CN109273273B - PAN-GO/PEDOT/PSS supercapacitor electrode material based on nanofiber yarn and preparation method thereof - Google Patents
PAN-GO/PEDOT/PSS supercapacitor electrode material based on nanofiber yarn and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a PAN-GO/PEDOT/PSS supercapacitor electrode material based on nanofiber yarns and a preparation method thereof. According to the invention, conductive cotton yarn is used as core yarn, PAN-GO nano-fiber is wound and cohered to form a skin layer to form core-spun yarn, and then PEDOT (Poly ethylene glycol Ether-Co-methyl) conductive organic matter is grafted on the surface layer to prepare the supercapacitor electrode material with good circulation stability and higher energy storage capacity, and the cost is low.
Description
Technical Field
The invention relates to the field of supercapacitors, in particular to a PAN-GO/PEDOT/PSS supercapacitor electrode material based on electrostatic spinning nanofiber yarns and a preparation method thereof.
Background
With the rapid development of social economy and the rapid increase of population, the gradual shortage of resources and energy and the gradual deterioration of ecological environment become problems to be solved at present. Therefore, the development and utilization of various energy-saving technologies, clean and renewable new energy technologies and environmental technologies, such as electric vehicles, wind energy, solar energy, tidal energy and the like, are receiving more extensive attention. Whether the development of the electric automobile industry or the utilization of secondary energy is adopted, the search for a proper energy storage device is a crucial link. Lead-acid, nickel-hydrogen, lithium-ion, and other new batteries can provide a reliable energy storage solution, have relatively high energy density, and have been widely used in many fields. However, chemical batteries, which generate faradaic charges for storage by electrochemical reactions, have a short service life and are greatly affected by temperature, and high currents affect the life of these batteries, and thus, these chemical reaction-based batteries have various disadvantages for certain applications requiring long life and high reliability in high-power systems.
Thus, the super capacitor is produced. The super capacitor acts as a power compensation and energy storage device, and how much of its stored charge is expressed in terms of the magnitude of the capacitance farad (F). The super capacitor is classified into an electric double layer capacitor and a faraday quasi-capacitor (also called a pseudo capacitor) according to the mechanism of storage and conversion of electric energy, wherein the faraday quasi-capacitor includes a metal oxide capacitor and a conductive polymer capacitor. In recent years, hybrid supercapacitors in which positive and negative electrodes are made of battery materials and activated carbon materials respectively have appeared.
Electrospinning is a process technique that utilizes a polymer solution or melt to perform jet spinning in a strong electric field. The most remarkable advantage of the method is that the method is economical and effective, the diameter of the prepared fiber is generally between 10 nm and several micrometers, and the method is one of effective methods for obtaining a large amount of micro-nano long fibers with high specific surface area. Compared with other preparation processes, such as vapor deposition method and the like, electrostatic spinning is a simple one-step manufacturing and low-cost production process. The processes currently used for electrostatic spinning and subsequent carbonization for the production of lithium battery electrodes, e.g. MnO2、V2O5、TiO2And the like. However, there has been little research on one-dimensional flexible yarn-type supercapacitors prepared by electrostatic spinning. Here we provide a method for preparing PAN-GO/PEDOT: PSS supercapacitor electrode materials based on electrospinning technology.
Disclosure of Invention
Aiming at the technical problems, the invention provides a PAN-GO/PEDOT: PSS supercapacitor electrode material based on nano-fiber yarns and a preparation method thereof. And the combination with the gel electrolyte is beneficial to the transmission of electric charges.
In order to solve the technical problems, the invention adopts the following technical scheme:
the PAN-GO/PEDOT/PSS supercapacitor electrode material based on the nanofiber yarn comprises a skin layer and a core layer, wherein the skin layer is twisted along the axial direction of the core layer to form a core-spun yarn structure, the skin layer is PAN nanofiber and graphene oxide, the core layer is conductive cotton yarn, and conductive polymer PEDOT/PSS particles are attached to the surface of the skin layer.
The conductive cotton yarn is nickel-plated conductive cotton yarn, the thickness of a nickel layer of the nickel-plated conductive cotton yarn is 1.80-2.60 micrometers, and the diameter of the nanofiber of the skin layer is 0.90-1.10 micrometers.
The preparation method of the PAN-GO/PEDOT/PSS supercapacitor electrode material based on the nano-fiber yarns comprises the following steps: (1) preparing nickel-plated conductive cotton yarn: placing the cotton yarn in chemical plating solution, and treating for 2-8h to obtain nickel-plated conductive cotton yarn;
(2) preparing a spinning solution: weighing graphene oxide, adding the graphene oxide into an N, N-dimethylformamide solvent, and performing ultrasonic oscillation for 12-24 hours at room temperature to obtain a dispersed graphene oxide solution; weighing Polyacrylonitrile (PAN) powder, adding the PAN powder into the dispersed graphene oxide solution, and heating for 2 hours at 65-70 ℃ under the condition of magnetic stirring to form a spinning solution;
(3) building an electrostatic spinning device, fixing two ends of the nickel-plated conductive cotton yarn prepared in the step (1) on a motor of the electrostatic spinning device, and winding the PAN nanofiber and the graphene oxide on the nickel-plated conductive cotton yarn through electrostatic spinning to obtain PAN-GO nanofiber core-spun yarn;
(4) preparing a mixed trichloromethane solution of 30-50 mmol/L of 3, 4-ethylenedioxythiophene (PEDOT) and 30-50 mmol/L of polystyrene sulfonate (PSS); then, the PAN nano-fiber core-spun yarn obtained in the step (2) is placed into a mixed trichloromethane solution to be fully soaked for 10-30 min; and finally, placing the ethanol solution of ferric trichloride with the concentration of 50-75 mmol/L on the yarn in the mixed trichloromethane solution by using a rubber head dropper, reacting at the temperature of 20-25 ℃ for 6-72 hours, taking out the yarn, and airing to obtain the PAN-GO/PEDOT/PSS supercapacitor electrode material. The addition amount of the ferric trichloride solution is as follows: ferric chloride solution: yarn =5 ml: 1g, v: and m is selected.
The preparation of the conductive cotton yarn in the step (1) comprises the following steps: a. removing impurities from cotton yarns, soaking the cotton yarns in 0.20-0.25 mol/L NaOH aqueous solution at the heating temperature of 80 ℃ for 30-60 min, and then drying at the temperature of 50 ℃ for 5-10 min to obtain dried cotton yarns;
b. soaking the dried cotton yarn obtained in the step (a) in a mixed aqueous solution of nickel sulfate hexahydrate with the concentration of 0.15-0.20 mol/L and hydrochloric acid with the concentration of 0.50-0.55 mol/L for 5-10 min, taking out, and soaking in a mixed aqueous solution of sodium borohydride with the concentration of 0.20-0.26 mol/L and sodium hydroxide with the concentration of 0.20-0.25 mol/L for 5-10 min to obtain soaked cotton yarn;
c. and (b) taking out the impregnated cotton yarn obtained in the step (b), washing the cotton yarn with deionized water, placing the cotton yarn into chemical plating solution, and treating for 2-8h to obtain the nickel-plated conductive cotton yarn. The method adopts commercial cotton yarn to remove redundant impurities in the cotton yarn, wherein the impurities mainly comprise juveniles, wax and the like.
The chemical electro-plating solution in the step (1) comprises the following components: nickel sulfate hexahydrate (NiSO) with concentration of 0.10-0.12 mol/L4•6H2O) sodium hypophosphite (NaHPO) with concentration of 0.10-0.14 mol/L2) Ammonium chloride (NH) at a concentration of 0.70 to 0.84mol/L4Cl) and trisodium citrate (Na) with the concentration of 0.08-0.10 mol/L3C6H5O7) And ammonia water (NH) with the concentration of 2.5-8 mL/L3•H2O）。
The mass fraction of the graphene oxide in the spinning solution prepared in the step (2) is 1.0-1.2% of the mass of the solute Polyacrylonitrile (PAN), and the mass fraction of the Polyacrylonitrile (PAN) is 13-14%.
The spinning voltage of the electrostatic spinning device in the step (3) is 15-20 kV, the spinning distance is 13-16 cm, and the spinning speed is 0.01-0.10 mm/min.
And (3) preparing a gel electrolyte, immersing the electrode material of the PAN-GO/PEDOT/PSS supercapacitor prepared in the step (4) in the gel electrolyte for 0.5-2 h, taking out and airing, distributing the gel electrolyte on the two electrodes in parallel, standing overnight, and testing the electrical properties of the electrode material.
The preparation method of the gel electrolyte in the step (5) comprises the following steps: stirring a mixed solution of polyvinyl alcohol (PVA), deionized water and phosphoric acid at 95 ℃ for 2-6 h to prepare the gel electrolyte, wherein the polyvinyl alcohol (PVA): phosphoric acid: the mass ratio of the deionized water is 1:1.5: 9.
Compared with the existing electrode material of the super capacitor and the preparation method thereof, the invention has the following advantages: conductive cotton yarn is used as core yarn, PAN-GO nano fiber is wound and cohered to form a skin layer to form core-spun yarn, then PEDOT (PEDOT) and PSS (PolyEthylenediamine) conductive organic matter are grafted on the surface layer, and the super capacitor electrode material with good circulation stability and high energy storage is prepared, and the cost is low. The whole manufacturing process is simple and convenient, easy to operate, simple in process and environment-friendly.
Drawings
FIG. 1 is a scanning electron microscope field emission electron microscope photograph of a cross section of a single fiber of a conductive cotton yarn prepared by the invention;
FIG. 2 is a high scanning electron micrograph of PAN-GO nanofibers made according to the present invention;
FIG. 3 is a graph of I-V curves for PAN-GO/PEDOT/PSS electrode materials prepared in accordance with the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The PAN-GO/PEDOT/PSS supercapacitor electrode material based on the nanofiber yarn comprises a skin layer and a core layer, wherein the skin layer is twisted along the axial direction of the core layer to form a core-spun yarn structure, the skin layer is PAN nanofiber and graphene oxide, the core layer is conductive cotton yarn, and conductive polymer PEDOT/PSS particles are attached to the surface of the skin layer. The conductive cotton yarn is nickel-plated conductive cotton yarn, the thickness of a nickel layer of the nickel-plated conductive cotton yarn is 1.80 microns, and the diameter of the nanofiber of the skin layer is 0.90 microns.
A preparation method of a PAN-GO/PEDOT/PSS supercapacitor electrode material based on nanofiber yarns comprises the following steps:
(1) preparing nickel-plated conductive cotton yarn: the method comprises the following steps:
a. removing impurities from cotton yarn, soaking the cotton yarn with 0.25mol/L NaOH aqueous solution at 80 deg.C for 30min, and drying at 50 deg.C for 10min to obtain dried cotton yarn;
b. soaking the dried cotton yarn obtained in the step (a) in 50ml of mixed aqueous solution of nickel sulfate hexahydrate with the concentration of 0.20mol/L and hydrochloric acid with the concentration of 0.55mol/L for 10min, taking out the cotton yarn, and soaking the cotton yarn in mixed aqueous solution of sodium borohydride with the concentration of 0.26mol/L and sodium hydroxide with the concentration of 0.25mol/L for 10min to obtain soaked cotton yarn;
c. and (b) taking out the impregnated cotton yarn obtained in the step (b), washing the cotton yarn with deionized water, placing the cotton yarn into 10ml of chemical electroplating solution, and treating for 3 hours to obtain the nickel-plated conductive cotton yarn. The method adopts commercial cotton yarn to remove redundant impurities in the cotton yarn, wherein the impurities mainly comprise juveniles, wax and the like. The chemistry described in step (1)The electric ferry liquid comprises the following components: nickel sulfate hexahydrate (NiSO) with concentration of 0.10mol/L4•6H2O), sodium hypophosphite (NaHPO) with a concentration of 0.14mol/L2) Ammonium chloride (NH) at a concentration of 0.84mol/L4Cl) with a concentration of 0.10mol/L trisodium citrate (Na)3C6H5O7) And ammonia water (NH) at a concentration of 8mL/L3•H2O）。
(2) Preparing a spinning solution: weighing graphene oxide, adding the graphene oxide into an N, N-dimethylformamide solvent, and performing ultrasonic oscillation for 12-24 hours at room temperature to obtain a dispersed graphene oxide solution; weighing Polyacrylonitrile (PAN) powder, adding the Polyacrylonitrile (PAN) powder into the graphene oxide solution dispersed previously, and heating for 2 hours at 70 ℃ under the condition of magnetic stirring to form a spinning solution; the mass fraction of graphene oxide in the spinning solution prepared in the prepared spinning solution is 1.2% of the mass of the solute Polyacrylonitrile (PAN), and the mass fraction of the Polyacrylonitrile (PAN) is 14%;
(3) building an electrostatic spinning device, fixing two ends of the nickel-plated conductive cotton yarn prepared in the step (1) on a motor of the electrostatic spinning device, and winding the PAN nanofiber and the graphene oxide on the nickel-plated conductive cotton yarn through electrostatic spinning to obtain PAN-GO nanofiber core-spun yarn; the spinning voltage of the electrostatic spinning device is 20kV, the spinning distance is 16cm, and the spinning speed is 0.01 mm/min.
(4) Preparing a mixed trichloromethane solution of 30mmol/L of 3, 4-ethylenedioxythiophene and 30mmol/L of polystyrene sulfonate; then, the PAN nano-fiber core-spun yarn obtained in the step (2) is placed into a mixed trichloromethane solution to be fully soaked for 10-30 min; and finally, putting an ethanol solution of ferric trichloride with the concentration of 50-75 mmol/L on the yarn in the mixed trichloromethane solution by using a rubber head dropper, reacting at the temperature of 20-25 ℃ for 6-72 hours, taking out the yarn, and airing to obtain the PAN-GO/PEDOT/PSS supercapacitor electrode material. The addition amount of the ferric trichloride solution is as follows: ferric chloride solution: yarn =5 ml: 1g, v: and m is selected.
(5) And (3) preparing a gel electrolyte, immersing the electrode material of the PAN-GO/PEDOT/PSS supercapacitor prepared in the step (4) in the gel electrolyte for 0.5h, taking out and airing, distributing the gel electrolyte on two electrodes in parallel, standing overnight, and testing the electrical properties of the gel electrolyte. The preparation method of the gel electrolyte in the step (5) comprises the following steps: stirring the mixed solution of polyvinyl alcohol (PVA), deionized water and phosphoric acid for 2h at 95 ℃ to prepare the gel electrolyte, wherein the weight ratio of polyvinyl alcohol (PVA): phosphoric acid: the mass ratio of the deionized water is 1:1.5: 9.
FIG. 1 is a field emission electron microscope (SEM) photograph of the cross section of a single fiber of the conductive cotton yarn prepared by the invention, and as can be seen from the photograph, the thickness of the nickel layer of the single fiber of the conductive cotton yarn is 1.80-2.60 μm. FIG. 2 is a high-power scanning electron microscope photograph of the PAN-GO nano-fibers prepared by the method, wherein the image shows that graphene oxide is distributed on the PAN nano-fibers in a sheet shape, and the diameter of the PAN nano-fibers is 0.90-1.10 um. FIG. 3 shows the cyclic voltammetry characteristics of symmetrical PAN-GO/PEDOT/PSS composite capacitors prepared according to the present invention at different scan rates, and the test conditions are a two-electrode system.
Example 2
The PAN-GO/PEDOT/PSS supercapacitor electrode material based on the nanofiber yarn comprises a skin layer and a core layer, wherein the skin layer is twisted along the axial direction of the core layer to form a core-spun yarn structure, the skin layer is PAN nanofiber and graphene oxide, the core layer is conductive cotton yarn, and conductive polymer PEDOT/PSS particles are attached to the surface of the skin layer. The conductive cotton yarn is nickel-plated conductive cotton yarn, the thickness of a nickel layer of the nickel-plated conductive cotton yarn is 2.60 micrometers, and the diameter of the nanofiber of the skin layer is 1.10 micrometers.
A preparation method of a PAN-GO/PEDOT/PSS supercapacitor electrode material based on nanofiber yarns comprises the following steps:
(1) preparing nickel-plated conductive cotton yarn: the method comprises the following steps:
a. removing impurities from cotton yarn, soaking the cotton yarn with 0.22mol/L NaOH aqueous solution at 80 deg.C for 30min, and drying at 50 deg.C for 8min to obtain dried cotton yarn;
b. soaking the dried cotton yarn obtained in the step (a) in 50ml of mixed aqueous solution of nickel sulfate hexahydrate with the concentration of 0.20mol/L and hydrochloric acid with the concentration of 0.55mol/L for 10min, taking out the cotton yarn, and soaking the cotton yarn in mixed aqueous solution of sodium borohydride with the concentration of 0.26mol/L and sodium hydroxide with the concentration of 0.25mol/L for 10min to obtain soaked cotton yarn;
c. and (b) taking out the impregnated cotton yarn obtained in the step (b), washing the cotton yarn with deionized water, and then placing the cotton yarn in 100ml of chemical plating solution for treating for 3 hours to obtain the nickel-plated conductive cotton yarn. The chemical electro-plating solution in the step (1) comprises the following components: nickel sulfate hexahydrate (NiSO) with concentration of 0.12mol/L4•6H2O), sodium hypophosphite (NaHPO) with a concentration of 0.14mol/L2) Ammonium chloride (NH) at a concentration of 0.84mol/L4Cl) with a concentration of 0.10mol/L trisodium citrate (Na)3C6H5O7) And ammonia water (NH) at a concentration of 8mL/L3•H2O）。
(2) Preparing a spinning solution: weighing graphene oxide, adding the graphene oxide into an N, N-dimethylformamide solvent, and performing ultrasonic oscillation for 24 hours at room temperature to obtain a dispersed graphene oxide solution; weighing Polyacrylonitrile (PAN) powder, adding the Polyacrylonitrile (PAN) powder into the graphene oxide solution dispersed previously, and heating for 2 hours at 70 ℃ under the condition of magnetic stirring to form a spinning solution; the mass fraction of graphene oxide in the prepared spinning solution is 1.2% of the mass of a solute Polyacrylonitrile (PAN), and the mass fraction of the Polyacrylonitrile (PAN) is 14%;
(3) building an electrostatic spinning device, fixing two ends of the nickel-plated conductive cotton yarn prepared in the step (1) on a motor of the electrostatic spinning device, and winding the PAN nanofiber and the graphene oxide on the nickel-plated conductive cotton yarn through electrostatic spinning to obtain PAN-GO nanofiber core-spun yarn; the spinning voltage of the electrostatic spinning device is 15kV, the spinning distance is 13cm, and the spinning speed is 0.10 mm/min.
(4) Preparing a mixed trichloromethane solution of 50mmol/L of 3, 4-ethylenedioxythiophene and 50mmol/L of polystyrene sulfonate; then, the PAN nano-fiber core-spun yarn obtained in the step (2) is placed into a mixed trichloromethane solution to be fully soaked for 30 min; and finally, putting the ethanol solution of ferric trichloride with the concentration of 75mmol/L on the yarn in the mixed trichloromethane solution by using a rubber head dropper, reacting for 6 hours at the temperature of 20 ℃, taking out the yarn, and airing to obtain the PAN-GO/PEDOT/PSS supercapacitor electrode material. The addition amount of the ferric trichloride solution is as follows: ferric chloride solution: yarn =5 ml: 1g, v: and m is selected.
(5) And (3) preparing a gel electrolyte, immersing the electrode material of the PAN-GO/PEDOT/PSS supercapacitor prepared in the step (4) in the gel electrolyte for 0.5h, taking out and airing, distributing the gel electrolyte on two electrodes in parallel, standing overnight, and testing the electrical properties of the gel electrolyte. The preparation method of the gel electrolyte in the step (5) comprises the following steps: stirring the mixed solution of polyvinyl alcohol (PVA), deionized water and phosphoric acid at 95 ℃ for 6h to prepare the gel electrolyte, wherein the weight ratio of polyvinyl alcohol (PVA): phosphoric acid: the mass ratio of the deionized water is 1:1.5: 9.
Example 3
The PAN-GO/PEDOT/PSS supercapacitor electrode material based on the nanofiber yarn comprises a skin layer and a core layer, wherein the skin layer is twisted along the axial direction of the core layer to form a core-spun yarn structure, the skin layer is PAN nanofiber and graphene oxide, the core layer is conductive cotton yarn, and conductive polymer PEDOT/PSS particles are attached to the surface of the skin layer. The conductive cotton yarn is nickel-plated conductive cotton yarn, the thickness of a nickel layer of the nickel-plated conductive cotton yarn is 2.2 micrometers, and the diameter of the nanofiber of the skin layer is 1.0 micrometer.
A preparation method of a PAN-GO/PEDOT/PSS supercapacitor electrode material based on nanofiber yarns comprises the following steps:
(1) preparing nickel-plated conductive cotton yarn: the method comprises the following steps:
a. removing impurities from cotton yarn, soaking the cotton yarn with 0.25mol/L NaOH aqueous solution at 80 deg.C for 30min, and drying at 50 deg.C for 10min to obtain dried cotton yarn;
b. soaking the dried cotton yarn obtained in the step (a) in 50ml of mixed aqueous solution of nickel sulfate hexahydrate with the concentration of 0.18mol/L and hydrochloric acid with the concentration of 0.52mol/L for 5min, taking out the cotton yarn, and soaking the cotton yarn in mixed aqueous solution of sodium borohydride with the concentration of 0.22mol/L and sodium hydroxide with the concentration of 0.22mol/L for 5min to obtain soaked cotton yarn;
c. impregnated as obtained in step (b)And taking out the cotton yarn, cleaning the cotton yarn by using deionized water, putting the cotton yarn into chemical plating solution, and treating for 3h to obtain the nickel-plated conductive cotton yarn. The method adopts commercial cotton yarn to remove redundant impurities in the cotton yarn, wherein the impurities mainly comprise juveniles, wax and the like. The chemical electro-plating solution in the step (1) comprises the following components: nickel sulfate hexahydrate (NiSO) with concentration of 0.11mol/L4•6H2O), sodium hypophosphite (NaHPO) with a concentration of 0.12mol/L2) Ammonium chloride (NH) at a concentration of 0.80mol/L4Cl) with a concentration of trisodium citrate (Na) of 0.09mol/L3C6H5O7) And ammonia water (NH) with the concentration of 2.5-8 mL/L3•H2O）。
(2) Preparing a spinning solution: weighing graphene oxide, adding the graphene oxide into an N, N-dimethylformamide solvent, and performing ultrasonic oscillation for 18 hours at room temperature to obtain a dispersed graphene oxide solution; weighing Polyacrylonitrile (PAN) powder, adding the Polyacrylonitrile (PAN) powder into the graphene oxide solution dispersed previously, and heating for 2 hours at 68 ℃ under the condition of magnetic stirring to form a spinning solution; the mass fraction of graphene oxide in the prepared spinning solution is 1.1% of the mass of a solute Polyacrylonitrile (PAN), and the mass fraction of the Polyacrylonitrile (PAN) is 13.5%;
(3) building an electrostatic spinning device, fixing two ends of the nickel-plated conductive cotton yarn prepared in the step (1) on a motor of the electrostatic spinning device, and winding the PAN nanofiber and the graphene oxide on the nickel-plated conductive cotton yarn through electrostatic spinning to obtain PAN-GO nanofiber core-spun yarn; the spinning voltage of the electrostatic spinning device is 18kV, the spinning distance is 15cm, and the spinning speed is 0.05 mm/min.
(4) Preparing a mixed trichloromethane solution of 40mmol/L of 3, 4-ethylenedioxythiophene and 40mmol/L of polystyrene sulfonate; then, putting the PAN nano-fiber core-spun yarn obtained in the step (2) into a mixed trichloromethane solution for fully soaking for 20 min; and finally, putting an ethanol solution of ferric trichloride with the concentration of 65mmol/L on the yarn in the mixed trichloromethane solution by using a rubber head dropper, reacting at the temperature of 20-25 ℃ for 30 hours, taking out the yarn, and airing to obtain the PAN-GO/PEDOT/PSS supercapacitor electrode material. The addition amount of the ferric trichloride solution is as follows: ferric chloride solution: yarn =5 ml: 1g, v: and m is selected.
(5) And (3) preparing a gel electrolyte, immersing the electrode material of the PAN-GO/PEDOT/PSS supercapacitor prepared in the step (4) in the gel electrolyte for 1h, taking out and airing, arranging the two electrodes in parallel, spraying the gel electrolyte, standing overnight, and testing the electrical properties of the gel electrolyte. The preparation method of the gel electrolyte in the step (5) comprises the following steps: stirring the mixed solution of polyvinyl alcohol (PVA), deionized water and phosphoric acid for 4h at 95 ℃ to prepare the gel electrolyte, wherein the weight ratio of polyvinyl alcohol (PVA): phosphoric acid: the mass ratio of the deionized water is 1:1.5: 9.
Example 4
The PAN-GO/PEDOT/PSS supercapacitor electrode material based on the nanofiber yarn comprises a skin layer and a core layer, wherein the skin layer is twisted along the axial direction of the core layer to form a core-spun yarn structure, the skin layer is PAN nanofiber and graphene oxide, the core layer is conductive cotton yarn, and conductive polymer PEDOT/PSS particles are attached to the surface of the skin layer. The conductive cotton yarn is nickel-plated conductive cotton yarn, the thickness of a nickel layer of the nickel-plated conductive cotton yarn is 2.2 micrometers, and the diameter of the nanofiber of the skin layer is 1.05 micrometers.
A preparation method of a PAN-GO/PEDOT/PSS supercapacitor electrode material based on nanofiber yarns comprises the following steps:
(1) preparing nickel-plated conductive cotton yarn: the method comprises the following steps:
a. removing impurities from cotton yarn, soaking the cotton yarn with 0.22mol/L NaOH aqueous solution at 80 deg.C for 40min, and drying at 50 deg.C for 8min to obtain dried cotton yarn;
b. soaking the dried cotton yarn obtained in the step (a) in a mixed aqueous solution of nickel sulfate hexahydrate with the concentration of 0.18mol/L and hydrochloric acid with the concentration of 0.52mol/L for 8min, taking out the cotton yarn, and soaking the cotton yarn in a mixed aqueous solution of sodium borohydride with the concentration of 0.24mol/L and sodium hydroxide with the concentration of 0.23mol/L for 8min to obtain soaked cotton yarn;
c. and (b) taking out the impregnated cotton yarn obtained in the step (b), washing the cotton yarn with deionized water, placing the cotton yarn in a chemical electroplating solution, and treating for 6 hours to obtain the nickel-plated conductive cotton yarn. Using commercial cotton yarn, removingThe excessive impurities in the cotton yarn are mainly larvae, wax and the like. The chemical electro-plating solution in the step (1) comprises the following components: nickel sulfate hexahydrate (NiSO) with concentration of 0.11mol/L4•6H2O), sodium hypophosphite (NaHPO) with a concentration of 0.10mol/L2) Ammonium chloride (NH) at a concentration of 0.8mol/L4Cl) with a concentration of trisodium citrate (Na) of 0.09mol/L3C6H5O7) And ammonia water (NH) at a concentration of 5mL/L3•H2O）。
(2) Preparing a spinning solution: weighing graphene oxide, adding the graphene oxide into an N, N-dimethylformamide solvent, and performing ultrasonic oscillation for 12 hours at room temperature to obtain a dispersed graphene oxide solution; weighing Polyacrylonitrile (PAN) powder, adding the Polyacrylonitrile (PAN) powder into the dispersed graphene oxide solution, and heating for 2 hours at 65 ℃ under the condition of magnetic stirring to form a spinning solution; the mass fraction of graphene oxide in the prepared spinning solution is 1.1% of the mass of a solute Polyacrylonitrile (PAN), and the mass fraction of the Polyacrylonitrile (PAN) is 14%;
(3) building an electrostatic spinning device, fixing two ends of the nickel-plated conductive cotton yarn prepared in the step (1) on a motor of the electrostatic spinning device, and winding the PAN nanofiber and the graphene oxide on the nickel-plated conductive cotton yarn through electrostatic spinning to obtain PAN-GO nanofiber core-spun yarn; the spinning voltage of the electrostatic spinning device is 18kV, the spinning distance is 14cm, and the spinning speed is 0.06 mm/min.
(4) Preparing a mixed trichloromethane solution of 45mmol/L of 3, 4-ethylenedioxythiophene and 50mmol/L of polystyrene sulfonate; then, putting the PAN nano-fiber core-spun yarn obtained in the step (2) into a mixed trichloromethane solution for fully soaking for 20 min; and finally, putting an ethanol solution of ferric trichloride with the concentration of 70mmol/L on the yarn in the mixed trichloromethane solution by using a rubber head dropper, reacting at the temperature of 22 ℃ for 60 hours, taking out the yarn, and airing to obtain the PAN-GO/PEDOT/PSS supercapacitor electrode material. The addition amount of the ferric trichloride solution is as follows: ferric chloride solution: yarn =5 ml: 1g, v: and m is selected.
(5) And (3) preparing a gel electrolyte, immersing the electrode material of the PAN-GO/PEDOT/PSS supercapacitor prepared in the step (4) in the gel electrolyte for 1.5h, taking out and airing, distributing the gel electrolyte on two electrodes in parallel, standing overnight, and testing the electrical properties of the gel electrolyte. The preparation method of the gel electrolyte in the step (5) comprises the following steps: stirring the mixed solution of polyvinyl alcohol (PVA), deionized water and phosphoric acid for 5h at 95 ℃ to prepare the gel electrolyte, wherein the weight ratio of polyvinyl alcohol (PVA): phosphoric acid: the mass ratio of the deionized water is 1:1.5: 9.
The PEDOT: PSS (poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid) composite material with the core-spun structure, which is prepared by the invention, is used as an electrode material of a supercapacitor, has a very large specific surface area, is favorable for the permeation of electrolyte, and provides more electrochemical sites for the redox reaction of an active material polypyrrole. Meanwhile, the close combination of the conductive cotton yarn and the nano-fiber is beneficial to the transmission of electrons. The composite electrode of the core-spun PEDOT and PSS based on the electrostatic spinning nanofiber yarn achieves ideal electrochemical performance and can be used as an ideal electrode material of a super capacitor.
Claims (7)
1. A preparation method of a PAN-GO/PEDOT/PSS supercapacitor electrode material based on nano fiber yarns is characterized by comprising the following steps of: the method comprises the following steps: (1) preparing nickel-plated conductive cotton yarn: placing the cotton yarn in chemical plating solution, and treating for 2-8h to obtain nickel-plated conductive cotton yarn;
(2) preparing a spinning solution: weighing graphene oxide, adding the graphene oxide into an N, N-dimethylformamide solvent, and performing ultrasonic oscillation for 12-24 hours at room temperature to obtain a dispersed graphene oxide solution; weighing Polyacrylonitrile (PAN) powder, adding the PAN powder into the dispersed graphene oxide solution, and heating for 2 hours at 65-70 ℃ under the condition of magnetic stirring to form a spinning solution;
(3) building an electrostatic spinning device, fixing two ends of the nickel-plated conductive cotton yarn prepared in the step (1) on a motor of the electrostatic spinning device, and winding the PAN nanofiber and the graphene oxide on the nickel-plated conductive cotton yarn through electrostatic spinning to obtain PAN-GO nanofiber core-spun yarn;
(4) preparing a mixed trichloromethane solution of 30-50 mmol/L of 3, 4-ethylenedioxythiophene and 30-50 mmol/L of polystyrene sulfonate; then, putting the PAN-GO nano-fiber core-spun yarn obtained in the step (3) into a mixed trichloromethane solution for fully soaking for 10-30 min; finally, an ethanol solution of ferric trichloride with the concentration of 50-75 mmol/L is placed on the yarn in the mixed trichloromethane solution by using a rubber head dropper, the yarn is taken out and dried after reacting for 6-72 hours at the temperature of 20-25 ℃, and the PAN-GO/PEDOT/PSS supercapacitor electrode material is obtained;
PSS super capacitor electrode material, including cortex and sandwich layer, the cortex forms the covering yarn structure along the axial twist of sandwich layer, the said cortex is PAN nanofiber and graphene oxide, the sandwich layer is the conductive cotton yarn, the surface of cortex adheres to the conductive polymer PEDOT: PSS granule;
the conductive cotton yarn is nickel-plated conductive cotton yarn, the thickness of a nickel layer of the nickel-plated conductive cotton yarn is 1.80-2.60 micrometers, and the diameter of the nanofiber of the skin layer is 0.90-1.10 micrometers.
2. The preparation method of the nanofiber yarn-based PAN-GO/PEDOT: PSS supercapacitor electrode material according to claim 1 is characterized in that: the preparation of the conductive cotton yarn in the step (1) comprises the following steps: a. removing impurities from cotton yarns, soaking the cotton yarns in 0.20-0.25 mol/L NaOH aqueous solution at the heating temperature of 80 ℃ for 30-60 min, and then drying at the temperature of 50 ℃ for 5-10 min to obtain dried cotton yarns;
b. soaking the dried cotton yarn obtained in the step (a) in a mixed aqueous solution of nickel sulfate hexahydrate with the concentration of 0.15-0.20 mol/L and hydrochloric acid with the concentration of 0.50-0.55 mol/L for 5-10 min, taking out, and soaking in a mixed aqueous solution of sodium borohydride with the concentration of 0.20-0.26 mol/L and sodium hydroxide with the concentration of 0.20-0.25 mol/L for 5-10 min to obtain soaked cotton yarn;
c. and (b) taking out the impregnated cotton yarn obtained in the step (b), washing the cotton yarn with deionized water, placing the cotton yarn into chemical plating solution, and treating for 2-8h to obtain the nickel-plated conductive cotton yarn.
3. The preparation method of the nanofiber yarn-based PAN-GO/PEDOT: PSS supercapacitor electrode material according to claim 1 is characterized in that: the chemical electro-plating solution in the step (1) comprises the following components: nickel sulfate hexahydrate with the concentration of 0.10-0.12 mol/L, sodium hypophosphite with the concentration of 0.10-0.14 mol/L, ammonium chloride with the concentration of 0.70-0.84 mol/L, trisodium citrate with the concentration of 0.08-0.10 mol/L and ammonia water with the concentration of 2.5-8 mL/L.
4. The preparation method of the nanofiber yarn-based PAN-GO/PEDOT: PSS supercapacitor electrode material according to claim 1 is characterized in that: the mass of the graphene oxide in the spinning solution prepared in the step (2) is 1.0-1.2% of that of the solute polyacrylonitrile, and the mass fraction of the polyacrylonitrile is 13-14%.
5. The preparation method of the nanofiber yarn-based PAN-GO/PEDOT: PSS supercapacitor electrode material according to claim 3, characterized by comprising the following steps: the spinning voltage of the electrostatic spinning device in the step (3) is 15-20 kV, the spinning distance is 13-16 cm, and the spinning speed is 0.01-0.10 mm/min.
6. The preparation method of the nanofiber yarn-based PAN-GO/PEDOT: PSS supercapacitor electrode material according to claim 1 is characterized in that: and (3) preparing a gel electrolyte, immersing the electrode material of the PAN-GO/PEDOT/PSS supercapacitor prepared in the step (4) in the gel electrolyte for 0.5-2 h, taking out and airing, distributing the gel electrolyte on the two electrodes in parallel, standing overnight, and testing the electrical properties of the electrode material.
7. The preparation method of the nanofiber yarn-based PAN-GO/PEDOT: PSS supercapacitor electrode material according to claim 6, is characterized in that: the preparation method of the gel electrolyte in the step (5) comprises the following steps: stirring the mixed solution of polyvinyl alcohol, deionized water and phosphoric acid for 2-6 h at 95 ℃ to prepare the gel electrolyte, wherein the weight ratio of polyvinyl alcohol: phosphoric acid: the mass ratio of the deionized water is 1:1.5: 9.
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