CN112159523B - Polyaniline/nickel disulfide/graphene nanofiber composite material and preparation method thereof - Google Patents
Polyaniline/nickel disulfide/graphene nanofiber composite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 84
- 239000002121 nanofiber Substances 0.000 title claims abstract description 79
- NKHCNALJONDGSY-UHFFFAOYSA-N nickel disulfide Chemical compound [Ni+2].[S-][S-] NKHCNALJONDGSY-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 66
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000009210 therapy by ultrasound Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000011085 pressure filtration Methods 0.000 claims description 7
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 7
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 7
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims 1
- JTRONPPAUSSTQI-UHFFFAOYSA-N ethane-1,2-diol;ethanol Chemical compound CCO.OCCO JTRONPPAUSSTQI-UHFFFAOYSA-N 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 7
- 230000008093 supporting effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003990 capacitor Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002604 ultrasonography Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 239000002134 carbon nanofiber Substances 0.000 description 10
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000007600 charging Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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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
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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Abstract
The invention discloses a polyaniline/nickel disulfide/graphene nanofiber composite material and a preparation method thereof, and belongs to the technical field of preparation of electrode materials of supercapacitors. The composite material is prepared by taking aniline as a monomer, taking graphene nanofiber-loaded nickel disulfide prepared by a hydrothermal method as a supporting framework and ammonium persulfate as an oxidant through a chemical oxidation reaction under the action of ultrasound. The composite material prepared by the invention has high specific capacitance and excellent electrochemical cycle stability, is mainly used for manufacturing the electrode of the super capacitor, and has obvious economic value and social benefit.
Description
Technical Field
The invention belongs to the technical field of preparation of electrode materials of supercapacitors, and particularly relates to a polyaniline/nickel disulfide/graphene nanofiber composite material and a preparation method thereof.
Background
As an important supercapacitor electrode material, polyaniline has the advantages of simple preparation, diversified structure, excellent electrical activity, low price, excellent chemical stability and the like. However, the specific surface area of polyaniline is small, so that the specific capacitance of polyaniline is low, and in the charging and discharging processes, the repeated embedding and releasing of doped ions causes repeated expansion and contraction of the polyaniline structure, which microscopically causes structural collapse of polyaniline, so that the specific capacitance of polyaniline is rapidly attenuated, and the electrochemical cycle stability is poor. The graphene nanofiber is a novel nano carbon material prepared by partially stripping the outer layer of the carbon nanofiber by adopting a chemical means. The outer layer of the graphene nanofiber presents the appearance of graphene, and the inner layer still keeps the state of the carbon nanofiber. The graphene nanofiber and the polymer electrode material are compounded, on one hand, the graphene on the outer layer of the graphene nanofiber can endow the polymer electrode material with a large specific surface area, and on the other hand, the carbon nanofiber on the inner layer can be used as a supporting/isolating material to effectively prevent the structure collapse of the polymer electrode material in the charging and discharging process, so that the graphene nanofiber can obviously improve the specific capacitance and the electrochemical cycle stability of the polymer electrode material.
The Chinese patent of invention (CN 110060878A) discloses a preparation method of a polyaniline/graphene oxide nanofiber composite material, wherein the composite material is prepared by using aniline as a monomer, graphene oxide nanofiber as a supporting framework and ammonium persulfate as an oxidant, and conducting polymerization of the aniline monomer on the graphene oxide nanofiber through cobalt ions by utilizing chemical oxidation polymerization reaction. Although the specific capacitance and the electrochemical cycle stability of polyaniline are improved to a certain extent by the guiding effect of cobalt ions and the supporting effect of graphene oxide in the composite material, the graphene nanofibers in the composite material are in an oxidized state, and the oxygen-containing functional groups on the surfaces of the graphene nanofibers influence the electron transport of the composite material, so that the effect of the graphene nanofibers is limited to a certain extent.
Disclosure of Invention
Aiming at the problems of low specific capacitance, poor electrochemical cycling stability and the like of the existing polyaniline, the invention provides a polyaniline/nickel disulfide/graphene nanofiber composite material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polyaniline/nickel disulfide/graphene nanofiber composite material is prepared by taking aniline as a monomer, taking graphene nanofiber load nickel disulfide prepared by a hydrothermal method as a supporting framework, taking ammonium persulfate as an oxidant and carrying out chemical oxidation reaction under the action of ultrasound; the preparation method of the composite material comprises the following specific steps:
(1) preparation method of graphene nanofiber loaded nickel disulfide
a) Adding 0.1-0.2 g of graphene oxide nano fibers into 100-200 mL of deionized water, and performing ultrasonic treatment at room temperature for 30-60 min to obtain a dispersion solution I of the graphene oxide nano fibers;
b) adding 3-9 g of sodium thiosulfate pentahydrate and 0.5-2 g of nickel chloride hexahydrate into 40-200 mL of glycol-ethanol mixed solution (volume ratio is 1: 1), and mechanically stirring at room temperature for 1-2 h to prepare mixed solution II of sodium thiosulfate and nickel chloride;
c) adding the mixed solution II into the dispersion solution I, mechanically stirring for 1-2 hours at room temperature, transferring to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 18-36 hours at 200-260 ℃, and after the reaction is finished, centrifuging, washing with deionized water, and vacuum drying for 24 hours at 60 ℃ to obtain the graphene nanofiber loaded nickel disulfide;
(2) preparation of composite materials
d) Adding 0.1-0.2 g of graphene nanofiber-loaded nickel disulfide into 100-200 mL of deionized water, and performing ultrasonic treatment at room temperature for 30-60 min to obtain graphene nanofiber-loaded nickel disulfide dispersion liquid III;
e) adding 1.5-2.5 g of aniline into 30-60 mL of 1 mol/L hydrochloric acid aqueous solution, and mechanically stirring at room temperature for 10-30 min to obtain hydrochloric acid aqueous solution IV of aniline;
f) and adding the solution IV into the dispersion liquid III, performing ultrasonic treatment at room temperature for 30-60 min, dropwise adding 20-60 mL of ammonium persulfate hydrochloric acid aqueous solution at the speed of 20-40 drops/min (in the ammonium persulfate hydrochloric acid aqueous solution, the concentration of ammonium persulfate is 1 mol/L, and the concentration of hydrochloric acid is 1 mol/L), continuing ultrasonic treatment at room temperature for 4-8 h after dropwise adding is finished, performing reduced pressure filtration, repeatedly washing the filtration product with deionized water and ethanol until the pH value of the filtrate is 7, and performing vacuum drying at 60 ℃ for 24 h to obtain the polyaniline/nickel disulfide/graphene nanofiber composite material.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, polyaniline and graphene nanofibers are compounded, so that on one hand, the outer-layer graphene structure of the graphene nanofibers can endow the composite material with a large specific surface area, and on the other hand, the inner-layer carbon nanofiber structure serving as a supporting/isolating material can effectively prevent the polyaniline from structural collapse in the charging and discharging processes, and endows the composite material with excellent electrochemical cycle stability.
(2) The nickel disulfide nano-microspheres and the graphene nano-fibers are easy to agglomerate, and the nickel disulfide nano-microspheres are uniformly distributed on the surfaces of the graphene nano-fibers by using a hydrothermal method, so that the nickel disulfide nano-microspheres and the graphene nano-fibers can be prevented from agglomerating.
(3) The graphene nanofiber-loaded nickel disulfide has a stable crystal structure and a unique three-dimensional microscopic morphology, can effectively ensure that electrolyte ions move rapidly in the composite material, and endows the composite material with excellent rate capability and high specific capacitance.
(4) The polyaniline/nickel disulfide/graphene nanofiber composite material prepared by the invention has high specific capacitance and excellent electrochemical cycle stability, when the charge-discharge current densities are respectively 2A/g, 3A/g, 4A/g and 5A/g, the specific capacitances are respectively 379F/g, 346F/g, 328F/g and 315F/g, the specific capacitances are respectively improved by 70.7%, 86.0%, 96.4% and 105.8% compared with polyaniline, after the polyaniline is charged and discharged for 1000 times, the specific capacitance is attenuated to 88.9% of the initial value and is improved by 27.2% compared with polyaniline, and the polyaniline-based composite material has obvious economic value and social benefit when being used for manufacturing electrodes of super capacitors.
Drawings
Fig. 1 is a raman spectrum of the graphene nanofiber loaded nickel disulfide prepared in example 1;
fig. 2 is a scanning electron microscope image of the graphene nanofiber loaded with nickel disulfide prepared in example 1;
FIG. 3 is a Raman spectrum of the polyaniline/nickel disulfide/graphene nanofiber composite prepared in example 1;
fig. 4 is a scanning electron microscope image of the polyaniline/nickel disulfide/graphene nanofiber composite prepared in example 1.
Detailed Description
The advantages and effects of the polyaniline/nickel disulfide/graphene nanofiber composite material and the preparation method thereof in the embodiment are further explained by three groups of examples and three groups of comparative examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The graphene oxide nanofiber references used are Higginbotham A L, Kosynkin D V, Sinitskii A, Sun Z, Tour J M, Lower-defect graphene oxide nanotubes from multi walled carbon nanotubes, ACS Nano, 2010, 4(4): 2059-.
Example 1
(1) Adding 0.15 g of graphene oxide nano fibers into 150 mL of deionized water, and performing ultrasonic treatment at room temperature for 45 min to obtain a dispersion solution I of the graphene oxide nano fibers; adding 6 g of sodium thiosulfate pentahydrate and 1.25 g of nickel chloride hexahydrate into 120 mL of glycol-ethanol mixed solution (the volume ratio is 1: 1), and mechanically stirring for 1.5 h at room temperature to prepare mixed solution II of sodium thiosulfate and nickel chloride; and adding the mixed solution II into the dispersion solution I, mechanically stirring for 1.5 h at room temperature, transferring to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 27 h at 230 ℃, and after the reaction is finished, centrifuging, washing with deionized water, and vacuum drying for 24 h at 60 ℃ to obtain the graphene nanofiber-loaded nickel disulfide.
(2) Adding 0.15 g of graphene nanofiber-loaded nickel disulfide into 150 mL of deionized water, and performing ultrasonic treatment for 45 min at room temperature to obtain graphene nanofiber-loaded nickel disulfide dispersion liquid III; adding 2 g of aniline into 45 mL of 1 mol/L hydrochloric acid aqueous solution, and mechanically stirring at room temperature for 20 min to obtain aniline hydrochloric acid aqueous solution IV; and adding the solution IV into the dispersion liquid III, carrying out ultrasonic treatment at room temperature for 45 min, dropwise adding 40 mL of ammonium persulfate aqueous hydrochloric acid at the speed of 30 drops/min (in the ammonium persulfate aqueous hydrochloric acid, the concentration of ammonium persulfate is 1 mol/L, and the concentration of hydrochloric acid is 1 mol/L), continuing ultrasonic treatment at room temperature for 6 h after dropwise adding, carrying out reduced pressure filtration, repeatedly washing a filtration product with deionized water and ethanol until the pH value of the filtrate is 7, and carrying out vacuum drying at 60 ℃ for 24 h to obtain the polyaniline/nickel disulfide/graphene nanofiber composite material.
Fig. 1 is a raman spectrum of the graphene nanofiber loaded with nickel disulfide prepared in this embodiment. As can be seen from the figure, at 1350 cm-1And 1580 cm-1The two peaks are characteristic peaks of the graphene nanofiber, namely a D peak caused by lattice defects and a G peak caused by in-plane bond stretching vibration of a C sp2 atom pair, and the graphene nanofiber loaded with nickel disulfide is successfully prepared.
Fig. 2 is a scanning electron microscope image of the graphene nanofiber loaded with nickel disulfide prepared in this embodiment. The figure shows that the molybdenum disulfide nano microspheres are distributed on the surface of the graphene nano fiber more uniformly.
Fig. 3 is a raman spectrum of the polyaniline/nickel disulfide/graphene nanofiber composite prepared in this example. As can be seen from the figure, the peak is 1160 cm except for the characteristic peak of the graphene nanofiber-1And 1480 cm-1C-H bond bending vibration peaks of polyaniline quinone rings and N-H bond bending vibration peaks in dipole structures are respectively shown, and the polyaniline/nickel disulfide/graphene nanofiber composite material is successfully prepared.
Fig. 4 is a scanning electron microscope image of the polyaniline/nickel disulfide/graphene nanofiber composite material prepared in this embodiment. The figure shows that polyaniline is uniformly coated on the surface of the graphene nanofiber loaded with molybdenum disulfide.
Example 2
(1) Adding 0.1 g of graphene oxide nano fibers into 100 mL of deionized water, and performing ultrasonic treatment at room temperature for 30 min to obtain a dispersion solution I of the graphene oxide nano fibers; adding 3 g of sodium thiosulfate pentahydrate and 0.5 g of nickel chloride hexahydrate into 40 m of glycol-ethanol mixed solution (the volume ratio is 1: 1), and mechanically stirring for 1 h at room temperature to prepare mixed solution II of sodium thiosulfate and nickel chloride; and adding the mixed solution II into the dispersion solution I, mechanically stirring for 1 h at room temperature, transferring to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 36 h at 200 ℃, and after the reaction is finished, centrifuging, washing with deionized water, and vacuum drying for 24 h at 60 ℃ to obtain the graphene nanofiber-loaded nickel disulfide.
(2) Adding 0.1 g of graphene nanofiber-loaded nickel disulfide into 100 mL of deionized water, and performing ultrasonic treatment at room temperature for 30 min to obtain graphene nanofiber-loaded nickel disulfide dispersion liquid III; adding 1.5 g of aniline into 30 mL of 1 mol/L hydrochloric acid aqueous solution, and mechanically stirring at room temperature for 10 min to obtain aniline hydrochloric acid aqueous solution IV; and adding the solution IV into the dispersion liquid III, carrying out ultrasonic treatment at room temperature for 30 min, dropwise adding 20 mL of ammonium persulfate aqueous hydrochloric acid at the speed of 20 drops/min (in the ammonium persulfate aqueous hydrochloric acid, the concentration of ammonium persulfate is 1 mol/L, and the concentration of hydrochloric acid is 1 mol/L), continuing ultrasonic treatment at room temperature for 4 h after dropwise adding, carrying out reduced pressure filtration, repeatedly washing a filtration product with deionized water and ethanol until the pH value of the filtrate is 7, and carrying out vacuum drying at 60 ℃ for 24 h to obtain the polyaniline/nickel disulfide/graphene nanofiber composite material.
Example 3
(1) Adding 0.2 g of graphene oxide nano fibers into 200 mL of deionized water, and performing ultrasonic treatment at room temperature for 60 min to obtain a dispersion solution I of the graphene oxide nano fibers; adding 9 g of sodium thiosulfate pentahydrate and 2 g of nickel chloride hexahydrate into 200 mL of glycol-ethanol mixed solution (the volume ratio is 1: 1), and mechanically stirring for 2 h at room temperature to prepare mixed solution II of sodium thiosulfate and nickel chloride; and adding the mixed solution II into the dispersion solution I, mechanically stirring for 2 h at room temperature, transferring to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 18 h at 260 ℃, and after the reaction is finished, centrifuging, washing with deionized water, and vacuum drying for 24 h at 60 ℃ to obtain the graphene nanofiber-loaded nickel disulfide.
(2) Adding 0.2 g of graphene nanofiber-loaded nickel disulfide into 200 mL of deionized water, and performing ultrasonic treatment at room temperature for 60 min to obtain graphene nanofiber-loaded nickel disulfide dispersion liquid III; adding 2.5 g of aniline into 60 mL of 1 mol/L hydrochloric acid aqueous solution, and mechanically stirring at room temperature for 30 min to obtain aniline hydrochloric acid aqueous solution IV; and adding the solution IV into the dispersion liquid III, carrying out ultrasonic treatment at room temperature for 60 min, dropwise adding 60 mL of ammonium persulfate aqueous hydrochloric acid at the speed of 40 drops/min (in the ammonium persulfate aqueous hydrochloric acid, the concentration of ammonium persulfate is 1 mol/L, and the concentration of hydrochloric acid is 1 mol/L), continuing ultrasonic treatment at room temperature for 8 h after dropwise adding, carrying out reduced pressure filtration, repeatedly washing a filtration product with deionized water and ethanol until the pH value of the filtrate is 7, and carrying out vacuum drying at 60 ℃ for 24 h to obtain the polyaniline/nickel disulfide/graphene nanofiber composite material.
Comparative example 1
Adding 2 g of aniline into 45 mL of 1 mol/L hydrochloric acid aqueous solution, mechanically stirring for 20 min at room temperature to prepare aniline hydrochloric acid aqueous solution, dropwise adding 40 mL of ammonium persulfate hydrochloric acid aqueous solution (the concentration of ammonium persulfate is 1 mol/L and the concentration of hydrochloric acid is 1 mol/L) into the solution at the speed of 30 drops/min, continuing ultrasonic treatment for 6 h at room temperature after dropwise adding is finished, filtering under reduced pressure, repeatedly washing a filtering product with deionized water and ethanol until the pH value of the filtrate is 7, and performing vacuum drying for 24 h at 60 ℃ to prepare polyaniline.
Comparative example 2
(1) Adding 6 g of sodium thiosulfate pentahydrate and 1.25 g of nickel chloride hexahydrate into 120 mL of glycol-ethanol mixed solution (the volume ratio is 1: 1), and mechanically stirring for 1.5 h at room temperature to prepare mixed solution I of sodium thiosulfate and nickel chloride; and (3) moving the mixed solution I into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 27 h at 230 ℃, and after the reaction is finished, centrifuging, washing with deionized water, and vacuum-drying for 24 h at 60 ℃ to obtain the nickel disulfide.
(2) Adding 0.15 g of nickel disulfide into 150 mL of deionized water, and performing ultrasonic treatment at room temperature for 45 min to prepare a nickel disulfide dispersion liquid II; adding 2 g of aniline into 45 mL of 1 mol/L hydrochloric acid aqueous solution, and mechanically stirring at room temperature for 20 min to obtain aniline hydrochloric acid aqueous solution III; and adding the solution III into the dispersion liquid II, carrying out ultrasonic treatment at room temperature for 45 min, dropwise adding 40 mL of ammonium persulfate aqueous hydrochloric acid at the speed of 30 drops/min (in the ammonium persulfate aqueous hydrochloric acid, the concentration of ammonium persulfate is 1 mol/L, and the concentration of hydrochloric acid is 1 mol/L), continuing ultrasonic treatment at room temperature for 6 h after dropwise adding, carrying out reduced pressure filtration, repeatedly washing a filtration product with deionized water and ethanol until the pH value of the filtrate is 7, and carrying out vacuum drying at 60 ℃ for 24 h to obtain the polyaniline/nickel disulfide composite material.
Comparative example 3
(1) Adding 0.15 g of carbon nanofiber into 150 mL of deionized water, and performing ultrasonic treatment for 45 min at room temperature to prepare a dispersion solution I of the carbon nanofiber; adding 6 g of sodium thiosulfate pentahydrate and 1.25 g of nickel chloride hexahydrate into 120 mL of glycol-ethanol mixed solution (the volume ratio is 1: 1), and mechanically stirring for 1.5 h at room temperature to prepare mixed solution II of sodium thiosulfate and nickel chloride; and adding the mixed solution II into the dispersion solution I, mechanically stirring for 1.5 h at room temperature, transferring to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 27 h at 230 ℃, and after the reaction is finished, centrifuging, washing with deionized water, and vacuum drying for 24 h at 60 ℃ to obtain the carbon nanofiber-loaded nickel disulfide.
(2) Adding 0.15 g of carbon nanofiber-loaded nickel disulfide into 150 mL of deionized water, and performing ultrasonic treatment at room temperature for 45 min to prepare a carbon nanofiber-loaded nickel disulfide dispersion liquid III; adding 2 g of aniline into 45 mL of 1 mol/L hydrochloric acid aqueous solution, and mechanically stirring at room temperature for 20 min to obtain aniline hydrochloric acid aqueous solution IV; and adding the solution IV into the dispersion liquid III, carrying out ultrasonic treatment at room temperature for 45 min, dropwise adding 40 mL of ammonium persulfate aqueous hydrochloric acid at the speed of 30 drops/min (in the ammonium persulfate aqueous hydrochloric acid, the concentration of ammonium persulfate is 1 mol/L, and the concentration of hydrochloric acid is 1 mol/L), continuing ultrasonic treatment at room temperature for 6 h after dropwise adding, carrying out reduced pressure filtration, repeatedly washing a filtration product with deionized water and ethanol until the pH value of the filtrate is 7, and carrying out vacuum drying at 60 ℃ for 24 h to obtain the polyaniline/nickel disulfide/carbon nanofiber composite material.
The products prepared in the examples and the comparative examples are mixed with acetylene black and polyvinylidene fluoride according to the weight ratio of 80:15:5, and then the mixture is uniformly coated on a stainless steel net to serve as a working electrode, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, 1 mol/L sulfuric acid aqueous solution is used as electrolyte, the specific capacitance of the products is tested by a constant current charging and discharging method, the electrochemical cycling stability of the products is tested by a cyclic voltammetry method, wherein the voltage range is-0.2V-0.8V, and the scanning rate is 100 mV/s. The specific surface area of the product was tested by nitrogen adsorption desorption. The test results are shown in Table 1.
TABLE 1 test results
The test results show that the polyaniline/nickel disulfide/graphene nanofiber composite material prepared by the method has larger specific surface area, higher specific capacitance and excellent electrochemical cycling stability, and the composite material prepared by the graphene nanofiber and used as a supercapacitor electrode can be better than the composite material prepared by the carbon nanofiber.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. A preparation method of a polyaniline/nickel disulfide/graphene nanofiber composite material is characterized by comprising the following steps: aniline is used as a monomer, graphene nanofiber-loaded nickel disulfide prepared by a hydrothermal method is used as a support framework, ammonium persulfate is used as an oxidant, and the composite material is prepared through a chemical oxidation reaction under the ultrasonic action; the method comprises the following specific steps:
(1) preparation method of graphene nanofiber loaded nickel disulfide
a) Adding 0.1-0.2 g of graphene oxide nano fibers into 100-200 mL of deionized water, and performing ultrasonic treatment at room temperature for 30-60 min to obtain a dispersion solution I of the graphene oxide nano fibers;
b) adding 3-9 g of sodium thiosulfate pentahydrate and 0.5-2 g of nickel chloride hexahydrate into 40-200 mL of glycol-ethanol mixed solution, and mechanically stirring at room temperature for 1-2 h to prepare mixed solution II of sodium thiosulfate and nickel chloride;
c) adding the mixed solution II into the dispersion solution I, mechanically stirring for 1-2 hours at room temperature, transferring to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 18-36 hours at 200-260 ℃, and after the reaction is finished, centrifuging, washing with deionized water, and vacuum drying for 24 hours at 60 ℃ to obtain the graphene nanofiber loaded nickel disulfide;
(2) preparation of composite materials
d) Adding 0.1-0.2 g of graphene nanofiber-loaded nickel disulfide into 100-200 mL of deionized water, and performing ultrasonic treatment at room temperature for 30-60 min to obtain graphene nanofiber-loaded nickel disulfide dispersion liquid III;
e) adding 1.5-2.5 g of aniline into 30-60 mL of 1 mol/L hydrochloric acid aqueous solution, and mechanically stirring at room temperature for 10-30 min to obtain hydrochloric acid aqueous solution IV of aniline;
f) adding the solution IV into the dispersion liquid III, carrying out ultrasonic treatment at room temperature for 30-60 min, dropwise adding 20-60 mL of ammonium persulfate hydrochloric acid aqueous solution at the speed of 20-40 drops/min, continuing ultrasonic treatment at room temperature for 4-8 h after dropwise adding, carrying out reduced pressure filtration, repeatedly washing a filtration product with deionized water and ethanol until the pH value of the filtrate is 7, and carrying out vacuum drying at 60 ℃ for 24 h to obtain the polyaniline/nickel disulfide/graphene nanofiber composite;
the volume ratio of the ethylene glycol to the ethanol in the ethylene glycol-ethanol mixed solution in the step b) is 1: 1.
2. The method for preparing the polyaniline/nickel disulfide/graphene nanofiber composite material as claimed in claim 1, wherein: in the hydrochloric acid aqueous solution of the ammonium persulfate in the step f), the concentration of the ammonium persulfate is 1 mol/L, and the concentration of the hydrochloric acid is 1 mol/L.
3. A polyaniline/nickel disulfide/graphene nanofiber composite made by the method of claim 1.
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