CN111554518A - NiO-graphene-polypyrrole supercapacitor composite electrode material and preparation method thereof - Google Patents
NiO-graphene-polypyrrole supercapacitor composite electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of super capacitors and discloses a NiO-graphene-polypyrrole super capacitor composite electrode material which comprises the following formula raw materials and components: the nanometer NiO load fluorine-doped graphene, a doping agent, an initiator and pyrrole. According to the NiO-graphene-polypyrrole supercapacitor composite electrode material, fluorine is doped on the surface of a graphene regular structure to generate a large number of folds and cracks, so that the NiO composite electrode material has an ultrahigh specific surface area, has a porous structure, is uniformly dispersed on the surface of a three-dimensional fluorine-doped graphene aerogel to expose a large number of electrochemical active sites, a layer of nano polypyrrole film is generated on the surface of the nano NiO-loaded fluorine-doped graphene, the NiO volume expansion phenomenon is inhibited, an internal electric field is induced between the polypyrrole and the NiO interface to generate a synergistic effect, meanwhile, a three-dimensional conductive network is formed between the graphene with excellent conductivity and the polypyrrole and the NiO, and the conductivity of the electrode material is enhanced.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to a NiO-graphene-polypyrrole super capacitor composite electrode material and a preparation method thereof.
Background
The super capacitor is an electrochemical energy storage device with great development prospect, and has the advantages of high power density, long service life, good safety and the like, wherein an electrode material is taken as a key material of the super capacitor and directly influences the electrochemical performance of the super capacitor, and the current electrode material of the super capacitor mainly comprises a conductive carbon material, a transition metal oxide, a conductive polymer and the like.
NiO has high theoretical specific capacity and is a supercapacitor electrode material with great extensive research and development potential, but the intrinsic conductivity of NiO is low, so that the conductivity of the NiO electrode material is poor, the transmission and diffusion of electrons are not facilitated, the stability of NiO is poor, and the electrochemical performance of the supercapacitor is affected by volume expansion easily in the long-time charging and discharging process.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a NiO-graphene-polypyrrole supercapacitor composite electrode material and a preparation method thereof, which solve the problem of poor conductivity of the NiO electrode material and solve the problem of easy volume expansion of NiO in the long charge-discharge process.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a NiO-graphene-polypyrrole supercapacitor composite electrode material comprises the following raw materials and components: the nanometer NiO-loaded fluorine-doped graphene, a doping agent, an initiator and pyrrole are mixed according to the mass ratio of 5-10:20-30:3-4: 1.
Preferably, the doping agent is sodium p-toluenesulfonate and initiator ammonium persulfate.
Preferably, the preparation method of the nano NiO-loaded fluorine-doped graphene comprises the following steps:
(1) adding 5-10% by mass of HF solution and graphene oxide into a reaction bottle, placing the reaction bottle in an ultrasonic treatment instrument, transferring the solution into a hydrothermal reaction kettle after uniform ultrasonic dispersion, placing the reaction kettle in a forced air drying box, heating to 120-phase and 180 ℃, reacting for 20-30h, filtering the solution to remove the solvent, washing the solid product with distilled water, freeze-drying and grinding to prepare the three-dimensional fluorine-doped graphene aerogel.
(2) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1-2:1, and adding three-dimensional solventAdding Ni (NO) after uniformly dispersing fluorine-doped graphene aerogel by ultrasonic3)2And (NH)4)2CO3Placing the mixture in a water bath, heating the mixture to 50-70 ℃, stirring the mixture at a constant speed for reaction for 10-20h, centrifugally separating the solution to remove the solvent, placing the solid mixture in an atmosphere resistance furnace, introducing a mixed gas of nitrogen and oxygen at a volume ratio of 1:5-12, heating the mixture at a heating rate of 2-5 ℃/min to 220-300 ℃, and carrying out heat preservation treatment for 2-5h to prepare the nano NiO loaded fluorine-doped graphene with the mesoporous structure.
Preferably, the three-dimensional fluorine-doped graphene aerogel and Ni (NO) are prepared by the method3)2And (NH)4)2CO3The mass ratio of (A) to (B) is 2-6:10-13: 10.
Preferably, the ultrasonic treatment instrument comprises a lifting device, the lifting device is provided with an adjuster, the adjuster is horizontally movably connected with an adjusting rod, the adjuster is vertically movably connected with a supporting rod, a base is fixedly connected above the supporting rod, a spring is fixedly connected between the base and the supporting rod, a reaction bottle is arranged above the base, a water bath tank is movably connected to the outer side of the base, and heating rings are fixedly connected to the two sides of the water bath tank.
Preferably, the preparation method of the NiO-graphene-polypyrrole supercapacitor composite electrode material comprises the following steps:
(1) adding a mixed solvent of ethanol and distilled water and nano NiO-loaded fluorine-doped graphene into a reaction bottle, adding a doping agent which is sodium p-toluenesulfonate after ultrasonic dispersion is uniform, adding pyrrole at 0-5 ℃, slowly dropwise adding an initiating agent ammonium persulfate, stirring at a constant speed for reaction for 20-30h, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the NiO-graphene-polypyrrole supercapacitor composite electrode material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the NiO-graphene-polypyrrole supercapacitor composite electrode material, hydrofluoric acid is used as a fluorine source, fluorine-doped graphene aerogel with a three-dimensional morphology structure is prepared by a high-pressure hydrothermal method, fluorine is doped in graphene to form a chemically inert C-F covalent bond and a chemically inert C-F ionic bond, the stability of the graphene three-dimensional nanostructure of the electrode material in a long-time electrochemical cycle period can be improved, and the regular structure on the surface of the graphene can be disordered by fluorine doping, so that a large number of folds and cracks are generated, and the three-dimensional fluorine-doped graphene aerogel has an ultrahigh specific surface area.
The NiO-graphene-polypyrrole supercapacitor composite electrode material takes three-dimensional fluorine-doped graphene aerogel with a huge specific surface as a carrier, (NH)4)2CO3CO production during ionization and hydrolysis3 2-And OH-With Ni2+Generating Ni on the surface of three-dimensional fluorine-doped graphene aerogel2CO3(OH)2The hydrate precursor is decomposed to generate nano NiO with a porous structure through high-temperature thermal treatment, and the nano NiO is uniformly dispersed on the surface of the three-dimensional fluorine-doped graphene aerogel, so that the agglomeration phenomenon of the porous nano NiO is effectively reduced, a large number of electrochemical active sites are exposed, and the specific capacitance and the electrochemical performance of an electrode material and a super capacitor are improved.
According to the NiO-graphene-polypyrrole supercapacitor composite electrode material, a layer of nanometer polypyrrole film is generated on the surface of nanometer NiO loaded fluorine-doped graphene through an in-situ polymerization method, the volume expansion phenomenon of NiO in the continuous charging and discharging process is effectively inhibited, an internal electric field is induced between the polypyrrole and the NiO interface by regulating and controlling the ratio of polypyrrole to NiO, a synergistic effect is generated, the electrochemical cycle stability of the electrode material is improved jointly, meanwhile, a three-dimensional conductive network is formed among the graphene with excellent conductivity, the polypyrrole and the NiO, and the conductivity of the electrode material is greatly enhanced.
Drawings
FIG. 1 is a schematic front view of a lift device;
fig. 2 is a schematic view of the adjustment of the lifting device.
1. A regulator; 2. adjusting a rod; 3. a support bar; 4. a base; 5. a spring; 6. a reaction bottle; 7. a water bath; 8. and (4) heating the ring.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a NiO-graphene-polypyrrole supercapacitor composite electrode material comprises the following raw materials and components: the nanometer NiO-loaded fluorine-doped graphene, a doping agent sodium p-toluenesulfonate, an initiator ammonium persulfate and pyrrole in a mass ratio of 5-10:20-30:3-4: 1.
The preparation method of the nano NiO-loaded fluorine-doped graphene comprises the following steps:
(1) adding 5-10% by mass of HF solution and graphene oxide into a reaction bottle, placing the reaction bottle in an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a lifting device, the lifting device is provided with an adjuster, the adjuster is horizontally and movably connected with an adjusting rod, the adjuster is vertically and movably connected with a supporting rod, a base is fixedly connected above the supporting rod, a spring is fixedly connected between the base and the supporting rod, the reaction bottle is arranged above the base, the outer side of the base is movably connected with a water bath, heating rings are fixedly connected to two sides of the water bath, after the ultrasonic dispersion is uniform, the solution is transferred into a hydrothermal reaction kettle and placed in a blast drying box, heating is carried out to 120 ℃ and 180 ℃, reacting for 20-30h, filtering the solution to remove the solvent, washing the solid product with distilled water, freeze drying and grinding to prepare the three-dimensional.
(2) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1-2:1, adding three-dimensional fluorine-doped graphene aerogel, ultrasonically dispersing uniformly, and adding Ni (NO)3)2And (NH)4)2CO3Placing the three materials in a water bath kettle, heating the mixture to 50-70 ℃ in a mass ratio of 2-6:10-13:10, stirring the mixture at a constant speed for reaction for 10-20h, centrifugally separating the solution to remove the solvent, placing the solid mixture in an atmosphere resistance furnace, introducing mixed gas of nitrogen and oxygen, wherein the volume ratio of the two is 1:5-12, the heating rate is 2-5 ℃/min, heating the mixture to 220 ℃ and 300 ℃, and carrying out heat preservation treatment for 2-5h to prepare the nano NiO loaded fluorine doped graphene with the mesoporous structure.
The preparation method of the NiO-graphene-polypyrrole supercapacitor composite electrode material comprises the following steps:
(1) adding a mixed solvent of ethanol and distilled water and nano NiO-loaded fluorine-doped graphene into a reaction bottle, adding a doping agent which is sodium p-toluenesulfonate after ultrasonic dispersion is uniform, adding pyrrole at 0-5 ℃, slowly dropwise adding an initiating agent ammonium persulfate, stirring at a constant speed for reaction for 20-30h, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the NiO-graphene-polypyrrole supercapacitor composite electrode material.
Example 1
(1) Preparing a three-dimensional fluorine-doped graphene aerogel component 1: adding 5% by mass of HF solution and graphene oxide into a reaction bottle, placing the reaction bottle in an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a lifting device, the lifting device is provided with an adjuster, the adjuster is horizontally and movably connected with an adjusting rod, the adjuster is vertically and movably connected with a supporting rod, a base is fixedly connected above the supporting rod, a spring is fixedly connected between the base and the supporting rod, the reaction bottle is arranged above the base, the outer side of the base is movably connected with a water bath, heating rings are fixedly connected to two sides of the water bath, after the ultrasonic dispersion is uniform, the solution is transferred into a hydrothermal reaction kettle and placed in a blast drying box, heating is carried out to 120 ℃, reacting is carried out for 20 hours, filtering the solution to remove a solvent, washing a solid product with distilled water, freeze drying and grinding are carried out, and.
(2) Preparing a nano NiO loaded fluorine-doped graphene component 1: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1:1, adding a three-dimensional fluorine-doped graphene aerogel component 1, and adding Ni (NO) after uniform ultrasonic dispersion3)2And (NH)4)2CO3Placing the three materials in a water bath kettle in a mass ratio of 2:10:10, heating to 50 ℃, stirring at a constant speed for reaction for 10 hours, centrifugally separating the solution to remove the solvent, placing the solid mixture in an atmosphere resistance furnace, introducing mixed gas of nitrogen and oxygen, heating to 220 ℃, carrying out heat preservation treatment for 2 hours, and obtaining the nano NiO loaded fluorine doped graphene component 1 with the mesoporous structure, wherein the volume ratio of the two materials is 1:5, the heating rate is 2 ℃/min.
(3) Preparing a NiO-graphene-polypyrrole supercapacitor composite electrode material 1: adding a mixed solvent of ethanol and distilled water and a nano NiO-loaded fluorine-doped graphene component 1 into a reaction bottle, adding a doping agent which is sodium p-toluenesulfonate after ultrasonic dispersion is uniform, adding pyrrole at 5 ℃, and slowly dropwise adding an initiating agent ammonium persulfate, wherein the mass ratio of the nano NiO-loaded fluorine-doped graphene component 1 to the sodium p-toluenesulfonate, the ammonium persulfate and the pyrrole is 5:20:3:1, stirring at a constant speed for reaction for 20 hours, filtering the solution to remove the solvent, washing a solid product with distilled water and ethanol, and fully drying to prepare the NiO-graphene-polypyrrole supercapacitor composite electrode material 1.
Example 2
(1) Preparing a three-dimensional fluorine-doped graphene aerogel component 2: adding 5-10% by mass of HF solution and graphene oxide into a reaction bottle, placing the reaction bottle in an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a lifting device, the lifting device is provided with an adjuster, the adjuster is horizontally and movably connected with an adjusting rod, the adjuster is vertically and movably connected with a supporting rod, a base is fixedly connected above the supporting rod, a spring is fixedly connected between the base and the supporting rod, the reaction bottle is arranged above the base, the outer side of the base is movably connected with a water bath, heating rings are fixedly connected to two sides of the water bath, after the ultrasonic dispersion is uniform, the solution is transferred into a hydrothermal reaction kettle and placed in a blast drying box, heating is carried out to 150 ℃, reacting is carried out for 20 hours, filtering the solution to remove a solvent, washing a solid product with distilled water, freeze drying and grinding are carried out, and.
(2) Preparing a nano NiO loaded fluorine-doped graphene component 2: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1:1, adding a three-dimensional fluorine-doped graphene aerogel component 2, and adding Ni (NO) after uniform ultrasonic dispersion3)2And (NH)4)2CO3The mass ratio of the three is 3:10.5:10, the three are placed in a water bath kettle, the mixture is heated to 60 ℃, the mixture is stirred at a constant speed for reaction for 20 hours, the solution is centrifugally separated to remove the solvent, the solid mixture is placed in an atmosphere resistance furnace, mixed gas of nitrogen and oxygen is introduced, the volume ratio of the two is 1:5-12, the heating rate is 5 ℃/min, the temperature is increased to 240 ℃, the heat preservation treatment is carried out for 5 hours, and the nano-tube with the mesoporous structure is preparedThe nanometer NiO loads a fluorine-doped graphene component 2.
(3) Preparing a NiO-graphene-polypyrrole supercapacitor composite electrode material 2: adding a mixed solvent of ethanol and distilled water and a nano NiO-loaded fluorine-doped graphene component 2 into a reaction bottle, adding a doping agent which is sodium p-toluenesulfonate after ultrasonic dispersion is uniform, adding pyrrole at 5 ℃, and slowly dropwise adding an initiating agent ammonium persulfate, wherein the mass ratio of the nano NiO-loaded fluorine-doped graphene component 2 to the sodium p-toluenesulfonate, the ammonium persulfate and the pyrrole is 6:22:3.3:1, stirring at a constant speed for reaction for 30 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the NiO-graphene-polypyrrole supercapacitor composite electrode material 2.
Example 3
(1) Preparing a three-dimensional fluorine-doped graphene aerogel component 3: adding an HF solution and graphene oxide with the mass fraction of 8% into a reaction bottle, placing the reaction bottle in an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a lifting device, the lifting device is provided with an adjuster, the adjuster is horizontally and movably connected with an adjusting rod, the adjuster is vertically and movably connected with a supporting rod, a base is fixedly connected above the supporting rod, a spring is fixedly connected between the base and the supporting rod, the reaction bottle is arranged above the base, the outer side of the base is movably connected with a water bath, heating rings are fixedly connected to the two sides of the water bath, after the ultrasonic dispersion is uniform, the solution is transferred into a hydrothermal reaction kettle and placed in a blast drying box, heating is carried out to 160 ℃, reacting is carried out for 25 hours, filtering the solution to remove the solvent, washing the solid product with distilled water, freeze drying and grinding are carried.
(2) Preparing a nano NiO loaded fluorine-doped graphene component 3: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1.5:1, adding a three-dimensional fluorine-doped graphene aerogel component 3, and adding Ni (NO) after uniform ultrasonic dispersion3)2And (NH)4)2CO3The mass ratio of the three components is 4:11:10, the three components are placed in a water bath kettle, heated to 60 ℃, stirred at a constant speed for reaction for 15 hours, the solution is centrifugally separated to remove the solvent, the solid mixture is placed in an atmosphere resistance furnace, nitrogen and oxygen are introduced for mixingAnd (3) gas, wherein the volume ratio of the gas to the NiO is 1:8, the heating rate is 4 ℃/min, the temperature is increased to 260 ℃, the heat preservation treatment is carried out for 3h, and the nano NiO loaded fluorine doped graphene component 3 with the mesoporous structure is prepared.
(3) Preparing a NiO-graphene-polypyrrole supercapacitor composite electrode material 3: adding a mixed solvent of ethanol and distilled water and a nano NiO-loaded fluorine-doped graphene component 3 into a reaction bottle, adding a doping agent which is sodium p-toluenesulfonate after ultrasonic dispersion is uniform, adding pyrrole at 2 ℃, and slowly dropwise adding an initiating agent ammonium persulfate, wherein the mass ratio of the nano NiO-loaded fluorine-doped graphene component 3 to the sodium p-toluenesulfonate, the ammonium persulfate and the pyrrole is 7:28:3.7:1, stirring at a constant speed for reaction for 25 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the NiO-graphene-polypyrrole supercapacitor composite electrode material 3.
Example 4
(1) Preparing a three-dimensional fluorine-doped graphene aerogel component 4: adding 10% by mass of HF solution and graphene oxide into a reaction bottle, placing the reaction bottle in an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a lifting device, the lifting device is provided with an adjuster, the adjuster is horizontally and movably connected with an adjusting rod, the adjuster is vertically and movably connected with a supporting rod, a base is fixedly connected above the supporting rod, a spring is fixedly connected between the base and the supporting rod, the reaction bottle is arranged above the base, the outer side of the base is movably connected with a water bath, heating rings are fixedly connected to two sides of the water bath, after the ultrasonic dispersion is uniform, the solution is transferred into a hydrothermal reaction kettle and placed in a blast drying box, heating is carried out to 120 ℃, reacting is carried out for 22 hours, filtering the solution to remove a solvent, washing a solid product with distilled water, freeze drying and grinding are carried out, and the.
(2) Preparing a nano NiO loaded fluorine-doped graphene component 4: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1-2:1, adding a three-dimensional fluorine-doped graphene aerogel component 4, and adding Ni (NO) after uniform ultrasonic dispersion3)2And (NH)4)2CO3The mass ratio of the three components is 5:12:10, the three components are placed in a water bath kettle and heated to 70 DEG CAnd stirring at a constant speed for reaction for 12h, centrifugally separating the solution to remove the solvent, placing the solid mixture in an atmosphere resistance furnace, introducing mixed gas of nitrogen and oxygen, heating to 280 ℃ at a heating rate of 2 ℃/min at a volume ratio of 1:5-12, and carrying out heat preservation treatment for 3h to obtain the nano NiO supported fluorine doped graphene component 4 with the mesoporous structure.
(3) Preparing a NiO-graphene-polypyrrole supercapacitor composite electrode material 4: adding a mixed solvent of ethanol and distilled water and a nano NiO-loaded fluorine-doped graphene component 4 into a reaction bottle, adding a doping agent which is sodium p-toluenesulfonate after ultrasonic dispersion is uniform, adding pyrrole at 5 ℃, and slowly dropwise adding an initiating agent ammonium persulfate, wherein the mass ratio of the nano NiO-loaded fluorine-doped graphene component 4 to the sodium p-toluenesulfonate, the ammonium persulfate and the pyrrole is 9:28:3.7:1, stirring at a constant speed for reaction for 30 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the NiO-graphene-polypyrrole supercapacitor composite electrode material 4.
Example 5
(1) Preparing a three-dimensional fluorine-doped graphene aerogel component 5: adding 10% by mass of HF solution and graphene oxide into a reaction bottle, placing the reaction bottle in an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a lifting device, the lifting device is provided with an adjuster, the adjuster is horizontally and movably connected with an adjusting rod, the adjuster is vertically and movably connected with a supporting rod, a base is fixedly connected above the supporting rod, a spring is fixedly connected between the base and the supporting rod, the reaction bottle is arranged above the base, the outer side of the base is movably connected with a water bath, heating rings are fixedly connected to two sides of the water bath, after the ultrasonic dispersion is uniform, the solution is transferred into a hydrothermal reaction kettle and placed in a blast drying box, heating is carried out to 180 ℃, reacting is carried out for 30 hours, filtering the solution to remove a solvent, washing a solid product with distilled water, freeze drying and grinding are carried out, and the.
(2) Preparing a nano NiO loaded fluorine-doped graphene component 5: adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2:1, adding a three-dimensional fluorine-doped graphene aerogel component 5, and adding Ni (NO) after uniform ultrasonic dispersion3)2And (NH)4)2CO3Placing the three components in a water bath according to the mass ratio of 6:13:10, heating to 70 ℃, stirring at a constant speed for reaction for 20 hours, centrifugally separating the solution to remove the solvent, placing the solid mixture in an atmosphere resistance furnace, introducing mixed gas of nitrogen and oxygen, heating to 300 ℃ at the rate of 5 ℃/min according to the volume ratio of 1:12, and carrying out heat preservation treatment for 2-5 hours to prepare the nano NiO loaded fluorine doped graphene component 5 with the mesoporous structure.
(3) Preparing a NiO-graphene-polypyrrole supercapacitor composite electrode material 5: adding a mixed solvent of ethanol and distilled water and a nano NiO-loaded fluorine-doped graphene component 5 into a reaction bottle, adding a doping agent which is sodium p-toluenesulfonate after ultrasonic dispersion is uniform, adding pyrrole at 5 ℃, and slowly dropwise adding an initiating agent ammonium persulfate, wherein the mass ratio of the nano NiO-loaded fluorine-doped graphene component 5 to the sodium p-toluenesulfonate, the ammonium persulfate and the pyrrole is 10:30:4:1, stirring at a constant speed for reaction for 30 hours, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the NiO-graphene-polypyrrole supercapacitor composite electrode material 5.
Putting the NiO-graphene-polypyrrole supercapacitor composite electrode material prepared in the examples 1 to 5 into an N-methyl pyrrolidone solvent, adding acetylene black and the polyvinylpyrrolidone solvent, uniformly dispersing to form slurry, uniformly coating the slurry on foamed nickel, drying and tabletting to prepare the supercapacitor working electrode material, taking a platinum sheet as a counter electrode, taking a saturated calomel electrode as a reference electrode, taking a 6mol/L potassium hydroxide solution as an electrolyte, and carrying out electrochemical performance test on the supercapacitor working electrode material through an RST5200 electrochemical workstation.
In summary, the NiO-graphene-polypyrrole supercapacitor composite electrode material is prepared by taking hydrofluoric acid as a fluorine source and using a high-pressure hydrothermal method to obtain fluorine-doped graphene aerogel with a three-dimensional morphology structure, fluorine is doped in graphene to form chemically inert C-F covalent bonds and C-F ionic bonds, so that the stability of the graphene three-dimensional nanostructure of the electrode material in a long-time electrochemical cycle period can be improved, and the regular structure on the surface of the graphene becomes disordered by fluorine doping, a large number of folds and cracks are generated, and the three-dimensional fluorine-doped graphene aerogel has an ultrahigh specific surface area.
Three-dimensional fluorine-doped graphene aerogel with huge specific surface is used as a carrier, (NH)4)2CO3CO production during ionization and hydrolysis3 2-And OH-With Ni2+Generating Ni on the surface of three-dimensional fluorine-doped graphene aerogel2CO3(OH)2The hydrate precursor is decomposed to generate nano NiO with a porous structure through high-temperature thermal treatment, and the nano NiO is uniformly dispersed on the surface of the three-dimensional fluorine-doped graphene aerogel, so that the agglomeration phenomenon of the porous nano NiO is effectively reduced, a large number of electrochemical active sites are exposed, and the specific capacitance and the electrochemical performance of an electrode material and a super capacitor are improved.
A layer of nano polypyrrole film is generated on the surface of the nano NiO loaded fluorine-doped graphene through an in-situ polymerization method, the volume expansion phenomenon of NiO in the continuous charging and discharging process is effectively inhibited, an internal electric field is induced between the polypyrrole and NiO interface through regulating and controlling the ratio of the polypyrrole to the NiO, a synergistic effect is generated, the electrochemical cycle stability of the electrode material is jointly improved, meanwhile, a three-dimensional conductive network is formed among the graphene, the polypyrrole and the NiO with excellent conductivity, and the conductivity of the electrode material is greatly enhanced.
Claims (6)
1. The NiO-graphene-polypyrrole supercapacitor composite electrode material comprises the following raw materials and components, and is characterized in that: the nanometer NiO-loaded fluorine-doped graphene, a doping agent, an initiator and pyrrole are mixed according to the mass ratio of 5-10:20-30:3-4: 1.
2. The NiO-graphene-polypyrrole supercapacitor composite electrode material according to claim 1, characterized in that: the dopant is sodium p-toluenesulfonate and initiator ammonium persulfate.
3. The NiO-graphene-polypyrrole supercapacitor composite electrode material according to claim 1, characterized in that: the preparation method of the nano NiO-loaded fluorine-doped graphene comprises the following steps:
(1) adding graphene oxide into an HF solution with the mass fraction of 5-10%, placing the solution in an ultrasonic treatment instrument, transferring the solution into a hydrothermal reaction kettle after uniform ultrasonic dispersion, heating the solution to 120-180 ℃, reacting for 20-30h, filtering, washing, freeze-drying and grinding to prepare the three-dimensional fluorine-doped graphene aerogel;
(2) adding three-dimensional fluorine-doped graphene aerogel into a mixed solvent of distilled water and ethanol with a volume ratio of 1-2:1, ultrasonically dispersing uniformly, and adding Ni (NO)3)2And (NH)4)2CO3Heating to 50-70 ℃ for reaction for 10-20h, placing the solid mixture in an atmosphere resistance furnace, introducing mixed gas of nitrogen and oxygen with the volume ratio of 1:5-12, heating at the rate of 2-5 ℃/min to 220-300 ℃, and carrying out heat preservation treatment for 2-5h to prepare the nano NiO loaded fluorine doped graphene with the mesoporous structure.
4. The NiO-graphene-polypyrrole supercapacitor composite electrode material according to claim 3, characterized in that: the three-dimensional fluorine-doped graphene aerogel and Ni (NO)3)2And (NH)4)2CO3The mass ratio of (A) to (B) is 2-6:10-13: 10.
5. The NiO-graphene-polypyrrole supercapacitor composite electrode material according to claim 3, characterized in that: the ultrasonic treatment instrument comprises a lifting device, wherein the lifting device is provided with an adjuster, an adjusting rod is horizontally movably connected with the adjuster, a supporting rod is vertically movably connected with the adjuster, a base is fixedly connected above the supporting rod, a spring is fixedly connected between the base and the supporting rod, a reaction bottle is arranged above the base, a water bath tank is movably connected to the outer side of the base, and heating rings are fixedly connected to the two sides of the water bath tank.
6. The NiO-graphene-polypyrrole supercapacitor composite electrode material according to claim 1, characterized in that: the preparation method of the NiO-graphene-polypyrrole supercapacitor composite electrode material comprises the following steps:
(1) adding nano NiO loaded fluorine-doped graphene into a mixed solvent of ethanol and distilled water, adding a dopant which is sodium p-toluenesulfonate after uniform ultrasonic dispersion, adding pyrrole at 0-5 ℃, slowly dropwise adding initiator ammonium persulfate, reacting for 20-30h, filtering, washing and drying to prepare the NiO-graphene-polypyrrole supercapacitor composite electrode material.
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