CN110060886B - Preparation method of fiber/graphene/FeOOF/Ag flexible electrode material - Google Patents

Preparation method of fiber/graphene/FeOOF/Ag flexible electrode material Download PDF

Info

Publication number
CN110060886B
CN110060886B CN201910417520.5A CN201910417520A CN110060886B CN 110060886 B CN110060886 B CN 110060886B CN 201910417520 A CN201910417520 A CN 201910417520A CN 110060886 B CN110060886 B CN 110060886B
Authority
CN
China
Prior art keywords
fiber
graphene
drying
feoof
graphene oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910417520.5A
Other languages
Chinese (zh)
Other versions
CN110060886A (en
Inventor
王薇
刘康
陆鑫
李涛
吴曼曼
张技术
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changshu Institute of Technology
Original Assignee
Changshu Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changshu Institute of Technology filed Critical Changshu Institute of Technology
Priority to CN201910417520.5A priority Critical patent/CN110060886B/en
Publication of CN110060886A publication Critical patent/CN110060886A/en
Application granted granted Critical
Publication of CN110060886B publication Critical patent/CN110060886B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses a preparation method of a fiber/graphene/FeOOF/Ag flexible electrode material, which is characterized by comprising the following steps: A. dipping the pretreated fiber fabric into a graphene oxide suspension, drying, repeating the step for a plurality of times to obtain a fiber/graphene oxide material, and carrying out in-situ reduction to obtain the fiber/graphene oxide material; B. immersing the fiber/graphene material obtained in the step A into FeF3·3H2Heating and reacting in a hydrothermal reaction kettle of O and an alcohol solution to synthesize a fiber/graphene/FeOOF material; C. and B, processing silver paste on the fiber/graphene/FeOOF material obtained in the step B by adopting a screen printing method, and drying to obtain the fiber/graphene/FeOOF/Ag flexible electrode material. The material prepared by the method combines a carbon material with good conductivity and FeOOF with high specific capacitance and poor conductivity, further introduces Ag, remarkably improves the electrochemical performance of the fabric-based flexible electrode material, and enables the electrode material to obtain high specific capacitance, high power density and high energy density.

Description

Preparation method of fiber/graphene/FeOOF/Ag flexible electrode material
Technical Field
The invention relates to a preparation method of a flexible electrode material, in particular to a preparation method of a fiber/graphene/FeOOF/Ag flexible electrode material.
Background
The electrochemical capacitor is widely applied to the fields of hybrid electric vehicles, communication, national defense, wearable electronics and the like based on the special functions of high capacity, high power density and the like. With the development trend of light weight, thinness and flexibility of electronic devices, portable and wearable electronic devices such as flexible display screens, distributed sensors, electronic paper and wearable multimedia devices increasingly enter people's daily lives. However, the conventional electrochemical capacitor has a large volume, a heavy weight and a fixed shape, and is far from meeting the development requirements of the current flexible electronic equipment. There is an urgent need to develop flexible electrochemical capacitors and electrode materials thereof having light weight, low cost, small volume, excellent electrochemical properties, and excellent processability.
At present, research and development of flexible electrochemical capacitors and electrode materials have become an international hotspot, a great deal of research on how to improve the wearing comfort of wearable energy storage devices and how to improve the electrochemical performance has been carried out at home and abroad, but the high manufacturing cost, poor flexibility, low durability and environmental dependence limit the real application of the wearable energy storage devices. Carrying new materials and designing new structures are important methods for improving the performance of the wearable energy storage device and improving the environmental adaptability of the wearable energy storage device.
The textile material is a natural wearable material, and has excellent wearing comfort, selection universality, mechanical stability and the like. The material and surface properties of textile materials are special, so that a three-dimensional continuous conductive network is difficult to form on the surface of conductive materials such as carbon and the like, in order to increase the interaction between the conductive materials and fabrics, a large amount of cross-linking agents, surfactants and even binders are often used, so that the conductive materials can be well attached to the fabrics, on one hand, the addition of the substances can block pores on the fabrics, so that the diffusion of electrolyte ions is not facilitated, the exertion of the electrochemical performance of the fabrics is influenced, on the other hand, the synthesis process of the materials is complicated and difficult, and the cost is increased.
As we know, the fabric occupies a high mass and volume fraction in the flexible electrode material. Therefore, the fabric is not conductive by itself and the weave structure thereof also becomes one of the main reasons for the larger internal resistance of the fabric-based flexible electrode material. The problem is more remarkable in macro preparation of the flexible electrode material, and the internal resistance of the device is remarkably increased, so that the performance of the capacitor device is seriously reduced. Although the electrochemical performance of the fabric-based composite electrode material is effectively improved by the synergistic use of the double-electrode layer material and the pseudocapacitance material, the high internal resistance of the textile fabric still affects the mass specific capacitance, the volume specific capacitance, the energy density and the like of the whole electrode. If an effective method can be adopted to improve the conductivity of the whole electrode, the problem of high internal resistance of the fabric is effectively solved, and the electrochemical performance of the fabric-based flexible electrode material is obviously improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a fiber/graphene/FeOOF/Ag flexible electrode material, solves the problems that a conductive network is difficult to form on the surface of a textile material, the bonding force between the conductive material and the textile is insufficient, and the textile is not conductive, and provides a material which can be applied to a super capacitor and a wearable product.
The technical scheme of the invention is as follows: a preparation method of a fiber/graphene/FeOOF/Ag flexible electrode material comprises the following steps:
A. dipping the pretreated fiber fabric into a graphene oxide suspension and drying, repeating the step for a plurality of times to obtain a fiber/graphene oxide material, and carrying out in-situ reduction to obtain the fiber/graphene oxide material, wherein the graphene oxide suspension is prepared by ultrasonically dispersing graphene oxide powder into deionized water;
B. immersing the fiber/graphene material obtained in the step A into FeF3·3H2Heating and reacting in a hydrothermal reaction kettle of O and an alcohol solution to synthesize a fiber/graphene/FeOOF material;
C. and B, processing silver paste on the fiber/graphene/FeOOF material obtained in the step B by adopting a screen printing method, and drying to obtain the fiber/graphene/FeOOF/Ag flexible electrode material.
Further, the concentration of the graphene oxide suspension is 0.5-3mg/mL, the dipping time in the step A is 20-60min, the drying temperature in the step A is 40-70 ℃, and the drying time is 2-3 h.
Preferably, the repetition frequency of the step A is 5 to 40 times.
Further, the step A is to dip the fiber/graphene oxide material into NaBH for in-situ reduction4Reducing in the solution, washing with deionized water, and drying, or heating and reducing the fiber/graphene oxide material under the protection of inert gas.
Preferably, the NaBH4The concentration of the solution is 0.1-1mol/L, and the solution is immersed in NaBH4The time of the solution is 4-12h,the drying temperature of the deionized water after cleaning is 90-120 ℃, and the drying time is 1-3 h; the heating temperature of the heating reduction is 150-2。
Further, the fiber fabric after pretreatment is pretreated by adopting an alkali solution, and then is cleaned by using deionized water and dried.
Preferably, the alkali solution is a sodium hydroxide solution or a sodium bicarbonate solution, the concentration of the alkali solution is 0.5-2mol/L, the pretreatment temperature is 90-120 ℃, the pretreatment time is 1-3h, the drying temperature in the pretreatment is 80-130 ℃, and the drying time is 1-3 h.
Further, the alcohol is one of ethanol, propanol, isopropanol and butanol.
Preferably, the heating temperature of the heating reaction in the step B is 160-220 ℃, and the reaction time is 4-20 h.
Preferably, the concentration of the silver paste in the step C is 15g/L-30g/L, the drying temperature is 80-100 ℃, and the time is 2-5 h.
The technical scheme provided by the invention has the advantages that:
1. the invention prepares a novel three-dimensional graphene/FeOOF/Ag super-capacitor electrode material based on textile fiber growth by combining layer-by-layer assembly and a hydrothermal method. Due to the non-conductivity of the fiber substrate and the high mass and volume fraction of the fiber substrate in the flexible electrode material, the internal resistance of the fabric-based flexible electrode material is large. The conductive branch channels formed by the Ag and the graphene/FeOOF composite material introduced by screen printing are mutually supported to form a conductive main channel for rapidly transmitting electrons, so that the transmission rate of electrons is enhanced, the problem of high internal resistance of the fabric is effectively solved, and meanwhile, the Ag has high conductivity, so that the electrochemical performance of the fabric-based flexible electrode material is remarkably improved, and the electrode material obtains high specific capacitance, high power density and high energy density.
2. The material prepared by the invention can be used as an electrode material of a super capacitor, the material utilizes a porous structure between flexible textile fibers to promote the diffusion of electrolyte ions, simultaneously gives full play to the high specific surface and high conductivity of the carbon material, effectively increases the contact interface between FeOOF and the carbon material, effectively disperses the FeOOF, provides more reaction active points for the pseudo-capacitance redox reaction, gives play to the advantages of the capacitance of the FeOOF, and ensures the rapid transmission of electrons in the electrode material, thereby being beneficial to the electrode material to obtain high specific capacitance, high power density and high energy density.
3. The prepared electrode material is light and soft, has the characteristics of higher area specific capacitance and power, excellent cycle performance, simple synthesis, lower cost and good durability, and has higher use value in the aspects of wearable electronic product energy storage and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
The graphene oxide powder in each embodiment of the preparation method of the fiber/graphene/FeOOF/Ag flexible electrode material is prepared by the following method: graphene oxide was prepared using an improved Hummers synthesis method. 1.5g of graphite powder was added to a mixture of 10mL of 98% concentrated sulfuric acid, 1.25g of potassium thiosulfate and 1.25g of phosphorus pentoxide, and stirred at 80 ℃ for 4.5 hours. Then the obtained product is washed by deionized water and dried in a vacuum drying oven at 50 ℃. Adding the dried product into 60mL of 98% concentrated sulfuric acid, then slowly adding 7.5g of potassium permanganate, keeping the temperature below 20 ℃ in the adding process of the potassium permanganate, and then adding 125mL of deionized water. After 2h, 200mL of deionized water and 10mL of 30% hydrogen peroxide were added and the solution turned bright yellow after 10 min. And centrifuging the obtained bright yellow solution, cleaning the solution by using a diluted hydrochloric acid solution (the volume ratio of concentrated hydrochloric acid to deionized water is 1/10) to remove metal ions and sulfate ions, cleaning the solution by using deionized water until the solution is nearly neutral, and finally drying the solution in a vacuum drying oven at 50 ℃ to obtain the graphene oxide. The silver paste used was SC666-80R, Uniwell.
Example 1
Adding graphene oxide powder into deionized water, and performing ultrasonic treatment for 60min to obtain the graphene oxide powderThe graphene oxide suspension with the concentration of 1.5mg/mL is formed. The cotton fabric is treated by 1mol/L sodium hydroxide solution at 100 ℃ for 2h, then is cleaned by deionized water and is dried in a drying oven at 110 ℃ for 2 h. And (3) dipping the pretreated cotton fabric into the prepared graphene oxide suspension, stirring at room temperature for 30min, drying in a vacuum oven at 50 ℃ for 2h, and repeating the dipping-drying process for 20 times. Soaking cotton cloth/graphene oxide composite fabric into NaBH with concentration of 0.5mol/L4And stirring the solution at room temperature for 12 hours, taking out the solution, washing the solution for 3 times by using deionized water, drying the solution at 100 ℃ for 2 hours, and reducing the solution to obtain the cotton cloth/graphene composite material.
Soaking cotton cloth/graphene composite material into FeF3·3H2Reacting O and ethanol (mass (g): volume (ml): 2.08:1) in a hydrothermal reaction kettle at 180 ℃ for 12 hours to synthesize a cotton cloth/graphene/FeOOF material, and drying the material at 80 ℃ for 2 hours; and then coating 20g/L silver paste on the fabric by adopting a screen printing method, and drying for 2h at 80 ℃ to obtain the fiber/graphene/FeOOF/Ag flexible electrode material, wherein when the scanning speed is 5m V/s, the specific capacitance can reach 503F/g, and the flexible electrode material has good flexibility.
Example 2
Adding the graphene oxide powder into deionized water, and carrying out ultrasonic treatment for 30min to prepare a graphene oxide suspension with the concentration of 2 mg/mL. The cotton fabric is treated by 0.5mol/L sodium bicarbonate solution at 90 ℃ for 3h, then is cleaned by deionized water and is dried in a drying oven at 100 ℃ for 2.5 h. And (3) dipping the pretreated cotton fabric into the prepared graphene oxide suspension, stirring at room temperature for 20min, drying in a vacuum oven at 50 ℃ for 3h, and repeating the dipping-drying process for 30 times. Soaking cotton cloth/graphene oxide composite fabric into NaBH with concentration of 0.1mol/L4And stirring the solution at room temperature for 12 hours, taking out the solution, washing the solution for 3 times by using deionized water, drying the solution at 100 ℃ for 2 hours, and reducing the solution to obtain the cotton cloth/graphene composite material.
Soaking cotton cloth/graphene composite material into FeF3·3H2O and ethanol (mass (g): volume (ml): 2.08:1) are reacted in a hydrothermal reaction kettle at 200 ℃ for 8 hours to synthesize cotton cloth/graphene/FeOOF material, and the cotton cloth/graphene/FeOOF material is synthesizedDrying at 80 ℃ for 2h, further coating 20g/L silver paste on the fabric by adopting a screen printing method, and drying at 100 ℃ for 2h to obtain the fiber/graphene/FeOOF/Ag flexible electrode material, wherein when the scanning speed is 5mV/s, the specific capacitance can reach 489F/g, and the fiber/graphene/FeOOF/Ag flexible electrode material has good flexibility.
Example 3
Adding the graphene oxide powder into deionized water, and carrying out ultrasonic treatment for 30min to prepare a graphene oxide suspension with the concentration of 3 mg/mL. The polyester fabric is treated by 2mol/L sodium bicarbonate solution at 120 ℃ for 1.5h, then is washed by deionized water and is dried in a drying oven at 80 ℃ for 3 h. And (3) dipping the pretreated terylene into the prepared graphene oxide suspension, stirring for 50min at room temperature, drying for 2.5h in a vacuum oven at 60 ℃, and repeating the dipping-drying process for 40 times. Placing the terylene/graphene oxide composite fabric in a high-temperature tube furnace, wherein the heating rate is 2 ℃/min, the temperature is 250 ℃, and the temperature is N2And (3) carrying out high-temperature reaction for 3 hours under the atmosphere condition, and reducing to obtain the terylene/graphene composite material.
Immersing the terylene/graphene composite material into FeF3·3H2O and propanol (mass (g): volume (ml): 2.08:1) are reacted in a hydrothermal reaction kettle at 160 ℃ for 20 hours to synthesize a terylene/graphene/FeOOF material, the terylene/graphene/FeOOF material is dried at 80 ℃ for 2 hours, then 15g/L silver paste is coated on a fabric by adopting a screen printing method, and the terylene/graphene/FeOOF/Ag flexible electrode material is dried at 120 ℃ for 2 hours to obtain the fiber/graphene/FeOOF/Ag flexible electrode material, wherein when the scanning speed is 5mV/s, the specific capacitance can reach 484F/g, and the fiber/graphene/FeOOF/Ag flexible electrode material has good flexibility.
Example 4
Adding the graphene oxide powder into deionized water, and carrying out ultrasonic treatment for 30min to prepare a graphene oxide suspension with the concentration of 0.5 mg/mL. The nylon fabric is treated by 1.5mol/L sodium hydroxide solution at 120 ℃ for 2.5h, then is cleaned by deionized water and is dried in a drying oven at 130 ℃ for 1.5 h. Dipping the pretreated chinlon into the prepared graphene oxide suspension, stirring at room temperature for 60min, drying in a vacuum oven at 70 ℃ for 2h, and repeating the dipping-drying process for 10 times. Immersing the chinlon/graphene oxide composite fabric into NaBH with the concentration of 0.5mol/L4Stirring the solution at room temperature for 12hAnd then taking out and washing the polyamide/graphene composite material for 3 times by using deionized water, drying the polyamide/graphene composite material for 2 hours at the temperature of 100 ℃, and reducing the polyamide/graphene composite material to obtain the polyamide/graphene composite material.
Immersing the chinlon/graphene composite material into a solution containing FeF3·3H2O and ethanol (mass (g): volume (ml): 2.08:1) react in a hydrothermal reaction kettle at 140 ℃ for 20 hours to synthesize a nylon/graphene/FeOOF material, the material is dried at 80 ℃ for 2 hours, then 25g/L silver paste is coated on a fabric by adopting a screen printing method, and the fabric/graphene/FeOOF/Ag flexible electrode material is obtained by drying at 80 ℃ for 3 hours, wherein when the scanning speed is 5mV/s, the specific capacitance can reach 414F/g, and the flexible electrode material has good flexibility.
Example 5
Adding the graphene oxide powder into deionized water, and carrying out ultrasonic treatment for 30min to prepare a graphene oxide suspension with the concentration of 1 mg/mL. Treating the non-woven fabric with 0.5mol/L sodium hydroxide solution at 100 ℃ for 3h, then cleaning with deionized water, and drying in a drying oven at 120 ℃ for 1 h. And (3) dipping the pretreated non-woven fabric into the prepared graphene oxide suspension, stirring at room temperature for 30min, drying in a vacuum oven at 40 ℃ for 3h, and repeating the dipping-drying process for 5 times. And (3) placing the non-woven fabric/graphene oxide composite fabric in a high-temperature tube furnace, wherein the heating rate is 2 ℃/min, and carrying out high-temperature reaction for 0.5h at 350 ℃ under the He atmosphere condition, so as to obtain the non-woven fabric/graphene composite material through reduction.
Immersing the non-woven fabric/graphene composite material into FeF3·3H2O and butanol (mass (g): volume (ml): 2.08:1) are reacted in a hydrothermal reaction kettle at 180 ℃ for 12 hours to synthesize a non-woven fabric/graphene/FeOOF material, the material is dried at 80 ℃ for 2 hours, then 30g/L silver paste is coated on the fabric by a printing method, and the material is dried at 100 ℃ for 2 hours to obtain the fiber/graphene/FeOOF/Ag flexible electrode material, wherein when the scanning speed is 5mV/s, the specific capacitance can reach 499F/g, and the fiber/graphene/FeOOF/Ag flexible electrode material has good flexibility.
Comparative example 1
Adding the graphene oxide powder into deionized water, and carrying out ultrasonic treatment for 60min to prepare a graphene oxide suspension with the concentration of 1.5 mg/mL. Treating cotton fabric with 1mol/L sodium hydroxide solution at 100 deg.C 2And h, cleaning with deionized water, and drying in a drying oven at 110 ℃ for 2 h. And (3) dipping the pretreated cotton fabric into the prepared graphene oxide suspension, stirring at room temperature for 30min, drying in a vacuum oven at 50 ℃ for 2h, and repeating the dipping-drying process for 20 times. Soaking cotton cloth/graphene oxide composite fabric into NaBH with concentration of 0.5mol/L4And stirring the solution at room temperature for 12 hours, taking out the solution, washing the solution for 3 times by using deionized water, drying the solution at 100 ℃ for 2 hours, and reducing the solution to obtain the cotton cloth/graphene composite material.
Soaking cotton cloth/graphene composite material into FeF3·3H2O and ethanol (mass (g): volume (ml): 2.08:1) are reacted in a hydrothermal reaction kettle at 180 ℃ for 12 hours to synthesize a cotton cloth/graphene/FeOOF material, the material is dried at 80 ℃ for 2 hours, and when the scanning speed is 5m V/s, the specific capacitance can be 256F/g.
Comparative example 2
Adding the graphene oxide powder into deionized water, and carrying out ultrasonic treatment for 30min to prepare a graphene oxide suspension with the concentration of 1 mg/mL. Treating the non-woven fabric with 0.5mol/L sodium hydroxide solution at 100 ℃ for 3h, then cleaning with deionized water, and drying in a drying oven at 120 ℃ for 1 h. And (3) dipping the pretreated non-woven fabric into the prepared graphene oxide suspension, stirring at room temperature for 30min, drying in a vacuum oven at 40 ℃ for 3h, and repeating the dipping-drying process for 5 times. And (3) placing the non-woven fabric/graphene oxide composite fabric in a high-temperature tube furnace, wherein the heating rate is 2 ℃/min, and carrying out high-temperature reaction for 0.5h at 350 ℃ under the He atmosphere condition, so as to obtain the non-woven fabric/graphene composite material through reduction.
Immersing the non-woven fabric/graphene composite material into FeF3·3H2O and butanol (mass (g): volume (ml): 2.08:1) are reacted in a hydrothermal reaction kettle at 180 ℃ for 12 hours to synthesize a non-woven fabric/graphene/FeOOF material, the material is dried at 80 ℃ for 2 hours, and when the scanning speed is 5mV/s, the specific capacitance can reach 189F/g.
Comparative example 3
Silver paste is coated on the dry cotton cloth by a screen printing method, and the silver paste is only in a conductive grid form and has no electrochemical performance.

Claims (1)

1. A preparation method of a fiber/graphene/FeOOF/Ag flexible electrode material is characterized by comprising the following steps:
A. dipping the pretreated fiber fabric into a graphene oxide suspension and drying, wherein the concentration of the graphene oxide suspension is 0.5-3mg/mL, the dipping time is 20-60min, the drying temperature is 40-70 ℃, and the drying time is 2-3 h; repeating the step for 5-40 times to obtain the fiber/graphene oxide material dipped in NaBH4Reducing in the solution, cleaning with deionized water, and drying, or heating and reducing the fiber/graphene oxide material under the protection of inert gas to obtain the fiber/graphene oxide material, wherein the graphene oxide suspension is prepared by ultrasonically dispersing graphene oxide powder in deionized water; the NaBH4The concentration of the solution is 0.1-1mol/L, and the solution is immersed in NaBH4The solution time is 4-12h, the drying temperature of the deionized water after cleaning and drying is 90-120 ℃, and the drying time is 1-3 h; the heating temperature of the heating reduction is 150-;
B. immersing the fiber/graphene material obtained in the step A into FeF3·3H2Heating and reacting in a hydrothermal reaction kettle of O and an alcohol solution to synthesize a fiber/graphene/FeOOF material, wherein the heating temperature is 160-220 ℃, the reaction time is 4-20 h, and the alcohol is one of ethanol, propanol, isopropanol and butanol;
C. b, processing silver paste on the fiber/graphene/FeOOF material obtained in the step B by adopting a screen printing method, and drying to obtain the fiber/graphene/FeOOF/Ag flexible electrode material, wherein the concentration of the silver paste is 15g/L-30g/L, the drying temperature is 80-100 ℃, and the drying time is 2-5 h;
the pretreated fiber fabric is prepared by pretreating the fiber fabric with an alkali solution, cleaning the pretreated fiber fabric with deionized water, and drying the fiber fabric for 1 to 3 hours, wherein the alkali solution is a sodium hydroxide solution or a sodium bicarbonate solution, the concentration of the alkali solution is 0.5 to 2mol/L, the pretreatment temperature is 90 to 120 ℃, the pretreatment time is 1 to 3 hours, and the drying temperature in the pretreatment is 80 to 130 ℃.
CN201910417520.5A 2019-05-20 2019-05-20 Preparation method of fiber/graphene/FeOOF/Ag flexible electrode material Active CN110060886B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910417520.5A CN110060886B (en) 2019-05-20 2019-05-20 Preparation method of fiber/graphene/FeOOF/Ag flexible electrode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910417520.5A CN110060886B (en) 2019-05-20 2019-05-20 Preparation method of fiber/graphene/FeOOF/Ag flexible electrode material

Publications (2)

Publication Number Publication Date
CN110060886A CN110060886A (en) 2019-07-26
CN110060886B true CN110060886B (en) 2021-08-31

Family

ID=67323479

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910417520.5A Active CN110060886B (en) 2019-05-20 2019-05-20 Preparation method of fiber/graphene/FeOOF/Ag flexible electrode material

Country Status (1)

Country Link
CN (1) CN110060886B (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104282882B (en) * 2014-09-26 2017-01-11 江苏华东锂电技术研究院有限公司 Composite positive electrode material and preparation method thereof
KR101704246B1 (en) * 2015-08-21 2017-02-08 한양대학교 산학협력단 Method for preparing conductive composite fiber based on graphene oxide and carbon nanotube, the conductive composite fiber prepared therefrom, and supercapacitor comprisng the same
CN106783220A (en) * 2016-12-19 2017-05-31 北京印刷学院 A kind of preparation method of flexible all-solid-state supercapacitor
US20180240609A1 (en) * 2017-02-17 2018-08-23 Aict High performance nano/micro composite fiber capable of storing electrical energy and method for fabricating thereof
CN108597905A (en) * 2018-06-13 2018-09-28 常熟理工学院 A kind of preparation method of fiber/graphene/cobalt sulfide nickel flexible electrode material
CN108766782A (en) * 2018-06-13 2018-11-06 常熟理工学院 A kind of preparation method of fiber/graphene/molybdenum sulfide flexible electrode material
CN108766783A (en) * 2018-06-13 2018-11-06 常熟理工学院 A kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material

Also Published As

Publication number Publication date
CN110060886A (en) 2019-07-26

Similar Documents

Publication Publication Date Title
CN108597906B (en) Preparation method of fiber/graphene/copper sulfide flexible electrode material
CN105088749B (en) A kind of graphene/cotton compliant conductive fabric and preparation method thereof
CN110323451B (en) Multifunctional composite material based on graphene and polymer fibers and preparation method and application thereof
CN111883745B (en) MOF/MXene/CF composite nano-sheet and synthesis method thereof
CN108258334A (en) A kind of composite and flexible electrode, preparation method and application
CN110164709B (en) Preparation method of fiber/graphene/carbon quantum dot/cobalt nickel sulfide flexible electrode material
CN109267047B (en) Preparation method of flexible cloth electrode based on nickel-manganese hydroxide
CN108597905A (en) A kind of preparation method of fiber/graphene/cobalt sulfide nickel flexible electrode material
CN108711520A (en) A kind of preparation method and applications of the oxidation carbon cloth based on polyacrylonitrile
CN108766783A (en) A kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material
CN110729438B (en) Heteroatom-doped porous graphene-modified carbon fiber paper and preparation method and application thereof
CN110060886B (en) Preparation method of fiber/graphene/FeOOF/Ag flexible electrode material
CN113186714B (en) Composite porous carbon material and preparation method thereof
CN109629228A (en) A kind of multifunctional fabric and its preparation method and application
CN110136976B (en) Preparation method of fiber/graphene/carbon quantum dot/FeOOF flexible electrode material
CN110136982B (en) Composite fabric electrode for flexible supercapacitor and preparation and application thereof
CN108766782A (en) A kind of preparation method of fiber/graphene/molybdenum sulfide flexible electrode material
CN109994721B (en) S-Ni-O-C bonding enhancement-based lithium-sulfur battery composite positive electrode material and preparation method thereof
CN115548339B (en) Lithium-sulfur battery interlayer, preparation method thereof and lithium-sulfur battery
CN111128559B (en) Preparation method of fabric-based metal/metal hydroxide flexible composite material
CN114496597B (en) Preparation method and application of electronic reinforced carbon nano-network
CN113012946B (en) Preparation method of phosphorus-doped NiCoB/graphene/fabric supercapacitor electrode material
CN109930140B (en) Preparation method of flexible electrode
BIAN et al. Fabrication of graphene/cotton and MnO2/graphene/cotton composite fabrics as flexible electrodes for electrochemical capacitors
CN114134529B (en) Hydrogen evolution electrode and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant