CN111524716B - Preparation and application of composite electrode material with manila herb as carbon source - Google Patents
Preparation and application of composite electrode material with manila herb as carbon source Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007772 electrode material Substances 0.000 title claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 46
- 239000010941 cobalt Substances 0.000 claims abstract description 46
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 33
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000005520 cutting process Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003990 capacitor Substances 0.000 claims abstract description 8
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 4
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000003763 carbonization Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 240000001102 Zoysia matrella Species 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 241001290610 Abildgaardia Species 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000002159 nanocrystal Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 102000029749 Microtubule Human genes 0.000 description 2
- 108091022875 Microtubule Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 210000004688 microtubule Anatomy 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000299507 Gossypium hirsutum Species 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000121220 Tricholoma matsutake Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
A preparation method of a composite material taking manila as a carbon source comprises the following steps: s1, drying the manila herb, cutting into sections, and carbonizing in a vacuum environment to obtain a porous carbon material; s2, immersing the porous carbon material in a cobalt source solution for ultrasonic treatment to enable the porous carbon material to be mutually infiltrated, so as to obtain a mixed solution; wherein the cobalt source solution is an aqueous solution of a cobalt-containing compound, and the cobalt-containing compound is selected from one or more of cobalt nitrate, cobalt chloride or cobalt oxalate; and S3, transferring the mixed solution into a high-pressure reaction kettle for solvothermal reaction, filtering, washing and drying a reaction product, and cooling to obtain the composite material. The invention also relates to a composite material prepared by the method and using the manila as a carbon source and application of the composite material in a super capacitor. The composite material taking the manila sedge as the carbon-based load has excellent electrochemical performance and has great application prospect in the fields of energy storage, conversion, catalysts and other related application fields.
Description
Technical Field
The invention relates to the field of supercapacitors, and particularly relates to a composite material taking manila as a carbon source, a preparation method and application thereof.
Background
Manila (also known as zoysia matsutake) is a perennial herb of zoysia of the order graminales. The manila herb is mainly composed of cellulose, and the microscopic appearance of the manila herb is porous after the manila herb is cleaned and dried. The natural manila fiber is smooth, soft and excellent in mechanical property, and has the structural characteristics of high specific surface area, large pore volume and the like.
Transition Metal Oxide (TMO) and its composites are considered ideal pseudocapacitive electrode materials due to their high theoretical specific capacitance. Because they can form nanostructures with large surface areas and rich oxidation states, efficient charge transfer by interfacial redox processes can be achieved. In recent years, researchers report several Co with special morphology through copying fine micro-nano structures of natural species such as cotton, sorghum stalks, wood and the like3O4A base electrode material. Wherein most of the electrode material has higher mass transfer capacityWeak and has a small interface with the electrolyte; and most are dense/blocky, lack effective charge transport channels and are prone to self-aggregation, limiting their potentially high-performance large-scale practical applications.
Disclosure of Invention
The invention aims to provide a composite material taking manila as a carbon source, which has excellent electrochemical performance.
The invention also aims to provide a preparation method of the composite material taking the manila as the carbon source, which has low cost and is simple and feasible.
The invention also aims to provide application of the composite material taking the manila as the carbon source in the super capacitor.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a preparation method of a composite material taking manila as a carbon source, which comprises the following steps:
s1, drying the manila herb, cutting into sections, and carbonizing in a vacuum environment to obtain a porous carbon material;
s2, immersing the porous carbon material in a cobalt source solution for ultrasonic treatment to enable the porous carbon material to be mutually infiltrated, so as to obtain a mixed solution; wherein the cobalt source solution is an aqueous solution of a cobalt-containing compound, and the cobalt-containing compound is selected from one or more of cobalt nitrate, cobalt chloride or cobalt oxalate;
and S3, transferring the mixed solution into a high-pressure reaction kettle for solvothermal reaction, filtering, washing and drying a reaction product, and cooling to obtain the composite material.
Further, in the preferred embodiment of the present invention, in step S1, the length of the cut piece of manila herb is 3-5 mm.
Further, in the preferred embodiment of the present invention, in step S1, the carbonization process specifically includes:
placing the segmented Manila into a crucible, transferring the crucible into a muffle furnace, carrying out carbonization reaction at 500-800 ℃ for 0.5-1.5h, and taking out.
Further, in a preferred embodiment of the present invention, the concentration of the cobalt source solution is 0.01-0.1mol/L, and the mass ratio of the porous carbon material to the cobalt-containing compound in the mixed solution is 1: 0.1-1.
Further, in a preferred embodiment of the present invention, the cobalt-containing compound is cobalt nitrate hexahydrate.
Further, in the preferred embodiment of the present invention, the ultrasonic treatment time is 10-30 min.
Further, in the preferred embodiment of the present invention, during the solvent thermal reaction, the organic solvent is added, and then the temperature is raised to 150 ℃ and 180 ℃ for reaction for 1.5-3h, wherein the temperature raising speed is 2-5 ℃ min-1。
Further, in the preferred embodiment of the present invention, in step S3, the reaction product is cooled in a water bath at a temperature of 15-25 deg.C for a period of 20-60 min.
The embodiment of the invention also provides a composite material taking the manila as the carbon source, which is obtained by the preparation method of the composite material taking the manila as the carbon source.
The embodiment of the invention also provides application of the composite material taking the manila as the carbon source in the super capacitor as the electrode material.
The composite material taking the manila as the carbon source, the preparation method and the application thereof have the following beneficial effects:
(1) the composite material taking the manila as the carbon source provided by the invention takes the manila as the biologically derived carbon source, and has the advantages of smoothness, softness and excellent mechanical properties. The composite material synthesized by taking the porous carbon material obtained after the carbonization of the manila as the carbon template combines the advantages of the carbonaceous material, the obtained composite material has uniform appearance, the electronic conductivity of the electrode material is improved, and the migration speed of electrons can be increased. The structural characteristics of high specific surface area, large pore volume and the like of the manila are utilized, so that the fluidity of the active substance is improved, and more active surface interfaces are provided for Faraday reaction. Has great application prospect in the fields of energy storage, conversion, catalysts and other related applications.
(2) The invention uses the solvent thermal reaction to load the cobalt-containing compound as a cobalt source on the porous carbon material, the solvent thermal reaction has low energy consumption and less agglomeration, and the formed particle shape is controllable. The pseudo-capacitance reaction of the heteroatom is introduced, so that the electrode material has better electrochemical performance when being used as an electrode material of a super capacitor.
(3) The preparation method provided by the invention is simple, the materials are easy to obtain, and the cost is low.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a scanning electron micrograph (magnification: 5000X) of a composite material prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph (magnification: 20KX) of a composite material prepared in example 1 of the present invention;
FIGS. 3(a) -3(d) are XP test charts for the composite material prepared in example 1 of the present invention;
FIG. 4 is a cyclic voltammogram of the composite material prepared in example 1 of the present invention;
FIG. 5 is a constant current discharge curve of the composite material prepared in example 1 of the present invention at different current densities;
FIG. 6 is a Nyquist plot for the composite material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The composite material using manila as a carbon source, the preparation method and the application thereof according to the embodiment of the present invention will be specifically described below.
The embodiment of the invention provides a preparation method of a composite material taking manila as a carbon source, which comprises the following steps:
s1, drying the manila herb, cutting into sections, and carbonizing in a vacuum environment to obtain the porous carbon material. In the embodiment, the length of the manila cut is 3-5 mm. After the manila herb is cut into sections, the subsequent mutual permeation with the cobalt source solution is more facilitated.
Further, in step S1, the carbonization process specifically includes: placing the segmented Manila into a crucible, transferring the crucible into a muffle furnace, carrying out carbonization reaction at 500-800 ℃ for 0.5-1.5h, and taking out.
The high reaction temperature is maintained at the initial stage of the carbonization reaction process, so that excessive fine holes are not formed. When the carbonization temperature is too high, the generation speed of the holes is too high and is also reduced. Preferably, the carbonization reaction is carried out for 1-1.5h at 500-700 ℃, and most preferably, the carbonization reaction is carried out for 1-1.5h at 600-700 ℃. When the carbonization time is longer, the pore structure is increased, the specific surface area is increased, and sufficient Co can be provided3O4A grain enrichment site.
S2, immersing the porous carbon material in a cobalt source solution for ultrasonic treatment to enable the porous carbon material to be mutually infiltrated, so as to obtain a mixed solution;
the cobalt source solution is an aqueous solution of a cobalt-containing compound, and the cobalt-containing compound is selected from one or more of cobalt nitrate, cobalt chloride or cobalt oxalate. Of course, other cobalt-containing compounds may also be selected, such as cobalt hydroxide, cobalt carbonate, Co (NH)6 3+Etc., the present invention is not particularly limited. Preferably, the cobalt-containing compound is cobalt nitrate hexahydrate.
Further, the concentration of the cobalt source solution is 0.01-0.1mol/L, and the mass ratio of the porous carbon material to the cobalt-containing compound in the mixed solution is 1: 0.1-1. More preferably, the concentration of the cobalt source solution is 0.01-0.05mol/L, and the mass ratio of the porous carbon material to the cobalt-containing compound in the mixed solution is 1: 0.1-1. When the content of the cobalt source is too smallThe loading capacity is small, and when the content of the cobalt source is too high, Co is easy to cause in the solvothermal reaction process3O4The aggregation is caused by the excessively high generation amount of the nano crystals, an effective charge transport channel is lacked, and the electrochemical performance of the composite material is reduced.
Further, the ultrasonic treatment time is 10-30min, and the ultrasonic treatment promotes the mutual permeation of the cobalt source solution and the porous carbon material, so that the cobalt-containing compound is dispersed more uniformly in the 3D carbon network of the porous carbon material.
And S3, transferring the mixed solution into a high-pressure reaction kettle for solvothermal reaction, filtering, washing and drying a reaction product, and cooling to obtain the composite material.
In the solvothermal reaction, the solvent is at a temperature and pressure above its critical point, and the cobalt-containing compound is dissolved in an organic solvent, in which Co is present2+Partial oxidation-reduction to carbon and Co, respectively3+Ionic, recrystallization to form Co3O4。Co3O4The nanocrystalline bonds Co ions to a 3D carbon skeleton of the starch through O-H, C ═ O and other groups, so that pseudo-capacitance reaction of heteroatoms is introduced, and the electrochemical performance of the nanocrystalline is improved. Under the condition of liquid phase or supercritical, reactants are dispersed in the solution and become more active, the product is slowly generated, the agglomeration is less, and the process is relatively simple and easy to control.
In this embodiment, the organic solvent may be a non-aqueous solvent such as ethanol, methanol, acetone, ethylene glycol, acetonitrile, ethylenediamine, dimethylformamide, and dimethylsulfoxide, and different solvents may be selected to obtain Co with different sizes, shapes, and dispersibility3O4Nanocrystals, the present invention is not particularly limited. Preferably, the organic solvent is ethanol.
Further, in the process of the solvent thermal reaction, adding an organic solvent, and then heating to 150-180 ℃ for reaction for 1.5-3h, wherein the heating speed is 2-5 ℃ min-1. In this embodiment, the crystal grains are controlled to grow slowly by slowly raising the temperature, so that the reaction process is controllable, the generation speed of the controlled crystal nuclei is adapted to the growth speed of the crystals, and the uniformly dispersed and large-sized crystal grains can be obtained.
Further, in step S3, the reaction product is cooled in water bath at 15-25 deg.C for 20-60 min. The rapid cooling mode can better protect the surface form of the sample after the reaction is finished, and the sample is prevented from structural contraction, collapse and the like in the natural cooling process.
The embodiment of the invention also provides a composite material taking the manila as the carbon source, which is obtained by the preparation method of the composite material taking the manila as the carbon source.
The embodiment of the invention also provides application of the composite material taking the manila as the carbon source as the electrode material in the super capacitor. Preparing a multi-stage carbon microtubule by taking manila as a carbon source, then loading Co on the inner wall and the outer wall of the microtubule by taking the manila as a carrier3O4The nano crystal introduces pseudo-capacitance reaction of hetero atoms, and combines the advantages of biomass materials, so that the nano crystal has better electrochemical performance when being used as an electrode material of a super capacitor.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a composite material taking manila as a carbon source, which comprises the following steps:
s1, cleaning and drying the manila officinalis, cutting the manila officinalis into sections with the length of 5mm, placing the sectioned manila officinalis in a crucible, transferring the crucible into a muffle furnace, carrying out carbonization reaction at 600 ℃ for 1h, and taking out the manila officinalis to obtain a porous carbon material;
s2, mixing 1.46g Co (NO)3)2·6H2Soaking O in 50ml ethanol solution to obtain 0.1mol/L cobalt source solution, soaking 1.5g porous carbon material in the cobalt source solution, and performing ultrasonic treatment for 15min to mutually soak the porous carbon material to obtain mixed solution;
s3, transferring the mixed solution into a high-pressure reaction kettle, adding an organic solvent, heating to 180 ℃ and reacting for 2h, wherein the heating speed is 2 ℃ min-1Cooling the reaction product in water bath at 15-25 deg.C for 30min, washing, and drying to obtain the final productA composite material.
Example 2
The embodiment provides a preparation method of a composite material taking manila as a carbon source, which comprises the following steps:
s1, cleaning and drying the manila officinalis, cutting the manila officinalis into sections with the length of 5mm, placing the sectioned manila officinalis in a crucible, transferring the crucible into a muffle furnace, carrying out carbonization reaction at 600 ℃ for 1h, and taking out the manila officinalis to obtain a porous carbon material;
s2, mixing 0.15gCo (NO)3)2·6H2Soaking O in 50ml ethanol solution to obtain 0.01mol/L cobalt source solution, soaking 1.5g porous carbon material in the cobalt source solution, and performing ultrasonic treatment for 15min to mutually soak the porous carbon material to obtain mixed solution;
s3, transferring the mixed solution into a high-pressure reaction kettle, adding an organic solvent, heating to 180 ℃ and reacting for 2h, wherein the heating speed is 2 ℃ min-1And cooling the reaction product in water bath at 15-25 ℃ for 30min, washing and drying to obtain the composite material.
Example 3
The embodiment provides a preparation method of a composite material taking manila as a carbon source, which comprises the following steps:
s1, cleaning and drying the manila officinalis, cutting the manila officinalis into sections with the length of 5mm, placing the sectioned manila officinalis in a crucible, transferring the crucible into a muffle furnace, performing carbonization reaction at 800 ℃ for 1h, and taking out the manila officinalis to obtain a porous carbon material;
s2, mixing 1.46g Co (NO)3)2·6H2Soaking O in 50ml ethanol solution to obtain 0.1mol/L cobalt source solution, soaking 1.5g porous carbon material in the cobalt source solution, and performing ultrasonic treatment for 15min to mutually soak the porous carbon material to obtain mixed solution;
s3, transferring the mixed solution into a high-pressure reaction kettle, adding an organic solvent, heating to 180 ℃ and reacting for 2h, wherein the heating speed is 2 ℃ min-1And cooling the reaction product in water bath at 15-25 ℃ for 30min, washing and drying to obtain the composite material.
Example 4
The embodiment provides a preparation method of a composite material taking manila as a carbon source, which comprises the following steps:
s1, cleaning and drying the manila officinalis, cutting the manila officinalis into sections with the length of 5mm, placing the sectioned manila officinalis in a crucible, transferring the crucible into a muffle furnace, carrying out carbonization reaction at 600 ℃ for 1h, and taking out the manila officinalis to obtain a porous carbon material;
s2, mixing 1.46g Co (NO)3)2·6H2Soaking O in 50ml ethanol solution to obtain 0.1mol/L cobalt source solution, soaking 1.5g porous carbon material in the cobalt source solution, and performing ultrasonic treatment for 15min to mutually soak the porous carbon material to obtain mixed solution;
s3, transferring the mixed solution into a high-pressure reaction kettle, adding an organic solvent, heating to 180 ℃ and reacting for 2h, wherein the heating speed is 5 ℃ min-1And cooling the reaction product in water bath at 15-25 ℃ for 30min, washing and drying to obtain the composite material.
Example 5
The embodiment provides a preparation method of a composite material taking manila as a carbon source, which comprises the following steps:
s1, cleaning and drying the manila officinalis, cutting the manila officinalis into sections with the length of 5mm, placing the sectioned manila officinalis in a crucible, transferring the crucible into a muffle furnace, carrying out carbonization reaction at 600 ℃ for 1h, and taking out the manila officinalis to obtain a porous carbon material;
s2, 1.19g CoCl2·6H2Soaking O in 50ml ethanol solution to obtain 0.1mol/L cobalt source solution, soaking 1.5g porous carbon material in the cobalt source solution, and performing ultrasonic treatment for 15min to mutually soak the porous carbon material to obtain mixed solution;
s3, transferring the mixed solution into a high-pressure reaction kettle, adding an organic solvent, heating to 180 ℃ and reacting for 2h, wherein the heating speed is 2 ℃ min-1And cooling the reaction product in water bath at 15-25 ℃ for 30min, washing and drying to obtain the composite material.
Test example 1
The composite material obtained in example 1 was subjected to scanning electron microscope microscopic analysis, and the results are shown in FIGS. 1 to 2. Wherein the content of the first and second substances,as can be seen from the figure, the manila herb presents obvious porous carbon characteristic appearance after the pre-carbonization treatment, the aperture is larger, and a plurality of tiny apertures are arranged in the middle. Co formed after solvothermal reaction as a whole3O4The nanocrystals are more uniformly attached to the 3D carbon skeleton of the porous carbon material.
Test example 2
The composite material obtained in example 1 was examined by X-ray energy spectrum, and the results are shown in FIGS. 3(a) to 3 (d). Wherein, FIG. 3(a) is a characteristic peak of Co 2 p; FIG. 3(b) is a characteristic peak of C, O, Co elements; FIG. 3(c) is a characteristic peak for O1 s; fig. 3(d) shows a characteristic peak of C1 s.
Test example 3
The composite material obtained in example 1 was subjected to electrochemical performance tests under the following test conditions:
the sample obtained in example 1 was subjected to Cyclic Voltammetry (CV) and alternating current impedance measurements (EIS) using the CHI660E electrochemical workstation, in a three-electrode system: uniformly dripping a sample on one side of 1 × 2 foamed nickel, drying, binding the dried sample at the tail end of a copper rod, taking 1mol/L Hg/HgO as a reference electrode and 6M KOH as electrolyte, performing all tests at room temperature, and introducing N before the test2Removing dissolved oxygen in the electrolyte. Wherein the content of the first and second substances,
the potential of the point in the scanning interval of the cyclic voltammetry test is 0-0.35V, the scanning speed is 10-100 mV/s, and the result is shown in FIG. 4. The potential of a constant current discharge test scanning interval is-0.2-0.8V, and the discharge current is 0.5 A.g-1～10A·g-1The results are shown in FIG. 5. The AC impedance test frequency range is 10-2～105Hz, the amplitude of the AC perturbation voltage is 5mV, and the result is shown in FIG. 6.
As can be seen from fig. 4, the cyclic voltammetry curve is an ideal rectangular shape specific to the capacitor material with ideal capacitance property and fast charge and discharge property as the voltage scan rate increases. Figure 5 shows that at different current densities the discharge time is short, indicating that the material has a higher conductivity, showing the desired capacitive properties. As can be seen from fig. 6, the slope of the impedance curve in the low frequency region is close to 90 °, showing a smaller diffusion resistance and a larger diffusion capacity for the electrolyte ions.
In summary, the composite material using the manila herb as the carbon source provided by the embodiment of the invention combines the advantages of the carbonaceous material, the carbonized manila herb is used as the porous carbon source, the morphology is uniform, the pore diameter is large, and the Co is subjected to hydrothermal reaction by using the carbonized manila herb as the carrier3O4The nano crystal is bonded to the porous carbon material to obtain the composite material with excellent electrochemical performance, and the composite material has great application prospect in the fields of energy storage, conversion, catalysts and other related application fields.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of a composite material taking manila as a carbon source is characterized by comprising the following steps:
s1, drying the manila herb, cutting into sections, and carbonizing in a vacuum environment to obtain a porous carbon material; the carbonization process specifically comprises the following steps: placing the segmented Manila into a crucible, transferring the crucible into a muffle furnace, carrying out carbonization reaction at 600-700 ℃ for 1-1.5h, and taking out;
s2, immersing the porous carbon material in a cobalt source solution for ultrasonic treatment to enable the porous carbon material to be mutually infiltrated, so as to obtain a mixed solution; wherein the cobalt source solution is an aqueous solution of a cobalt-containing compound, and the cobalt-containing compound is selected from one or more of cobalt nitrate, cobalt chloride or cobalt oxalate; the concentration of the cobalt source solution is 0.01-0.1mol/L, and the mass ratio of the porous carbon material to the cobalt-containing compound in the mixed solution is 1: 0.1-1;
and S3, transferring the mixed solution into a high-pressure reaction kettle for solvothermal reaction, filtering, washing and drying a reaction product, and cooling to obtain the composite material.
2. The method for preparing a composite material using manila as a carbon source as claimed in claim 1, wherein the length of the manila cut pieces is 3-5mm in step S1.
3. The method for preparing a composite material using manila grass as a carbon source as claimed in claim 1, wherein the cobalt-containing compound is cobalt nitrate hexahydrate.
4. The method for preparing a composite material using manila grass as a carbon source as claimed in claim 1, wherein the ultrasonic treatment time is 10-30 min.
5. The method as claimed in claim 4, wherein the temperature of the mixture is raised to 150-180 ℃ for 1.5-3h, wherein the temperature is raised at 2-5 ℃ min-1。
6. The method for preparing a composite material using manila as a carbon source as claimed in claim 1, wherein the reaction product is cooled in water bath at 15-25 ℃ for 20-60min in step S3.
7. A composite material using manila grass as a carbon source, which is obtained by the method for producing a composite material using manila grass as a carbon source according to any one of claims 1 to 6.
8. The composite material which takes the manila officinalis as the carbon source and is claimed in claim 7 is applied to a super capacitor as an electrode material.
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