CN115072720A - 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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- 239000007772 electrode material Substances 0.000 title claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 230000000694 effects Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003518 caustics Substances 0.000 claims abstract description 19
- 238000001994 activation Methods 0.000 claims abstract description 11
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 42
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000008098 formaldehyde solution Substances 0.000 claims description 3
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- 239000003575 carbonaceous material Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 11
- 239000003990 capacitor Substances 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract description 2
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- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- 239000000047 product Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 125000000524 functional group Chemical group 0.000 description 3
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
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- 238000010277 constant-current charging Methods 0.000 description 1
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- 230000014759 maintenance of location 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
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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- 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 pseudocapacitance activity and a preparation method thereof, belonging to the technical field of electrochemical super capacitors. In the caustic activation process of the present invention, sp occurs 3 C to sp 2 The conductivity of the material is improved by the transformation of the structure C; simultaneously etching and activating the carbon microspheres by caustic alkaliThe porous carbon material is converted into the porous flaky carbon material, the specific surface area is increased, the balance among good conductivity, porosity and high oxygen doping amount is realized, the electron transfer and the ion transmission are facilitated, and when the porous carbon material is applied to the test of the electrode material of the supercapacitor, the oxygen-doped porous carbon material shows higher pseudo-capacitance performance.
Description
Technical Field
The invention relates to an oxygen-doped porous carbon electrode material with high pseudocapacitance activity and a preparation method thereof, belonging to the technical field of electrochemical super capacitors.
Background
The super capacitor is a novel energy storage device which is widely concerned by people, and has the characteristics of high charging and discharging speed, high Power density, long cycle life and the like (Journal of Power Sources,2017,337: 73-81). Supercapacitors can be divided into two categories according to the energy storage mechanism: an electric double layer super capacitor (Carbon,2016,111:419-427) for storing electric Energy by an electric double layer formed on the surface of an electrode and a pseudo-capacitor (Advanced Energy Materials,2014,4:1300816) in which reversible chemical redox reaction occurs between the surface of an electrode material and an electrolyte or inside the electrode material or a pseudo-capacitor is generated by an active material through a chemical adsorption and desorption process.
The electrode material is the key of the super capacitor, and determines the main performance index of the super capacitor. Among many supercapacitor electrode materials, carbon-based materials are of great interest due to their large specific surface area, ease of modification, and low cost. Due to the complex surface chemical structure of carbon material, two energy storage mechanisms exist in carbon-based electrode materials, one is the formation of an electric double layer between the electrode and the electrolyte, and the other is the redox reaction of surface functional groups (Electrochimica Acta,2018,270: 339-. Heteroatom functionalities (N, O, P, S, etc.) on the surface of carbon-based materials have been shown to improve the performance of carbon-based supercapacitors by contributing pseudocapacitance and to increase the wettability of the material surface (ChemSusChem,2016,9: 513-. In particular, quinone carbonyl groups have high theoretical capacity, excellent electrochemical reversibility, and excellent redox reactivity as compared with other oxygen-containing functional groups such as carboxylate groups, and thus have received much attention (Journal of Materials Chemistry A,2020,8: 3717-. However, the incorporation of a large number of oxygen atoms into the carbon material has drawbacks that affect the conductivity of the material itself and, in turn, the capacity of the material. Therefore, how to achieve the balance among good conductivity, large specific surface area and high oxygen doping amount is still worth deeply researching.
Disclosure of Invention
The technical problem to be solved by the invention is to develop a resorcinol-formaldehyde resin oxygen-doped porous carbon electrode material with good conductivity, porosity and high oxygen doping amount under the condition of low-temperature heat treatment.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the invention provides an oxygen-doped porous carbon electrode material with high pseudocapacitance activity, which is prepared by mixing resorcinol, formalin and ammonia water, polymerizing the mixture by a hydrothermal method to obtain resorcinol-formaldehyde resin, and then carbonizing the resorcinol-formaldehyde resin at a low temperature and activating the resorcinol-formaldehyde resin with low-temperature caustic alkali.
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, carrying out hydrothermal reaction, alternately cleaning the solid product with water/ethanol, and drying to obtain resorcinol-formaldehyde resin;
(3) carrying out heat treatment on resorcinol-formaldehyde resin in a nitrogen atmosphere for 3-8 h, and cooling to obtain a black brown sample;
(4) grinding the black brown sample and caustic alkali to obtain a uniform mixture, and activating for 4-10 hours at 450-550 ℃ in a nitrogen atmosphere; cooling, washing the residual 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, the molar ratio of the resorcinol to the aqueous formaldehyde solution to the ammonia water in the step (1) 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 molar ratio of the resorcinol to the aqueous formaldehyde solution to the ammonia water is 1:1:1, the concentration of the ammonia water is 12.5mmol/L, and the stirring time is 1 h.
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 h.
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, the mass ratio of the dark brown sample to the caustic alkali in the step (4) is 1:6, the activation temperature is 475 ℃, and the activation time is 8h, and the caustic alkali is selected from one of KOH, NaOH and LiOH.
The invention also provides application of the oxygen-doped porous carbon electrode material prepared by the preparation method in a super capacitor.
Due to the adoption of the technical scheme, the invention has the technical progress that:
the invention takes resorcinol, formalin and ammonia water as main materials to obtain resorcinol-formaldehyde resin by hydrothermal polymerization, and then carries out heat treatment, wherein a large amount of sp is reserved in the heat treatment process 3 C, the conductivity of the material is poor, but sp is generated during the caustic activation process 3 C to sp 2 The conversion of C improves the graphitization degree of the material, thereby improving the conductivity of the material; meanwhile, the etching effect of caustic alkali converts the carbon microspheres into porous flaky carbon materials, so that the specific surface area is increased, the balance among good conductivity, porosity and high oxygen doping amount is realized, and the electron transfer and ion transmission are facilitatedTherefore, when the oxygen-doped porous carbon electrode material prepared by the method is applied to a supercapacitor electrode material test, the oxygen-doped porous carbon electrode material shows high pseudo-capacitance performance.
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, in which:
FIG. 1 is a scanning electron microscope photograph of an oxygen-doped porous carbon electrode material having high pseudocapacitance activity according to example 1 of the present invention;
FIG. 2 is a nitrogen desorption curve and a pore size distribution spectrum of the phenolic resin 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 pseudocapacitance activity according to example 1 of the present invention;
FIG. 4 is a Raman spectrum of an oxygen-doped porous carbon electrode material with high pseudocapacitance activity according to example 1 of the present invention;
FIG. 5 is an XPS plot of an oxygen-doped porous carbon electrode material with high pseudocapacitance activity of example 1 of the present invention;
FIG. 6 is a constant current charging and discharging curve of the oxygen-doped porous carbon electrode material with high pseudocapacitance activity in a three-electrode system in example 1 of the present invention;
FIG. 7 is a cyclic voltammogram of an oxygen-doped porous carbon electrode material with high pseudocapacitance activity in a three-electrode system in example 1 of the present invention;
FIG. 8 is a narrow range (-0.05V-0V vs. SCE) cyclic voltammogram of the oxygen-doped porous carbon electrode material with high pseudocapacitance activity in a three-electrode system in example 1 of the present invention;
FIG. 9 is the electric double layer capacity as measured by Electrochemical Surface Area (ESA) over the voltage range (-0.05V-0V vs. SCE) for the oxygen-doped porous carbon electrode material with high pseudocapacitance activity of example 1 of the present invention in a three-electrode system;
FIG. 10 is a graph showing the cycle stability of the three-electrode system assembled by oxygen-doped porous carbon electrode materials with high pseudocapacitance activity in the sulfuric acid electrolyte solution of 1mol/L at a current density of 10A/g in example 1.
Detailed Description
The following disclosure provides many different embodiments or examples for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
The oxygen-doped porous carbon electrode material with high pseudocapacitance activity is prepared by stirring resorcinol, formalin and ammonia water at room temperature, polymerizing by a hydrothermal method to obtain resorcinol-formaldehyde resin, alternately cleaning with water/ethanol, drying, carbonizing at low temperature, activating with low-temperature caustic alkali, pickling with hydrochloric acid, and washing with water and drying.
The preparation method comprises the following specific steps:
(1) dissolving resorcinol, a 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), and stirring at room temperature to form a mixed solution, wherein the concentration of resorcinol, the concentration of formaldehyde and the concentration of ammonia water are respectively 12.5mmol/L, 12.5mmol/L and 6.25-25 mmol/L (preferably 12.5mmol/L), and the stirring time is 0.5-2 h (preferably 1 h);
(2) transferring the stirred mixed solution into a 100mL reaction kettle, carrying out hydrothermal reaction to obtain a solid product, wherein the hydrothermal temperature is 150-180 ℃ (preferably 160 ℃), the hydrothermal time is 3-5 h (preferably 4h), 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) in a nitrogen atmosphere at 450-550 ℃ (preferably 475 ℃) for 3-8 h (preferably 4h), and naturally cooling to room temperature to obtain a dark brown sample;
(4) grinding the black brown sample prepared in the step (3) and caustic alkali according to the mass ratio of 1: 5-1: 7 (preferably 1:6) to obtain a uniform mixture, and activating for 4-10 h (preferably 8h) under the condition of 450-550 ℃ (preferably 475 ℃) in a nitrogen atmosphere. Naturally cooling to room temperature, washing the residual caustic alkali in the solid product with hydrochloric acid until the pH value is less than or equal to 7, washing with distilled water for a plurality of times, and drying to obtain the oxygen-doped porous carbon electrode material with high pseudo-capacitance activity.
Example 1
0.22g of resorcinol is weighed and dissolved in 80mL of distilled water, 465 μ L of formalin is added after stirring till complete dissolution, 250 μ L of ammonia water is added after stirring for 5min, and stirring is carried out at room temperature for 1 h. Then, the solution was transferred to a 100mL reaction vessel, reacted at 160 ℃ for 4 hours, the product was washed with water/ethanol alternately, and dried at 60 ℃ for 12 hours to obtain resorcinol-formaldehyde resin.
The sample is heated from room temperature to 475 ℃ under the protection of nitrogen and is kept warm for 4 h. And naturally cooling to room temperature, grinding and uniformly mixing the sample obtained by carbonization and KOH according to the mass ratio of 1:6, heating the mixed sample to 475 ℃ from room temperature in a nitrogen atmosphere, and preserving heat for 8 hours. And naturally cooling to room temperature, washing away the residual KOH 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 pseudo-capacitance activity.
The oxygen-doped porous carbon material with high pseudocapacitance activity prepared in example 1 is shown in fig. 1 by scanning electron microscopy, and the material has a porous sheet structure.
The oxygen-doped porous carbon electrode material with high pseudocapacitance activity prepared in example 1 has nitrogen adsorption/desorption experiment results shown in FIG. 2, and the specific surface area is 690.6m 2 /g。
For the oxygen-doped porous carbon material with high pseudocapacitive activity prepared in example 1, the X-ray diffraction pattern (XRD) test result is shown in fig. 3, and corresponds to the (002) crystal plane of graphitic carbon at 24.2 °.
Raman test results of the oxygen-doped porous carbon material with high pseudocapacitance activity prepared in example 1 are shown in FIG. 4 and are at 1345cm -1 And 1573cm -1 Each having an absorption peak corresponding to that of the carbon materialD band and G band, indicating that the phenolic resin finally achieved carbonization.
The oxygen-doped porous carbon material with high pseudocapacitance activity prepared in example 1 has XPS test results as shown in fig. 5, and characteristic peaks appear at 531.8 and 533.2eV respectively corresponding to-C ═ O band and-C-OH functional group in the carbon material, and the oxygen content in the oxygen-doped porous carbon electrode material is 16.97 at.%.
When the oxygen-doped porous carbon electrode material with high pseudocapacitance activity prepared in example 1 is applied as an electrode material of a supercapacitor, electrochemical performance test is carried out on the oxygen-doped porous carbon electrode material based on a three-electrode system in 1mol/L sulfuric acid solution.
The oxygen-doped porous carbon electrode material with high pseudocapacitance activity prepared in example 1 has a constant current charge and discharge test result as shown in fig. 5, and when the current density is 1A/g, the specific capacitance is 430.6F/g; when the current density is 20A/g, the specific capacitance is 316.8F/g respectively, and good rate performance is shown.
The cyclic voltammetry test of the oxygen-doped porous carbon electrode material with high pseudocapacitance activity prepared in example 1 shows that the cyclic voltammetry curve has obvious symmetric redox potential and has good pseudocapacitance behavior and electrochemical reversibility at different scanning rates as shown in fig. 6.
The narrow range (-0.05V to 0V vs. sce) cyclic voltammetry test of the oxygen-doped porous carbon electrode material with high pseudocapacitance activity prepared in example 1 shows that the curves at different scanning speeds are close to a quasi-rectangular shape and have the characteristic of typical electric double layer capacity, as shown in fig. 7.
The electrochemical surface area of the oxygen-doped porous carbon electrode material with high pseudocapacitance 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.
An electrochemical cycle stability test of the oxygen-doped porous carbon electrode material with high pseudocapacitance activity prepared in example 1 is shown in fig. 9, and the capacity retention rate is 91.5% after the current density is 10A/g and the charging and discharging are carried out for 10000 times, so that good cycle stability is shown.
Example 2
0.22g of resorcinol is weighed and dissolved in 80mL of distilled water, 465 μ L of formalin is added after stirring till the resorcinol is completely dissolved, 125 μ L of ammonia water is added after stirring for 5min, and stirring is carried out at room temperature for 0.5 h. Then, the solution was transferred to a 100mL reaction vessel, reacted at 180 ℃ for 3 hours, the product was washed with water/ethanol alternately, and dried at 60 ℃ for 12 hours to obtain resorcinol-formaldehyde resin.
The sample is heated from room temperature to 450 ℃ under the protection of nitrogen, and the temperature is kept for 8 h. And naturally cooling to room temperature, grinding and uniformly mixing the sample obtained by carbonization and KOH according to the mass ratio of 1:7, heating the mixed sample to 450 ℃ from room temperature in a nitrogen atmosphere, and preserving heat for 10 hours. And naturally cooling to room temperature, washing away the residual KOH 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 pseudo-capacitance activity.
Example 3
0.22g of resorcinol is weighed and dissolved in 80mL of distilled water, 465 μ L of formalin is added after stirring until the resorcinol is completely dissolved, 375 μ L of ammonia water is added after stirring for 5min, and stirring is carried out at room temperature for 1 h. Then, the solution was transferred to a 100mL reaction vessel, reacted at 170 ℃ for 4 hours, the product was washed with water/ethanol alternately, and dried at 60 ℃ for 12 hours to obtain resorcinol-formaldehyde resin.
The sample is heated from room temperature to 520 ℃ under the protection of nitrogen, and the temperature is kept for 6 h. And naturally cooling to room temperature, grinding and uniformly mixing the sample obtained by carbonization with KOH according to the mass ratio of 1:6, heating the mixed sample to 520 ℃ from room temperature in a nitrogen atmosphere, and preserving heat for 6 hours. And naturally cooling to room temperature, washing away the residual KOH 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 pseudo-capacitance activity.
Example 4
0.22g of resorcinol is weighed and dissolved in 80mL of distilled water, 465 μ L of formalin is added after stirring till the resorcinol is completely dissolved, 500 μ L of ammonia water is added after stirring for 5min, and stirring is carried out at room temperature for 2 h. Then, the solution was transferred to a 100mL reaction vessel, reacted at 150 ℃ for 5 hours, the product was washed with water/ethanol alternately, and dried at 60 ℃ for 12 hours to obtain resorcinol-formaldehyde resin.
The sample is heated from room temperature to 550 ℃ under the protection of nitrogen, and the temperature is kept for 3 h. And naturally cooling to room temperature, grinding and uniformly mixing the sample obtained by carbonization with KOH according to the mass ratio of 1:5, heating the mixed sample to 550 ℃ from room temperature in a nitrogen atmosphere, and preserving heat for 4 hours. And naturally cooling to room temperature, washing away the residual KOH 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 pseudo-capacitance 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 disclosed 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 will be understood that the invention is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (10)
1. The oxygen-doped porous carbon electrode material with high pseudocapacitance activity is characterized in that resorcinol-formaldehyde resin is obtained by mixing resorcinol, formaldehyde aqueous solution and ammonia water and polymerizing through a hydrothermal method, and then the resorcinol-formaldehyde resin is prepared by low-temperature carbonization and low-temperature caustic alkali activation.
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 formalin and the ammonia water into water, and stirring to form a mixed solution;
(2) transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction, alternately cleaning a solid product with water/ethanol, and drying to obtain the resorcinol-formaldehyde resin;
(3) carrying out heat treatment on the resorcinol-formaldehyde resin in a nitrogen atmosphere for 3-8 h, and cooling to obtain a black brown sample;
(4) grinding the black brown sample and the caustic alkali to obtain a uniform mixture, and activating for 4-10 hours at 450-550 ℃ in a nitrogen atmosphere; and cooling, washing the residual 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.
3. The preparation method of the oxygen-doped porous carbon electrode material according to claim 2, wherein the molar ratio of the resorcinol to the formalin to the ammonia water in the step (1) is 1:1: 0.5-1: 1: 2; in the mixed solution, the concentration of the resorcinol is 12.5mmol/L, the concentration of the formaldehyde is 12.5mmol/L, the concentration of the ammonia water is 6.25-25 mmol/L, and the stirring time is 0.5-2 h.
4. The method for preparing the oxygen-doped porous carbon electrode material according to claim 3, wherein the molar ratio of the resorcinol to the aqueous formaldehyde solution to the ammonia water in the step (1) is 1:1:1, the concentration of the ammonia water is 12.5mmol/L, and the stirring time is 1 h.
5. The preparation method of the oxygen-doped porous carbon electrode material according to claim 2, wherein the hydrothermal temperature in the step (2) is 150-180 ℃, and the hydrothermal time is 3-5 h.
6. The preparation method of the oxygen-doped porous carbon electrode material according to claim 2, wherein the heat treatment temperature in the step (3) is 450-550 ℃, and the heat treatment time is 3-8 h.
7. The method for preparing the oxygen-doped porous carbon electrode material according to claim 6, wherein the heat treatment temperature in the step (3) is 475 ℃, and the heat treatment time is 4 h.
8. The preparation method of the oxygen-doped porous carbon electrode material according to claim 2, wherein the mass ratio of the dark 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.
9. The preparation method of the oxygen-doped porous carbon electrode material according to claim 8, wherein the mass ratio of the dark brown sample to the caustic alkali in the step (4) is 1:6, the activation temperature is 475 ℃, and the activation time is 8h, and the caustic alkali is selected from one of KOH, NaOH and LiOH.
10. The oxygen-doped porous carbon electrode material prepared by the preparation method according to any one of claims 2 to 9 is applied to a supercapacitor.
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