CN113394028A - Preparation of Co by gas phase diffusion3O4Method for compounding supercapacitor material with graphene - Google Patents
Preparation of Co by gas phase diffusion3O4Method for compounding supercapacitor material with graphene Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 51
- 238000013329 compounding Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000002131 composite material Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 44
- 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 39
- 239000002244 precipitate Substances 0.000 claims abstract description 34
- 239000003990 capacitor Substances 0.000 claims abstract description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 19
- 238000009792 diffusion process Methods 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 230000003068 static effect Effects 0.000 claims abstract description 9
- 239000013543 active substance Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000010998 test method Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 4
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 239000000843 powder Substances 0.000 claims 2
- 239000011521 glass Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012716 precipitator Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 238000009388 chemical precipitation Methods 0.000 abstract description 10
- 239000008367 deionised water Substances 0.000 abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 238000011085 pressure filtration Methods 0.000 abstract 1
- 239000011882 ultra-fine particle Substances 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- H—ELECTRICITY
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- 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
- H01G11/84—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- 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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Abstract
The invention discloses a method for preparing Co by gas phase diffusion3O4A method for compounding a supercapacitor material with graphene adopts a gas diffusion chemical precipitation method, ammonia water, metal cobalt salt, graphene and deionized water react for a certain time according to a certain proportion under a sealed static condition to obtain a precipitate, and the precipitate is subjected to reduced pressure filtration by a sand core filtering device to obtain Co3O4And graphene composite supercapacitor materials. Co prepared by gas phase diffusion chemical precipitation method3O4And graphene composite superThe grade capacitor material has uniform particle size and ultrafine particle size, is used as an electrode active substance of a super capacitor, and shows excellent specific capacitance and rate performance.
Description
Technical Field
The invention belongs to the technical field of electrode materials of super capacitors, and particularly relates to a method for preparing Co by gas phase diffusion3O4And a method for compounding a supercapacitor material with graphene.
Background
The materials currently applied to the supercapacitor electrode mainly include carbon-based materials, metal oxides and conductive polymers. Carbon-based materials for the electrode of the super capacitor mainly comprise carbon nanotubes, activated carbon and the like, and since graphene is successfully prepared, people can explore the application of the carbon material with a limit structure in the super capacitor. Graphene has been gradually used as an electrode material of a supercapacitor by many people due to its characteristics of large specific surface area, excellent conductivity, good flexibility, and the like. The specific capacitance and energy density of the super capacitor can be improved by compounding the graphene with metal oxide, high molecular polymer and the like.
Co3O4Due to the ultrahigh theoretical specific capacitance and excellent economy, the method is concerned by researchers and super capacitor manufacturers in recent years. But the redox reaction occurs in the charge and discharge process, which often results in poor cycle performance of the capacitor, and Co3O4Poor conductivity, to compensate for Co3O4The material is insufficient, and the compounding with the graphene is an effective way. In the preparation of composite materials, there are many reports of methods such as hydrothermal method, solvothermal method, chemical precipitation method, thermal decomposition method, sol-gel method, templating method, electrodeposition method, chemical vapor deposition method, chemical bath deposition, in-situ self-organization method, etc. Co synthesized by most synthetic methods3O4Although the electrode material has excellent performance, the synthesis condition is difficult, and the development of actual industrial preparation is influenced. The chemical precipitation method is a method which is simple and easy to operate, has low requirements on equipment technology, can be rapidly industrialized, is more and more concerned by scientific researchers and preparation process designers, and has the defects of wide particle size distribution and poor dispersibility of particles prepared by the chemical precipitation method. Therefore, a Co which is low in cost, simple and easy to synthesize and excellent in performance has been developed3O4The method for preparing the graphene composite electrode material also becomes one of the key problems to be solved in the field.
Disclosure of Invention
Based on the defects of the prior art, the technical problem solved by the invention is to provide a method for preparing Co by gas phase diffusion3O4And a method for compounding the super capacitor material with graphene, wherein a gas phase diffusion precipitation method is an improvement of a chemical precipitation method. The method not only retains the advantages of simplicity and quickness of a chemical precipitation method, but also has the characteristic of being capable of synthesizing the supercapacitor material with small and uniformly dispersed particles. Prepared Co3O4Is an ultrafine nano particle and is loaded on a graphene sheet layer.
In order to solve the technical problems, the invention is realized by the following technical scheme: the invention provides a method for preparing Co by gas phase diffusion3O4And a method for compounding the supercapacitor material with graphene:
s1: mixing a cobalt salt solution and a graphene solution, putting the mixture into a 100mL beaker, magnetically stirring for half an hour, pouring ammonia water into a 50mL beaker, putting the two beakers into a closed dryer at the same time, reacting for 4-10 hours, observing generation of a precipitate at room temperature, filtering out a sand core funnel, washing with ethanol and distilled water, and drying in a vacuum drying oven at 60 ℃ to obtain a dried precipitate;
s2: heating the precipitate obtained in the step S1 to 300 ℃ at the speed of 5 ℃/min under the protection of high-purity nitrogen in a tube furnace, carrying out heat treatment at the temperature of 300 ℃ for 3 hours, and then naturally cooling to finally obtain black Co3O4And graphene composite supercapacitor materials;
s3: mixing the Co obtained in step S23O4And the graphene composite super capacitor material is used as a super capacitor active substance, and a specific capacitance is 389.4F/g, a specific capacitance is 323.6F/g under a current density of 10A/g and a rate capability is 83.1% by adopting a three-electrode test method under a current density of 1A/g.
Preferably, the cobalt source is cobalt chloride; the graphene solution is prepared by a Hummers method; the concentration of the ammonia water is 25-28%; the water is deionized water.
Further, the cobalt salt is 2.5mmol, the graphene concentration is 1g/L, the volume change is from 0mL to 40mL, the total volume of the cobalt salt and the graphene is kept at 50mL, the ammonia water is 5mL to 20mL, and the reaction time is 4 to 10 hours.
According to the method, a gas diffusion chemical precipitation method is adopted, a cobalt chloride solution, a graphene solution and ammonia water react for 4-10 hours at a room temperature in a static state according to a certain molar ratio to obtain a precipitate, the precipitate is filtered out, and then the precipitate is cleaned and dried to obtain Co3O4And graphene composite supercapacitor materials. The method of the invention is to synthesize Co3O4Provides a new method for preparing a graphene composite super capacitor material, and the synthesized Co3O4And graphene composite supercapacitor material of Co3O4The ultrafine nanoparticles are loaded on the graphene sheet layers.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments, together with the accompanying drawings.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is a diagram of the gas phase diffusion process for preparing Co according to the present invention3O4The scanning electron microscope image of the @ GO composite supercapacitor material.
FIG. 2 shows the Co obtained by the present invention3O4The energy spectrum element analysis image of the @ GO composite supercapacitor material.
FIG. 3 shows Co obtained by the method of the present invention3O4And Co3O4The discharge curve of the @ GO composite supercapacitor material at a current density of 1A/g.
FIG. 4 shows Co obtained by the method of the present invention3O4And Co3O4Specific capacity of @ GO composite supercapacitor material at different current densities。
FIG. 5 shows Co obtained by the method of the present invention3O4And Co3O4@ GO composite supercapacitor materials Cyclic voltammograms at 10mV/s scan rate.
FIG. 6 shows Co obtained by the method of the present invention3O4@ GO composite supercapacitor materials cyclic voltammograms at different scan rates.
FIG. 7 shows Co obtained by the method of the present invention3O4And Co3O4The @ GO composite supercapacitor material is on an alternating current impedance curve.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which form a part of this specification, and which illustrate, by way of example, the principles of the invention. In the referenced drawings, the same or similar components in different drawings are denoted by the same reference numerals.
Mixing a cobalt salt solution and a graphene solution according to a certain proportion, putting the mixture into a 100mL beaker, uniformly stirring, putting ammonia water into a 50mL beaker, putting two beakers into a dryer, keeping the beakers static, covering the dryer cover, reacting for a certain time, filtering the obtained precipitate sand core by a filtering device under reduced pressure, washing the precipitate sand core by distilled water, and drying the precipitate sand core at 60 ℃ to obtain a precipitate; putting the precipitate into a tube furnace under the protection of high-purity nitrogen, carrying out heat treatment at the temperature of 300 ℃ for 3 hours, and then naturally cooling to finally obtain black Co3O4And graphene composite supercapacitor material, and the invention synthesizes Co3O4The graphene composite supercapacitor material is prepared by adopting a gas diffusion chemical precipitation method, and the prepared material is in a nanosheet layer shape and is loaded with superfine nanoparticles.
Example 1:
2.5mmol of cobalt chloride and 50mL of deionized water are uniformly mixed and put into a 100mL beaker, 10mL of ammonia water is put into a 50mL beaker, the two beakers are simultaneously put into a closed reactor and kept stillStopping the reaction for 6 hours through gaseous diffusion of ammonia water, filtering the precipitate product by a sand core filtering device under reduced pressure, separating, washing, drying at 60 ℃ to obtain dry precipitate, heating the precipitate to 300 ℃ at the temperature of 300 ℃ for 3 hours at the temperature of 300 ℃ under the protection of high-purity nitrogen in a tubular furnace at the speed of 5 ℃/min, and then naturally cooling to obtain black Co3O4A supercapacitor material.
Example 2:
uniformly mixing 2.5mmol of cobalt chloride, 30mL of deionized water and 20mL of graphene solution, putting the mixture into a 100mL beaker, wherein the density of the graphene solution is 1g/L, putting 10mL of ammonia water into a 50mL beaker, putting two beakers into a closed reactor at the same time, keeping the beakers static, reacting for 8 hours through gaseous diffusion of the ammonia water, filtering a precipitate product by a sand core filter device under reduced pressure, separating, washing, drying at 60 ℃ to obtain a dry precipitate, heating the precipitate to 300 ℃ at 5 ℃/min under the protection of high-purity nitrogen in a tubular furnace, carrying out heat treatment at 300 ℃ for 3 hours, then naturally cooling, and finally obtaining Co3O4And the graphene composite supercapacitor material is of a sheet structure, and ultrafine nanoparticles are loaded on the sheet structure, as shown in figure 1.
Example 3:
uniformly mixing 2.5mmol of cobalt acetate, 30mL of deionized water and 20mL of graphene solution, putting the mixture into a 100mL beaker, wherein the density of the graphene solution is 1g/L, putting 10mL of ammonia water into a 50mL beaker, putting two beakers into a closed reactor at the same time, keeping the beakers static, reacting for 8 hours through gaseous diffusion of the ammonia water, filtering a precipitate product by a sand core filter device under reduced pressure, separating, washing, drying at 60 ℃ to obtain a dry precipitate, heating the precipitate to 300 ℃ at 5 ℃/min under the protection of high-purity nitrogen in a tubular furnace, carrying out heat treatment at 300 ℃ for 3 hours, then naturally cooling, and finally obtaining Co3O4And the graphene composite super capacitor material is of a sheet structure, superfine nano particles are loaded on the graphene composite super capacitor material, the appearance of a synthetic product is not changed and the particle size is changed due to the change of metal cobalt salt, and in comparative example 2, Co is used as a material for preparing the super capacitor3O4Increases in size.
Example 4:
uniformly mixing 2.5mmol of cobalt chloride, 30mL of deionized water and 20mL of graphene solution, putting the mixture into a 100mL beaker, wherein the density of the graphene solution is 1g/L, putting 20mL of ammonia water into a 50mL beaker, putting two beakers into a closed reactor at the same time, keeping the beakers static, reacting for 8 hours through gaseous diffusion of the ammonia water, filtering a precipitate product by a sand core filter device under reduced pressure, separating, washing, drying at 60 ℃ to obtain a dry precipitate, heating the precipitate to 300 ℃ at 5 ℃/min under the protection of high-purity nitrogen in a tubular furnace, carrying out heat treatment at 300 ℃ for 3 hours, then naturally cooling, and finally obtaining Co3O4And the graphene composite super capacitor material is of a sheet structure, and the superfine nano particles are loaded on the graphene composite super capacitor material, and compared with the example 2, the amount of the prepared material is obviously less, because a part of precipitate is generated to form a complex to be dissolved in water under the condition of excessive ammonia water.
As shown in FIG. 1, it is Co obtained in example 2 of the present invention3O4Scanning electron microscope spectrogram of @ GO composite supercapacitor material sample, in which Co can be found3O4The nano particles are loaded on the graphene sheet layers, are distributed uniformly and have uniform particle sizes.
As shown in FIG. 2, Co obtained in example 2 of the present invention3O4The surface scanning energy spectrum of the @ GO composite supercapacitor material is analyzed, and elements and contents at a mark are shown in a table 1:
table 1 example 2 Co prepared3O4Element content distribution of @ GO composite supercapacitor material
| Element(s) | Line type | Weight percent of | Wt % Sigma | Atomic percent |
| C | K line system | 28.70 | 0.15 | 51.58 |
| O | K line system | 22.71 | 0.11 | 30.63 |
| Co | L-shaped wire system | 48.59 | 0.18 | 17.79 |
| Total amount of | 100.00 | 100.00 |
As can be seen from the table, it is,
FIG. 3 shows the Co obtained by the present invention3O4And Co3O4Discharge curve of @ GO composite supercapacitor material at 1A/g current density, Co3O4For preparation according to example 1, Co3O4@ GO composite supercapacitor material prepared for example 2, figureCan be found in (A) Co3O4Material ratio pure Co of @ GO composite super capacitor3O4The material ratio of the super capacitor material is nearly doubled compared with the capacitance, pure Co3O4The specific capacitance at 1A/g current density is 202F/g, Co3O4The material of the @ GO composite supercapacitor is 389.4F/g.
FIG. 4 shows Co obtained according to examples 1 and 2 of the method of the present invention3O4And Co3O4Specific capacity of @ GO composite supercapacitor material at different current densities, pure Co3O4The rate performance is 86.0 percent under the current density of 10A/g, and Co3O4The material of the @ GO composite supercapacitor is 83.1%, and the material and the supercapacitor both have excellent rate capability.
FIG. 5 shows Co3O4And Co3O4The cyclic voltammetry curve of the @ GO composite supercapacitor material at the scanning rate of 10mV/s can be found that each curve has an oxidation-reduction characteristic peak and has pseudo-capacitance characteristics, and Co3O4The @ GO composite supercapacitor material has a larger closed area, and can be explained to have excellent specific capacity.
FIG. 6 shows Co3O4The area enclosed by the curve is obviously increased along with the increase of the scanning rate, which shows that the area of the material of the @ GO composite super capacitor is obviously increased under different scanning rates3O4The @ GO composite supercapacitor material has better stability.
FIG. 7 shows Co prepared according to example 1 and example 23O4And Co3O4@ GO composite supercapacitor material AC impedance curve. Pure Co3O4Internal resistance of 0.75, Co3O40.73 of the material of the @ GO composite supercapacitor; co can be found by the slope3O4@ GO composite supercapacitor material significantly larger than Co3O4The charge transfer resistance of the composite material is minimum, and the charge transfer performance of the material is improved after the composite material is compounded.
Co of the invention3O4@ GO composite superThe material of the stage capacitor is prepared by diffusing ammonia gas in ammonia water, reacting metal cobalt salt, deionized water, graphene solution and ammonia water according to a certain molar ratio in a sealed dryer under a static condition for a certain time by a chemical precipitation method to obtain a precipitate, filtering the precipitate by a sand core filtering device under reduced pressure, cleaning and drying the precipitate to obtain a precipitate, heating the precipitate to 300 ℃ at a certain speed under the protection of high-purity nitrogen in a tubular furnace, carrying out heat treatment at the temperature of 300 ℃ for 3 hours, naturally cooling the precipitate, and finally obtaining Co3O4And graphene composite supercapacitor materials.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (3)
1. Preparation of Co by gas phase diffusion3O4The method for compounding the supercapacitor material with the graphene is characterized by comprising the following steps of:
s1: preparing 50mL of mixed solution from 2.5mmol of cobalt chloride raw material powder and a graphene oxide solution with the concentration of 1g/L, putting the mixed solution into a 100mL beaker, magnetically stirring the mixed solution until the mixed solution is uniform, putting the cobalt salt solution with the volume of 50-10mL and the graphene solution with the volume of 0-40mL into the 50mL beaker, putting 5-20 mL of ammonia water serving as a gas phase diffusion precipitator into the 50mL beaker, putting the two beakers into a sealed dryer, keeping the two beakers in a static state, covering the glass sealed cover of the dryer, keeping the reaction for 4-10 hours, stopping the reaction, filtering the reaction precipitate in the 100mL beaker under reduced pressure by using a sand core filtering device, washing the reaction product with absolute ethyl alcohol and distilled water for three times, and drying the reaction product for 2 hours at 60 ℃ to obtain blue-green powder;
s2: heating the precipitate obtained in the step S1 to 300 ℃ at the speed of 5 ℃/min under the protection of high-purity nitrogen in a tube furnace, carrying out heat treatment at the temperature of 300 ℃ for 3 hours, and then naturally cooling to finally obtain black Co3O4And graphene composite super capacitor equipmentFeeding;
s3: mixing the Co obtained in step S23O4And the graphene composite super capacitor material is used as a super capacitor active substance, and a specific capacitance is 389.4F/g, a specific capacitance is 323.6F/g under a current density of 10A/g and a rate capability is 83.1% by adopting a three-electrode test method under a current density of 1A/g.
2. Co according to claim 13O4And a method for compounding the supercapacitor material with graphene, which is characterized in that reactants are kept static, and a gas-phase diffusion mode is adopted.
3. Gas phase diffusion Co production according to claim 13O4The method for preparing the graphene composite supercapacitor material is characterized in that the cobalt salt is cobalt chloride and cobalt acetate, the graphene solution is prepared by a Hummers method, and the concentration of ammonia water is 25-28%.
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| CN202110668905.6A CN113394028A (en) | 2021-06-17 | 2021-06-17 | Preparation of Co by gas phase diffusion3O4Method for compounding supercapacitor material with graphene |
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| CN202110668905.6A CN113394028A (en) | 2021-06-17 | 2021-06-17 | Preparation of Co by gas phase diffusion3O4Method for compounding supercapacitor material with graphene |
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