CN113628892B - Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 Preparation method of electrode material - Google Patents
Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 Preparation method of electrode material Download PDFInfo
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Abstract
The invention provides a nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 Preparation of an electrode comprising the steps of: firstly, preparing nitrogen and sulfur co-doped graphene oxide; secondly, preparing nitrogen and sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole; three, nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 Preparing; four, nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 And (4) preparing an electrode. The preparation method has the characteristics of stable process, easiness in operation, reliable quality, low cost, light weight, no pollution and the like, and has good commercial prospect.
Description
Technical Field
The invention relates to a nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 A preparation method of an electrode material belongs to the field of composite materials and electrochemical materials.
Background
The super capacitor has the characteristics of high charging and discharging speed, high energy density and power density, long cycle service life and the like, and has wide application prospects in the fields of communication, electronics, energy, traffic and the like. The excellence of the supercapacitor performance depends mainly on the choice of electrode material. The activity, size and conductivity of the electrode material determine the performance of the supercapacitor. At present, carbon materials, conductive polymers and transition metal compounds are mainly selected as electrode materials. The carbon material has good conductivity and chemical stability, but has low specific capacitance; conductive polymers have high specific capacitance but poor cycling stability; the transition metal compound has high specific capacitance and good chemical stability, but has poor conductivity and high price. Therefore, how to compound the three materials to prepare the electrode material with good conductivity, high specific capacitance, good chemical stability and long cycle service life becomes a hotspot of research.
Graphene (Graphene) is sp 2 The hybridized and connected carbon atoms are tightly packed into a new material with a single-layer two-dimensional honeycomb lattice structure. The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future.
In order to increase the specific capacitance of graphene materials, researchers often complex graphene with conductive polymers or transition metal sulfides or oxides. For example, wang et al first reduce octadecylamine-grafted graphene oxide with hydrazine hydrate to obtain functionalized graphene, and then blend the functionalized graphene with polyaniline to obtain a graphene/polyaniline nanocomposite. Compared with pure polyaniline, the specific capacitance of the graphene/polyaniline nanocomposite material is increased from 426F/g to 787F/g under the condition that the current density is 1A/g (Wanoli, et al. preparation and electrochemical properties of the functionalized graphene/polyaniline composite electrode material, physical and chemical reports, 2014,30, 1659). Liu et al functionalize graphene oxide with oxalic acid to obtain carboxylated graphene oxide, and then chemically polymerize with aniline in situ to obtain an electrode composite material with a specific capacitance of 525F/g (Liu Y, et al, Carboxyl-functionalized graphene oxide-polyaniline composite as a formulating supercapacitive material, J.Mater. chem.2012,22,13619).
The invention content is as follows:
the invention aims to provide a nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 A preparation method of an electrode material, which aims to solve the problems in the prior art.
In order to achieve the purpose, the technical scheme of the invention is as follows:
nitrogen-sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 The preparation method of the electrode material comprises the following steps:
preparing nitrogen and sulfur co-doped graphene oxide;
soaking the nitrogen-sulfur co-doped graphene oxide in a mixed solution of sulfuric acid and nitric acid for activation, washing and drying, transferring the activated graphene oxide into dimethyl sulfoxide, and converting carboxyl into acyl chloride to obtain acyl chloride modified nitrogen-sulfur co-doped graphene oxide;
preparing p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide by using the acyl chloride modified nitrogen and sulfur co-doped graphene oxide;
adding the phenylenediamine modified nitrogen and sulfur co-doped graphene oxide and sodium dodecyl benzene sulfonate into deionized water, uniformly mixing, injecting a pyrrole monomer and a thiophene monomer, and then adding FeC1 3 Continuously stirring for reaction to obtain nitrogen and sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole;
adding the nitrogen-sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole into N, N-dimethylformamide, dispersing uniformly, adding a cobalt acetate aqueous solution, stirring uniformly, adjusting the pH value to 9, and carrying out hydrothermal reaction to obtain the nitrogen-sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 An electrode material.
As a preferred scheme, the preparation method of the nitrogen and sulfur co-doped graphene oxide comprises the following steps:
preparing a graphene oxide/polythiazole compound;
soaking the graphene oxide/polythiazole compound in an ammonium chloride solution with the mass concentration of 0.1-2% for activation, heating to 260-310 ℃ from 25 ℃ under the protection of nitrogen, preserving heat for 2h, heating to 760-810 ℃ from 260-310 ℃, preserving heat for 2h, and obtaining the nitrogen-sulfur co-doped graphene oxide.
As a preferred scheme, the preparation method of the graphene oxide/polythiazole compound comprises the following steps:
dispersing graphite oxide and sodium dodecyl benzene sulfonate in deionized water, adding thiazole and FeC1 3 And carrying out reaction to obtain the graphene oxide/polythiazole compound.
Preferably, the mass ratio of the graphene oxide to the thiazole is (8-12): (3-6).
As a preferred scheme, the preparation method of the p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide comprises the following steps:
adding the acyl chloride modified nitrogen and sulfur co-doped graphene oxide and p-phenylenediamine into a mixed solution of N, N-dimethylformamide and triethylamine, reacting at 120 ℃ under a gas protection condition, filtering a product, washing with ethanol, and drying to obtain the p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide.
According to a preferable scheme, the mass ratio of the p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide to the pyrrole monomer to the thiophene monomer is (1-2): (2-4): (2-4).
As a preferred scheme, the mass ratio of the nitrogen-sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole to the cobalt acetate is (1-2): (5-10), wherein the temperature of the hydrothermal reaction is 180 ℃.
Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co obtained by preparation method 3 O 4 An electrode material.
A preparation method of an electrode for a supercapacitor comprises the following steps:
the nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 Dispersing the electrode material, acetylene black and PTFE in absolute ethyl alcohol, uniformly mixing, coating on the surface of foamed nickel, drying at 60 ℃ in vacuum, and tabletting to obtain the nitrogen-sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 And the electrode is the electrode for the super capacitor.
As a preferred scheme, the nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 The mass ratio of the electrode material to the acetylene black to the PTFE is 8: 1: 1.
the mechanism of the invention is as follows:
1) the method comprises the steps of taking graphene oxide as a carrier, taking thiazole as a nitrogen source and a sulfur source, and obtaining the nitrogen-sulfur co-doped graphene oxide through polymerization, activation, pre-oxidation and carbonization.
2) And carrying out acid activation, p-phenylenediamine modification and graft copolymerization on the nitrogen and sulfur co-doped graphene oxide to obtain the nitrogen and sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole.
3) Finally, Co is reacted by hot water 3 O 4 Loaded on nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole to obtain nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 。
Compared with the prior art, the invention has the following beneficial effects:
1) by utilizing the large specific surface area and high porosity of the graphene oxide, the polymer and the metal oxide are grafted and the burden is placed on the graphene oxide, so that the wettability between the electrode material and the electrolyte is improved, and the specific capacitance of the material is improved.
2) Compared with graphene oxide, nitrogen and sulfur co-doped graphene oxide doped with nitrogen and sulfur elements can generate N-C and S-C bonds, wherein C atoms adjacent to N and S atoms can carry more positive charges, so that the electronegativity of the graphene material can be effectively enhanced, the active sites of the reaction are increased, and the specific capacitance is improved.
3) Compared with the compounding of common polymers and graphene materials, the polythiophene and the polypyrrole are grafted on the graphene materials, and due to the fact that covalent bond connection is formed among the polythiophene, the polypyrrole and the graphene, transmission of electrons between the polymers and the graphene is improved, and specific capacitance of the materials is greatly improved.
4) Grafting polythiophene and polypyrrole onto a graphene electrode, and then mixing with transition metal Co 3 O 4 The composite material overcomes the defect of low specific capacitance of a single graphene electrode material, and greatly improves the specific capacitance of the electrode material.
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Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 shows that the nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co prepared in example 1 of the present invention 3 O 4 Scanning electron micrographs.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the invention.
Example 1
The embodiment provides a nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 The preparation method of the electrode specifically comprises the following steps:
1) preparation of nitrogen and sulfur co-doped graphene oxide
1.2g of graphene oxide, 4g of sodium dodecyl benzene sulfonate and 300mL of deionized water are added into a three-neck flask, and magnetic stirring is carried out at normal temperature to form a dispersion liquid. To the dispersion were added 0.5g thiazole and 1.6g FeC1 3 And continuously stirring for reaction for 12 hours, and filtering, washing and drying the product to obtain the graphene oxide/polythiazole compound. Soaking the compound in 100mL of ammonium chloride solution with the mass concentration of 1.5% for 12h, washing,And (5) drying. And (3) putting the compound into a tube furnace, heating from 25 ℃ to 280 ℃ under the protection of argon, preserving heat for 2h, heating from 280 ℃ to 780 ℃ and preserving heat for 2h to obtain the nitrogen-sulfur co-doped graphene oxide (NSGO).
2) Nitrogen and sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole
0.5g of nitrogen and sulfur co-doped graphene oxide is soaked in a mixed solution of sulfuric acid and nitric acid for 5 hours, and the activated nitrogen and sulfur co-doped graphene oxide is obtained through washing and drying. And soaking the activated nitrogen-sulfur co-doped graphene oxide in 40mL of thionyl chloride for 3h, converting carboxyl into acyl chloride, taking out after soaking, and drying to obtain the acyl chloride modified nitrogen-sulfur co-doped graphene oxide. Adding 50mL of N, N-dimethylformamide and 10mL of triethylamine into a three-neck flask, adding 0.4g of acyl chloride modified nitrogen and sulfur co-doped graphene oxide and 2g of p-phenylenediamine into the three-neck flask, reacting for 30 hours at 120 ℃ under the protection of nitrogen, filtering a product, washing with ethanol, and drying to obtain the p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide.
0.18g of p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide and 0.2g of sodium dodecyl benzene sulfonate are added into 100mL of deionized water at room temperature and stirred. After being stirred evenly, 0.4g of pyrrole monomer and 0.3g of thiophene monomer are injected, and then 3g of FeC1 is added 3 The reaction was continued with stirring for 12 h. And washing the product with water and absolute ethyl alcohol for 3 times, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the nitrogen-sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole.
3) Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4
Adding 0.15g of nitrogen and sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole into 30g N, N-dimethylformamide, performing ultrasonic dispersion to form a dispersion liquid, dissolving 0.65g of cobalt acetate in 20mL of deionized water, adding an aqueous solution of cobalt acetate into the dispersion liquid, stirring uniformly, adjusting the pH to 9 by using ammonia water, adding the obtained mixture into a 100mL hydrothermal kettle, preserving the temperature at 180 ℃ for 3h, cooling to room temperature, performing suction filtration on the obtained reaction liquid, washing with deionized water and ethanol for 3 times, and performing vacuum drying at 50 ℃ for 24h to obtain the nitrogen and sulfur co-doped graphene oxide grafted polythiophene-co-pyrrolepyrrole/Co 3 O 4 The scanning electron micrograph of the electrode material is shown in FIG. 1.
4) Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 Preparation of the electrodes
Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 Acetylene black and PTFE were mixed as 8: 1: 1 in absolute ethyl alcohol, performing ultrasonic dispersion for 40min, coating the mixture on foamed nickel, performing vacuum drying at 60 ℃ for 6h, and pressing the dried product under the pressure of 10MPa to obtain the nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 And an electrode.
Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co prepared in the embodiment 3 O 4 Under the condition that the current density is 1A/g, the specific capacitance is 370F/g, and after 800 times of cyclic use, the capacitance is 82.1 percent of the initial value.
Example 2
The embodiment provides a nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 The preparation method of the electrode specifically comprises the following steps:
1) preparation of nitrogen and sulfur co-doped graphene oxide
1g of graphene oxide, 4g of sodium dodecyl benzene sulfonate and 300mL of deionized water are added into a three-neck flask, and magnetic stirring is carried out at normal temperature to form a dispersion liquid. To the dispersion were added 0.45g of thiazole and 1.6g of FeC1 3 And continuously stirring for reaction for 12 hours, and filtering, washing and drying the product to obtain the graphene oxide/polythiazole compound. And soaking the compound in 100mL of ammonium chloride solution with the mass concentration of 1.4% for 12h, washing and drying. And (3) putting the compound into a tube furnace, heating up to 285 ℃ from 25 ℃ under the protection of argon, preserving heat for 2h, heating up to 790 ℃ from 285 ℃, and preserving heat for 2h to obtain the nitrogen-sulfur co-doped graphene oxide (NSGO).
2) Nitrogen and sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole
0.5g of nitrogen and sulfur co-doped graphene oxide is soaked in a mixed solution of sulfuric acid and nitric acid for 5 hours, and the activated nitrogen and sulfur co-doped graphene oxide is obtained through washing and drying. And soaking the activated nitrogen-sulfur co-doped graphene oxide in 40mL of thionyl chloride for 3h, converting carboxyl into acyl chloride, taking out after soaking, and drying to obtain the acyl chloride modified nitrogen-sulfur co-doped graphene oxide. Adding 50mL of N, N-dimethylformamide and 10mL of triethylamine into a three-neck flask, adding 0.4g of acyl chloride modified nitrogen and sulfur co-doped graphene oxide and 2g of p-phenylenediamine into the three-neck flask, reacting for 30 hours at 120 ℃ under the protection of nitrogen, filtering a product, washing with ethanol, and drying to obtain the p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide.
0.2g of p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide and 0.2g of sodium dodecyl benzene sulfonate are added into 100mL of deionized water at room temperature and stirred. After being stirred evenly, 0.35g of pyrrole monomer and 0.25g of thiophene monomer are injected, and then 3g of FeC1 is added 3 The reaction was continued with stirring for 12 h. And washing the product with water and absolute ethyl alcohol for 3 times, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the nitrogen-sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole.
3) Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4
Adding 0.17g of nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole into 30g of N, N-dimethylformamide, performing ultrasonic dispersion to form a dispersion liquid, dissolving 0.7g of cobalt acetate in 20mL of deionized water, adding an aqueous solution of cobalt acetate into the dispersion liquid, stirring uniformly, adjusting the pH to 9 by using ammonia water, adding the obtained mixture into a 100mL hydrothermal kettle, preserving the temperature at 180 ℃ for 3h, cooling to room temperature, performing suction filtration on the obtained reaction liquid, washing with deionized water and ethanol for 3 times, and performing vacuum drying at 50 ℃ for 24h to obtain the nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 。
4) Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 Preparation of the electrodes
Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 Acetylene black and PTFE were mixed as 8: 1: 1 in absolute ethyl alcohol, ultrasonically dispersing for 40min, coating on foamed nickel, vacuum drying at 60 ℃ for 6h, and then pressing at 10MPaPressing the sheet under force to prepare the nitrogen-sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 And an electrode.
Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co prepared in the embodiment 3 O 4 The specific capacitance is 355F/g under the condition that the current density is 1A/g, and after 800 times of cyclic use, the capacitance is 79.4 percent of the initial value.
Example 3
The embodiment provides a nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 The preparation method of the electrode specifically comprises the following steps:
1) preparation of nitrogen and sulfur co-doped graphene oxide
0.9g of graphene oxide, 4g of sodium dodecyl benzene sulfonate and 300mL of deionized water are added into a three-neck flask, and magnetic stirring is carried out at normal temperature to form a dispersion liquid. To the dispersion were added 0.55g of thiazole and 1.6g of FeC1 3 And continuously stirring for reaction for 12 hours, and filtering, washing and drying the product to obtain the graphene oxide/polythiazole compound. And soaking the compound in 100mL of ammonium chloride solution with the mass concentration of 1.5% for 12h, washing and drying. And (3) putting the compound into a tube furnace, heating to 295 ℃ from 25 ℃ under the protection of argon, preserving heat for 2h, heating to 805 ℃ from 295 ℃, and preserving heat for 2h to obtain the nitrogen-sulfur co-doped graphene oxide (NSGO).
2) Nitrogen and sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole
0.5g of nitrogen and sulfur co-doped graphene oxide is soaked in a mixed solution of sulfuric acid and nitric acid for 5 hours, and the activated nitrogen and sulfur co-doped graphene oxide is obtained through washing and drying. And soaking the activated nitrogen-sulfur co-doped graphene oxide in 40mL of thionyl chloride for 3h, converting carboxyl into acyl chloride, taking out after soaking, and drying to obtain the acyl chloride modified nitrogen-sulfur co-doped graphene oxide. Adding 50mL of N, N-dimethylformamide and 10mL of triethylamine into a three-neck flask, adding 0.4g of acyl chloride modified nitrogen and sulfur co-doped graphene oxide and 2g of p-phenylenediamine into the three-neck flask, reacting for 30 hours at 120 ℃ under the protection of nitrogen, filtering a product, washing with ethanol, and drying to obtain the p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide.
0.16g of p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide and 0.2g of sodium dodecyl benzene sulfonate are added into 100mL of deionized water at room temperature and stirred. After being stirred evenly, 0.3g of pyrrole monomer and 0.35g of thiophene monomer are injected, and then 3g of FeC1 is added 3 The reaction was stirred for 12 h. And washing the product with water and absolute ethyl alcohol for 3 times, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the nitrogen-sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole.
3) Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4
Adding 0.18g of nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole into 30g N N-dimethylformamide, performing ultrasonic dispersion to form a dispersion liquid, dissolving 0.75g of cobalt acetate in 20mL of deionized water, adding an aqueous solution of cobalt acetate into the dispersion liquid, stirring uniformly, adjusting the pH to 9 by using ammonia water, adding the obtained mixture into a 100mL hydrothermal kettle, preserving the temperature at 180 ℃ for 3h, cooling to room temperature, performing suction filtration on the obtained reaction liquid, washing with deionized water and ethanol for 3 times, and performing vacuum drying at 50 ℃ for 24h to obtain the nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 。
4) Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 Preparation of the electrodes
Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 Acetylene black and PTFE were mixed as 8: 1: 1 in absolute ethyl alcohol, performing ultrasonic dispersion for 40min, coating the mixture on foamed nickel, performing vacuum drying at 60 ℃ for 6h, and pressing the dried product under the pressure of 10MPa to obtain the nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 And an electrode.
Nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co prepared in the embodiment 3 O 4 The specific capacitance is 381F/g under the condition that the current density is 1A/g, and after 800 times of cyclic use, the capacitance is 81.1 percent of the initial value.
Comparative example 1
In contrast to example 1, step 1) is omitted and oxygen is directly introducedAdding graphene into the reaction in the step 2), and finally obtaining the graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 The electrode has a specific capacitance of 250F/g under the condition of a current density of 1A/g, and the capacitance is 70.8 percent of the initial value after 800 times of cyclic use.
Comparative example 2
Different from the embodiment 1, the step 2) is omitted, and the finally obtained nitrogen and sulfur Co-doped graphene oxide/Co 3 O 4 The electrode has a specific capacitance of 219F/g under the condition of a current density of 1A/g, and the capacitance is 70.7% of the initial value after 800 times of cyclic use.
Comparative example 3
Different from the embodiment 1, in the step 2), only thiophene monomer is added, no pyrrole monomer is added, and finally the obtained nitrogen and sulfur Co-doped graphene oxide grafted polythiophene/Co 3 O 4 The electrode has a specific capacitance of 288F/g under the condition of a current density of 1A/g, and the capacitance is 80.8 percent of the initial value after 800 times of cyclic use.
Comparative example 4
Different from the embodiment 1, in the step 2), only pyrrole monomer is added, thiophene monomer is not added, and finally the obtained nitrogen and sulfur Co-doped graphene oxide grafted polypyrrole/Co 3 O 4 The electrode had a specific capacitance of 278F/g at a current density of 1A/g, and the capacitance was 77.1% of the initial value after 800 cycles.
Comparative example 5
The difference from the embodiment 1 is that the step 3) is omitted, the specific capacitance of the finally obtained nitrogen and sulfur co-doped graphene oxide grafted polythiophene-co pyrrole electrode is 290F/g under the condition that the current density is 1A/g, and the capacitance is 72.1% of the initial value after 800 times of cyclic use.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. Nitrogen-sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole/Co 3 O 4 The preparation method of the electrode material is characterized by comprising the following steps:
preparing nitrogen and sulfur co-doped graphene oxide;
soaking the nitrogen-sulfur co-doped graphene oxide in a mixed solution of sulfuric acid and nitric acid for activation, washing and drying, transferring the activated graphene oxide into dimethyl sulfoxide, and converting carboxyl into acyl chloride to obtain acyl chloride modified nitrogen-sulfur co-doped graphene oxide;
preparing p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide by using the acyl chloride modified nitrogen and sulfur co-doped graphene oxide;
adding the phenylenediamine modified nitrogen and sulfur co-doped graphene oxide and sodium dodecyl benzene sulfonate into deionized water, uniformly mixing, injecting a pyrrole monomer and a thiophene monomer, and then adding FeC1 3 Continuously stirring for reaction to obtain nitrogen and sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole;
adding the nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole into N, N-dimethylformamide, uniformly dispersing, adding a cobalt acetate aqueous solution, uniformly stirring, adjusting the pH value to 9, and carrying out hydrothermal reaction to obtain the nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 An electrode material.
2. The nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co of claim 1 3 O 4 The preparation method of the electrode material is characterized in that the preparation method of the nitrogen and sulfur co-doped graphene oxide comprises the following steps:
preparing a graphene oxide/polythiazole compound;
soaking the graphene oxide/polythiazole compound in an ammonium chloride solution with the mass concentration of 0.1-2% for activation, heating to 260-310 ℃ from 25 ℃ under the protection of nitrogen, preserving heat for 2h, heating to 760-810 ℃ from 260-310 ℃, preserving heat for 2h, and obtaining the nitrogen-sulfur co-doped graphene oxide.
3. The nitrogen and sulfur co-doped graphene oxide junction of claim 2Branched polythiophene-Co-pyrrole/Co 3 O 4 The preparation method of the electrode material is characterized in that the preparation method of the graphene oxide/poly thiazole compound comprises the following steps:
dispersing graphite oxide and sodium dodecyl benzene sulfonate in deionized water, adding thiazole and FeC1 3 And carrying out reaction to obtain the graphene oxide/polythiazole compound.
4. The nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co as claimed in claim 3 3 O 4 The preparation method of the electrode material is characterized in that the mass ratio of the graphene oxide to the thiazole is (8-12): (3-6).
5. The nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co of claim 1 3 O 4 The preparation method of the electrode material is characterized in that the preparation method of the p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide comprises the following steps:
adding the acyl chloride modified nitrogen and sulfur co-doped graphene oxide and p-phenylenediamine into a mixed solution of N, N-dimethylformamide and triethylamine, reacting at 120 ℃ under a gas protection condition, filtering a product, washing with ethanol, and drying to obtain the p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide.
6. The nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co of claim 1 3 O 4 The preparation method of the electrode material is characterized in that the mass ratio of the p-phenylenediamine modified nitrogen and sulfur co-doped graphene oxide to the pyrrole monomer to the thiophene monomer is (1-2): (2-4): (2-4).
7. The nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co of claim 1 3 O 4 The preparation method of the electrode material is characterized in that the mass ratio of the nitrogen-sulfur co-doped graphene oxide grafted polythiophene-co-pyrrole to the cobalt acetate is (1-2): (5-10), wherein the temperature of the hydrothermal reaction is 180 ℃.
8. Nitrogen-sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co obtained by the preparation method of claim 1 3 O 4 And (3) an electrode material.
9. A preparation method of an electrode for a supercapacitor is characterized by comprising the following steps:
the nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co of claim 8 3 O 4 Dispersing the electrode material, acetylene black and PTFE in absolute ethyl alcohol, uniformly mixing, coating on the surface of foamed nickel, drying at 60 ℃ in vacuum, and tabletting to obtain the nitrogen-sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 And the electrode is the electrode for the super capacitor.
10. The method for preparing the electrode for the supercapacitor according to claim 9, wherein the nitrogen and sulfur Co-doped graphene oxide grafted polythiophene-Co-pyrrole/Co 3 O 4 The mass ratio of the electrode material to the acetylene black to the PTFE is 8: 1: 1.
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