the current density is 20-1A/g, the specific capacitance reaches 315-376F/g, and the high capacity and good rate performance are shown.
Fig. 4 is cycle life data of the pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in this embodiment as a supercapacitor electrode in a three-electrode system 1mol/L sulfuric acid solution at a current density of 10A/g, the specific capacity after 10,000 cycles is 330F/g, the capacity retention rate is close to 105%, and good cycle stability is shown.
Example 2
A. Adding 3-fluorophenol, a hydroxypyridine monomer and hexamethylenetetramine into 80 mL of distilled water according to the mass ratio of 1:0.85:0.85 to be completely dissolved to form a uniform solution, wherein the concentration of the hydroxypyridine monomer in the solution is 0.011 mol/L, then adding the solution into a 100 mL reaction kettle, and reacting the solution in a 180 mL reaction kettleoHydrothermal reaction for 24 hours under C, the product was washed with distilled water to pH =7 at 60oDrying for 24 hours to obtain a sample of the pyridine phenolic resin nanosphere;
B. putting the pyridine phenolic resin nanosphere sample in the step A into a tube furnace, and heating the sample from room temperature to 500 ℃ in a nitrogen atmosphereoC, performing heat treatment for 4 hours, naturally cooling to room temperature, and collecting a product II;
C. weighing the product II obtained in the step B and potassium hydroxide according to the mass ratio of 1:6, grinding, fully mixing, putting into a tube furnace,heating from room temperature to 500 deg.C in nitrogen atmosphereoC, activating for 8 hours, naturally cooling to room temperature, and collecting a product III. The collected product was washed with three-way 0.5 mol/L hydrochloric acid solution and distilled water in order to pH =7, and then at 120oAnd C, drying for 12 hours in vacuum to obtain the pyridine phenolic resin based nitrogen-doped carbon material.
Fig. 5 is a transmission electron micrograph of the pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in the embodiment. The figure shows that the nitrogen-doped carbon material is of a spherical structure, and the particle size is 350-750 nm.
Fig. 6 is a cyclic voltammetry curve of the pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in this example as a supercapacitor electrode in a three-electrode system 1mol/L sulfuric acid solution, and symmetric redox peaks show pseudocapacitance characteristics and electrochemical reversibility.
Fig. 7 is a constant current charge and discharge curve of the pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in the embodiment as a supercapacitor electrode in a 1mol/L sulfuric acid solution of a three-electrode system, the current density is 20-1A/g, the specific capacitance reaches 204-301F/g, and the material shows higher capacity and better rate performance.
Fig. 8 is cycle life data of the pyridine phenolic resin based nitrogen-doped carbon electrode material prepared in this embodiment as a supercapacitor electrode in a three-electrode system 1mol/L sulfuric acid solution at a current density of 10A/g, the specific capacity after 10,000 cycles is 211F/g, the capacity retention rate is close to 98%, and good cycle stability is shown.
Claims (9)
1. The preparation method of the pyridine phenolic resin based nitrogen-doped carbon electrode material is characterized by comprising the following steps of: preparing hydroxypyridine, 3-fluorophenol and hexamethylenetetramine by a hydrothermal method to obtain pyridine phenolic resin, and then performing heat treatment and activation processes on the pyridine phenolic resin to obtain a pyridine phenolic resin based nitrogen-doped carbon material;
the preparation method comprises the following steps:
A. adding 3-fluorophenol, a hydroxypyridine monomer and hexamethylenetetramine into 80 mL of distilled water according to a certain proportion, completely dissolving to form a uniform solution, adding the uniform solution into a 100 mL reaction kettle, carrying out hydrothermal reaction to obtain a product I, washing the product with distilled water to pH =7, and drying under a certain condition to obtain a pyridine phenolic resin nanosphere sample;
B. putting the pyridine phenolic resin nanosphere sample in the step A into a tube furnace, and heating the sample to 500-800 ℃ from room temperature in a nitrogen atmosphereoC, carrying out heat treatment for a period of time, naturally cooling to room temperature, and collecting a product II;
C. and B, mixing the product II in the step B with potassium hydroxide according to a certain proportion, fully grinding, putting into a tubular furnace, heating from room temperature to a certain temperature in a nitrogen atmosphere for activation reaction, naturally cooling to room temperature, collecting a product III, washing the product III with a hydrochloric acid solution and distilled water in sequence until the pH value is =7, and then carrying out vacuum drying under a certain condition to obtain the pyridine phenolic resin based nitrogen-doped carbon material.
2. The method for preparing the pyridine phenolic resin based nitrogen-doped carbon electrode material according to claim 1, which is characterized by comprising the following steps: in the step A, the mass ratio of 3-fluorophenol to a hydroxypyridine monomer to hexamethylenetetramine is 1:0.85: 0.8-0.9, wherein the hydroxypyridine monomer is 2-hydroxypyridine, 3-hydroxypyridine or 4-hydroxypyridine, the concentration of the hydroxypyridine monomer is 0.009-0.015 mol/L, and the particle size of the pyridine phenolic resin nanosphere is 350-750 nm.
3. The method for preparing the pyridine phenolic resin based nitrogen-doped carbon electrode material according to claim 2, which is characterized by comprising the following steps: the mass ratio of the 3-fluorophenol to the hydroxypyridine monomer to the hexamethylenetetramine is 1:0.85:0.85, and the concentration of the hydroxypyridine monomer is 0.011 mol/L.
4. The method for preparing the pyridine phenolic resin based nitrogen-doped carbon electrode material according to claim 1, which is characterized by comprising the following steps: the temperature of the hydrothermal reaction in the step A is 170-190%oC, the time of the hydrothermal reaction is 23-25 hours, and the drying temperature is 50-70oAnd C, drying for 24-36 hours.
5. The method for preparing the pyridine phenolic resin based nitrogen-doped carbon electrode material according to claim 4, wherein the method comprises the following steps: the temperature of the hydrothermal reaction in the step A is 180 DEGoC, the time of the hydrothermal reaction is 24 hours, and the drying temperature is 60 DEGoAnd C, drying for 24 hours.
6. The method for preparing the pyridine phenolic resin based nitrogen-doped carbon electrode material according to claim 1, which is characterized by comprising the following steps: and the heat treatment time in the step B is 3-5 hours.
7. The method for preparing the pyridine phenolic resin based nitrogen-doped carbon electrode material according to claim 6, wherein the method comprises the following steps: the heat treatment time in the step B is 4 hours.
8. The method for preparing the pyridine phenolic resin based nitrogen-doped carbon electrode material according to claim 1, which is characterized by comprising the following steps: the mass ratio of the product II to the potassium hydroxide in the step C is 1: 5-7, and the temperature of the activation reaction is 500-600oC, activating for 7-9 hours, wherein the concentration of the hydrochloric acid solution is 0.5 mol/L, and the vacuum drying temperature is 110-120 DEGoAnd C, vacuum drying for 11-13 hours.
9. The method for preparing the pyridine phenolic resin based nitrogen-doped carbon electrode material according to claim 8, wherein the method comprises the following steps: the mass ratio of the product II to the potassium hydroxide in the step C is 1:6, and the temperature of the activation reaction is 500oC, the activation time is 8 hours, and the vacuum drying temperature is 120oAnd C, vacuum drying for 12 hours.
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| CN106629650A (en) * | 2016-09-23 | 2017-05-10 | 武汉理工大学 | Method for preparing monodisperse phenolic resin microspheres and porous carbon microspheres in macroscopic quantity |
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