CN112670099B - PANI-Co3O4Preparation method and application of nano material - Google Patents
PANI-Co3O4Preparation method and application of nano material Download PDFInfo
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- CN112670099B CN112670099B CN202011274731.7A CN202011274731A CN112670099B CN 112670099 B CN112670099 B CN 112670099B CN 202011274731 A CN202011274731 A CN 202011274731A CN 112670099 B CN112670099 B CN 112670099B
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses PANI-Co3O4The preparation and the application of the nano material can polymerize aniline in situ on Co under the low temperature condition3O4Drying the surface of the nano rod to obtain the PANI-Co of the invention3O4A composite nanomaterial. PANI-Co3O4The nano material has a current density of 1 A.g‑1When the specific capacitance is 3105.46F g‑1（31.05F·cm‑2). At 10 A.g‑1Under the current density of (3), the capacitance retention rate can reach 74.81% after 3000 discharging-charging cycles. Co due to the high conductivity of PANI3O4The rich active sites and the synergistic effect enable PANI-Co3O4Has excellent electrochemical performance and good stability. The method is simple, easy to operate and low in cost, and has a great application prospect in the aspect of electrode materials of the super capacitor.
Description
Technical Field
The invention belongs to the technical field of preparation of electrode materials of a super capacitor, and particularly relates to PANI-Co3O4A preparation method and application of the nano material.
Background
A supercapacitor is an energy storage device that can store energy by adsorbing positive and negative ions or undergoing rapid surface reversible redox reactions, and has higher power density, faster charge and discharge capacities, and longer cycle life. The method plays an important role in the fields of digital communication, hybrid electric vehicles, mobile electronic equipment, renewable energy power generation and the like. The performance of the supercapacitor is determined by the electrode material. Therefore, there is a need to develop new electrode materials with higher storage capacity, better rate performance and cycling stability.
Co3O4Is one of typical transition metal oxides, has higher electrical activity and theoretical specific capacitance, and has the advantages of low price, simple synthesis and environmental protection. PANI has the advantages of easy synthesis, good redox reversibility, remarkable electrochemical properties and the like, and is widely concerned, but PANI has poor stability.
Disclosure of Invention
The invention aims to solve the problem of low specific capacitance of a super capacitor electrode material and prepare PANI-Co3O4Composite nanometer material, Co prepared by using foamed nickel as substrate3O4Then polymerizing PANI at low temperature to synthesize PANI-Co3O4The composite material not only improves the capacitance performance, but also greatly improves the stability of the material.
The invention is realized by adopting the following technical scheme:
PANI-Co3O4The preparation method of the nano material comprises the following steps:
(1) removing surface oxides and impurities from the foamed nickel, and drying at 60 ℃ to obtain a treated foamed nickel substrate;
(2) dissolving cobalt chloride, urea and ammonium fluoride in deionized water, magnetically stirring for 15min, and transferring the uniformly mixed light red solution and the foamed nickel treated in the step (1) into the inner liner of the reaction kettle;
(3) heating the reaction kettle at 130-170 ℃ for 7-9 h to obtain Co attached to the foamed nickel3O4And putting the precursor in a tube furnace for annealing at 400 ℃ for 1-3 h to obtain foamed nickel loaded Co3O4A nanomaterial;
(4) dissolving ammonium persulfate in 1mol/L hydrochloric acid solution, dropwise adding aniline while stirring at-5 ℃, and continuously stirring for 2 hours;
(5) immersing the product obtained in the step (3) into the solution obtained in the step (4), and enabling aniline to be in nickel-based Co at room temperature3O4Polymerizing the surface for 6-10 h; taking out the foamed nickel, and drying at 60 ℃ overnight to obtain PANI-Co3O4And (3) nano materials.
Preferably, in step (2), the molar ratio of cobalt chloride, urea and ammonium fluoride is 2:6: 15.
Preferably, in the step (3), the reaction kettle is hydrothermally operated at 150 ℃ for 8 h.
Preferably, in step (3), Co adhered to the nickel foam3O4The precursor is placed in a tube furnace for annealing for 2h at 400 ℃.
Preferably, in the step (4), the molar amount of ammonium persulfate is 1% of that of cobalt chloride.
Preferably, in step (5), aniline is subjected to nickel-based Co at room temperature3O4Surface polymerization was carried out for 8 h.
The method of the invention polymerizes aniline in Co in situ under low temperature3O4The surface of the nano rod is taken out and dried to obtain the PANI-Co3O4A composite nanomaterial. PANI-Co3O4The nano material has a current density of 1 A.g-1When the specific capacitance is 3105.46F g-1（31.05F·cm-2). At 10 A.g-1Under the current density of (2), the capacitance retention rate can reach 74.81% after 3000 times of cycle test.
The invention has reasonable design, simple method, easy operation and low cost, and the composite material has ultrahigh specific capacitance and good stability, is a potential electrode material of the super capacitor and has good practical application value.
Drawings
FIG. 1 shows Co in the preparation of example 2 of the method of the present invention3O4And PANI-Co3O4XRD pattern of the nanomaterial.
FIG. 2a shows Co in the preparation of example 2 of the present invention3O4SEM image (10 μm) of the nanomaterial.
FIG. 2b shows Co in the preparation of example 2 of the present invention3O4SEM image (500 nm) of the nanomaterial.
FIG. 3a shows PANI-Co during the preparation of example 2 of the present invention3O4SEM image (10 μm) of the composite material.
FIG. 3b shows PANI-Co during the preparation of example 2 of the present invention3O4SEM image (2 μm) of the composite material.
FIG. 4a shows PANI-Co prepared according to example 2 of the present invention3O4CV test pattern of composite material.
FIG. 4b shows PANI-Co prepared according to example 2 of the present invention3O4Constant current charge and discharge test chart of the composite material.
FIG. 5 shows PANI-Co prepared according to example 2 of the present invention3O4Cycle stability test chart of the composite material.
FIG. 6 shows different embodiments at 1A g-1Comparative charge and discharge at current density.
Detailed Description
The following detailed description of specific embodiments of the invention refers to the accompanying drawings.
Example 1
PANI-Co3O4The preparation method of the nano material comprises the following steps:
(1) cutting the foamed nickel into 3 multiplied by 3cm, ultrasonic cleaning the foamed nickel by acetone, dilute hydrochloric acid, absolute ethyl alcohol and deionized water in sequence to remove surface oxides and impurities, and drying the foamed nickel in a drying oven at 60 ℃ to obtain the processed foamed nickel substrate.
(2) And (3) dissolving 1mmol of cobalt chloride, 3mmol of urea and 7.5mmol of ammonium fluoride in 30mL of deionized water, magnetically stirring for 15min, and transferring the uniformly mixed light red solution and the foamed nickel treated in the step (1) into the inner liner of the reaction kettle.
(3) Heating the reaction kettle at 130 ℃ for 7 hours to obtain Co attached to the foamed nickel3O4The precursor is then placed inAnnealing for 1h in a tube furnace at 400 ℃ to obtain foamed nickel loaded Co3O4And (3) nano materials.
(4) 0.01mol of ammonium persulfate is weighed and dissolved in 100mL of 1mol/L hydrochloric acid solution, 1mL of aniline is added dropwise within 30min while stirring at-5 ℃, and stirring is continued for 2 h.
(5) Immersing the product obtained in the step (3) into the solution obtained in the step (4), and enabling aniline to be in nickel-based Co at room temperature3O4Surface polymerization was carried out for 6 h. Taking out the foamed nickel, and drying at 60 ℃ overnight to obtain PANI-Co3O4And (3) nano materials.
Example 2
PANI-Co3O4The preparation method of the nano material comprises the following steps:
(1) cutting the foamed nickel into 3 multiplied by 3cm, ultrasonic cleaning by acetone, dilute hydrochloric acid, absolute ethyl alcohol and deionized water in sequence to remove surface oxides and impurities, and drying in a drying oven at 60 ℃ to obtain the processed foamed nickel substrate.
(2) And dissolving 1mmol of cobalt chloride, 3mmol of urea and 7.5mmol of ammonium fluoride in 30mL of deionized water, magnetically stirring for 15min, and transferring the uniformly mixed light red solution and the foamed nickel treated in the step (1) into the inner liner of the reaction kettle.
(3) Hydrothermal reaction kettle at 150 deg.C for 8 hr to obtain Co attached to foamed nickel3O4The precursor is placed in a tube furnace to be annealed for 2 hours at 400 ℃ to obtain foamed nickel loaded Co3O4And (3) nano materials.
(4) 0.01mol of ammonium persulfate is weighed and dissolved in 100mL of 1mol/L hydrochloric acid solution, 1mL of aniline is added dropwise within 30min while stirring at-5 ℃, and stirring is continued for 2 h.
(5) Immersing the product obtained in the step (3) into the solution obtained in the step (4), and enabling aniline to be in nickel-based Co at room temperature3O4Surface polymerization was carried out for 8 h. Taking out the foamed nickel, and drying at 60 ℃ overnight to obtain PANI-Co3O4And (3) nano materials.
Example 3
A kind ofPANI-Co3O4The preparation method of the nano material comprises the following steps:
(1) cutting the foamed nickel into 3 multiplied by 3cm, ultrasonic cleaning the foamed nickel by acetone, dilute hydrochloric acid, absolute ethyl alcohol and deionized water in sequence to remove surface oxides and impurities, and drying the foamed nickel in a drying oven at 60 ℃ to obtain the processed foamed nickel substrate.
(2) And (3) dissolving 1mmol of cobalt chloride, 3mmol of urea and 7.5mmol of ammonium fluoride in 30mL of deionized water, magnetically stirring for 15min, and transferring the uniformly mixed light red solution and the foamed nickel treated in the step (1) into the inner liner of the reaction kettle.
(3) Heating the reaction kettle at 170 ℃ for 9 hours to obtain Co attached to the foamed nickel3O4The precursor is placed in a tube furnace to be annealed for 3 hours at the temperature of 400 ℃ to obtain the foamed nickel loaded Co3O4And (3) nano materials.
(4) 0.01mol of ammonium persulfate is weighed and dissolved in 100mL of 1mol/L hydrochloric acid solution, 1mL of aniline is added dropwise within 30min while stirring at-5 ℃, and stirring is continued for 2 h.
(5) Immersing the product obtained in the step (3) into the solution obtained in the step (4), and enabling aniline to be in nickel-based Co at room temperature3O4Surface polymerization was carried out for 10 h. Taking out the foamed nickel, and drying at 60 ℃ overnight to obtain PANI-Co3O4And (3) nano materials.
Co of the invention prepared by example 23O4And PANI-Co3O4XRD of the nanomaterial is shown in fig. 1. Co can be seen from the figure3O4The diffraction peak is matched with the JCPDS number 42-1467 of the standard card, and the diffraction peak marked with "#" is matched with the JCPDS number 04-0850 of the Ni standard card. Because of Co3O4The water grows on the surface of the foamed nickel, so that a diffraction peak of Ni appears.
Co of the invention prepared by example 23O4The SEM of the nanomaterials is shown in fig. 2a and 2 b. From the figure, Co can be found3O4Is a nano rod composed of a plurality of nanospheres, and the nano rod covers the surface of the foam nickel in the form of an open network structure and can be used for coatingTo increase its specific surface, promote electron transfer and ion exchange. PANI-Co3O4SEM of the composite is shown in FIGS. 3a and 3b, from which Co can be seen3O4The nano particles are coated by PANI to form PANI-Co with irregular laminated structure3O4A composite material.
PANI-Co prepared by example 2 of the invention3O4CV test patterns (fig. 4 a) and constant current charge and discharge test patterns (fig. 4 b) of the composite material. As can be seen from fig. 4a, the CV curve is almost rectangular, illustrating that the electrodes have a low resistance and a good capacitance. The specific capacitance at different current densities can be calculated by equation (1), and from FIG. 4b, it can be seen that PANI-Co3O4The electrode is at 1-10 A.g-1The specific capacitance of each of the following layers is 3105.46F g-1、2416.11F·g-1、2076.17F·g-1、1666.00F·g-1、1266.74F·g-1And 1060.57F g-1（31.05F·cm-2、24.16F·cm-2、20.76F·cm-2、16.66F·cm-2、12.67F·cm-2And 10.61F-cm-2) And the capacitor shows excellent capacitance performance.
PANI-Co prepared by example 2 of the invention3O4The cycle stability test pattern of the composite material is shown in fig. 5. The figure shows that the capacitance retention rate can reach 74.81% after 3000 times of cycle tests, which indicates that PANI-Co3O4The cycling stability is good.
PANI-Co prepared by three different examples of the invention3O4The composite material is 1 A.g-1As shown in FIG. 6, the comparative graph of charge and discharge at current density shows that the specific capacitances of examples 1, 2 and 3 are 1607.55F g-1、722.75F·g-1、3105.46F·g-1. In which PANI-Co prepared by example 23O4The specific capacitance of the composite material is maximum, and excellent electrochemical performance is shownThe chemical properties show that the hydrothermal and annealing conditions and the polymerization time in this experiment have a great influence on the prepared electrode material.
In conclusion, the method can be used for in-situ polymerization of aniline in Co under low-temperature conditions3O4Drying the surface of the nano rod to obtain PANI-Co3O4The composite nano material has a great application prospect in the aspect of electrode materials of super capacitors. PANI-Co3O4The nano material has a current density of 1 A.g-1When the specific capacitance is 3105.46F g-1（31.05F·cm-2). At 10 A.g-1Under the current density of (3), the capacitance retention rate can reach 74.81% after 3000 discharging-charging cycles. Co due to the high conductivity of PANI3O4The rich active sites and the synergistic effect enable PANI-Co3O4Has excellent electrochemical performance and good stability.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and although the detailed description is given with reference to the embodiments of the present invention, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which shall all be covered by the protection scope of the claims of the present invention.
Claims (1)
1. PANI-Co3O4The preparation method of the nano material is characterized by comprising the following steps: the method comprises the following steps:
(1) removing surface oxides and impurities from the foamed nickel, and drying at 60 ℃ to obtain a treated foamed nickel substrate;
(2) dissolving cobalt chloride, urea and ammonium fluoride in deionized water, magnetically stirring for 15min, and transferring the uniformly mixed light red solution and the foamed nickel treated in the step (1) into the inner liner of the reaction kettle; wherein the molar ratio of cobalt chloride to urea to ammonium fluoride is 2:6: 15;
(3) hydrothermal reaction kettle at 150 deg.C for 8 hr to obtain Co attached to foamed nickel3O4Precursor bodyThen placing the mixture in a tube furnace to anneal for 2 hours at 400 ℃ to obtain foamed nickel loaded Co3O4A nanomaterial;
(4) dissolving ammonium persulfate in 1mol/L hydrochloric acid solution, dropwise adding aniline while stirring at-5 ℃, and continuously stirring for 2 hours; wherein the molar amount of ammonium persulfate is 1 percent of that of cobalt chloride;
(5) immersing the product obtained in the step (3) into the solution obtained in the step (4), and enabling aniline to be in nickel-based Co at room temperature3O4Surface polymerization is carried out for 8 h; taking out the foamed nickel, and drying at 60 ℃ overnight to obtain PANI-Co3O4And (3) nano materials.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104008889A (en) * | 2014-06-17 | 2014-08-27 | 西南大学 | High-performance super capacitor and manufacturing method thereof |
| CN110970226A (en) * | 2019-12-19 | 2020-04-07 | 华东理工大学 | Composite electrode material, preparation method and super capacitor |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104008889A (en) * | 2014-06-17 | 2014-08-27 | 西南大学 | High-performance super capacitor and manufacturing method thereof |
| CN110970226A (en) * | 2019-12-19 | 2020-04-07 | 华东理工大学 | Composite electrode material, preparation method and super capacitor |
Non-Patent Citations (2)
| Title |
|---|
| Self-Assembly of 3D Fennel-Like Co 3 O 4 with Thirty-Six Surfaces for High Performance Supercapacitor;Yanfang Li等;《Journal of Nanomaterials》;20170307;1-8页 * |
| Thin Chemisorbed Polyaniline Film on Cobalt Oxide as an Electrode for Hybrid Energy Storage Devices;Izan Izwan Misnon等;《ChemistrySelect》;20200713;7973-7983页 * |
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