CN110467182B - Reaction template-based hierarchical porous carbon-based material and preparation method and application thereof - Google Patents
Reaction template-based hierarchical porous carbon-based material and preparation method and application thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000011148 porous material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000011261 inert gas Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000007833 carbon precursor Substances 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 235000014653 Carica parviflora Nutrition 0.000 claims abstract description 4
- 241000243321 Cnidaria Species 0.000 claims abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 38
- 239000012018 catalyst precursor Substances 0.000 claims description 20
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 19
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
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- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 4
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
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- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 claims description 2
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- ASHFQILZQVAPMW-UHFFFAOYSA-L disodium;2-[2-[carboxylatomethyl(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron Chemical compound [Na+].[Na+].[Fe].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ASHFQILZQVAPMW-UHFFFAOYSA-L 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 19
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- XDIYNQZUNSSENW-UUBOPVPUSA-N (2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O XDIYNQZUNSSENW-UUBOPVPUSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- 238000001237 Raman spectrum Methods 0.000 description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 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
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/84—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the technical field of porous carbon-based materials, and particularly relates to a reaction template-based hierarchical porous carbon-based material and a preparation method and application thereof. The reaction template-based hierarchical porous carbon-based material mainly contains C and O elements, has high graphitization degree, coral reef-like appearance and three-dimensional pore structure, the pore diameter distribution of the material is 0.5-4.1 nm, and the pore volume of the material is 0.94-1.28 cm3g‑1The specific surface area is 900 to 2000m2g‑1(ii) a The hierarchical porous carbon-based material is prepared by mixing a basic carbonate, a carbon precursor and a carbonate in a solid phase, carbonizing under the protection of inert gas, treating with acid, and drying. The invention not only has high specific capacitance, high rate performance and good cycling stability as a symmetrical super capacitor electrode material, can realize efficient and lasting charge and discharge in alkaline electrolyte, but also has low cost of raw materials, simple and controllable preparation method, flexible process steps and easy large-scale production.
Description
Technical Field
The invention belongs to the technical field of non-noble metal catalysts in electrocatalysis, and particularly relates to a reaction template-based hierarchical porous carbon-based material and a preparation method thereof.
Background
Supercapacitors, also known as electrochemical capacitors. The new energy storage device has not only higher energy density than the conventional capacitor, but also higher power density than the battery, and the combination performance is between the conventional electrolytic capacitor and the battery. Due to the unique energy storage manner of the super capacitor, such as being capable of storing and releasing a large amount of energy in a short time, faster charging and discharging rate and excellent cycling stability, the super capacitor has a great application prospect in the aspect of storing intermittent pulse energy sources such as solar energy, wind energy and the like, and is favored in recent years. However, due to the disadvantages of low energy density and narrow potential interval, the super capacitor cannot replace the lithium battery in a short time, and the super capacitor and the lithium battery are mainly in a complementary relationship at present. Therefore, the performance of the super capacitor is further improved, and the reduction of the cost is still the main direction of research of the super capacitor. The super capacitor mainly comprises an electrode material, a diaphragm and an electrolyte, and the research on the electrode material is key to further improve the performance of the super capacitor.
The carbon material has the characteristics of controllable aperture, large specific surface area, excellent conductivity, good stability, low price and the like, so that the carbon material has very large application potential in the fields of new energy such as ultracapacitors, batteries and the like. The preparation methods of the porous carbon at present mainly comprise two types: template method and activation method. In the conventional template method, for example, a carbon material prepared by using materials such as silicon dioxide and the like as a sacrificial hard template has the problems of single pore diameter, low micropore content, low carbon material purity, complex process, high preparation cost and the like, and acid or alkali used for etching the template is harmful to human bodies and pollutes the environment. The carbon material prepared by the common KOH activation method has the problems of small pore size, low yield and the like, and KOH has strong corrosivity. These disadvantages make the preparation of porous carbon materials very limited and not easy to scale up.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a reaction template-based hierarchical porous carbon-based material, which has not only a high graphitization degree but also a micro-mesoporous hierarchical pore structure and an ultra-high specific surface area.
The invention also aims to provide a preparation method of the reaction template-based hierarchical porous carbon-based material, which is simple and controllable, low in raw material cost, flexible in process steps and easy for large-scale production.
The invention is realized by the following technical scheme:
the hierarchical porous carbon-based material based on the reaction template mainly comprises C and O elements, the pore diameter of the hierarchical porous carbon-based material is distributed in the range of 0.5-4.1 nm, and the pore volume of the hierarchical porous carbon-based material is 0.94-1.28 cm3 g-1The specific surface area is 900 to 2000m2 g-1；
The reaction template-based hierarchical porous carbon-based material is prepared from a carbon precursor, basic carbonate and carbonate, wherein the mass ratio of the carbon precursor to the basic carbonate to the carbonate is 2: 0.5-4. Wherein the basic carbonate and the carbonate are respectively used as a reaction template and a porous activator.
Preferably, the carbon precursor is one or a combination of glucose, chitosan, methyl cellulose, soluble starch, disodium EDTA, ferric sodium EDTA and ferric oxalate.
Preferably, the basic carbonate is one or a combination of more of basic zinc carbonate, basic magnesium carbonate, basic nickel carbonate and basic iron carbonate.
Preferably, the carbonate is one or a combination of potassium carbonate, ammonium bicarbonate and urea.
The preparation method of the reaction template-based hierarchical porous carbon-based material comprises the following steps:
1) taking the carbon precursor, the basic carbonate and the carbonate according to the proportion, and fully mixing the carbon precursor, the basic carbonate and the carbonate in a solid-phase mechanical mixing mode to obtain solid powder A;
2) heating the A obtained in the step 1) to 600-1000 ℃ at a speed of 5 +/-2 ℃/min under the protection of flowing inert gas, keeping for 1-3 h, naturally cooling to room temperature, and uniformly grinding to obtain a catalyst precursor B; wherein too slow a temperature rise rate for too long a time also requires more consumption, and too fast a rate may result in volatilization of the sample before carbonization or structural inhomogeneity, and is therefore optimal with 5 + -2 deg.C/min. The heat treatment process is a carbonization process for obtaining a carbon material, and thus the carbonization process must be performed with an inert gas, and if the carbonization process is a reactive gas, a reaction occurs during a high temperature process, and even a desired sample cannot be obtained.
3) Treating the catalyst precursor B obtained in the step 2) with an acidic aqueous solution for 1.0-24 h, then carrying out suction filtration and drying, and finally obtaining the carbon-based material without the template and impurities, namely the multi-stage porous carbon-based material based on the reaction template, which is marked as HPC.
Preferably, in order to further improve the pore structure, specific surface area and graphitization degree. Subjecting the HPC obtained in the step 3) to 180-220 mL min-1Under the protection of flowing gas, the temperature is raised to 700-900 ℃ at the speed of 5 ℃/min and kept for 0.5-3 h, then the temperature is naturally cooled to room temperature, and the further improved multi-stage porous carbon-based material based on the reaction template is obtained, and the product at this stage is marked as HPC-HT2 (although the obtained material is still HPC), mainly aiming at comparing with 3 HPC and facilitating the research of the reason for leading to the HPC structure.
Preferably, the carbon precursor, the basic carbonate and the carbonate are mixed sufficiently, and the mixture can be dispersed in water by ultrasonic or mixed by solid phase mechanical. Wherein, the mixing mode of solid phase mechanical mixing is simpler, more convenient and more economical because the steps of solvent dispersion, subsequent filtration, drying and the like are not needed.
Preferably, in step 2), the flowing inert gas is N2Or He.
Preferably, in the step 3), the treatment is carried out by using an aqueous solution of acid, wherein the acid in the acid treatment is HCl or H2SO4Or HNO3One or more of the solutionsA composition; the method specifically comprises the following steps: adding the catalyst precursor B into an acid aqueous solution with the mass fraction of 5-20%, stirring for 1.0-24 h at 25-60 ℃, then repeatedly washing for 3 times by using deionized water, carrying out suction filtration and drying. In the acid treatment, HCl is further preferred as an acid, an aqueous solution of an acid with an acid concentration of 5-20% by mass is preferred, and an aqueous solution of an acid with a mass fraction of 8-12% by mass is further preferred, because the concentration is too low, impurities cannot be removed at the same volume, and the volume is too large, so that the sample cannot be submerged.
Preferably, the flowing gas is an inert gas or an active gas NH3(ii) a Wherein a reactive gas NH is used3The purpose of (a) is to allow heteroatom doping and further porogenic formation.
The invention adopts basic carbonate (basic zinc carbonate, basic magnesium carbonate, basic nickel carbonate or basic iron carbonate) as a reaction hard template, and aims to use zinc oxide particles obtained by decomposition at high temperature as the hard template, combine with the steps of activating agent carbonate (potassium carbonate, ammonium bicarbonate or urea) and acid treatment etching the hard template, and cut out a micro-mesoporous hierarchical porous carbon-based material with large specific surface area, wherein the micro-mesoporous hierarchical porous carbon-based material has a coral reef-like appearance and a three-dimensional pore structure. The pore diameter distribution of the porous silicon dioxide is 0.5-4.1 nm, and the pore volume is 0.94-1.28 cm3 g-1The specific surface area is 900 to 2000m2 g-1The reaction template-based multi-level pore carbon-based material has a coral reef-like appearance and a three-dimensional pore structure (see fig. l and 11). The micro/mesoporous hierarchical pore is not only beneficial to increasing electron adsorption and improving electron transmission rate, but also can improve the performance of the double electric layer capacitor, thereby further improving the performance of the super capacitor. Potassium carbonate is selected to replace potassium hydroxide as an activator or a pore-forming agent, so that the reaction rate is reduced, the carbon material yield is improved, and the harm and pollution to human bodies and the environment caused by the toxicity and corrosivity of the potassium hydroxide are avoided; the graphitization degree of the carbon material can be further increased and the hierarchical pore structure can be regulated by utilizing secondary heat treatment; thereby cooperating to obtain the super capacitor electrode material with excellent performance.
The invention relates to a multi-stage porous carbon base based on a reaction templateThe scanning electron microscope test result shows that the carbon material is a porous spongy structure; the pore diameter distribution of the nitrogen gas is 0.5-4.1 nm and the specific surface area is 900-2000 m determined by nitrogen gas isothermal adsorption and desorption analysis2 g-1. The hierarchical porous carbon-based material based on the reaction template is used as an electrode material to assemble a symmetrical two-electrode system of the supercapacitor, and test results show that when the current density is 1A g-1At time, the specific capacitance value is 241F g-1The current density was increased to 10A g-1Specific capacitance value of 218F g-1The product shows good rate performance; under the condition of constant current charge and discharge test, after circulation for 10000 times, the initial current density can still be kept more than 98%, which shows that the charge and discharge stability is good.
Compared with the prior art, the invention has the following beneficial effects:
1) the preparation process uses various cheap and environment-friendly raw materials;
2) in the preparation process, the basic carbonate is used as a hard template and is combined with acid treatment, so that a micro-mesoporous hierarchical pore structure can be effectively created and a large specific surface area can be obtained, the available electron adsorption area can be increased, and the electron transmission rate can be improved;
3) under the alkaline condition and the test of a symmetrical two-electrode, the hierarchical porous carbon-based material shows good rate performance (90.5%) and charge-discharge stability (more than 98% is still kept after 10000 times);
4) the hierarchical porous carbon-based material has wide practical range, can be used as an electrode material of a super capacitor and can also be used as a cathode oxygen reduction catalyst of a fuel cell.
The preparation method disclosed by the invention has the advantages of low cost of raw materials required in the preparation process, safety, environmental friendliness, simple preparation process, controllable operation, high yield and easiness in large-scale production. The prepared hierarchical porous carbon-based material based on the reaction template has ordered grading and large specific surface area, and solves the problem that the carbon material is urgently needed to be solved when being applied to the super capacitor at present.
Drawings
FIG. 1 is an SEM photograph of HPC (G-BZC-PC), HPC (G-PC) and HPC (G-BZC).
FIG. 2 shows N of HPC (G-BZC-PC), HPC (G-PC) and HPC (G-BZC)2Adsorption/desorption isotherms.
FIG. 3 shows the pore size distribution of HPC (G-BZC-PC), HPC (G-PC) and HPC (G-BZC).
FIG. 4 is a wide angle XRD spectrum of HPC (G-BZC-PC), HPC (G-PC) and HPC (G-BZC).
FIG. 5 shows the Raman spectra of HPC (G-BZC-PC), HPC (G-PC) and HPC (G-BZC).
FIG. 6 shows XPS survey spectra of HPC (G-BZC-PC), HPC (G-PC) and HPC (G-BZC).
FIG. 7 shows cyclic voltammograms (room temperature, sweep rate 10mV s) of HPC (G-BZC-PC), HPC (G-PC) and HPC (G-BZC) in 6M KOH-1)。
FIG. 8 shows the constant current charge and discharge curves (room temperature, 1A G) of HPC (G-BZC-PC), HPC (G-PC) and HPC (G-BZC) in 6M KOH-1)。
FIG. 9 shows the discharge capacitance of HPC (G-BZC-PC), HPC (G-PC) and HPC (G-BZC) in 6M KOH at different current densities.
FIG. 10 shows the cycling stability of HPC (G-BZC-PC), HPC (G-PC) and HPC (G-BZC) in 6M KOH (room temperature, 5A G)-110000 times).
FIG. 11 is a TEM photograph of HPC (G-BZC-PC).
Detailed Description
The present invention is described in further detail below with reference to specific embodiments to assist those skilled in the art in understanding the present invention.
Example 1
1) Firstly, 2g of glucose, 1g of basic zinc carbonate and 1g of potassium carbonate are added into an agate mortar for full solid-phase mixing to obtain solid powder A;
2) subjecting A obtained in step 1) to 200mL min-1Under the protection of flowing inert gas, heating to 750 ℃ at the speed of 5 ℃/min, keeping for 1.5h, then naturally cooling to room temperature, and grinding uniformly to obtain a catalyst precursor B;
3) treating the catalyst precursor B obtained in the step 2) with an aqueous solution of an acid at room temperature for 20 hours, and performing suction filtration and drying after the treatment to obtain the carbon-based material without the template and impurities, wherein the carbon-based material is marked as HPC.
Example 2
1) Adding 1g of EDTA disodium, 1g of basic magnesium carbonate and 1g of potassium carbonate into an agate mortar for full solid-phase mixing to obtain solid powder A;
2) subjecting A obtained in step 1) to 180mL min-1Under the protection of flowing inert gas, heating to 800 ℃ at the speed of 7 ℃/min, keeping for 1h, then naturally cooling to room temperature, and grinding uniformly to obtain a catalyst precursor B;
3) treating the catalyst precursor B obtained in the step 2) with an acid aqueous solution at room temperature for 12 hours, and performing suction filtration and drying after the treatment to obtain a carbon-based material without the template and impurities, wherein the carbon-based material is marked as HPC;
example 3
1) Firstly, 2g of chitosan, 0.5g of basic nickel carbonate and 2g of potassium carbonate are added into an agate mortar for full solid-phase mixing to obtain solid powder A;
2) subjecting A obtained in step 1) to 250mL min-1Under the protection of flowing inert gas, heating to 1000 ℃ at a speed of 4 ℃/min, keeping for 1h, then naturally cooling to room temperature, and grinding uniformly to obtain a catalyst precursor B;
3) treating the catalyst precursor B obtained in the step 2) with an acid aqueous solution at room temperature for 5 hours, and performing suction filtration and drying after the treatment to obtain a carbon-based material without the template and impurities, wherein the carbon-based material is marked as HPC;
4) subjecting the HPC obtained in step 3) to a temperature of 180mL min-1Flowing active gas NH3Under protection, the temperature is raised to 900 ℃ at the speed of 5 ℃/min and kept for 0.5h, and then the temperature is naturally cooled to room temperature, so that the reaction template-based hierarchical porous carbon-based material is further improved, and the product at this stage is marked as HPC-HT 2.
Example 4
1) Firstly, 2g of glucose, 1g of basic zinc carbonate and 1g of potassium carbonate are added into an agate mortar for full solid-phase mixing to obtain solid powder A;
2) subjecting A obtained in step 1) to 200mL min-1Heating to 800 deg.C at a rate of 5 deg.C/min under the protection of flowing inert gas, maintaining for 1h, naturally cooling to room temperature, and grinding to obtain the final productTo catalyst precursor B;
3) treating the catalyst precursor B obtained in the step 2) with an acid aqueous solution at room temperature for 12 hours, and performing suction filtration and drying after the treatment to obtain a carbon-based material without the template and impurities, wherein the carbon-based material is marked as HPC;
4) subjecting the HPC obtained in step 3) to 200mL min-1The reaction template-based hierarchical porous carbon-based material is further improved by raising the temperature to 800 ℃ at the temperature of 6 ℃/min under the protection of flowing gas and keeping the temperature for 2 hours, and then naturally cooling the material to room temperature, and the product at this stage is marked as HPC-HT 2.
Example 5
1) Firstly, 2g of glucose, 1g of basic zinc carbonate and 1g of potassium carbonate are added into an agate mortar for full solid-phase mixing to obtain solid powder A;
2) subjecting A obtained in step 1) to 200mL min-1Under the protection of flowing inert gas, heating to 800 ℃ at the speed of 5 ℃/min, keeping for 1h, then naturally cooling to room temperature, and grinding uniformly to obtain a catalyst precursor B;
3) treating the catalyst precursor B obtained in the step 2) with an aqueous acid solution at room temperature for 12 hours, performing suction filtration and drying after the treatment to obtain a carbon-based material without a template and impurities, which is marked as HPC (G-BZC-PC), namely the hierarchical porous carbon-based material based on the reaction template, wherein G-BZC-PC is the English abbreviation of glucose (glucose), basic zinc carbonate (basic zinc carbonate) and potassium carbonate (potassium carbonate).
Example 6
A multi-level porous carbon-based material based on a reaction template is prepared by the following method:
the experimental procedure is the same as in example 5, except that a heat treatment is added after the experimental procedure 3), specifically: at 200mL min-1The product is marked as HPC-HT2(G-BZC-PC), namely the multi-stage porous carbon-based material based on the reaction template, at the stage of raising the temperature to 800 ℃ at the temperature of 5 ℃/min under the protection of flowing inert gas and keeping the temperature for 1h, and then naturally cooling to the room temperature.
Example 7
A multi-level porous carbon-based material based on a reaction template is prepared by the following method:
the experimental procedure was the same as in example 5, except that in experimental step 1) glucose was exchanged for chitosan, and the product at this stage was labeled HPC (C-BZC-PC), a reaction template-based hierarchical porous carbon-based material as described.
Example 8
A multi-level porous carbon-based material based on a reaction template is prepared by the following method:
the experimental procedure was the same as in example 5, except that in experimental step 1) the glucose was changed to ferric oxalate, and the product at this stage was labeled HPC (FO-BZC-PC), a reaction template-based hierarchical porous carbon-based material as described.
In the examples of the present invention, unless otherwise specified, the characterization and electrochemical testing means are conventional in the art.
The above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, so that equivalent changes or modifications made by the features and principles of the present invention as described in the claims should be included in the scope of the present invention.
Comparative example 1
1) Firstly, 2g of glucose and 1g of potassium carbonate are added into an agate mortar for full solid-phase mixing to obtain solid powder A;
2) heating the A obtained in the step 1) to 800 ℃ at a speed of 5 ℃/min for 1h under the protection of 200mL min-1 flowing inert gas, naturally cooling to room temperature, and uniformly grinding to obtain a catalyst precursor B;
3) treating the catalyst precursor B obtained in the step 2) with an aqueous acid solution at room temperature for 12 hours, performing suction filtration and drying after the treatment to obtain the carbon-based material with impurities removed, wherein the carbon-based material is marked as HPC (G-PC), and the G-PC is the English abbreviation of glucose (glucose) and potassium carbonate (potassium carbonate).
This preparation was compared as a control electrode material without using basic zinc carbonate as a reaction template with an electrode material prepared using basic zinc carbonate as a hard template and potassium carbonate as follows.
Comparative example 2
1) Firstly, 2g of glucose and 1g of basic zinc carbonate are added into an agate mortar for full solid-phase mixing to obtain solid powder A;
2) subjecting A obtained in step 1) to 200mL min-1Under the protection of flowing inert gas, heating to 800 ℃ at the speed of 5 ℃/min, keeping for 1h, then naturally cooling to room temperature, and grinding uniformly to obtain a catalyst precursor B;
3) treating the catalyst precursor B obtained in the step 2) with an aqueous acid solution at room temperature for 12 hours, performing suction filtration and drying after the treatment to obtain the carbon-based material with the template and impurities removed, wherein the carbon-based material is marked as HPC (G-BZC), and G-BZC is the English abbreviation of glucose (glucose) and basic zinc carbonate (basic zinc carbonate).
This preparation used basic zinc carbonate as a reaction template, but did not use potassium carbonate as an activator, and was still used as a control electrode material, as compared to the electrode material prepared using basic zinc carbonate as a hard template and potassium carbonate as described below.
And (3) performance testing:
the HPC (G-BZC-PC) synthesized in example 5, the HPC (G-PC) synthesized in comparative examples 1 and 2, SEM (scanning Electron microscope) of the HPC (G-BZC), and N2The adsorption/desorption isotherms and pore size distributions, XRD, Raman and XPS analyses are shown in figures 1, 2, 3, 4, 5 and 6, respectively.
3mg of a multi-graded porous reaction template-based carbon-based material prepared in comparative examples 1 and 2, and example 5, and a control sample were weighed with carbon black, PTFE at a ratio of 8: 1: 1 in ethanol, uniformly mixing, dripping on a dry foam nickel electrode sheet cleaned by acetone, deionized water and ethanol, drying overnight in vacuum, pressing into a sheet under 10Mpa, and assembling into a symmetrical two-electrode system of a super capacitor to test in 6M KOH.
The cyclic voltammograms, galvanostatic charge and discharge curves, discharge capacitances at different current densities, and cyclic stabilities of HPC (G-PC), HPC (G-BZC), and HPC (G-BZC-PC) synthesized in comparative examples 1, 2, and example 5 in 6M KOH are shown in FIGS. 7, 8, 9, and 10, respectively.
Table 1 structural property parameters of reaction template based hierarchical porous carbon-based materials
TABLE 2 specific capacitance of the reaction template based hierarchical porous carbon based materials in 6M KOH
The cyclic voltammograms, galvanostatic charge and discharge curves, discharge capacitance curves at different current densities, and cyclic stability of HPC (G-PC), HPC (G-BZC), and HPC (G-BZC-PC) synthesized in comparative examples 1, 2, and example 5 in 6M KOH are shown in FIGS. 7, 8, 9, 10, and Table 3, respectively.
FIGS. 1, 2, 3 show SEM, N for HPC (G-PC), HPC (G-BZC), and HPC (G-BZC-PC) synthesized in comparative examples 1, 2, and example 52The absorption and desorption curves and the pore size distribution are combined with texture parameters in the table 1, which shows that only basic zinc carbonate is taken as a reaction template, no activator potassium hydroxide is added, a mesoporous structure with a certain order degree can be created, a carbon-based material obtained only by using the activator potassium hydroxide mainly takes micropores as main components and has a large specific surface area, and when the basic zinc carbonate is taken as the reaction template and the potassium hydroxide is taken as the activator, a micro-mesoporous hierarchical pore (the average pore size is 0.55nm) based on the reaction template and the high specific surface area (1946 m) can be obtained2 g-1) And pore volume (1.28 cm)3 g-1) The spongy carbon-based material of (1). Fig. 4, 5 and 6 show wide-angle XRD spectra, Raman spectra and XPS full spectra of HPC (G-PC), HPC (G-BZC) and HPC (G-BZC-PC) synthesized in comparative examples 1, 2 and 5, and it can be seen that these carbon-based materials have a high degree of graphitization, containing only C and O elements, indicating that the reaction template basic zinc carbonate, the activator potassium carbonate and their oxides generated during the heat treatment are easily removed all by the acid treatment. Combining the data of FIGS. 1, 2, 3 and Table 1, the results demonstrate the use of basic carbonThe acid salt is used as a reaction template, and the carbonate is used as an activating agent, so that the pure carbon-based material with higher graphitization degree, micro-mesoporous hierarchical pore structure, large pore volume and specific surface area can be cut.
FIGS. 7, 8, 9, 10 and Table 2 show the electrochemical performance in 6M KOH of 3 samples of HPC (G-PC), HPC (G-BZC) and HPC (G-BZC-PC) synthesized in comparative examples 1, 2 and example 5, showing that they have good electrical double layer capacitance, rate capability, especially that of 241.2F G for the HPC (G-BZC-PC) synthesized in example 6, which has specific capacitance, rate capability and cycle stability performance up to 241.2-1(1A g-1) 90.5% (from 1A g)-1To 10A g-1) And more than 98% (10000 cycles), disclosing that glucose, basic zinc carbonate and potassium carbonate are respectively used as a carbon precursor, a reaction template and an activator, and the obtained HPC (G-BZC-PC) has micro-mesoporous hierarchical pores and high specific surface area, which is beneficial to increasing the available area for electron adsorption and improving the electron transfer rate, thereby improving the specific capacitance of the electrode material; in addition, compared with the HPC (G-PC) synthesized in comparative examples 1 and 2 and the HPC (G-BZC), the HPC (G-BZC-PC) has higher specific capacitance, rate capability and cycling stability, so that under optimized preparation conditions, the potential is very high to cooperate with a super capacitor electrode material.
Claims (7)
1. The hierarchical porous carbon-based material based on the reaction template is characterized by mainly containing C and O elements, wherein the pore diameter distribution of the hierarchical porous carbon-based material is 0.5-4.1 nm, and the pore volume is 0.94-1.28 cm3 g-1The specific surface area is 900 to 2000m2 g-1(ii) a The reaction template-based hierarchical porous carbon-based material is in a coral reef-like appearance and a three-dimensional pore structure; the reaction template-based hierarchical porous carbon-based material is prepared from a carbon precursor, basic carbonate and carbonate, wherein the mass ratio of the carbon precursor to the basic carbonate to the carbonate is 2: 0.5-4;
the carbon precursor is one or a combination of glucose, chitosan, methyl cellulose, soluble starch, EDTA disodium, EDTA ferric sodium and ferric oxalate;
the basic carbonate is one or a combination of more of basic zinc carbonate, basic magnesium carbonate, basic nickel carbonate or basic iron carbonate;
the carbonate is one or a combination of potassium carbonate and ammonium bicarbonate.
2. The method of preparing a reaction template-based, multi-stage, porous carbon-based material as recited in claim 1, comprising the steps of:
1) taking the carbon precursor, the basic carbonate and the carbonate according to the proportion, and fully mixing to obtain solid powder A;
2) heating the A obtained in the step 1) to 600-1000 ℃ at a speed of 5 +/-2 ℃/min under the protection of flowing inert gas, keeping for 1-3 h, naturally cooling to room temperature, and uniformly grinding to obtain a catalyst precursor B;
3) treating the catalyst precursor B obtained in the step 2) with an acidic aqueous solution for 1.0-24 h, then carrying out suction filtration and drying, and finally obtaining the carbon-based material without the template and impurities, namely the multi-stage porous carbon-based material based on the reaction template, which is marked as HPC.
3. The method for preparing the reaction template-based hierarchical porous carbon-based material according to claim 2, wherein the HPC obtained in the step 3) is prepared in 180-220 mL min-1Under the protection of flowing gas, heating to 700-900 ℃ at the speed of 5 +/-2 ℃/min, keeping for 0.5-3 h, and then naturally cooling to room temperature to obtain the further improved hierarchical porous carbon-based material based on the reaction template, wherein the product at this stage is marked as HPC-HT 2.
4. The method for preparing a multi-graded porous carbon-based material based on a reaction template according to claim 2, wherein the flowing inert gas is N in the step 2)2Or He.
5. The method for preparing a reaction template-based hierarchical porous carbon-based material according to claim 2, wherein in step 3), the porous carbon-based material is prepared by a method comprising a step of forming a porous carbon-based materialTreating with aqueous solution of acid, wherein the acid is HCl or H2SO4Or HNO3One or more compositions in solution; the method specifically comprises the following steps: adding the catalyst precursor B into an acid aqueous solution with the mass fraction of 5-20%, stirring for 1.0-24 h at 25-60 ℃, then repeatedly washing for 3 times by using deionized water, carrying out suction filtration and drying.
6. The method of claim 3, wherein the flowing gas is an inert gas or a reactive gas NH3。
7. The reactive template-based multi-graded pore carbon-based material of claim 1, wherein the reactive template-based multi-graded pore carbon-based material is used in a supercapacitor.
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