CN110970226A - Composite electrode material, preparation method and super capacitor - Google Patents
Composite electrode material, preparation method and super capacitor Download PDFInfo
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- CN110970226A CN110970226A CN201911319584.8A CN201911319584A CN110970226A CN 110970226 A CN110970226 A CN 110970226A CN 201911319584 A CN201911319584 A CN 201911319584A CN 110970226 A CN110970226 A CN 110970226A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003990 capacitor Substances 0.000 title abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 49
- 239000004744 fabric Substances 0.000 claims abstract description 49
- 239000002135 nanosheet Substances 0.000 claims abstract description 36
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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 claims abstract description 20
- 238000004070 electrodeposition Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 14
- 239000013110 organic ligand Substances 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000011258 core-shell material Substances 0.000 abstract description 15
- 229920000767 polyaniline Polymers 0.000 abstract description 15
- 239000013543 active substance Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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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
- H01G11/24—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, 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
-
- 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
-
- 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
- H01G11/48—Conductive polymers
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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)
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- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a composite electrode material, a preparation method thereof and a super capacitor. The preparation method of the composite electrode material comprises the following steps: calcining the carbon cloth loaded with the Co-MOF to obtain the carbon cloth loaded with the Co3O4Carbon cloth of nanosheets; will be loaded with Co3O4The carbon cloth of the nanosheet is used as a working electrode and is obtained by electrodeposition in electrolyte; the electrolyte comprises aniline and 0.8-1.2M sulfuric acid; the time of electrodeposition is 10-14 min. The composite electrode material is a composite electrode material with a carbon cloth loaded with nanosheets with core-shell structures, wherein the core is Co3O4The nano-sheet and the shell are made of polyaniline. Co obtained in preparation of composite electrode material3O4The nanosheets and the core-shell nanosheets in the product are uniformly grown on the carbon cloth, and collapse cannot occur; the composite electrode material can be directly used as a working electrode, has high specific capacitance, good cycle stability and large specific surface area, and can improve the utilization rate of active substances.
Description
Technical Field
The invention particularly relates to a composite electrode material, a preparation method and a super capacitor.
Background
Supercapacitors are a new type of energy storage device. The super capacitor has been widely researched due to the advantages of excellent power density, fast charge and discharge rate, long service life and the like, but the energy density of the super capacitor is far lower than that of a lithium ion battery, which means that the super capacitor cannot be widely used in real life like the lithium ion battery. In order to apply the super capacitor to portable devices, backup power sources, and large electric machines, it is imperative to increase the energy density of the super capacitor. The electrode material of the super capacitor is very important, and the development of the high-performance electrode material is the key point for realizing the breakthrough of energy density.
Polyaniline (PANI) is an excellent conductive polymer material, has the characteristics of simple synthesis, low cost, good conductivity, high theoretical capacitance and the like, and thus becomes a research hotspot of electrode materials of super capacitors. However, the PANi has a volume expansion/contraction phenomenon in the charging and discharging processes to cause the rapid attenuation of the structural stability and the cycling stability, which seriously affects the application of the PANi in the super capacitor. At present, in order to improve the cycling stability of the PANI, one solution is to compound a metal oxide, a carbon material and the PANI to form a multi-element composite material, and inorganic components in the composite material play a role in buffering, thereby being beneficial to the mechanical stability of the material. However, in the composite material containing metal oxide, carbon and polyaniline in the prior art, the metal oxide is usually directly used as an inner core, and the overall performance of the capacitor is not obviously improved. For example, Gemini (core-shell structure PANI-Co)3O4Preparation of composite nano-particles and performance research thereof, 2016.5.23, database of Chinese Master thesis) discloses a core-shell structure PANI-Co3O4The preparation of composite nano-particles is carried out by mixing shredded absorbent cotton with cobalt nitrate aqueous solution, calcining at 600 deg.C for 2h to obtain Co3O4Particles, then will contain Co3O4The hydrochloric acid aqueous solution of the particles is stirred and reacted with aniline and ammonium persulfate in sequence to obtain the core-shell structure PANI-Co3O4Composite nanoparticles. The powder structure PANI-Co obtained in this document3O4Can not be directly used as an electrode material, and can be used as a working electrode in a three-electrode system only by multi-step operation such as mixing with acetylene black and polyvinylidene fluoride. The internal resistance of the electrode is increased and the specific capacitance is reduced in the process of preparing the working electrode.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, cobaltosic oxide is usually directly used as an inner core, the overall performance of an electrode material cannot be obviously improved, the specific capacitance is low, and the cycle stability is poor; and the defect that the metal oxide is easy to collapse from the base material in the material compounded by the metal oxide and the base material in the prior art, thereby providing the composite electrode material, the preparation method and the supercapacitor. The composite electrode material is a composite electrode material with a carbon cloth loaded with nanosheets with core-shell structures, wherein the core is Co3O4The nano-sheet and the shell are made of polyaniline. Co obtained in preparation of composite electrode material3O4The nanosheets and the nanosheets with the core-shell structures in the final product are uniformly grown on the carbon cloth, and collapse is avoided; the composite electrode material can be directly used as a working electrode, has high specific capacitance, good cycle stability and large specific surface area, and can improve the utilization rate of active substances.
At present, although Co has been reported in the prior art3O4Is a composite electrode material with a core-shell structure and a shell of polyaniline. However, they have a number of disadvantages, for example, they are in the form of particles which cannot be used directly as working electrodes, and their core structure is composed of the usual metals onlyThe salt is obtained by high-temperature calcination, and the performance of the composite electrode material is not obviously improved. The inventor of the invention successfully screens a plurality of process parameters, such as deposition time in electrodeposition, concentration of sulfuric acid in electrolyte and other parameters through a plurality of experiments, and can have Co with a porous structure3O4The core-shell structure with the core and the polyaniline as the shell uniformly grows on the base material, and the phenomenon of collapse cannot occur, so that the composite electrode material with better performance is finally obtained.
The invention solves the technical problems through the following technical scheme.
The invention provides a preparation method of a composite electrode material, which comprises the following steps: calcining the carbon cloth loaded with the Co-MOF to obtain the carbon cloth loaded with the Co3O4Carbon cloth of nanosheets; loading the load with Co3O4The carbon cloth of the nanosheet is used as a working electrode and is obtained by electrodeposition in electrolyte;
the electrolyte comprises aniline and sulfuric acid, and the concentration of the sulfuric acid is 0.8-1.2M;
the time of the electrodeposition is 10-14 min.
In the present invention, the Co-MOF refers to a Metal-Organic framework (Metal-Organic Frameworks) using cobalt ions as Metal ions.
In the present invention, the preparation process of the Co-MOF loaded carbon cloth can be conventional in the art, and generally comprises the following steps: and (3) immersing the carbon cloth into a mixed solution containing cobalt salt and an organic ligand, and standing.
Wherein the carbon cloth is typically a carbon fiber cloth, as known to those skilled in the art.
The size of the carbon cloth may be conventional in the art, and may be, for example, 1X 2cm2。
Wherein, the preparation of the mixed solution can be conventional in the field, and generally comprises the following steps: and mixing the cobalt salt, the organic ligand and a solvent, and stirring.
In the mixed solution, the mass ratio of the cobalt salt to the organic ligand may be a mass ratio conventional in the art, and is preferably 1: (2.25-7), for example 1.312: 0.582.
The solvent in the mixture may be a solvent conventional in the art, preferably deionized water.
The stirring time may be a stirring time conventional in the art, and is preferably 4 to 6min, for example 5 min.
The concentration of the cobalt salt can be conventional in the art, and is preferably 10-15 mg/mL, such as 14.55 mg/mL.
The concentration of the organic ligand can be conventional in the art, and is preferably 30-35 mg/mL, such as 32.8 mg/mL.
The cobalt salt may be any one conventional in the art, and preferably cobalt nitrate hexahydrate.
Wherein, the organic ligand can be the organic ligand in Co-MOF conventional in the field, and is preferably dimethyl imidazole.
The operation and conditions of the standing can be conventional in the art, and the time of the standing is preferably 3-6 h, for example 4 h.
Wherein the operation of said resting is followed by a washing, as known to the skilled person.
The washing operation and conditions may be those conventional in the art, and preferably washing with deionized water 2 or more times.
In the present invention, the supported Co-MOFs may be two-dimensional nanosheet structures, as known to those skilled in the art.
Wherein the length of the Co-MOF can be 1.4-1.6 μm.
Wherein the width of the Co-MOF can be 600-800 nm.
Wherein the thickness of the Co-MOF can be 100-120 nm.
In the carbon cloth loaded with the Co-MOF obtained in the invention, the Co-MOF uniformly grows on the carbon cloth.
In the present invention, the equipment for carrying out the calcination may be conventional in the art. For example, the calcination is carried out by placing the Co-MOF loaded carbon in a magnetic ark and placing in a tube furnace.
In the present invention, the calcination temperature is preferably 300 to 400 ℃, for example, 350 ℃.
Wherein the rate of heating to the calcination temperature is preferably 2-10 deg.C/min, such as 5 deg.C/min. In the present invention, the calcination temperature and temperature rise rate are strictly controlled to avoid Co-MOF obtained after calcination3O4The nanosheet collapsed.
In the invention, the calcination time can be conventional in the art, and is preferably 2-3 h.
In the present invention, the calcination generally includes a natural cooling operation to room temperature, as known to those skilled in the art.
In the present invention, the Co3O4The thickness of the nanoplatelets can be 50-70 nm, for example 60 nm.
In the present invention, the electrodeposition is generally carried out using a three-electrode system, as is known to those skilled in the art. In the three-electrode system, a platinum sheet is generally used as a counter electrode, and silver/silver chloride is used as a reference electrode.
Wherein the platinum sheet may have a size conventional in the art, for example, 2X 2cm2。
The temperature of the electrodeposition may be conventional in the art, and is typically room temperature.
The electrodeposition may be carried out in an apparatus conventional in the art, for example, electrodeposition on Chenghua CHI660E electrochemical workstation.
The electrodeposition method may be a method conventional in the art, and is typically potentiostatic deposition.
The voltage for potentiostatic deposition may be conventional in the art, and is preferably-1.0V.
Wherein the time of the electrodeposition is preferably 11 to 13min, such as 12 min.
In the present invention, the concentration of aniline can be conventional in the art, and is preferably 0.05-0.15M, such as 0.1M.
In the present invention, the concentration of the sulfuric acid is preferably 0.9 to 1.1M, for example, 1M.
In the present invention, when the composite electrode material is used as a working electrode, it is preferable that no additive is added, that is, the composite electrode material of the present invention can be directly used as a working electrode. The additive can be additive which is conventionally used in the field of super capacitors, such as a conductive agent and a binder.
In the invention, the room temperature is generally 0-40 ℃.
The invention also provides a composite electrode material which is prepared by adopting the preparation method.
In the invention, the composite electrode material is a carbon cloth composite electrode material loaded with nanosheets with core-shell structures, and the core is Co3O4Nanosheets, the shell being polyaniline.
The thickness of the core-shell structure nanosheet can be 200-300 nm.
The invention also provides a super capacitor, and the electrode material of the super capacitor is the composite electrode material.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the composite electrode material obtained by the invention is a flexible composite electrode material with a core-shell structure nanosheet loaded on carbon cloth, wherein the carbon cloth is used as a base material for loading an active substance, and Co in the composite electrode material3O4The nano sheets are mutually interwoven, so that the specific surface area is large;
(2) the invention skillfully combines the metal-organic framework material with the porous structure with the electro-deposited polyaniline to prepare the Co with the porous structure3O4The nano-sheet is a core, and the polyaniline is a core-shell structure of the shell and uniformly grows on the carbon cloth. Wherein, Co3O4The phenomenon of collapse of the nanosheets on the surface of the carbon cloth can not occur. While screening by specific electrodeposition processes in Co3O4The nano-sheets are evenly coated with polyaniline. The composite electrode material finally obtained by the invention can be directly used as workThe electrode has high specific capacitance, good cycling stability and large specific surface area.
(3) Porous Co in the present invention3O4The nano-sheet is more beneficial to full contact of the active substance and the electrolyte, improves the utilization rate of the active substance, can well adapt to strain, and simultaneously reduces the influence of volume change on the structural stability in the polyaniline doping/dedoping process, thereby obtaining the composite electrode material with better performance.
Drawings
FIG. 1 is a scanning electron micrograph of a Co-MOF-loaded carbon cloth according to example 2.
FIG. 2 shows the Co-supporting case of example 23O4Scanning electron microscope images of carbon cloth of the nanosheets.
FIG. 3 is a scanning electron micrograph of the composite electrode material of example 2.
FIG. 4 is a graph of cyclic voltammetry tests performed on the composite electrode material of example 2.
Fig. 5 is a graph of a constant current charge and discharge test performed on the composite electrode material of example 2.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
The composite electrode material of the present example was prepared by the following steps:
(1) dissolving 1.312g of dimethylimidazole and 0.582g of cobalt nitrate hexahydrate in deionized water respectively to obtain a mixed solution, immediately stirring for 5min, and then adding a carbon cloth (1 × 2 cm)2) Adding the mixture into the mixed solution, standing and depositing for 4 hours until the reaction is complete to obtain the carbon cloth loaded with the Co-MOF, and washing the carbon cloth with the Co-MOF for more than 2 times by using deionized water to obtain the carbon cloth loaded with the Co-MOF.
(2) Placing the carbon cloth loaded with Co-MOF in a ceramic square boat and a high-temperature tube furnace, setting the heating rate of heating to the calcining temperature to be 5 ℃/min, and carrying out air treatmentCalcining at 350 ℃ for 2h, and naturally cooling to room temperature to obtain the Co-loaded material3O4Carbon cloth of nano-sheet.
(3) To be loaded with Co3O4Carbon cloth of nano-sheet is used as working electrode, silver/silver chloride electrode is used as reference electrode, platinum sheet (2X 2 cm)2) As a counter electrode, 0.1M aniline and 1M sulfuric acid were used as electrolytes, and electrodeposition was performed on Chenghua CHI660E electrochemical workstation. And performing electrodeposition at room temperature for 10min under a constant potential of-1.0V to obtain the composite electrode material.
The carbon cloth in examples 1 to 3 and comparative examples 1 and 2 is referred to as a carbon fiber cloth.
The parameters of examples 1-3 and comparative examples 1 and 2 are shown in Table 1 below, wherein the process parameters not listed are the same as those of example 1
TABLE 1
| Speed of temperature rise | Calcination temperature | Concentration of sulfuric acid | By electrodeposition |
| Rate/min | Degree C. | Degree (M) | Time min | |
| Example 1 | 5 | 350 | 1 | 10 |
| Example 2 | 5 | 350 | 1 | 12 |
| Example 3 | 5 | 350 | 1 | 14 |
| Comparative example 1 | 5 | 350 | 1 | 6min |
| Comparative example 2 | 5 | 350 | 1 | 16min |
Effect example 1
(1) Topography characterization
Co-MOF-Supported carbon cloth, Co-supported carbon cloth in example 2, and the like were subjected to field emission scanning electron microscopy3O4And carrying out morphology characterization on the carbon cloth of the nanosheet and the obtained composite electrode material.
Fig. 1 is a field emission scanning electron microscope image of the carbon cloth loaded with Co-MOF in example 2, and it can be seen from the image that Co-MOF is a sheet structure, is uniformly loaded on the carbon cloth, and is respectively and uniformly grown on one carbon fiber of the carbon cloth. As can be seen from FIG. 1, the Co-MOF nanosheets supported in example 2 had a length of 1.4 to 1.6 μm, a width of 600 to 800nm, and a thickness of 100 to 120 nm.
FIG. 2 shows the Co-supporting case of example 23O4Field emission scanning electron microscopy of carbon cloth of nanosheets, from which Co was obtained3O4The collapse phenomenon does not occur on the carbon cloth loaded with the nano sheets uniformly, and the Co can be obtained from the figure 23O4The thickness of the nanosheets was 60 nm.
FIG. 3 is a field emission scanning electron microscope image of the composite electrode material of example 2 at Co3O4Polyaniline is uniformly deposited on the surface of the nano sheet to form Co3O4The nano-sheet is a core-shell structure with a core and the polyaniline is a shell. The thickness of the nanosheet with the core-shell structure can be obtained from FIG. 3 and is 200-300 nm.
(2) Characterization of electrochemical Properties
The composite electrode materials in examples 1 to 3 and comparative examples 1 to 2 were used as a positive electrode, a platinum sheet was used as a counter electrode, a silver/silver chloride electrode was used as a reference electrode, and a 1M sulfuric acid solution was used as an electrolyte to form a three-electrode test system, which was subjected to cyclic voltammetry and constant current charge and discharge tests in a chenhua CHI660E instrument, and the specific capacitance at a current density of 5A/g was as shown in table 2 below.
TABLE 2
Specifically, the electrochemical performance of example 2 was taken as an example for analysis. Fig. 4 is a cyclic voltammetry test graph of the composite electrode material of example 2 at different scan rates of 5-100 mV, from which it can be seen that the composite electrode material of this embodiment exhibits similar symmetric redox peaks at high current density, and it can be seen that the composite electrode material has better rate capability and relatively small resistance.
Fig. 5 is a constant current charge and discharge curve of the composite electrode material of example 2, and the specific capacitance under different current densities can be calculated, and the test results are shown in table 3 below.
TABLE 3
Claims (10)
1. The preparation method of the composite electrode material is characterized in that the Co-MOF-loaded carbon cloth is calcined to obtain the Co-loaded carbon cloth3O4Carbon cloth of nanosheets; loading the load with Co3O4The carbon cloth of the nanosheet is used as a working electrode and is obtained by electrodeposition in electrolyte;
the electrolyte comprises aniline and sulfuric acid, and the concentration of the sulfuric acid is 0.8-1.2M;
the time of the electrodeposition is 10-14 min.
2. The method of claim 1, wherein the method of making the Co-MOF loaded carbon cloth comprises the steps of: and immersing the carbon cloth into a mixed solution containing cobalt salt and an organic ligand, and standing.
3. The method of claim 2, wherein the mass ratio of the cobalt salt to the organic ligand is 1: (2.25-7);
and/or the cobalt salt is cobalt nitrate hexahydrate;
and/or the organic ligand is dimethyl imidazole;
and/or the solvent in the mixed solution is deionized water;
and/or, the still standing is followed by washing.
4. The method according to claim 3, wherein the concentration of the cobalt salt is 10-15 mg/mL, preferably 14.55 mg/mL;
and/or the concentration of the organic ligand is 30-35 mg/mL, preferably 32.8 mg/mL;
and/or the standing time is 3-6 h, preferably 4 h;
and/or, the washing is washing for more than 2 times by deionized water.
5. The method of any one of claims 1 to 4, wherein the temperature of the calcination is 300 to 400 ℃, preferably 350 ℃;
and/or the calcining time is 2-3 h.
6. The method of claim 5, wherein the rate of heating to the calcination temperature is 2-10 ℃/min, preferably 5 ℃/min.
7. The production method according to any one of claims 1 to 4, wherein the deposition potential of the electrodeposition is potentiostatic deposition; wherein the voltage of the potentiostatic deposition is preferably-0.1V;
and/or the time of the electrodeposition is 11-13 min, preferably 12 min;
and/or the concentration of the aniline is 0.05-0.15M, preferably 0.1M;
and/or the concentration of the sulfuric acid is 0.9-1.1M, preferably 1M.
8. The method of claim 1, wherein no additive is added when the composite electrode material is used as a working electrode.
9. A composite electrode material produced by the production method according to any one of claims 1 to 8.
10. A supercapacitor, wherein the electrode material of the supercapacitor is the composite electrode material according to claim 9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112670099A (en) * | 2020-11-16 | 2021-04-16 | 中北大学 | PANI-Co3O4Preparation method and application of nano material |
| CN112967890A (en) * | 2021-01-29 | 2021-06-15 | 湖北大学 | Topological electrode material and preparation method and application thereof |
| CN114583166A (en) * | 2020-12-01 | 2022-06-03 | 河南大学 | Lithium-sulfur battery and preparation method thereof |
| CN114694977A (en) * | 2022-04-22 | 2022-07-01 | 江苏科技大学 | Super capacitor electrode material and preparation method thereof |
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2019
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112670099A (en) * | 2020-11-16 | 2021-04-16 | 中北大学 | PANI-Co3O4Preparation method and application of nano material |
| CN112670099B (en) * | 2020-11-16 | 2022-05-31 | 中北大学 | PANI-Co3O4Preparation method and application of nano material |
| CN114583166A (en) * | 2020-12-01 | 2022-06-03 | 河南大学 | Lithium-sulfur battery and preparation method thereof |
| CN112967890A (en) * | 2021-01-29 | 2021-06-15 | 湖北大学 | Topological electrode material and preparation method and application thereof |
| CN114694977A (en) * | 2022-04-22 | 2022-07-01 | 江苏科技大学 | Super capacitor electrode material and preparation method thereof |
| CN114694977B (en) * | 2022-04-22 | 2023-09-05 | 江苏科技大学 | Super-capacitor electrode material and preparation method thereof |
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