CN115072720B - Oxygen-doped porous carbon electrode material with high pseudocapacitance activity and preparation method thereof - Google Patents
Oxygen-doped porous carbon electrode material with high pseudocapacitance activity and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 239000007772 electrode material Substances 0.000 title claims abstract description 50
- 230000000694 effects Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001301 oxygen Substances 0.000 claims abstract description 32
- 239000003518 caustics Substances 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 238000001994 activation Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 53
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000003990 capacitor Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract description 2
- 239000004005 microsphere Substances 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000000524 functional group Chemical group 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
- 238000003795 desorption Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- 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
-
- 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
- H01G11/84—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
Abstract
The invention discloses an oxygen doped porous carbon electrode material with high pseudo-capacitance activity and a preparation method thereof, and belongs to the technical field of electrochemical supercapacitors. The invention generates sp in the caustic alkali activation process 3 Sp in C direction 2 The conductivity of the material is improved by the conversion of the C structure; meanwhile, the etching and activating effects of caustic alkali convert the carbon microsphere into a porous sheet-shaped carbon material, the specific surface area is increased, balance among good conductivity, porosity and high oxygen doping amount is realized, electron transfer and ion transmission are facilitated, and when the oxygen-doped porous carbon material is applied to the testing of the supercapacitor electrode material, the oxygen-doped porous carbon material shows higher pseudocapacitance performance.
Description
Technical Field
The invention relates to an oxygen doped porous carbon electrode material with high pseudo-capacitance activity and a preparation method thereof, belonging to the technical field of electrochemical supercapacitors.
Background
The super capacitor is a novel energy storage device which is widely focused by people, and has the characteristics of high charge and discharge speed, high power density, long cycle life and the like (Journal of Power Sources,2017, 337:73-81). Supercapacitors can be divided into two types according to energy storage mechanisms: an electric double layer supercapacitor (Carbon, 2016, 111:419-427) for electric energy storage by an electric double layer formed on the surface of an electrode and a pseudocapacitance supercapacitor (Advanced Energy Materials,2014, 4:1300816) in which a reversible chemical redox reaction of anions and cations occurs between or in the surface of an electrode material and an electrolyte or an active material generates a pseudocapacitance by a chemisorption and desorption process.
Electrode materials are the key to supercapacitors and determine the main performance index of supercapacitors. Among many supercapacitor electrode materials, carbon-based materials are attracting attention because of their large specific surface area, ease of modification, and low cost. Due to the complex surface chemistry of carbon materials, there are typically two energy storage mechanisms simultaneously present in carbon-based electrode materials, one being the formation of an electric double layer between the electrode and the electrolyte, and the other being the redox reactions that occur at the surface functional groups (Electrochimica Acta,2018, 270:339-351). Heteroatom functionality (N, O, P, S, etc.) on the surface of carbon-based materials has been demonstrated to improve the performance of carbon-based supercapacitors by contributing pseudocapacitance and to increase the wettability of the material surface (ChemSusChem 2016, 9:513-520). In particular, quinone carbonyl groups have a high theoretical capacity, excellent electrochemical reversibility and excellent redox reactivity compared to other oxygen-containing functional groups such as carboxylate groups, and are therefore of great interest (Journal of Materials Chemistry A,2020, 8:3717-3725). However, incorporation of a large amount of oxygen atoms in a carbon material brings about defects, which affect the conductivity of the material itself and thus the capacity of the material. Therefore, it is still worth intensively studying how to achieve the balance of good conductivity, large specific surface area and high oxygen doping amount.
Disclosure of Invention
The invention aims to develop the resorcinol-formaldehyde resin-based oxygen doped porous carbon electrode material with good conductivity, porosity and high oxygen doping amount under the low-temperature heat treatment condition.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides an oxygen-doped porous carbon electrode material with high pseudo-capacitance activity, which is prepared by mixing resorcinol, formaldehyde aqueous solution and ammonia water, polymerizing by a hydrothermal method to obtain resorcinol-formaldehyde resin, and then carbonizing at low temperature and activating with caustic alkali at low temperature.
The invention also provides a preparation method of the oxygen doped porous carbon electrode material, which comprises the following steps:
(1) Dissolving resorcinol, formaldehyde aqueous solution and ammonia water in water, and stirring to form a mixed solution;
(2) Transferring the mixed solution into a reaction kettle, performing hydrothermal reaction, alternately cleaning a solid product with water/ethanol, and drying to obtain resorcinol-formaldehyde resin;
(3) Performing heat treatment on resorcinol-formaldehyde resin in a nitrogen atmosphere for 3-8 hours, and cooling to obtain a blackish brown sample;
(4) Grinding the black brown sample and caustic alkali to obtain a uniform mixture, and activating the uniform mixture for 4 to 10 hours at the temperature of 450 to 550 ℃ in a nitrogen atmosphere; cooling, washing the rest caustic alkali with hydrochloric acid until the pH value is less than or equal to 7, washing with water, and drying to obtain the oxygen doped porous carbon electrode material.
Preferably, in the step (1), the mol ratio of resorcinol to formaldehyde aqueous solution to ammonia water is 1:1:0.5-1:1:2; in the mixed solution, the concentration of resorcinol is 12.5mmol/L, the concentration of formaldehyde is 12.5mmol/L, the concentration of ammonia water is 6.25-25 mmol/L, and the stirring time is 0.5-2 h.
Preferably, in the step (1), the mol ratio of resorcinol to formaldehyde aqueous solution to ammonia water is 1:1:1, the concentration of ammonia water is 12.5mmol/L, and the stirring time is 1h.
Preferably, the hydrothermal temperature in the step (2) is 150-180 ℃ and the hydrothermal time is 3-5 h.
Preferably, the heat treatment temperature in the step (3) is 450-550 ℃, and the heat treatment time is 3-8 h.
Preferably, the heat treatment temperature in the step (3) is 475 ℃, and the heat treatment time is 4 hours.
Preferably, the mass ratio of the black brown sample to the caustic alkali in the step (4) is 1:5-1:7, the activation temperature is 450-550 ℃, and the activation time is 4-10 h.
Preferably, in the step (4), the mass ratio of the black brown sample to the caustic alkali is 1:6, the activation temperature is 475 ℃, the activation time is 8 hours, and the caustic alkali is one of KOH, naOH, liOH.
The invention also provides application of the oxygen doped porous carbon electrode material prepared by the preparation method in a super capacitor.
By adopting the technical scheme, the invention has the following technical progress:
the resorcinol-formaldehyde resin is prepared by polymerizing resorcinol, formaldehyde aqueous solution and ammonia water by a hydrothermal method, and then heat treatment is carried out, wherein a large amount of sp is reserved in the heat treatment process 3 C, making the material less conductive, but sp occurs during caustic activation 3 Sp in C direction 2 C, conversion improves the graphitization degree of the material, and further improves the conductivity of the material; meanwhile, the etching effect of caustic alkali converts the carbon microsphere into a porous sheet-shaped carbon material, the specific surface area is increased, balance among good conductivity, porosity and high oxygen doping amount is realized, and electron transfer and ion transmission are facilitated.
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 a scanning electron microscope image of an oxygen doped porous carbon electrode material with high pseudocapacitive activity in example 1 of the present invention;
FIG. 2 is a graph showing the nitrogen adsorption and desorption curves and pore size distribution of the phenolic resin-based oxygen-doped microporous carbon electrode material in example 1 of the present invention;
FIG. 3 is an XRD pattern of an oxygen doped porous carbon electrode material with high pseudocapacitive activity in example 1 of the present invention;
FIG. 4 is a Raman spectrum diagram of an oxygen doped porous carbon electrode material with high pseudocapacitive activity in example 1 of the present invention;
FIG. 5 is an XPS plot of an oxygen-doped porous carbon electrode material with high pseudocapacitive activity in example 1 of the present invention;
FIG. 6 is a constant current charge-discharge curve of an oxygen doped porous carbon electrode material with high pseudocapacitive activity in a three electrode system according to example 1 of the present invention;
FIG. 7 is a cyclic voltammogram of an oxygen doped porous carbon electrode material with high pseudocapacitive activity in a three electrode system in accordance with example 1 of the present invention;
FIG. 8 is a cyclic voltammogram of a narrow interval (-0.05V to 0V vs. SCE) of an oxygen-doped porous carbon electrode material with high pseudocapacitive activity in a three electrode system in accordance with example 1 of the present invention;
FIG. 9 is an electrical double layer capacity as measured by Electrochemical Surface Area (ESA) in a voltage range (-0.05V to 0V vs. SCE) in a three electrode system for an oxygen doped porous carbon electrode material having high pseudocapacitive activity in example 1 of the present invention;
FIG. 10 is a graph of the cyclic stability test of an oxygen-doped porous carbon electrode material assembled three electrode system with high pseudocapacitive activity in example 1 of the present invention at a current density of 10A/g in a 1mol/L sulfuric acid electrolyte solution.
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.
The oxygen doped porous carbon electrode material with high pseudo-capacitance activity is prepared by stirring resorcinol, formaldehyde aqueous solution and ammonia water at room temperature, then polymerizing by a hydrothermal method to obtain resorcinol-formaldehyde resin, alternately cleaning by water/ethanol, drying, carbonizing at low temperature, activating by low-temperature caustic alkali, pickling by hydrochloric acid, washing by water and drying.
The preparation method comprises the following specific steps:
(1) Dissolving resorcinol, formaldehyde aqueous solution and ammonia water in a molar ratio of 1:1:0.5-1:1:2 (preferably 1:1:1) in 80mL of distilled water (or ultrapure water), stirring at room temperature to form a mixed solution, wherein the concentration of resorcinol in the mixed solution is 12.5mmol/L, the concentration of formaldehyde is 12.5mmol/L, the concentration of ammonia water is 6.25-25 mmol/L (preferably 12.5 mmol/L), and stirring time is 0.5-2 h (preferably 1 h);
(2) Transferring the stirred mixed solution into a 100mL reaction kettle, performing hydrothermal reaction to obtain a solid product, wherein the hydrothermal temperature is 150-180 ℃ (preferably 160 ℃), the hydrothermal time is 3-5 h (preferably 4 h), and then alternately cleaning the solid product with water/ethanol, and drying at 60 ℃ for 12h to obtain resorcinol-formaldehyde resin;
(3) Carrying out heat treatment on the resorcinol-formaldehyde resin prepared in the step (2) for 3-8 h (preferably 4 h) in a nitrogen atmosphere at 450-550 ℃ (preferably 475 ℃), and naturally cooling to room temperature to obtain a black brown sample;
(4) Grinding the black brown sample prepared in the step (3) and caustic alkali according to a mass ratio of 1:5-1:7 (preferably 1:6) to obtain a uniform mixture, and activating the uniform mixture for 4-10 h (preferably 8 h) under the condition of 450-550 ℃ (preferably 475 ℃) in a nitrogen atmosphere. Naturally cooling to room temperature, washing off the residual caustic alkali in the solid product by using hydrochloric acid until the pH value is less than or equal to 7, washing for a plurality of times by using distilled water, and drying to obtain the oxygen doped porous carbon electrode material with high pseudocapacitance activity.
Example 1
0.22g of resorcinol was weighed and dissolved in 80mL of distilled water, and after stirring until complete dissolution, 465. Mu.L of aqueous formaldehyde solution was added, and after stirring for 5min, 250. Mu.L of aqueous ammonia was added, and stirring was carried out at room temperature for 1h. Then, the solution was transferred to a 100mL reaction vessel, reacted at 160℃for 4 hours, the product was alternately washed with water/ethanol, and dried at 60℃for 12 hours to obtain resorcinol-formaldehyde resin.
The sample is heated to 475 ℃ from room temperature under the protection of nitrogen, and the temperature is kept 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. Naturally cooling to room temperature, washing the residual KOH in the solid product by hydrochloric acid until the pH value is less than or equal to 7, washing for a plurality of times by distilled water, and drying to obtain the oxygen doped porous carbon electrode material with high pseudocapacitance activity.
The result of the scanning electron microscope of the oxygen doped porous carbon material with high pseudocapacitance activity prepared in example 1 is shown in fig. 1, and the material has a porous sheet structure.
The oxygen-doped porous carbon electrode material with high pseudocapacitance activity prepared in example 1 has a specific surface area of 690.6m as shown in FIG. 2 as a result of nitrogen adsorption/desorption experiments 2 /g。
The X-ray diffraction pattern (XRD) test results of the oxygen-doped porous carbon material with high pseudocapacitive activity prepared in example 1 are shown in fig. 3, corresponding to the (002) crystal plane of graphitic carbon at 24.2 °.
The Raman test result of the oxygen-doped porous carbon material with high pseudocapacitance activity prepared in example 1 is shown in FIG. 4 and is shown at 1345cm -1 And 1573cm -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 XPS test result of the oxygen doped porous carbon material with high pseudocapacitance activity prepared in example 1 is shown in fig. 5, and a characteristic peak appears at 531.8 and 533.2eV, which correspond to-c=o band and-C-OH functional group in the carbon material, respectively, and the oxygen content in the oxygen doped porous carbon electrode material is 16.97at.%.
When the oxygen-doped porous carbon electrode material with high pseudocapacitive activity prepared in example 1 was applied as an electrode material of a supercapacitor, electrochemical performance was tested on the basis of a three-electrode system in a 1mol/L sulfuric acid solution.
The oxygen-doped porous carbon electrode material with high pseudocapacitance activity prepared in example 1, the constant current charge and discharge test results are shown in FIG. 5, and the specific capacitance is 430.6F/g when the current density is 1A/g; when the current density is 20A/g, the specific capacitance is 316.8F/g respectively, and good rate capability is shown.
The cyclic voltammetry test of the oxygen-doped porous carbon electrode material with high pseudocapacitive activity prepared in example 1 shows that the cyclic voltammetry curve has obvious symmetrical oxidation-reduction potential at different scanning rates, and has good pseudocapacitive behavior and electrochemical reversibility.
The oxygen-doped porous carbon electrode material with high pseudocapacitance activity prepared in example 1 has a narrow interval (-0.05V-0V vs. SCE) cyclic voltammetry test, and the results are shown in FIG. 7, wherein curves at different scanning speeds are similar to rectangles, and the oxygen-doped porous carbon electrode material has the characteristic of typical double-layer capacity.
The electrochemical surface area of the oxygen-doped porous carbon electrode material with high pseudocapacitive activity prepared in example 1 is shown in FIG. 8, and the Electrochemical Surface Area (ESA) is 228.9mF/cm 2 The electric double layer capacity was 220.7F/g, accounting for 56% of the total capacity.
The electrochemical cycle stability test of the oxygen-doped porous carbon electrode material with high pseudocapacitive activity prepared in example 1 is shown in fig. 9, and after 10000 times of charge and discharge, the capacity retention rate is 91.5%, showing good cycle stability.
Example 2
0.22g of resorcinol was weighed and dissolved in 80mL of distilled water, and after stirring until complete dissolution, 465. Mu.L of aqueous formaldehyde solution was added, and after stirring for 5min, 125. Mu.L of aqueous ammonia was added, and stirring was carried out at room temperature for 0.5h. Then, the solution was transferred to a 100mL reaction vessel, reacted at 180℃for 3 hours, the product was alternately washed with water/ethanol, and dried at 60℃for 12 hours to obtain resorcinol-formaldehyde resin.
The sample is heated to 450 ℃ from room temperature under the protection of nitrogen, and the temperature is kept for 8 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 450 ℃ from room temperature in nitrogen atmosphere, and preserving heat for 10 hours. Naturally cooling to room temperature, washing the residual KOH in the solid product by hydrochloric acid until the pH value is less than or equal to 7, washing for a plurality of times by distilled water, and drying to obtain the oxygen doped porous carbon electrode material with high pseudocapacitance activity.
Example 3
0.22g of resorcinol was weighed and dissolved in 80mL of distilled water, and after stirring until complete dissolution, 465. Mu.L of aqueous formaldehyde solution was added, and after stirring for 5min, 375. Mu.L of aqueous ammonia was added, and stirring was carried out at room temperature for 1h. Then, the solution was transferred to a 100mL reaction vessel, reacted at 170℃for 4 hours, the product was alternately washed with water/ethanol, and dried at 60℃for 12 hours to obtain resorcinol-formaldehyde resin.
The sample is heated to 520 ℃ from room temperature under the protection of nitrogen, and the temperature is kept for 6 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 520 ℃ from room temperature in nitrogen atmosphere, and preserving heat for 6 hours. Naturally cooling to room temperature, washing the residual KOH in the solid product by hydrochloric acid until the pH value is less than or equal to 7, washing for a plurality of times by distilled water, and drying to obtain the oxygen doped porous carbon electrode material with high pseudocapacitance activity.
Example 4
0.22g of resorcinol was weighed and dissolved in 80mL of distilled water, and after stirring until complete dissolution, 465. Mu.L of aqueous formaldehyde solution was added, and after stirring for 5min, 500. Mu.L of aqueous ammonia was added, and stirring was carried out at room temperature for 2h. Then, the solution was transferred to a 100mL reaction vessel, reacted at 150℃for 5 hours, the product was alternately washed with water/ethanol, and dried at 60℃for 12 hours to obtain resorcinol-formaldehyde resin.
The sample was heated from room temperature to 550℃under nitrogen protection and incubated for 3h. 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 550 ℃ from room temperature in nitrogen atmosphere, and preserving heat for 4 hours. Naturally cooling to room temperature, washing the residual KOH in the solid product by hydrochloric acid until the pH value is less than or equal to 7, washing for a plurality of times by distilled water, and drying to obtain the oxygen doped porous carbon electrode material with high pseudocapacitance activity.
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 (6)
1. The oxygen doped porous carbon electrode material with high pseudo-capacitance activity is characterized in that the oxygen doped porous carbon electrode material is prepared by mixing resorcinol, formaldehyde aqueous solution and ammonia water, polymerizing by a hydrothermal method to obtain resorcinol-formaldehyde resin, and then carbonizing at low temperature and activating with caustic alkali at low temperature;
the preparation method of the oxygen doped porous carbon electrode material comprises the following steps:
(1) Dissolving the resorcinol, the formaldehyde aqueous solution and the ammonia water in water, and stirring to form a mixed solution;
(2) Transferring the mixed solution into a reaction kettle, performing hydrothermal reaction, alternately cleaning a solid product with water/ethanol, and then drying to obtain the resorcinol-formaldehyde resin;
(3) Performing heat treatment on the resorcinol-formaldehyde resin in a nitrogen atmosphere for 3-8 hours, and cooling to obtain a black brown sample;
(4) Grinding the blackish brown sample and the caustic alkali to obtain a uniform mixture, and activating the uniform mixture for 4 to 10 hours at the temperature of 450 to 550 ℃ in nitrogen atmosphere; cooling, washing out the rest caustic alkali with hydrochloric acid until the pH value is less than or equal to 7, washing with water, and drying to obtain the oxygen doped porous carbon electrode material;
in the step (1), the mol ratio of the resorcinol to the formaldehyde aqueous solution to the ammonia water is 1:1:0.5-1:1:2; in the mixed solution, the concentration of resorcinol is 12.5mmol/L, the concentration of formaldehyde is 12.5mmol/L, the concentration of ammonia water is 6.25-25 mmol/L, and the stirring time is 0.5-2 h;
the hydrothermal temperature in the step (2) is 150-180 ℃, and the hydrothermal time is 3-5 h;
the heat treatment temperature in the step (3) is 450-550 ℃;
in the step (4), the mass ratio of the black brown sample to the caustic alkali is 1:5-1:7, the activation temperature is 450-550 ℃, and the activation time is 4-10 h.
2. The method for preparing an oxygen-doped porous carbon electrode material according to claim 1, comprising the steps of:
(1) Dissolving the resorcinol, the formaldehyde aqueous solution and the ammonia water in water, and stirring to form a mixed solution;
(2) Transferring the mixed solution into a reaction kettle, performing hydrothermal reaction, alternately cleaning a solid product with water/ethanol, and then drying to obtain the resorcinol-formaldehyde resin;
(3) Performing heat treatment on the resorcinol-formaldehyde resin in a nitrogen atmosphere for 3-8 hours, and cooling to obtain a black brown sample;
(4) Grinding the blackish brown sample and the caustic alkali to obtain a uniform mixture, and activating the uniform mixture for 4 to 10 hours at the temperature of 450 to 550 ℃ in nitrogen atmosphere; cooling, washing out the rest caustic alkali with hydrochloric acid until the pH value is less than or equal to 7, washing with water, and drying to obtain the oxygen doped porous carbon electrode material;
in the step (1), the mol ratio of the resorcinol to the formaldehyde aqueous solution to the ammonia water is 1:1:0.5-1:1:2; in the mixed solution, the concentration of resorcinol is 12.5mmol/L, the concentration of formaldehyde is 12.5mmol/L, the concentration of ammonia water is 6.25-25 mmol/L, and the stirring time is 0.5-2 h;
the hydrothermal temperature in the step (2) is 150-180 ℃, and the hydrothermal time is 3-5 h;
the heat treatment temperature in the step (3) is 450-550 ℃;
the mass ratio of the blackish brown sample to the caustic alkali in the step (4) is 1:5-1:7.
3. The method for producing an oxygen-doped porous carbon electrode material according to claim 2, wherein the molar ratio of the resorcinol, the aqueous formaldehyde solution and the aqueous ammonia in step (1) is 1:1:1, the concentration of the aqueous ammonia is 12.5mmol/L, and the stirring time is 1h.
4. The method for producing an oxygen-doped porous carbon electrode material according to claim 2, wherein the heat treatment temperature in step (3) is 475 ℃ and the heat treatment time is 4 hours.
5. The method for producing an oxygen-doped porous carbon electrode material according to claim 2, wherein the mass ratio of the blackish brown sample to the caustic alkali in the step (4) is 1:6, the activation temperature is 475 ℃, the activation time is 8 hours, and the caustic alkali is one selected from KOH, naOH, liOH.
6. The application of the oxygen-doped porous carbon electrode material prepared by the preparation method according to any one of claims 2-5 in super capacitors.
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