CN111354513B - Silver-doped polypyrrole-coated graphite composite material and preparation method thereof - Google Patents
Silver-doped polypyrrole-coated graphite composite material and preparation method thereof Download PDFInfo
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- CN111354513B CN111354513B CN201811562243.9A CN201811562243A CN111354513B CN 111354513 B CN111354513 B CN 111354513B CN 201811562243 A CN201811562243 A CN 201811562243A CN 111354513 B CN111354513 B CN 111354513B
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H—ELECTRICITY
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
Abstract
The invention discloses a silver-doped polypyrrole-coated graphite composite material and a preparation method thereof. The method comprises the steps of firstly placing natural crystalline flake graphite in a mixed solution of an oxidant and an intercalator for oxidation intercalation treatment to obtain expandable graphite, then mixing a silver nitrate solution, a pyrrole monomer solution and the expandable graphite, using silver nitrate as the oxidant to promote in-situ polymerization of pyrrole monomers, and simultaneously reducing the silver nitrate into silver simple substances doped in polypyrrole to obtain the core-shell type silver-doped polypyrrole-coated graphite composite material. The method is simple, and the prepared silver-doped polypyrrole-coated graphite composite material has the conductivity of 18.037S/cm and good conductivity.
Description
Technical Field
The invention relates to a silver-doped polypyrrole-coated graphite composite material and a preparation method thereof, belonging to the field of preparation of electrode materials.
Background
The polypyrrole is a conjugated conductive polymer with good stability, simple and convenient synthesis, high temperature resistance and good oxidation resistance, and can be applied to the fields of electronic devices, sensing devices, optical devices, conductive materials, electromagnetic shielding, metal corrosion prevention and the like. However, polypyrrole has some limitations in solubility, processability, and the like. The method for preparing the composite material by compounding the polypyrrole and the carbon material solves the processing problem of the material and improves the conductivity of the material to a certain extent.
Chinese patent CN107522269A discloses a preparation method of a porous graphene/polypyrrole electrode material, wherein a Fenton reagent (a system consisting of ferrous ions and hydrogen peroxide) is used as an oxidizing agent, ascorbic acid, glutathione or sodium benzene sulfinate is used as a reducing agent, but the composite material has the problem of graphene agglomeration, so that the conductivity of the composite material is influenced.
Disclosure of Invention
The invention aims to provide a silver-doped polypyrrole-coated graphite composite material and a preparation method thereof, which improve the conductivity of polypyrrole/graphite by doping silver particles.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the silver-doped polypyrrole-coated graphite composite material comprises the following steps of taking silver nitrate as an oxidant to promote in-situ polymerization of pyrrole monomers, reducing the silver nitrate into silver simple substances to be doped in polypyrrole, and preparing the integrated silver-doped polypyrrole-coated graphite composite material, wherein the specific steps are as follows:
step 1, placing natural crystalline flake graphite in a mixed solution of an oxidant and an intercalating agent for oxidation intercalation treatment, filtering out a solid matter, washing with water to be neutral, drying to obtain expandable graphite, and heating the expandable graphite at 260 +/-10 ℃ to obtain the expandable graphite;
and 2, mixing the silver nitrate solution, the pyrrole monomer solution and the expanded graphite according to the mass ratio of the pyrrole monomer to the silver nitrate of 2-4: 1, stirring and reacting in a water bath at 30-50 ℃, naturally cooling and aging at room temperature after the reaction is finished, washing, filtering and drying to obtain the silver-doped polypyrrole coated graphite composite material.
Preferably, in step 1, potassium permanganate, nitric acid, perchloric acid and glacial acetic acid are used as an oxidation intercalation system, and the usage ratio of graphite to potassium permanganate, nitric acid, perchloric acid and glacial acetic acid is as follows: graphite: potassium permanganate: nitric acid: perchloric acid: glacial acetic acid 5: 1.7:3.0:8.0:2.5, g: g: mL: mL: and (mL).
Preferably, in step 1, the time for the oxidative intercalation treatment is 30 ± 10 min.
Preferably, in the step 2, the concentration of the silver nitrate solution is 0.1-0.2 mol/L, and the pH value is 2 +/-0.1.
Preferably, in the step 2, the mass ratio of the expanded graphite to the pyrrole monomer is 1: 1-3.
Preferably, in the step 2, the mass ratio of the pyrrole monomer to the silver nitrate is 2: 1.
Preferably, in the step 2, the water bath reaction time is 3-5 h.
Preferably, in step 2, the temperature of the water bath is 40 ℃.
Preferably, in the step 2, the aging time is 2-20 h.
Compared with the prior art, the invention has the following advantages:
the silver-doped polypyrrole coated graphite composite material has the advantages of generally available raw materials, low cost, safe preparation process, and simplicity and convenience; the composite material is synthesized in one step by using an in-situ polymerization method and taking silver nitrate as an oxidant without introducing other additives, so that the process is simplified, the components in the obtained product interact with each other, and silver particles and polypyrrole are uniformly distributed on a graphite matrix, so that the formed composite material with the integrated core-shell structure has the advantages of high conductivity up to 18.037S/cm and good conductivity.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Fig. 2 is a scanning electron microscope image of the graphite and silver-doped polypyrrole coated graphite composite material after oxidation treatment in example 1.
Fig. 3 is an infrared spectrum of the silver-doped polypyrrole-coated graphite composite material in example 1.
Referring to the process flow of fig. 1, two different sets of process parameters were selected within the conventional range of the art and are specifically described in conjunction with the following 2 specific examples and the accompanying drawings.
Detailed Description
Example 1
Step 1, according to potassium permanganate (g): nitric acid (mL): perchloric acid (mL): glacial acetic acid (mL): treating 5g of graphite according to the dosage of 1.7:3.0:8.0:2.5, washing and drying, and then heating the expandable graphite at 260 ℃ to obtain expanded graphite with slightly increased volume;
step 2, weighing 0.17g of silver nitrate, adding 10mL of deionized water, and dripping nitric acid to mix uniformly to prepare a silver nitrate solution with the pH value of 2; weighing 0.14g of pyrrole monomer, adding 10mL of deionized water with the temperature of about 40 ℃, and uniformly mixing to prepare a pyrrole monomer solution; pouring a silver nitrate solution into a pyrrole monomer solution, adding expanded graphite, stirring and reacting for 4 hours in a constant-temperature water bath at 40 ℃, naturally cooling, and aging for 20 hours at room temperature; the product is washed and filtered (the pH value of the last washing liquid is required to be 6-7), and the product is dried in an oven at 60 ℃ for 4 hours to obtain the silver-doped polypyrrole coated graphite composite material with dark gray and no luster, and the conductivity of the composite material is 18.037S/cm. FIG. 2 is an SEM image of the composite material of expanded graphite and silver-doped polypyrrole coated graphite in example 1; as can be seen from fig. 2, the silver particles are uniformly distributed on the graphite surface. FIG. 3 is an infrared spectrum of the silver-doped polypyrrole-coated graphite composite material of example 1, illustrating some interactions between polypyrrole and graphite in the composite material.
Example 2
Step 1, according to potassium permanganate (g): nitric acid (mL): perchloric acid (mL): glacial acetic acid (mL): treating 5g of graphite according to the dosage of 1.7:3.0:8.0:2.5, washing and drying, and then heating the expandable graphite at 260 ℃ to obtain expanded graphite with slightly increased volume;
step 2, weighing 0.13g of silver nitrate, adding 10mL of deionized water, and dripping 1 drop of nitric acid to mix uniformly to prepare a silver nitrate solution; weighing 0.14g of pyrrole monomer, adding 10mL of deionized water with the temperature of about 40 ℃, and uniformly mixing to prepare a pyrrole monomer solution; pouring a silver nitrate solution into a pyrrole monomer solution, adding expanded graphite, stirring and reacting for 4 hours in a constant-temperature water bath at 40 ℃, naturally cooling, and aging for 20 hours at room temperature; the product is washed and filtered (the pH value of the last washing liquid is required to be 6-7), and the product is dried in an oven at 60 ℃ for 4 hours to obtain the silver-doped polypyrrole coated graphite composite material with dark gray and no luster, and the conductivity of the composite material is 9.904S/cm.
Example 3
Step 1, according to potassium permanganate (g): nitric acid (mL): perchloric acid (mL): glacial acetic acid (mL): treating 5g of graphite according to the dosage of 1.7:3.0:8.0:2.5, washing and drying, and then heating the expandable graphite at 260 ℃ to obtain expanded graphite with slightly increased volume;
step 2, weighing 0.17g of silver nitrate, adding 10mL of deionized water, and dripping 1 drop of nitric acid to mix uniformly to prepare a silver nitrate solution; weighing 0.14g of pyrrole monomer, adding 10mL of deionized water with the temperature of about 50 ℃, and uniformly mixing to prepare a pyrrole monomer solution; pouring a silver nitrate solution into a pyrrole monomer solution, adding expanded graphite, stirring and reacting for 4 hours in a constant-temperature water bath at 50 ℃, naturally cooling, and aging for 20 hours at room temperature; the product is washed and filtered (the pH value of the last washing liquid is required to be 6-7), and the product is dried in an oven at 60 ℃ for 4 hours to obtain the silver-doped polypyrrole coated graphite composite material with dark gray and no luster, and the conductivity of the composite material is 9.926S/cm.
Comparative example 1
This comparative example is essentially the same as example 1, except that the amount of azole monomer and silver nitrate are present in a ratio of 8: 1. The conductivity of the obtained silver-doped polypyrrole-coated graphite composite material is 5.21S/cm.
Comparative example 2
This comparative example is essentially the same as example 1, except that the water bath temperature is 60 ℃. The conductivity of the obtained silver-doped polypyrrole-coated graphite composite material is 6.352S/cm.
Claims (1)
1. The preparation method of the silver-doped polypyrrole-coated graphite composite material is characterized by comprising the following specific steps of:
step 1, according to potassium permanganate: nitric acid: perchloric acid: treating 5g of graphite by using glacial acetic acid =1.7g, 3.0mL, 8.0mL and 2.5mL, washing and drying, and then heating the expandable graphite at 260 ℃ to obtain expanded graphite with slightly increased volume;
step 2, weighing 0.17g of silver nitrate, adding 10mL of deionized water, and dripping nitric acid to mix uniformly to prepare a silver nitrate solution with the pH value of 2; weighing 0.14g of pyrrole monomer, adding 10mL of deionized water with the temperature of 40 ℃, and uniformly mixing to prepare a pyrrole monomer solution; pouring a silver nitrate solution into a pyrrole monomer solution, adding expanded graphite, stirring and reacting for 4 hours in a constant-temperature water bath at 40 ℃, naturally cooling, and aging for 20 hours at room temperature; and washing and filtering the product, wherein the pH value of the last washing liquid is 6-7, and drying in an oven at 60 ℃ for 4h to obtain the silver-doped polypyrrole-coated graphite composite material with dark gray and no luster.
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| US8497225B2 (en) * | 2007-08-27 | 2013-07-30 | Nanotek Instruments, Inc. | Method of producing graphite-carbon composite electrodes for supercapacitors |
| CN104292458B (en) * | 2014-11-06 | 2016-09-21 | 黑龙江科技大学 | The preparation method of polypyrrole/exfoliated-graphite composite |
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