CN115240986B - Nitrogen-oxygen co-doped carbon electrode material and preparation method thereof - Google Patents
Nitrogen-oxygen co-doped carbon electrode material and preparation method thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 48
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004005 microsphere Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- VTSFNCCQCOEPKF-UHFFFAOYSA-N 3-amino-1h-pyridin-2-one Chemical compound NC1=CC=CN=C1O VTSFNCCQCOEPKF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 13
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 13
- 230000004913 activation Effects 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003990 capacitor Substances 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000001994 activation Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- OIIBRAGQGFLUFI-UHFFFAOYSA-N 3-amino-1h-pyridin-4-one Chemical compound NC1=CNC=CC1=O OIIBRAGQGFLUFI-UHFFFAOYSA-N 0.000 claims description 5
- SJTBRFHBXDZMPS-UHFFFAOYSA-N 3-fluorophenol Chemical compound OC1=CC=CC(F)=C1 SJTBRFHBXDZMPS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- MNOJRWOWILAHAV-UHFFFAOYSA-N 3-bromophenol Chemical compound OC1=CC=CC(Br)=C1 MNOJRWOWILAHAV-UHFFFAOYSA-N 0.000 claims description 3
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 claims description 3
- GDOIKKMNCIMDAO-UHFFFAOYSA-N 5-amino-1h-pyridin-2-one Chemical compound NC1=CC=C(O)N=C1 GDOIKKMNCIMDAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000002989 phenols Chemical class 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 15
- 125000005842 heteroatom Chemical group 0.000 abstract description 10
- 238000003763 carbonization Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005695 dehalogenation reaction Methods 0.000 abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- 230000021615 conjugation Effects 0.000 abstract description 4
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009396 hybridization Methods 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000012153 distilled water Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
-
- 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
- H01G11/32—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, 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
-
- 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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- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a nitrogen-oxygen co-doped carbon electrode materialThe material and the preparation method thereof belong to the technical field of electrochemical super capacitors, and the material is prepared by mixing amino hydroxypyridine, 3-halophenol and hexamethylenetetramine at room temperature, polymerizing by a hydrothermal method to obtain halogenated resin microspheres rich in nitrogen and oxygen elements, performing low-temperature dehalogenation carbonization and activating with KOH. The low-temperature dehalogenation carbonization is beneficial to improving the conjugation degree of the aromatic ring; the low-temperature KOH is activated, a large amount of hydroquinone hydroxyl/quinone carbonyl with pseudocapacitance activity is introduced, and the nitrogen-containing functional group is converted into pyrrole nitrogen with pseudocapacitance activity, so that the doping amount of hetero atoms with pseudocapacitance activity is effectively increased; at the same time, low temperature KOH activation promotes sp 3 Hybridization of carbon atoms to sp 2 The conversion of the hybridized carbon atoms improves the conjugation degree and conductivity and the electrochemical multiplying power performance. When the nitrogen-oxygen co-doped carbon material is used as an electrode material of the super capacitor, the nitrogen-oxygen co-doped carbon material has high capacity and good rate capability and stability.
Description
Technical Field
The invention relates to the technical field of electrochemical supercapacitors, in particular to a nitrogen-oxygen co-doped carbon electrode material and a preparation method thereof.
Background
The super capacitor is a novel energy storage device which is widely focused by people, and has the characteristics of high power density, long cycle life, good safety and the like. The performance of supercapacitors depends mainly on the electrode material. The carbon material is a supercapacitor electrode material widely used at present, and has the advantages of good conductivity, stable physical and chemical properties, low cost, easy obtainment and the like. In general, the realization of excellent electrochemical properties of carbon materials depends on two main factors: high conductivity and excellent surface pore structure (New Journal of Chemistry,2019, 43, 15892-15898), but for pure carbon materials, the energy density is low when used for supercapacitor electrode materials, and the actual requirements cannot be met, so in order to further improve the electrochemical performance of the carbon materials, heteroatom doping is an effective means, especially doping of nitrogen atoms can change the surface conjugated structure and electron distribution of the carbon materials, thereby improving wettability (Electrochimica Acta 294 (2019) 183-191;Advanced Science 2017,1600408). At the same time, the presence of nitrogen-and oxygen-containing functional groups can provide additional pseudocapacitance by redox reactions with electrolyte ions, thereby enhancing energy storage capacity (Journal of Materials Chemistry,2012,22,14076).
Polymers are widely used as precursors for carbon materials due to their advantages of abundant sources, simple synthesis, uniform doping of heteroatoms, etc., for example, phenolic resins are favored by a large number of researchers because of their high carbon residue. However, in the existing method, when phenolic resin is subjected to high-temperature heat treatment, the obtained carbon material has high graphitization degree and good conductivity, but a large amount of hetero atoms are lost; although the low-temperature heat treatment can retain more hetero atoms, the graphitization degree is not high enough, the conductivity is poor, the electrochemical activity is low, and the electrode material is difficult to use. Therefore, how to balance the relationship between high heteroatom doping levels and conductivity remains an important challenge in developing high performance heteroatom doped carbon electrode materials.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a nitrogen-oxygen co-doped carbon electrode material, which is developed under the low-temperature heat treatment condition and has high heteroatom doping amount and good conductivity.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a nitrogen-oxygen co-doped carbon electrode material, which is prepared by mixing amino hydroxypyridine, 3-halophenol and hexamethylenetetramine, preparing resin microspheres by hydrothermal polymerization, performing low-temperature dehalogenation carbonization and performing low-temperature KOH activation.
The invention also provides a preparation method of the nitrogen-oxygen co-doped carbon electrode material, which comprises the following steps:
(1) Dissolving amino hydroxypyridine, 3-halophenol and hexamethylenetetramine in water, and stirring to form a mixed solution;
(2) Transferring the mixed solution into a reaction kettle for hydrothermal reaction, centrifuging the solid product, alternately cleaning with water and ethanol, and drying to obtain halogenated resin microspheres rich in nitrogen and oxygen elements;
(3) Carbonizing the resin microspheres through heat treatment in nitrogen atmosphere, and cooling to obtain a black sample;
(4) And grinding and mixing the black sample with KOH uniformly, activating in nitrogen atmosphere, cooling, washing off the residual KOH in the solid product by using hydrochloric acid solution, washing with water to be neutral, and vacuum drying to obtain the nitrogen-oxygen co-doped carbon electrode material.
Preferably, in the step (1), the molar ratio of the amino hydroxypyridine to the 3-halophenol to the hexamethylenetetramine is 1:1:0.86-1:1:1, the concentration of the amino hydroxypyridine is 0.0125mol/L, the amino hydroxypyridine is selected from one of 3-amino-4-hydroxypyridine and 5-amino-2-hydroxypyridine, and the 3-halophenol is selected from one of 3-fluorophenol, 3-chlorophenol and 3-bromophenol.
Preferably, the hydrothermal temperature in the step (2) is 170-190 ℃ and the hydrothermal time is 22-26 h.
Preferably, the hydrothermal temperature in the step (2) is 180 ℃ and the hydrothermal time is 24 hours.
Preferably, the heat treatment temperature in the step (3) is 475-525 ℃, and the heat treatment time is 3-5 h.
Preferably, the heat treatment time in step (3) is 4 hours.
Preferably, in the step (4), the mass ratio of the black sample to KOH is 1:5-1:7, the activation temperature is 475-525 ℃, the activation time is 7-9 h, the vacuum drying temperature is 110-130 ℃, and the drying time is 11-13 h.
Preferably, in the step (4), the mass ratio of the black sample to KOH is 1:6, the activation time is 8 hours, the vacuum drying temperature is 120 ℃, and the drying time is 12 hours.
The invention also provides application of the nitrogen-oxygen co-doped carbon electrode material prepared by the preparation method in a supercapacitor. Compared with the prior art, the invention has the advantages that:
the preparation method takes amino hydroxypyridine, 3-halophenol and hexamethylenetetramine as precursors, obtains halogenated resin microspheres rich in nitrogen and oxygen elements through hydrothermal polymerization, and obtains the nitrogen and oxygen co-doped carbon material through low-temperature dehalogenation carbonization and low-temperature KOH activation. Wherein, the low-temperature defluorination and carbonization are beneficial to improving the conjugation degree of the aromatic ring; the low-temperature KOH activation process introduces a large amount of hydroquinone hydroxyl/quinone carbonyl with pseudocapacitance activity, and simultaneously the nitrogen-containing functional group is converted into pyrrole nitrogen with pseudocapacitance activity, so that the doping amount of hetero atoms with pseudocapacitance activity is effectively improved; at the same time, low temperature KOH activation promotes sp 3 Hybridization of carbon atoms to sp 2 The conversion of the hybridized carbon atoms improves the conjugation degree and the conductivity, thereby improving the electrochemical multiplying power performance. When the nitrogen-oxygen co-doped carbon material is used as an electrode material of a super capacitor, the nitrogen-oxygen co-doped carbon material prepared by the invention has high capacity and good multiplying power performance and stability.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention, wherein:
FIG. 1 is an X-ray diffraction chart of a nitrogen-oxygen co-doped carbon electrode material in example 1 of the present invention;
FIG. 2 is a Raman spectrum of the nitrogen-oxygen co-doped carbon electrode material in example 1 of the present invention;
FIGS. 3 a-3 b are X-ray photoelectron spectroscopy (XPS) diagrams of the nitrogen-oxygen co-doped carbon electrode material of example 1 of the present invention; FIG. 4 is a constant current charge-discharge curve of the nitrogen-oxygen co-doped carbon electrode material of example 1 of the present invention in a three-electrode system;
FIG. 5 is a cyclic voltammogram of a three electrode system of a nitrogen-oxygen co-doped carbon electrode material of example 1 of the present invention;
fig. 6 is an electrochemical cycling profile of the nitrogen-oxygen co-doped carbon electrode material of example 1 of the present invention.
FIG. 7 is a constant current charge-discharge curve of the nitrogen-oxygen co-doped carbon electrode material of example 2 of the present invention in a three-electrode system;
FIG. 8 is a cyclic voltammogram of a nitrogen-oxygen co-doped carbon electrode material in example 2 of the present invention under a three electrode system;
fig. 9 is an electrochemical cycle performance of the nitrogen-oxygen co-doped carbon electrode material of example 2 of the present invention.
Detailed Description
The following disclosure provides many different embodiments, or examples, for implementing different features of the invention. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, which are for the purpose of brevity and clarity, and which do not themselves indicate the relationship between the various embodiments and/or arrangements discussed.
A nitrogen-oxygen co-doped carbon electrode material is prepared by stirring amino hydroxypyridine, 3-halophenol and hexamethylenetetramine at normal temperature, polymerizing by a hydrothermal method to obtain halogenated resin microspheres rich in nitrogen-oxygen elements, and performing low-temperature dehalogenation carbonization and low-temperature KOH activation.
The preparation method of the nitrogen-oxygen co-doped carbon electrode material comprises the following steps:
(1) Dissolving amino hydroxypyridine, 3-halophenol and hexamethylenetetramine in a molar ratio of 1:1:0.86-1:1:1 in 80mL of distilled water (or ultrapure water), and stirring at room temperature to form a mixed solution;
(2) Transferring the stirred mixed solution into a 100mL reaction kettle for hydrothermal reaction, wherein the hydrothermal temperature is 170-190 ℃ (preferably 180 ℃), and the hydrothermal time is 22-26 hours (preferably 24 hours); centrifuging the solid product, alternately cleaning with distilled water and ethanol, and drying to obtain halogenated resin microspheres rich in nitrogen and oxygen elements;
(3) Carrying out heat treatment on the resin microspheres prepared in the step (2) in nitrogen atmosphere at 475-525 ℃ for 3-5 h (preferably 4 h), and then naturally cooling to room temperature to obtain a black sample;
(4) And (3) mixing the black sample prepared in the step (3) with KOH in a mass ratio of 1:5 to 1:7 (preferably 1:6), activating in nitrogen atmosphere at 475-525 ℃ for 7-9 h (preferably 8 h), naturally cooling to room temperature, washing off the residual KOH in the solid product by using 0.46mol/L hydrochloric acid solution, washing to pH=7 by using distilled water (or ultrapure water), and vacuum drying at 110-130 ℃ (preferably 120 ℃) for 11-13 h (preferably 12 h) to obtain the nitrogen-oxygen co-doped carbon electrode material.
Example 1
0.11g of 3-amino-4-hydroxypyridine, 0.112g of 3-fluorophenol, and 0.12g of hexamethylenetetramine were weighed out and dissolved in 80mL of distilled water, and stirred at room temperature to form a mixed solution. And transferring the mixed solution into a 100mL reaction kettle, reacting for 24 hours at 180 ℃, centrifuging the product, and alternately cleaning and drying distilled water and ethanol to obtain the fluorine-substituted resin microsphere rich in nitrogen and oxygen.
And heating the fluoro-resin microsphere to 475 ℃ from room temperature under the protection of nitrogen, and preserving heat for 4 hours. And naturally cooling to room temperature, grinding and uniformly mixing the carbonized sample and KOH according to the mass ratio of 1:6, heating the mixed sample to 475 ℃ from room temperature in nitrogen atmosphere, and preserving heat for 8 hours. And naturally cooling to room temperature, washing off the residual KOH in the solid product by using 0.46mol/L hydrochloric acid solution, washing with distilled water to pH=7, and vacuum drying at 120 ℃ for 12 hours to obtain the nitrogen-oxygen co-doped carbon electrode material.
The results of the X-ray diffraction pattern (XRD) test of the nitrogen-oxygen co-doped carbon material prepared in example 1 are shown in fig. 1, where 24.6 ° corresponds to the (002) plane of graphitic carbon and 43.2 ° corresponds to the (100)/(101) plane of graphitic carbon.
The results of the raman test of the nitrogen-oxygen co-doped carbon electrode material prepared in example 1 are shown in fig. 2, at 1356 and 1584cm -1 An absorption peak appears at each position, and the absorption peaks correspond to the D band and the G band of the carbon material respectively, which shows that the phenolic resin finally realizes carbonization.
The results of X-ray photoelectron spectroscopy (XPS) test of the nitrogen-oxygen co-doped carbon material prepared in the example 1 are shown in fig. 3a and 3b, wherein nitrogen atoms exist in the form of pyrrole nitrogen and pyridine nitrogen, oxygen atoms exist in the form of hydroxyl oxygen and carbonyl oxygen, and the heteroatom content is up to 20.5%.
When the nitrogen-oxygen co-doped carbon electrode material prepared in example 1 is applied as an electrode material of a supercapacitor, electrochemical performance tests are carried out on the nitrogen-oxygen co-doped carbon electrode material based on a three-electrode system in a 1mol/L sulfuric acid solution, and the electrochemical performance tests are as follows:
(1) the constant current charge and discharge test results are shown in FIG. 4, and the specific capacitance is 486.4F/g when the current density is 1A/g; the specific capacitance was 319.7F/g when the current density was 20A/g, indicating that the nitrogen-oxygen co-doped carbon electrode material prepared in example 1 exhibited good rate capability when applied to a supercapacitor.
(2) The cyclic voltammetry test results are shown in figure 5, and the cyclic voltammetry curves have obvious symmetrical oxidation-reduction potentials at different scanning rates, and have good pseudocapacitance behaviors and electrochemical reversibility.
(3) The results of the cycle stability test are shown in FIG. 6, and the electrochemical cycle stability is good when the capacity retention rate reaches 91.34% after 1 ten thousand cycles at a current density of 10A/g.
Example 2
0.11g of 5-amino-2-hydroxypyridine, 0.112g of 3-fluorophenol, and 0.14g of hexamethylenetetramine were weighed out and dissolved in 80mL of distilled water, and stirred at room temperature to form a mixed solution. And transferring the solution into a 100mL reaction kettle, reacting for 24 hours at 180 ℃, centrifuging the product, and alternately cleaning and drying distilled water and ethanol to obtain the fluorine-substituted resin microsphere rich in nitrogen and oxygen.
And heating the fluoro-resin microsphere to 500 ℃ from room temperature under the protection of nitrogen, and preserving heat for 4 hours. And naturally cooling to room temperature, grinding and uniformly mixing the carbonized sample and KOH according to the mass ratio of 1:6, heating the mixed sample to 500 ℃ from room temperature in nitrogen atmosphere, and preserving heat for 8 hours. Naturally cooling to room temperature, washing off the residual KOH in the solid product by using 0.46mol/L hydrochloric acid solution, washing with distilled water to pH=7, and vacuum drying at 120 ℃ for 12 hours to obtain the nitrogen-oxygen co-doped carbon electrode material.
When the nitrogen-oxygen co-doped carbon electrode material prepared in example 2 is applied as an electrode material of a supercapacitor, electrochemical performance tests are carried out on the nitrogen-oxygen co-doped carbon electrode material based on a three-electrode system in a 1mol/L sulfuric acid solution, and the electrochemical performance tests are as follows:
(1) the constant current charge and discharge test results are shown in FIG. 7, and the specific capacitance is 405.5F/g when the current density is 1A/g; when the current density was 20A/g, the specific capacitance was 243.1F/g, showing good rate capability.
(2) The result of the cyclic voltammetry test is shown in figure 8, and the cyclic voltammetry curve has obvious symmetrical oxidation-reduction potential under different scanning rates, and has good pseudocapacitance behavior and electrochemical reversibility.
(3) The results of the cycle stability test are shown in FIG. 9, and the capacity retention rate reaches 92.6% after 1 ten thousand cycles at a current density of 10A/g, showing good electrochemical cycle stability.
Example 3
0.11g of 3-amino-4-hydroxypyridine, 0.129g of 3-chlorophenol, and 0.13g of hexamethylenetetramine were weighed out and dissolved in 80mL of distilled water, and stirred at room temperature to form a mixed solution. Then transferring the solution into a 100mL reaction kettle, reacting for 26 hours at 170 ℃, centrifuging the product, alternately cleaning with distilled water and ethanol, and drying to obtain the chlorine substituted resin microsphere rich in nitrogen and oxygen.
And heating the chlorinated resin microsphere to 500 ℃ from room temperature under the protection of nitrogen, and preserving heat for 5 hours. And naturally cooling to room temperature, grinding and uniformly mixing the carbonized sample and KOH according to the mass ratio of 1:7, heating the mixed sample to 500 ℃ from room temperature in nitrogen atmosphere, and preserving heat for 9 hours. Naturally cooling to room temperature, washing off the residual KOH in the solid product by using 0.46mol/L hydrochloric acid solution, washing with distilled water to pH=7, and vacuum drying at 130 ℃ for 11 hours to obtain the nitrogen-oxygen co-doped carbon electrode material.
Example 4
0.11g of 3-amino-4-hydroxypyridine, 0.173g of 3-bromophenol, and 0.12g of hexamethylenetetramine were weighed out and dissolved in 80mL of distilled water, and stirred at room temperature to form a mixed solution. And transferring the mixed solution into a 100mL reaction kettle, reacting for 22 hours at 190 ℃, centrifuging the product, alternately cleaning distilled water and ethanol, and drying to obtain the brominated resin microspheres rich in nitrogen and oxygen.
And heating the brominated resin microspheres from room temperature to 525 ℃ under the protection of nitrogen, and preserving heat for 3 hours. And naturally cooling to room temperature, grinding and uniformly mixing the carbonized sample and KOH according to the mass ratio of 1:5, heating the mixed sample to 525 ℃ from room temperature in nitrogen atmosphere, and preserving heat for 7h. And naturally cooling to room temperature, washing off the residual KOH in the solid product by using 0.46mol/L hydrochloric acid solution, washing with distilled water to pH=7, and vacuum drying at 110 ℃ for 13 hours to obtain the nitrogen-oxygen co-doped carbon electrode material.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention herein. This invention is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It is to be understood that the invention is not limited to the precise arrangements and instrumentalities shown in the drawings, which have been described above, and that various modifications and changes may be effected without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (8)
1. The preparation method of the nitrogen-oxygen co-doped carbon electrode material is characterized by comprising the following steps of:
(1) Dissolving amino hydroxypyridine, 3-halophenol and hexamethylenetetramine in water, and stirring to form a mixed solution; the molar ratio of the amino hydroxypyridine to the 3-halogenated phenol to the hexamethylenetetramine is 1:1:0.86-1:1:1;
(2) Transferring the mixed solution into a reaction kettle for hydrothermal reaction, centrifuging a solid product, alternately cleaning with water and ethanol, and drying to obtain halogenated resin microspheres rich in nitrogen and oxygen elements; the hydrothermal temperature is 170-190 ℃, and the hydrothermal time is 22-26 hours;
(3) Carbonizing the resin microspheres through heat treatment in nitrogen atmosphere, and cooling to obtain a black sample; the heat treatment temperature is 475-525 ℃, and the heat treatment time is 3-5 h;
(4) Grinding and mixing the black sample with KOH uniformly, activating in nitrogen atmosphere, cooling, washing the residual KOH in the solid product by using hydrochloric acid solution, washing to be neutral by using water, and vacuum drying to obtain the nitrogen-oxygen co-doped carbon electrode material; the mass ratio of the black sample to the KOH is 1:5 to 1:7, the activation temperature is 475-525 ℃, and the activation time is 7-9 h.
2. The method for producing a nitrogen-oxygen co-doped carbon electrode material according to claim 1, wherein the concentration of the amino hydroxypyridine in the step (1) is 0.0125mol/L, the amino hydroxypyridine is one selected from 3-amino-4-hydroxypyridine and 5-amino-2-hydroxypyridine, and the 3-halophenol is one selected from 3-fluorophenol, 3-chlorophenol and 3-bromophenol.
3. The method for preparing a nitrogen-oxygen co-doped carbon electrode material according to claim 1, wherein the hydrothermal temperature in the step (2) is 180 ℃ and the hydrothermal time is 24 hours.
4. The method for producing a nitrogen-oxygen co-doped carbon electrode material according to claim 1, wherein the heat treatment time in step (3) is 4 hours.
5. The method for preparing a nitrogen-oxygen co-doped carbon electrode material according to claim 1, wherein the vacuum drying temperature in the step (4) is 110-130 ℃, and the vacuum drying time is 11-13 h.
6. The method for preparing a nitrogen-oxygen co-doped carbon electrode material according to claim 5, wherein the mass ratio of the black sample to the KOH in the step (4) is 1:6, the activation time is 8h, the vacuum drying temperature is 120 ℃, and the vacuum drying time is 12h.
7. The nitrogen-oxygen co-doped carbon electrode material prepared by the preparation method of any one of claims 1 to 6.
8. The application of the nitrogen-oxygen co-doped carbon electrode material prepared by the preparation method of any one of claims 1-6 in super capacitors.
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