CN108198701B - Cobaltosic oxide/carbon composite electrode material, preparation method and application thereof - Google Patents
Cobaltosic oxide/carbon composite electrode material, preparation method and application thereof Download PDFInfo
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- CN108198701B CN108198701B CN201711294068.5A CN201711294068A CN108198701B CN 108198701 B CN108198701 B CN 108198701B CN 201711294068 A CN201711294068 A CN 201711294068A CN 108198701 B CN108198701 B CN 108198701B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
Abstract
The invention provides a preparation method of cobaltosic oxide/carbon composite electrode material, which specifically comprises the steps of taking Co-MOFs crystal ZIF-67 prepared from cobalt salt and dimethyl imidazole as a precursor, coating a layer of uniform Phenolic Resin (PR) outside ZIF-67 nanoparticles in situ, and then carrying out high-temperature treatment twice under specific conditions to obtain the cobaltosic oxide/carbon composite electrode. The coating of the phenolic resin allows the sample of ZIF-67 to remain well structured as a regular polyhedron when subjected to high temperature calcination. The specific surface area and the electrochemical activity of the nano particles are greatly improved by carbonizing the phenolic resin. The carbon shell layer formed by the phenolic resin precursor presents higher graphitization degree and has higher conductivity compared with amorphous carbon. The composite electrode structure can obviously improve the specific capacity, energy density and cycling stability of the electrode, and is expected to have good application prospect in the field of super capacitor materials.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a preparation method of a cobaltosic oxide/carbon composite electrode material, which can be used as an application of a super capacitor electrode material.
Background
The super capacitor is a novel green energy storage device, and has a plurality of significant advantages, such as high power density at high charge and discharge rates, ultra-long service life (>100000 times), and wide use temperature range, and thus has received extensive attention and application by researchers. The advantages of the super capacitor enable the super capacitor to have good application prospects in the fields of green energy, mobile energy systems, hybrid electric vehicles, storage backup systems, military equipment and the like. However, the existing super capacitor still has a plurality of disadvantages, wherein the most significant disadvantage is the relatively low energy density, and the low energy density limits the practical application of the super capacitor. The electrode material is always the core of the super capacitor, and the development of good electrode materials is required for improving the performance of the super capacitor.
Metal Organic Frameworks (MOFs) are highly porous materials made by complexing metal ions with organic complexes. The MOFs are very easy to regulate and control due to a regular polyhedral structure, can be subjected to complex and fine structural design, and simultaneously contain metal ions suitable for being used as metal oxide precursors, so that the MOFs are considered to have great potential and advantages in the field of electrode materials of supercapacitors. Although cobaltosic oxide taking ZIF-67MOFs as precursors can show higher energy density and good cycling stability, the poor conductivity of cobaltosic oxide limits the application prospect, and the performance of cobaltosic oxide under high magnification cannot be supported by high resistance. The feasible solution is to compound the carbon material with the carbon material to prepare the composite electrode material, the existence of the carbon can greatly improve the conductivity of the electrode material, and meanwhile, the carbon material has high power density and cycling stability and can improve the electrochemical performance of the electrode material.
Disclosure of Invention
In order to overcome the defects of low specific capacity and poor rate capability of the cobaltosic oxide electrode material taking ZIF-67 as a precursor in practical application in the prior art, the invention aims to provide a method for preparing the cobaltosic oxide/carbon composite electrode material so as to overcome the limitation of the cobaltosic oxide application.
The idea of the invention is that:
preparing ZIF-67MOFs by using cobalt salt and dimethyl imidazole, uniformly coating phenolic resin on the outer layer of the ZIF-67MOFs, and sequentially carrying out carbonization and oxidation treatment under specific conditions to prepare the cobaltosic oxide/carbon nano composite electrode material. The phenolic resin coating allows the sample of ZIF-67 to remain well structured as a regular polyhedron when subjected to high temperature calcination. The carbonized carbon layer of the phenolic resin has special surface bulges, so that uniform and regular distribution is formed, the specific surface area of nano particles is greatly improved, and active sites of electrochemical reaction are increased. The carbon shell layer formed by the phenolic resin precursor presents higher graphitization degree, has higher conductivity compared with amorphous carbon, and is beneficial to reducing the impedance of the electrode material. The composite electrode structure can obviously improve the specific capacity, energy density and cycling stability of the electrode.
The invention is realized by the following technical scheme:
a preparation method of cobaltosic oxide/carbon composite electrode material is characterized by comprising the following steps:
(1) respectively dissolving 1.43-4.29 g of cobalt nitrate hexahydrate and 3.24-9.72 g of dimethyl imidazole in methanol, and continuously stirring for 20-40 min. And standing and aging for 24h at room temperature, then repeatedly performing suction filtration and cleaning by using methanol and performing vacuum drying to obtain ZIF-67.
(2) And (2) taking 0.2-0.6 g of ZIF-67 obtained in the step (1), and fully dissolving the ZIF-67 and 1.5-4.5 g of hexadecyl trimethyl bromamine (CTAB) in a mixed solution of 30-90 ml of ethanol and 9-27 ml of deionized water. And after fully stirring for 20-40 min, adding 0.105-0.315 g of resorcinol and 0.12-0.36 ml of strong ammonia water, and continuously stirring for 20-40 min, and then adding 0.15-0.45 ml of formaldehyde. Reacting for 4-8 hours under the condition of stirring, centrifugally separating and collecting a product ZIF-67@ Phenocolicin (PR), and drying in an oven at 60-80 ℃ overnight.
(3) And (3) heating the ZIF-67@ PR compound obtained in the step (2) to 600-800 ℃ in a tubular furnace in a nitrogen atmosphere at a heating rate of 5 ℃ min < -1 >, preserving heat for 1-3 hours, and naturally cooling to room temperature. And opening the flange of the tube furnace to be airtight, connecting the atmosphere, raising the temperature to 300 ℃ at the speed of 5 ℃ min-1 again, and preserving the heat for 2 hours to obtain the cobaltosic oxide/carbon composite electrode material.
The ZIF-67 has uniform size distribution of nano particles, and the particle diameter is about 250-300 nm.
In the step (3), the step of connecting the atmosphere needs to strictly control the air tightness, only a little air is needed, and the temperature needs to be controlled at 300 ℃.
The cobaltosic oxide/carbon composite material obtained by the preparation method is applied to a super capacitor as an electrode material.
Has the advantages that:
the carbon layer formed by taking the phenolic resin as the carbon source has special surface bulges and is uniformly and regularly distributed, so that the specific surface area of the nano particles is improved, the electrochemical active sites are increased, and great help is brought to the improvement of the specific capacity of the electrode material. And the carbon shell layer is highly graphitized, so that the impedance of the electrode material is reduced, and the multiplying power performance under large current is improved. A large number of gaps are reserved in the carbon layer, so that the function of ion storage is achieved, and the loose structure provides a good ion diffusion channel. The composite electrode material obtained by the invention shows excellent performance in electrochemical tests, and shows that the composite electrode material has wide application prospect in the field of electrode materials of super capacitors.
Drawings
FIG. 1 is a scanning electron micrograph of the ZIF-67 which was not coated with the phenol in example 1 after the two-step heat treatment.
FIG. 2 is a transmission electron micrograph of the ZIF-67 which was not coated with the phenol in example 1 after the two-step heat treatment.
FIG. 3 is a scanning electron micrograph of the phenolic coated ZIF-67 of example 2 after two-step heat treatment.
FIG. 4 is a transmission electron micrograph of the phenolic coated ZIF-67 of example 2 after two-step heat treatment.
FIG. 5 is a cyclic voltammogram of the electrode material produced in example 1.
FIG. 6 is a cyclic voltammogram of the electrode material produced in example 2.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope to these examples. Other variations and modifications which may occur to those skilled in the art without departing from the spirit and scope of the invention are intended to be included within the scope of the invention.
First, a method for producing ZIF-67 is explained as follows:
1.43g cobalt nitrate hexahydrate (Co (NO)2·6H2O) and 3.24g of dimethylimidazole were dissolved in 100ml of methanol, respectively, and the two solutions were directly mixed after sufficient dissolution and continuously stirred for 20 min. Standing and aging the mixed solution at room temperature for 24h, repeatedly performing suction filtration and cleaning by using methanol, separating to obtain purple ZIF-67, and finally drying in a vacuum oven at 150 ℃ for 8 h.
Example 1
And (3) putting the obtained ZIF-67 in a porcelain ark, heating to 600 ℃ in a tubular furnace in a nitrogen atmosphere at the heating rate of 5 ℃ for min-1, preserving heat for 2 hours, and naturally cooling to room temperature. And opening the flange of the tube furnace to be airtight, connecting the atmosphere, raising the temperature to 300 ℃ at the speed of 5 ℃ min-1 again, and preserving the heat for 2 hours to obtain the carbonized ZIF-67, namely the sample 1.
Example 2
0.2g of the thus-obtained ZIF-67 was thoroughly dissolved in a mixed solution of 30ml of ethanol and 9ml of deionized water together with 1.5g of cetyltrimethyl bromide (CTAB). After stirring well for 30min, 0.105g resorcinol and 0.12ml strong ammonia water were added, and stirring was continued for 30min immediately followed by the addition of 0.15ml formaldehyde. The reaction was carried out for 6 hours with stirring, and the product ZIF-67@ Phenylolic Resin (PR) was collected by centrifugation and dried in an oven at 80 ℃ overnight. And then heating the obtained ZIF-67@ PR compound to 600 ℃ in a tubular furnace in a nitrogen atmosphere at the heating rate of 5 ℃ for min-1, preserving the heat for 2 hours, and naturally cooling to room temperature. Then opening the flange of the tube furnace to be airtight, connecting the atmosphere, raising the temperature to 300 ℃ at the speed of 5 ℃ min-1 again, and preserving the heat for 2 hours to obtain cobaltosic oxide/carbon (Co)3O4/C) composite electrode material, sample 2.
The morphologies of sample 1 and sample 2 prepared in examples 1 and 2 above were characterized by field emission scanning electron microscopy and transmission electron microscopy. Fig. 1 is a scanning electron micrograph and a transmission electron micrograph of sample 1 in which the phenolic resin was not coated in example 1, and fig. 2 is a scanning electron micrograph and a transmission electron micrograph of sample 2 in which the phenolic resin was coated in example 2.
The electrode materials prepared in examples 1 and 2, conductive carbon black and polyvinylidene fluoride emulsion were mixed in a mass ratio of 80: 10: and (10) mixing uniformly to obtain the electrode. The prepared composite electrode plate is used as a working electrode, a platinum sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and an electrolyte is NaOH with the concentration of 1mol/L to form a three-electrode testing system, and electrochemical performance testing is carried out on a Chenghua CHI660E instrument. Wherein the voltage range of the cyclic voltammetry test is-0.1-0.4 v, and the results are shown in FIG. 3 and FIG. 4. The specific capacity results for the electrode materials prepared in examples 1 and 2 at scan rates of 5mV/s,10mV/s,20mV/s, and 50mV/s are shown in the following table:
Claims (7)
1. a preparation method of a cobaltosic oxide/carbon composite electrode material comprises the steps of coating a layer of uniform phenolic resin on the outer portion of ZIF-67 nano particles in situ to form a ZIF-67@ PR compound, and then carrying out high-temperature treatment twice to obtain the cobaltosic oxide/carbon composite electrode, wherein the ZIF-67 nano particles are uniform in size distribution and have the particle diameter of 250 ~ 300nm, the phenolic resin is uniformly coated on the ZIF-67 to form a compound particle with the size close to that of the ZIF-67;
the two high-temperature treatments are as follows: the first high temperature treatment is carried out by putting ZIF-67@ PR compound in a tubular furnace with nitrogen atmosphere for 5 ℃ min-1Heating to 600 ~ 800 deg.C at a heating rate, maintaining for 1 ~ 3h, naturally cooling to room temperature, opening the flange of the tube furnace to seal air, introducing air, and performing a second high temperature treatment at 5 deg.C for 5 min-1The temperature is raised to 300 ℃ at the speed of 2 hours, and the cobaltosic oxide/carbon composite electrode material is obtained.
2. The method according to claim 1, characterized in that said ZIF-67 nanoparticles are Co-MOFs crystalline ZIF-67 made from cobalt salt and dimethylimidazole.
3. The method of claim 2, wherein 1.43 ~ 4.29.29 g of cobalt nitrate hexahydrate and 3.24 ~ 9.72.72 g of dimethylimidazole were dissolved in methanol, respectively, and stirring was continued for 20 ~ 40min, and the mixture was left to stand and age for 24h at room temperature, and then washed with methanol by repeated suction filtration and dried in vacuum to obtain ZIF-67 nanoparticles.
4. The method of claim 1, wherein said ZIF-67@ PR complex is prepared by dissolving 0.2 ~ 0.6.6 g of ZIF-67 nanoparticles and 1.5 ~ 4.5.5 g of cetyltrimethyl bromamine in 30 ~ 90ml of a mixture of ethanol and 9 ~ 27ml of deionized water, stirring for 20 ~ 40min, adding 0.105 ~ 0.315.315 g of resorcinol and 0.12 ~ 0.36ml of concentrated ammonia, stirring for 20 ~ 40min, adding 0.15 ~ 0.45.45 ml of formaldehyde, reacting for 4 ~ 8 hours under stirring, centrifuging, and drying in an oven at 60 ~ 80 ℃ overnight.
5. A cobaltosic oxide/carbon composite electrode material characterized by being produced by the production method according to claim 1.
6. The cobaltosic oxide/carbon composite electrode material as claimed in claim 5, wherein the cobaltosic oxide/carbon composite electrode material has an outer layer of a carbon shell with a uniform nano-lattice, a certain graphitization and an inner portion of loose Co3O4。
7. Use of the cobaltosic oxide/carbon composite electrode material prepared according to claim 1, wherein the cobaltosic oxide/carbon composite electrode material is used as an electrode material in a supercapacitor.
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| CN109585823A (en) * | 2018-11-23 | 2019-04-05 | 重庆文理学院 | A kind of preparation method of cobaltous selenide/graphite carbon composite |
| CN109616660B (en) * | 2018-12-23 | 2021-07-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cobaltosic oxide supported carbon nanosheet electrode material, product and application thereof |
| CN111346642B (en) * | 2020-02-05 | 2023-02-28 | 临沂大学 | High-dispersion metal nanoparticle/biomass carbon composite electrode material and preparation method and application thereof |
| CN111799099A (en) * | 2020-07-21 | 2020-10-20 | 厦门理工学院 | Composite electrode material taking needle mushroom as carbon-based load and preparation method and application thereof |
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| CN107175084B (en) * | 2017-05-24 | 2020-03-31 | 中国科学院上海高等研究院 | Metal organic framework-phenolic resin composite material and preparation method thereof |
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