CN108766785B - Graphene-polypyrrole-cobalt-nickel double-metal hydroxide composite material and preparation method and application thereof - Google Patents
Graphene-polypyrrole-cobalt-nickel double-metal hydroxide composite material and preparation method and application thereof Download PDFInfo
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
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- 238000001035 drying Methods 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
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- 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
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention discloses a graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material, and a preparation method thereof comprises the following steps: 1) preparing a solution; 2) preparing graphene-polypyrrole; 3) and (3) preparing the graphene-polypyrrole loaded cobalt-nickel double metal hydroxide composite material. When the material is used as an electrode material of a super capacitor, the material is charged and discharged in the range of 0-0.35V, and the specific capacitance can reach 2500-. According to the invention, distilled water is used as a solvent, graphene-polypyrrole is used as a substrate material, cobalt and nickel salt are added and stirred at room temperature until the cobalt and nickel salt are dissolved and mixed uniformly, and the mixture is transferred to a reaction kettle for hydrothermal reaction, so that the graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material is prepared. The conductivity of the material is improved by doping the graphene and the polypyrrole; the cobalt-nickel double metal hydroxide is distributed on the surface of the substrate material, so that the conductivity of the material is improved, the preparation process is simple, the excellent electrochemical property is shown, and the cobalt-nickel double metal hydroxide can be used as an electrode material of a super capacitor.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to a graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material and a preparation method and application thereof.
Background
Super capacitor has been widely paid attention in recent years as a novel energy storage device, and has the advantages of long cycle life, high power density, light weight, short charging and discharging time and the like. The electrode material of the super capacitor mainly comprises a carbon material, and although the carbon material has good cycling stability and high specific surface area, the specific capacitance of the carbon material is low, so that the use of the carbon material is limited; another class of materials are pseudocapacitive electrode materials, transition metal oxides or hydroxides, and conductive polymers. Although the transition metal oxide can provide a specific capacitance 10 times higher than that of the carbon material, it is inferior in conductivity and stability, and is liable to be corroded and changed in volume during charge and discharge; the conductive polymer is low in price, but poor in thermal stability, chemical stability and cyclability, so that the application of the conductive polymer is limited to a certain extent; the double metal hydroxides are highly ordered materials with various excellent functions, and ionic bonds, covalent bonds, hydrogen bonds, electrostatic forces and van der Waals force interaction among the double metal hydroxides, due to the special layered structure, the diversity and adjustability of anions between layers, a wide space is provided for the rapid development of the materials, and the double metal hydroxides can be used as novel high-performance super capacitors.
One of the biggest drawbacks limiting the use of double metal hydroxides is their poor electrical conductivity, which will seriously affect the transport of electrons in the electrode material and thus its electrochemical performance; another factor limiting the electrochemical performance is the extremely high charge density of the laminated double-metal hydroxide plate, which causes serious agglomeration of the plate, so that the active component can not be fully utilized, thereby reducing the specific capacitance of the laminated double-metal hydroxide plate. Therefore, how to improve the conductivity of the double metal hydroxide and fully utilize the active components thereof is a difficult problem to be solved.
Graphene is a crystal of a hexagonal honeycomb lattice structure formed by close packing of single-layer carbon atoms, and has excellent electrical, thermal, mechanical and chemical properties due to a unique two-dimensional structure. As a carbon material, the composite material has high conductivity and stability, and the composite material and the double metal hydroxide are a feasible method for preparing the electrode material with high specific capacitance. The dispersion of the double-metal hydroxide particles is improved by utilizing the carrier effect of the graphene, so that more electrocatalytic active centers are exposed, and the conductivity of the composite material can be improved by adding the graphene. However, graphene is easily agglomerated during the preparation process, and the double metal hydroxide is directly nucleated and grows in a liquid phase, so that the double metal hydroxide is not uniformly compounded with the graphene, thereby limiting the electrochemical performance of the double metal hydroxide.
Disclosure of Invention
The invention provides a graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material, a preparation method thereof and application thereof in the field of supercapacitors. The technical problems of low specific capacitance, poor conductivity and slow electronic transmission in the prior art are effectively solved.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material is prepared by mixing graphene and polypyrrole as a substrate material, adding cobalt nitrate, nickel nitrate, hexamethylenetetramine and urea, performing hydrothermal reaction to obtain cobalt-nickel double metal hydroxide, and loading the cobalt-nickel double metal hydroxide on the surface of the substrate material through in-situ reaction by adopting a method combining an in-situ chemical polymerization method and a hydrothermal reaction. The polypyrrole has a nanowire structure; the hexamethylene tetramine is a precipitator, and the urea provides an alkali source for rapidly decomposing and releasing ammonia gas under a hydrothermal condition.
The preparation method of the graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material comprises the following steps:
step 1) preparing a solution, namely dissolving hydrochloric acid and pyrrole into an aqueous solution with the mass ratio of hydrochloric acid to pyrrole to graphene to water being 0.1:0.5 (0.1-0.3): 100, then ultrasonically dispersing graphene into the solution, marking as a solution M, and adding ammonium persulfate into the aqueous solution with the mass ratio of ammonium persulfate to water being 1:10, marking as a solution N;
step 2) preparing a graphene-polypyrrole composite material, namely slowly dropwise adding the solution N in the step 1 into the solution M with the mass ratio of the solution N to the solution M being 1:5, stirring by using a magnetic stirrer, reacting the solution for 2-4 hours after dropwise adding is finished, and then filtering, washing and drying to obtain the graphene-polypyrrole composite material;
and 3) preparing the graphene-polypyrrole supported cobalt-nickel double metal hydroxide composite material, namely adding the graphene-polypyrrole composite material obtained in the step 2) into a beaker, stirring the mixture at room temperature until the mixture is dissolved and mixed uniformly, transferring the mixture to a reaction kettle for hydrothermal reaction, and then filtering, washing and drying the mixture to obtain the composite material, wherein the mass ratio of the graphene-polypyrrole composite material to cobalt nitrate, nickel nitrate, hexamethylenetetramine, urea and water is (0.02-0.1) to 1:3:0.5:0.2: 69.
The application of the graphene-polypyrrole-cobalt-nickel double-metal hydroxide composite material as the electrode material of the super capacitor can realize charging and discharging in the range of 0-0.35V, and when the discharge current density is 1A/g, the specific capacitance can reach 2500 plus 2600F/g.
The experimental detection shows that the graphene-polypyrrole loaded cobalt-nickel double metal hydroxide composite material has the following results:
the scanning electron microscope test shows that the cobalt-nickel bimetal hydroxide loaded on the graphene-polypyrrole is loaded on the surface of the substrate material.
And (3) testing the electrochemical performance of the graphene-polypyrrole load cobalt-nickel double-metal hydroxide composite material, wherein the charging and discharging are detected within the range of 0-0.35V, and when the discharging current density is 1A/g, the specific capacitance range of the electrode of the graphene-polypyrrole load cobalt-nickel double-metal hydroxide composite material super capacitor is 2500-.
The specific capacitance of the simply prepared graphene and the graphene polypyrrole without the cobalt-nickel double metal hydroxide is 30-50F/g, under the same current density, the discharge time of the graphene-polypyrrole loaded cobalt-nickel double metal hydroxide composite material is obviously longer than that of the simply prepared graphene and graphene polypyrrole electrode material, the discharge time is improved by more than 68 times, the specific capacitance performance is obviously improved, and the graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material has good super capacitance performance.
Therefore, compared with the prior art, the graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material has the following advantages:
1. in-situ chemical polymerization and hydrothermal reaction are adopted to obtain the graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material, and polypyrrole is synthesized at normal temperature; and non-toxic reagents such as urea and the like are adopted for reaction, so that the harm to human health and the environmental pollution are reduced.
2. The invention adopts cobalt nitrate and nickel nitrate, nickel and cobalt transition metal hydroxide are dispersed on the surface of the substrate, the synergistic effect between the materials is fully utilized, and the obtained material has large specific capacitance
3. The graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material is simple in preparation method and process, stable in product performance, suitable for large-batch preparation and simple in post-treatment process.
Therefore, the invention has wide application prospect in the field of super capacitors.
Description of the drawings:
fig. 1 is a scanning electron microscope image of a graphene-polypyrrole-cobalt-nickel double hydroxide composite material prepared by an embodiment of the invention;
fig. 2 is a comparative graph of discharge curves of graphene-polypyrrole-cobalt nickel double hydroxide composite materials prepared according to embodiments of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, which are given by way of examples, but are not intended to limit the present invention.
Examples
A graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material:
step 1) preparing a solution, namely adding 0.1 g of hydrochloric acid and 0.55 g of pyrrole solution into 100 mL of aqueous solution, then adding 0.2 g of graphene into the solution, performing ultrasonic dispersion for 1 h, marking as a solution M, and dissolving 2 g of ammonium persulfate into 20 mL of aqueous solution, marking as a solution N;
step 2) preparing a graphene-polypyrrole composite material, namely slowly dropwise adding 20 ml of the solution N obtained in the step 1 into 100 ml of the solution M, stirring by using a magnetic stirrer, reacting the solution for 3 hours after dropwise adding is completed, and then filtering, washing and drying to obtain the graphene-polypyrrole composite material;
and 3) preparing the graphene-polypyrrole supported cobalt-nickel double hydroxide composite material, namely adding 0.01 g of the graphene-polypyrrole composite material obtained in the step 2) into a beaker, mixing with 0.44g of cobalt nitrate, 1.3 g of nickel nitrate, 0.21 g of hexamethylenetetramine, 0.09 g of urea and 30 ml of water at room temperature, stirring until the mixture is dissolved and mixed uniformly, transferring the mixture to a reaction kettle for hydrothermal reaction, and then filtering, washing and drying to obtain the graphene-polypyrrole-cobalt-nickel double hydroxide composite material.
The microscopic morphology of the graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material obtained by scanning electron microscope testing is shown in figure 1. It can be seen from the figure that cobalt nickel double hydroxide is dispersed on the graphene-polypyrrole matrix.
The electrochemical performance test method of the graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material comprises the following steps: weighing 0.008 g of graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material, 0.001 g of acetylene black and 0.001 g of polytetrafluoroethylene micro powder, placing the materials in a small agate grinding bowl, and adding 0.5 mL of ethanol for grinding; and pressing the ground sample with a foamed nickel current collector with the thickness of 1 mm under the pressure of 10 kPa, drying in air at room temperature, cutting into 2 cm multiplied by 2 cm to prepare the electrode of the super capacitor, and testing the specific capacitance of the electrode.
As shown in fig. 2, the following results were obtained: the super capacitor is charged and discharged within the range of 0-0.35V, when the discharge current density is 1A/g, the specific capacitance of the electrode of the super capacitor made of the graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material can reach 2500F/g, the specific capacitance of the electrode of the simply prepared graphene and the electrode of the graphene polypyrrole without the cobalt-nickel double metal hydroxide are both 30-50F/g, under the same current density, the discharge time of the graphene-polypyrrole-loaded cobalt-nickel double metal hydroxide composite material is obviously longer than that of the electrode material of the simply prepared graphene and graphene polypyrrole, the discharge time is improved by more than 68 times, the specific capacitance performance of the material is obviously improved, and the graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material has good super capacitance performance.
Claims (4)
1. A graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material is characterized in that: by adopting a method combining in-situ chemical polymerization and hydrothermal reaction, mixing graphene and polypyrrole to serve as a substrate material, adding cobalt nitrate, nickel nitrate, hexamethylenetetramine and urea, carrying out hydrothermal reaction to obtain a cobalt-nickel double hydroxide, and carrying out in-situ reaction on the surface of the substrate material to finally obtain a graphene-polypyrrole-cobalt-nickel double hydroxide composite material; the polypyrrole has a nanowire structure; graphene and polypyrrole are coated on the surface of the graphene by an in-situ chemical polymerization method.
2. The preparation method of the graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material according to claim 1, characterized by comprising the following steps:
step 1) preparing a solution, namely dissolving hydrochloric acid and pyrrole into an aqueous solution by using hydrochloric acid, pyrrole, graphene and water to meet a certain mass ratio, then ultrasonically dispersing the graphene into the solution, marking as a solution M, adding ammonium persulfate into the aqueous solution by using ammonium persulfate and water to meet a certain mass ratio, and marking as a solution N; the mass ratio of hydrochloric acid, pyrrole, graphene and water in the step 1) is 0.1:0.5 (0.1-0.3) to 100, and the mass ratio of ammonium persulfate and water is 1: 10;
step 2) preparing a graphene-polypyrrole composite material, namely slowly dropwise adding the solution N obtained in the step 1 into the solution M according to a certain proportion, stirring by using a magnetic stirrer, reacting the solution for 2-4 hours after dropwise adding is completed, and then filtering, washing and drying to obtain the graphene-polypyrrole composite material; the mass ratio of the solution N to the solution M in the step 2 is 1: 5;
step 3) preparing a graphene-polypyrrole supported cobalt-nickel double metal hydroxide composite material, namely adding the graphene-polypyrrole composite material obtained in the step 2, cobalt nitrate, nickel nitrate, hexamethylenetetramine, urea and water in a certain mass ratio into a beaker, stirring at room temperature until the materials are dissolved and mixed uniformly, transferring the mixture to a reaction kettle for hydrothermal reaction, and then filtering, washing and drying the mixture to obtain the composite material; the mass ratio of the graphene-polypyrrole composite material, the cobalt nitrate, the nickel nitrate, the hexamethylenetetramine, the urea and the water in the step 3 is (0.02-0.1) to 1:3 to 0.5:0.2: 69; the hydrothermal reaction condition of the step 3) is that the reaction temperature is 100 ℃ and 160 ℃, and the reaction time is 3-6 h; the target product is filtered, washed, dried and then dried in vacuum at 60-85 ℃.
3. The method of claim 2, wherein: the ammonium persulfate in the step 1 is an initiator of polymerization reaction; the hexamethylenetetramine in the step 3 is a precipitator, and the urea provides an alkali source for rapidly decomposing and releasing ammonia gas under the hydrothermal condition.
4. The application of the graphene-polypyrrole-cobalt-nickel double metal hydroxide composite material as the electrode material of the supercapacitor, according to the claim 1, is characterized in that: when the discharge is performed in the range of 0-0.35V, the specific capacitance can reach 2500-.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800432A (en) * | 2012-08-23 | 2012-11-28 | 上海第二工业大学 | Method for preparing oxidized graphene/conductive polypyrrole nano wire composite material |
| CN105719850A (en) * | 2016-01-25 | 2016-06-29 | 中国石油大学(华东) | Grapheme@polypyrrole/layer double hydroxide nanowire ternary composite and preparation method and application thereof |
| CN107017094A (en) * | 2017-06-01 | 2017-08-04 | 上海应用技术大学 | A kind of graphene@NiMn LDH combination electrode materials of polyaniline-coated and preparation method thereof |
| CN107128879A (en) * | 2017-05-17 | 2017-09-05 | 北京师范大学 | A kind of preparation method of layered double hydroxide and its product of preparation |
-
2018
- 2018-07-02 CN CN201810708455.7A patent/CN108766785B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800432A (en) * | 2012-08-23 | 2012-11-28 | 上海第二工业大学 | Method for preparing oxidized graphene/conductive polypyrrole nano wire composite material |
| CN105719850A (en) * | 2016-01-25 | 2016-06-29 | 中国石油大学(华东) | Grapheme@polypyrrole/layer double hydroxide nanowire ternary composite and preparation method and application thereof |
| CN107128879A (en) * | 2017-05-17 | 2017-09-05 | 北京师范大学 | A kind of preparation method of layered double hydroxide and its product of preparation |
| CN107017094A (en) * | 2017-06-01 | 2017-08-04 | 上海应用技术大学 | A kind of graphene@NiMn LDH combination electrode materials of polyaniline-coated and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Electrostatic Self-Assembly of Sandwich-Like CoAl-LDH/Polypyrrole/Graphene Nanocomposites with Enhanced Capacitive Performance;Yu Zhang et al;《ACS Appl. Mater. Interfaces》;20170901;20170901;第9卷;第31700页实验部分至第31701页结果与讨论 * |
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