CN110600277A - Preparation method and application of porous graphene-based composite film material - Google Patents
Preparation method and application of porous graphene-based composite film material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparation method of a porous graphene-based composite film material, which comprises the following steps: (1) preparing a porous graphene dispersion liquid; (2) preparing a carbon nano tube @ pseudocapacitance material dispersion liquid; (3) preparing a composite film material: mixing the porous graphene dispersion liquid and the carbon nanotube @ pseudocapacitance material dispersion liquid, and performing ultrasonic treatment; and (3) carrying out vacuum filtration, naturally drying a filter cake, and stripping to obtain the porous graphene/carbon nanotube @ pseudocapacitance material composite film material. The porous graphene-based composite film material prepared by the invention can be directly used as a flexible electrode material without a conductive agent and a binder, has excellent rate characteristic, high energy/power density and long cycle service life, is low in raw material cost, simple in process and environment-friendly, and has good application prospect in the field of electrode materials of flexible supercapacitors.
Description
Technical Field
The invention relates to structural design and preparation of a flexible composite electrode material, belongs to the technical field of material science and electrochemistry, and particularly relates to a preparation method and application of a porous graphene-based composite film material.
Background
With the rapid development of electronic technology, mobile electronic devices are gradually becoming flexible, light, thin, and wearable. However, the conventional energy storage device (such as a battery) is a rigid product, and when the conventional energy storage device is folded or bent, the electrode material and the current collector are easily separated, the electrochemical performance is reduced, even a short circuit is caused, and a great potential safety hazard exists. Therefore, in order to adapt to the development of a new generation of flexible electronic devices, a novel electrochemical energy storage device which is light, thin and flexible becomes a research hotspot nowadays.
In many energy storage devices, the super capacitor is used as a novel green energy storage device, has the characteristics of high charging and discharging efficiency, long cycle life, high power density and the like, and can make up for the defects of batteries. However, the energy density of the flexible supercapacitor is still low at present, and the electrochemical stability of the device is difficult to guarantee during the bending and folding process, which limits the practical application of the flexible supercapacitor to a certain extent. Therefore, how to improve the energy density of the super capacitor while maintaining the original higher power density and longer cycle life of the super capacitor is a new challenge in the research field of flexible energy storage devices in recent years.
As is well known, the core of flexible supercapacitors is a flexible electrode sheet with high performance. At present, flexible electrode pole pieces mainly comprise two types: a non-conductive flexible matrix adopting high molecular polymers, paper, woven cloth and the like hardly contributes to the capacity of an electrode, and has poor conductivity, so that the energy density and the rapid charge and discharge capacity of a super capacitor are reduced, and the possibility of reaction with an electrolyte exists; and the other one adopts a conductive flexible matrix such as graphene, active substances are attached to the structural units of the flexible matrix skeleton to form an integral flexible electrode, and any conductive agent and binder are not required to be added.
However, the graphene sheet layer is easy to agglomerate, and the application of the graphene sheet layer as a flexible electrode sheet substrate is influenced. The researchers at home and abroad proposeA support is introduced between graphene sheet layers, for example, yamingWang et al self-assemble carbon black particles and graphene nano sheets into a graphene/carbon black composite film flexible electrode material (J.Power Sources,2014,271,269-277), the carbon black particles play a role of spacing the graphene nano sheets and show excellent rate characteristics; however, due to the limitation of the double electric layer energy storage mechanism, the specific capacity of the graphene/carbon black composite film is only 112F g-1. Pooi See Lee et al introduce a pseudocapacitance material between graphene sheets, effectively inhibit the agglomeration of graphene, and improve the specific capacity of a flexible electrode material (adv. Mater.,2013,25(20): 2809-2815); however, for pseudo-capacitive materials, particularly metal oxides, added to graphene-based flexible electrode materials tend to destroy the conductive network of graphene. To solve the problem, Jie Liu et al introduce a third phase of carbon nanotubes into graphene/manganese dioxide powder to improve the conductivity and flexibility of the composite material, and prepare a graphene/manganese dioxide/carbon nanotube composite film (Nano lett, 2012,12(8):4206--1(ii) a However, most electrolyte ions are transmitted and diffused in the direction between graphene layers, and the ion transfer capability in the radial direction is poor, so that the specific capacity of the electrode material is rapidly attenuated under the condition of large-current charging and discharging, the rate characteristic of the electrode material is poor, and the specific capacity retention rate is only 45%.
Therefore, how to improve the specific capacity of the flexible electrode material and ensure the specific capacity retention rate under the condition of large-current charge and discharge becomes a technical problem to be solved in the field.
Disclosure of Invention
In view of the above, the porous graphene prepared by a chemical etching method and the carbon nanotube @ pseudocapacitor material prepared by a hydrothermal method are used as elementary materials, and a thin film material with integrated functions of a three-dimensional ion diffusion channel, an integral conductive network, surface modification, high pseudocapacitor and the like is constructed in a vacuum filtration manner.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a porous graphene-based composite film material comprises the following steps:
(1) preparing a porous graphene dispersion liquid: preparing graphite oxide dispersion liquid by a Hummers method, uniformly dispersing by ultrasonic, adding potassium permanganate and carrying out microwave treatment; after cooling, adding hydrazine hydrate and ammonia water in turn under the stirring condition, and heating the obtained mixed system in a water bath; cooling the solution, adding oxalic acid, and stirring; performing suction filtration and washing, and preparing a filter cake into a porous graphene dispersion liquid by using deionized water;
(2) preparing a carbon nano tube @ pseudocapacitance material dispersion liquid: ultrasonically dispersing the carbon nano tube in a solvent, adding metal oxide, metal salt or metal salt plus alkali to obtain a hydrothermal treatment system, and carrying out hydrothermal treatment; after cooling, carrying out suction filtration, washing and drying, and preparing a carbon nanotube @ pseudocapacitance material dispersion liquid by using deionized water;
(3) preparing a composite film material: mixing the porous graphene dispersion liquid and the carbon nanotube @ pseudocapacitance material dispersion liquid, and performing ultrasonic treatment; and (3) carrying out vacuum filtration, naturally drying a filter cake, and stripping to obtain the porous graphene/carbon nanotube @ pseudocapacitor material, namely the composite film material.
Preparing a composite film material by taking porous graphene prepared by a chemical etching method and a carbon nanotube @ pseudocapacitor material prepared by a hydrothermal method as elements, growing the pseudocapacitor material on the carbon nanotube in situ, and constructing the carbon nanotube @ pseudocapacitor material with high internal conductivity and high external pseudocapacitor, wherein the carbon nanotube @ pseudocapacitor material is supported between graphene layers, so that the graphene sheet layer agglomeration can be inhibited, and an interlayer ion diffusion channel can be built in the graphene sheet layer; the porous graphene is a supporting framework and a conductive network of the composite film material, and a pore channel on a graphene sheet layer ensures that electrolyte ions can be rapidly diffused in the radial direction, so that a three-dimensional developed ion diffusion channel is established, and the porous graphene can also buffer the volume expansion of the pseudo-capacitor material in the charging and discharging processes.
Preferably, in the step (1):
the concentration of the graphite oxide in the graphite oxide dispersion liquid is 0.2-2.0mg mL-1；
The mass ratio of the potassium permanganate to the graphite oxide is 1:1-8: 1;
the dosage of hydrazine hydrate is 0.05-5mL/150mL mixed system;
the dosage of the ammonia water is 0.3-8mL/150mL mixed system.
Preferably, in the step (1):
the microwave treatment time is 5-30min, and the power is 800-;
heating in water bath for 10-60min at 90-100 deg.C;
the dosage of the oxalic acid is 2g/150mL of the mixed system, and the mixed system is stirred for at least 12h after the oxalic acid is added.
Preferably, in the step (2):
the pseudocapacitance material comprises a metal oxide or metal hydroxide;
the metal oxide comprises manganese dioxide, ferric oxide, tin dioxide or vanadium pentoxide;
the metal hydroxide includes nickel hydroxide.
Preferably, in the step (2):
the concentration of the carbon nano tube in the hydrothermal treatment system is 0.1-0.35mg mL-1；
The concentration of the metal oxide or the metal salt in the hydrothermal treatment system is 5-50 mu mol mL-1；
The hydrothermal treatment temperature is 80-240 ℃ and the time is 1-12 h.
Preferably, in the step (3):
the mass ratio of the porous graphene in the porous graphene dispersion liquid to the carbon nano tube @ pseudocapacitance material in the carbon nano tube @ pseudocapacitance material dispersion liquid is 1:4-3: 1.
Further preferably, the mass ratio of the porous graphene to the carbon nanotube @ pseudocapacitance material is 1:1, 1:2, 1:3, 1:4, 2:1 or 3: 1.
The porous graphene-based composite film material prepared by the preparation method.
Preferably, the unit mass of the composite film material is 0.5-2mg cm-2。
An application of a porous graphene-based composite film material as an electrode material in a flexible supercapacitor. In 1Ag-1At current densityThe specific capacitance can reach 200-900F g-1The energy density of the asymmetric super capacitor can reach 20-50Whkg-1After circulation for 2000 times and 10000 times, the service life can reach 60-110% of the initial specific capacity.
According to the technical scheme, the porous graphene-based composite film material prepared by the invention can be directly used as a flexible electrode material without a conductive agent and a binder, has excellent rate characteristic, high energy/power density and long cycle service life, is low in raw material cost, simple in process and environment-friendly, and has a good application prospect in the field of electrode materials of flexible super capacitors.
Drawings
FIG. 1 shows the porous graphene/carbon nanotube @ MnO obtained in example 12A composite film material object photo;
FIG. 2 shows the porous graphene/carbon nanotube @ MnO obtained in example 12SEM pictures of the composite film material under different magnifications;
FIG. 3 shows the porous graphene/carbon nanotube @ MnO obtained in example 12Constant current charge-discharge curve of the composite film material under different current densities;
FIG. 4 shows the porous graphene/carbon nanotube @ MnO obtained in example 12The specific capacity attenuation curve of the composite film material under different current densities;
FIG. 5 shows the porous graphene/carbon nanotubes @ MnO obtained in example 12Cycle life curve of the composite film material;
FIG. 6 shows the porous graphene/carbon nanotube @ MnO obtained in example 12CV curves of asymmetric supercapacitors assembled by taking the composite film material as a positive electrode and taking the porous graphene/carbon nanotube composite film material as a negative electrode at different scanning speeds;
FIG. 7 shows the porous graphene/carbon nanotube @ MnO obtained in example 12The composite film material is an asymmetric supercapacitor power-energy density diagram assembled by a positive electrode and a porous graphene/carbon nanotube composite film material as a negative electrode.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparing a porous graphene dispersion liquid: preparing graphite oxide dispersion liquid by using a Hummers method, wherein the concentration of graphite oxide in the water dispersion liquid is 0.5mg mL-1Carrying out ultrasonic treatment on 100mL of graphite oxide dispersion liquid for 1 hour to uniformly disperse the graphite oxide dispersion liquid; 0.0606g of KMnO was added with constant stirring4Heating with 1000W microwave for 5 min; when the temperature is reduced to room temperature, adding 50mL of deionized water, 100 mu L of hydrazine hydrate and 350 mu L of ammonia water in sequence; after being mixed evenly, the mixture is heated in a water bath at 100 ℃ for 20min, and after being cooled to room temperature, 2g of oxalic acid is added and stirred for at least 12 h; suction filtration, washing the final product to neutrality with deionized water, and preparing into 0.33mg mL-1The porous graphene dispersion liquid of (1).
(2) Carbon nanotube @ MnO2Preparation of the dispersion: 20mg of carbon nanotubes are dispersed in 200mL of deionized water, and 160mg of KMnO is added4And heating in water bath at 80 deg.C for 2 hr; cooling to room temperature, performing suction filtration, washing a product to be neutral by using deionized water, and drying in a forced air oven at the temperature of 80 ℃ for 12 hours; prepared into 0.3mg mL by deionized water-1Carbon nanotube @ MnO of2And (3) dispersing the mixture.
(3) Porous graphene/carbon nanotube @ MnO2Preparing a composite film material: according to porous graphene and carbon nanotubes @ MnO2Measuring the dispersion liquid according to the mass ratio of 1:4, diluting the dispersion liquid to 500mL by using deionized water, and uniformly dispersing the dispersion liquid by ultrasonic treatment; then carrying out vacuum filtration by using a mixed cellulose filter membrane (the aperture is 0.45 mu m); naturally drying the obtained filter cake in the shade, and carefully stripping to obtain the porous graphene/carbon nano tube @ MnO2Composite film materials, as shown in FIGS. 1 and 2The unit mass is 0.5mg cm-2。
(4) Preparing a porous graphene/carbon nanotube composite film material: weighing porous graphene dispersion liquid and carbon nanotubes according to the mass ratio of the porous graphene to the carbon nanotubes of 9:1, diluting the porous graphene dispersion liquid and the carbon nanotubes to 500mL by using deionized water, and uniformly dispersing the porous graphene dispersion liquid and the carbon nanotubes by ultrasonic treatment; then carrying out vacuum filtration by using a mixed cellulose filter membrane (the aperture is 0.45 mu m); naturally drying the obtained filter cake in the shade, and carefully peeling to obtain the porous graphene/carbon nano tube composite film material with the unit mass of 0.5mg cm-2。
Porous graphene/carbon nanotube @ MnO Using the obtained2The composite film material is used as a super capacitor electrode material for electrochemical performance test: preparing the porous graphene/carbon nano tube @ MnO2Cutting the composite film material into 1 × 1cm2Pressing the nickel foam current collector between two pieces of nickel foam current collectors by an oil press under the pressure of 5MPa to prepare the integral electrode without adhesive and conductive agent. Testing the electrochemical performance of the integral electrode by adopting a three-electrode system, wherein the porous graphene/carbon nano tube @ MnO is2The composite film integral electrode, the platinum sheet electrode and the saturated calomel electrode are respectively a working electrode, an auxiliary electrode and a reference electrode, and the electrolyte is 1mol L-1Na2SO4And testing the solution within a voltage range of-0.2-0.8V. All electrochemical tests (cyclic voltammetry, constant current charging and discharging, alternating current impedance) were performed on the Shanghai Chenghua CHI760E electrochemical workstation.
As shown in FIGS. 3-5, at 1Ag-1At current density, its specific capacity can be up to 320F g-1When the current density was increased to 50Ag-1When the specific capacity of the electrode material is up to 230F g-172% of the initial capacity can be maintained, and meanwhile, the capacity retention rate is 110% after 5000 times of testing by using cyclic voltammetry.
Porous graphene/carbon nano tube composite film material is used as a negative electrode, and porous graphene/carbon nano tube @ MnO is used2The composite film material is used as a positive electrode to assemble an asymmetric super capacitor, and the volume of the composite film material is 1mol L-1Na2SO4Under the solution system, the voltage range is 0-1.8VThe test was performed. All electrochemical tests (cyclic voltammetry, constant current charging and discharging, alternating current impedance) were performed on the Shanghai Chenghua CHI760E electrochemical workstation.
As shown in FIGS. 6 and 7, the energy density can reach 26.43Wh kg at most-1。
Example 2
(1) Preparing a porous graphene dispersion liquid: preparing graphite oxide dispersion liquid by using a Hummers method, wherein the concentration of graphite oxide in the water dispersion liquid is 0.2mg mL-1Carrying out ultrasonic treatment on 100mL of graphene oxide suspension for 1h to uniformly disperse the graphene oxide suspension; 0.0545g of KMnO were added with constant stirring4Heating with 800W microwave for 10 min; when the temperature is reduced to room temperature, adding 50mL of deionized water, 200 mu L of hydrazine hydrate and 500 mu L of ammonia water in sequence; after being mixed evenly, the mixture is heated in a water bath at the temperature of 95 ℃ for 40min, and after being cooled to the room temperature, 2g of oxalic acid is added and stirred for at least 12 h; suction filtration, washing the final product to neutrality with deionized water, and preparing into 0.2mg mL-1The porous graphene dispersion liquid of (1).
(2) Carbon nanotube @ Fe2O3Preparation of the dispersion: taking 280mg FeCl3·6H2Adding O into 160mL of deionized water, stirring uniformly, adding 20mg of carbon nano tubes, and performing ultrasonic treatment to uniformly disperse the carbon nano tubes; then transferring the mixture into a high-pressure kettle for hydrothermal treatment at 180 ℃ for 12 h; cooling to room temperature, performing suction filtration, washing with deionized water to neutrality, and drying in a forced air oven at 80 deg.C for 12 h; prepared into 0.5mg mL by deionized water-1Carbon nanotube @ Fe2O3And (3) dispersing the mixture.
(3) Porous graphene/carbon nanotube @ Fe2O3Preparing a composite film material: according to porous graphene and carbon nano tube @ Fe2O3Measuring the dispersion liquid according to the mass ratio of 1:1, diluting the dispersion liquid to 500mL by using deionized water, and uniformly dispersing the dispersion liquid by ultrasonic treatment; then carrying out vacuum filtration by using a mixed cellulose filter membrane (the aperture is 0.45 mu m); naturally drying the obtained filter cake in the shade, and carefully stripping to obtain the porous graphene/carbon nano tube @ Fe2O3The unit mass of the composite film material is 0.8mg cm-2。
Porous graphene/carbon nanotube @ Fe obtained by using2O3The composite film material is used as a super capacitor electrode material for electrochemical performance test: preparing the porous graphene/carbon nano tube @ Fe2O3Cutting the composite film material into 1 × 1cm2Pressing the nickel foam current collector between two pieces of nickel foam current collectors by an oil press under the pressure of 5MPa to prepare the integral electrode without adhesive and conductive agent. Porous graphene/carbon nanotube @ Fe2O3The composite film integral electrode, the platinum sheet electrode and the mercury/mercury oxide electrode are respectively a working electrode, an auxiliary electrode and a reference electrode, and 1mol L of the composite film integral electrode, the platinum sheet electrode and the mercury/mercury oxide electrode are respectively used as a working electrode, an auxiliary electrode and a reference electrode-1The KOH solution is used as electrolyte, electrochemical performance tests are carried out within the voltage range of-1.1-0V, and all electrochemical tests (cyclic voltammetry, constant current charging and discharging and alternating current impedance) are carried out on the Shanghai Chenghua CHI760E electrochemical workstation.
Current density of 1Ag-1Its specific capacity can be up to 982F g-1When the current density was increased to 50Ag-1When the specific capacity of the electrode material is still 509F g-1The initial capacity can be maintained at 52%, and the capacity retention rate is 61% after 2000 times of cyclic voltammetry tests.
Example 3
(1) Preparing a porous graphene dispersion liquid: preparing graphite oxide dispersion liquid by using a Hummers method, wherein the concentration of graphite oxide in the water dispersion liquid is 1mg mL-1Carrying out ultrasonic treatment on 100mL of graphene oxide suspension for 1h to uniformly disperse the graphene oxide suspension; 0.7271g of KMnO were added with constant stirring4Heating with 1200W microwave for 8 min; when the temperature is reduced to room temperature, adding 50mL of deionized water, 500 mu L of hydrazine hydrate and 700 mu L of ammonia water in sequence; after being mixed evenly, the mixture is heated in a water bath at the temperature of 98 ℃ for 30min, and after being cooled to the room temperature, 2g of oxalic acid is added and stirred for at least 12 h; suction filtration, washing the final product with deionized water to neutrality, and preparing into 0.8mg mL-1The porous graphene dispersion liquid of (1).
(2) Carbon nanotube @ Ni (OH)2Preparation of the dispersion: ultrasonically dispersing 20mg of carbon nano tube in 40mL of deionized water, and adding 4mmol of NiCl2·6H2O, after stirring evenlyAdding 40mL of 0.2M NaOH; then transferring the mixture into a high-pressure kettle to perform hydrothermal treatment for 6 hours at 180 ℃; cooling to room temperature, performing suction filtration, washing with deionized water to neutrality, and drying in a forced air oven at 80 ℃ for 12 h; prepared into 0.8mg mL by deionized water-1Carbon nanotube @ Ni (OH)2And (3) dispersing the mixture.
(3) Porous graphene/carbon nanotubes @ Ni (OH)2Preparing a composite film material: according to porous graphene and carbon nanotubes @ Ni (OH)2Measuring the dispersion liquid according to the mass ratio of 1:1, diluting the dispersion liquid to 500mL by using deionized water, and uniformly dispersing the dispersion liquid by ultrasonic treatment; then carrying out vacuum filtration by using a mixed cellulose filter membrane (the aperture is 0.45 mu m); naturally drying the obtained filter cake in the shade, and carefully stripping to obtain porous graphene/carbon nano tube @ Ni (OH)2The unit mass of the composite film material is 0.7mg cm-2。
Use of the porous graphene/carbon nanotubes obtained @ Ni (OH)2The composite film material is used as a super capacitor electrode material for electrochemical performance test: preparing porous graphene/carbon nano tube @ Ni (OH)2Cutting the composite film material into 1 × 1cm2Pressing the nickel foam current collector between two pieces of nickel foam current collectors by an oil press under the pressure of 5MPa to prepare the integral electrode without adhesive and conductive agent. Porous graphene/carbon nanotubes @ Ni (OH)2The composite film integral electrode, the platinum sheet electrode and the mercury/mercury oxide electrode are respectively a working electrode, an auxiliary electrode and a reference electrode, and 1mol L of the composite film integral electrode, the platinum sheet electrode and the mercury/mercury oxide electrode are respectively used as a working electrode, an auxiliary electrode and a reference electrode-1The KOH solution is used as electrolyte, electrochemical performance tests are carried out within the voltage range of 0-0.58V, and all electrochemical tests (cyclic voltammetry, constant current charging and discharging and alternating current impedance) are carried out on the Shanghai Hua CHI760E electrochemical workstation.
When the current density is 1Ag-1Its specific capacity can be up to 617F g-1When the current density was increased to 50Ag-1The specific capacity of the electrode material can still reach 440F g-171% of the initial capacity can be maintained, and meanwhile, the capacity retention rate is 97% after 5000 times of cyclic voltammetry tests.
Porous graphene/carbon nanotubes @ Ni (OH)2The composite film material is used as a positive electrodeExample 2 porous graphene/carbon nanotube @ Fe2O3The composite film material is used as a negative electrode to assemble an asymmetric super capacitor, and the volume of the capacitor is 1mol L-1The energy density can reach 42Whkg at most under the KOH solution system-1。
Example 4
(1) Preparing a porous graphene dispersion liquid: preparing a porous graphene dispersion liquid: preparing graphite oxide dispersion liquid by using a Hummers method, wherein the concentration of graphite oxide in the water dispersion liquid is 0.8mg mL-1Carrying out ultrasonic treatment on 100mL of graphene oxide suspension for 1h to uniformly disperse the graphene oxide suspension; 0.1454g of KMnO was added with constant stirring4Heating with 1100W microwave for 10 min; when the temperature is reduced to room temperature, adding 50mL of deionized water, 200 mu L of hydrazine hydrate and 450 mu L of ammonia water in sequence; after being mixed evenly, the mixture is heated in a water bath at the temperature of 90 ℃ for 60min, and after being cooled to the room temperature, 2g of oxalic acid is added and stirred for at least 12 h; suction filtration, washing the final product with deionized water to neutrality, and preparing into 0.5mg mL-1A porous graphene dispersion of concentration.
(2) Carbon nanotube @ V2O5Preparation of the dispersion: adding 0.2mL of triisopropoxytriantiovanadiumoxide (VOT) into 80mL of isopropanol under stirring, adding 25mg of carbon nano tubes after uniformly stirring, and performing ultrasonic treatment to uniformly disperse the carbon nano tubes; then transferring the mixture into a high-pressure kettle, and carrying out hydrothermal treatment at 200 ℃ for 10 hours; filtering, washing with ethanol, drying in a forced air oven at 80 deg.C for 12h, and baking in air at 320 deg.C for 1 h; prepared into 0.8mg mL by deionized water-1Carbon nanotube @ V2O5And (3) dispersing the mixture.
(3) Porous graphene/carbon nanotube @ V2O5Preparing a composite film material: according to porous graphene and carbon nano tube @ V2O5Measuring the dispersion liquid according to the mass ratio of 1:3, diluting the dispersion liquid to 500mL by using deionized water, and uniformly dispersing the dispersion liquid by ultrasonic treatment; then carrying out vacuum filtration by using a mixed cellulose filter membrane (the aperture is 0.45 mu m); naturally drying the obtained filter cake in the shade, and carefully stripping to obtain the porous graphene/carbon nano tube @ V2O5The unit mass of the composite film material is 1.0mg cm-2。
Porous graphene/carbon nanotube @ V obtained by using2O5The composite film material is used as a super capacitor electrode material for electrochemical performance test: preparing the porous graphene/carbon nano tube @ V2O5Cutting the composite film material into 1 × 1cm2Pressing the nickel foam current collector between two pieces of nickel foam current collectors by an oil press under the pressure of 5MPa to prepare the integral electrode without adhesive and conductive agent. Porous graphene/carbon nanotube @ V2O5The composite film integral electrode, the platinum sheet electrode and the saturated calomel electrode are respectively a working electrode, an auxiliary electrode and a reference electrode, and 1mol L of the composite film integral electrode, the platinum sheet electrode and the saturated calomel electrode are used-1LiNO of3The solution is an electrolyte, electrochemical performance tests are carried out in a voltage range of-0.8-0.2V, and all electrochemical tests (cyclic voltammetry, constant current charging and discharging and alternating current impedance) are carried out on an electrochemical workstation of Chen Hua CHI 760E.
Current density of 1Ag-1When the specific capacity is up to 225F g-1When the current density increased to 50A g-1When the specific capacity of the electrode material is up to 142F g-163% of the initial capacity can be maintained, and meanwhile, the capacity retention rate is 62% after 2000 times of cyclic voltammetry tests.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A preparation method of a porous graphene-based composite film material is characterized by comprising the following steps:
(1) preparing a porous graphene dispersion liquid: preparing graphite oxide dispersion liquid by a Hummers method, uniformly dispersing by ultrasonic, adding potassium permanganate and carrying out microwave treatment; after cooling, adding hydrazine hydrate and ammonia water in turn under the stirring condition, and heating the obtained mixed system in a water bath; cooling the solution, adding oxalic acid, and stirring; performing suction filtration and washing, and preparing a filter cake into a porous graphene dispersion liquid by using deionized water;
(2) preparing a carbon nano tube @ pseudocapacitance material dispersion liquid: ultrasonically dispersing the carbon nano tube in a solvent, adding metal oxide, metal salt or metal salt plus alkali to obtain a hydrothermal treatment system, and carrying out hydrothermal treatment; after cooling, carrying out suction filtration, washing and drying, and preparing a carbon nanotube @ pseudocapacitance material dispersion liquid by using deionized water;
(3) preparing a composite film material: mixing the porous graphene dispersion liquid and the carbon nanotube @ pseudocapacitance material dispersion liquid, and performing ultrasonic treatment; and (3) carrying out vacuum filtration, naturally drying a filter cake, and stripping to obtain the porous graphene/carbon nanotube @ pseudocapacitor material, namely the composite film material.
2. The method for preparing a porous graphene-based composite thin film material according to claim 1, wherein in the step (1):
the graphite oxide concentration in the graphite oxide dispersion liquid is 0.2-2.0mgmL-1；
The mass ratio of the potassium permanganate to the graphite oxide is 1:1-8: 1;
the dosage of hydrazine hydrate is 0.05-5mL/150mL mixed system;
the dosage of the ammonia water is 0.3-8mL/150mL mixed system.
3. The method for preparing a porous graphene-based composite thin film material according to claim 1 or 2, wherein in the step (1):
the microwave treatment time is 5-30min, and the power is 800-;
heating in water bath for 10-60min at 90-100 deg.C;
the dosage of the oxalic acid is 2g/150mL of the mixed system, and the mixed system is stirred for at least 12h after the oxalic acid is added.
4. The method for preparing a porous graphene-based composite thin film material according to claim 1, wherein in the step (2):
the pseudocapacitance material comprises a metal oxide or metal hydroxide;
the metal oxide comprises manganese dioxide, ferric oxide, tin dioxide or vanadium pentoxide;
the metal hydroxide includes nickel hydroxide.
5. The method for preparing a porous graphene-based composite thin film material according to claim 1 or 4, wherein in the step (2):
the concentration of the carbon nano tube in the hydrothermal treatment system is 0.1-0.35mgmL-1；
The concentration of the metal oxide or the metal salt in the hydrothermal treatment system is 5-50 mu molmL-1；
The hydrothermal treatment temperature is 80-240 ℃ and the time is 1-12 h.
6. The method for preparing a porous graphene-based composite thin film material according to claim 1, wherein in the step (3):
the mass ratio of the porous graphene in the porous graphene dispersion liquid to the carbon nano tube @ pseudocapacitance material in the carbon nano tube @ pseudocapacitance material dispersion liquid is 1:4-3: 1.
7. A porous graphene-based composite thin film material prepared by the preparation method of any one of claims 1-6.
8. The porous graphene-based composite film material according to claim 7, wherein the unit mass of the composite film material is 0.5-2mgcm-2。
9. Use of the porous graphene-based composite thin film material of claim 7 or 8 as an electrode material in a flexible supercapacitor.
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| CN112017869A (en) * | 2020-08-19 | 2020-12-01 | 五邑大学 | Self-supporting flexible composite film and preparation method thereof |
| CN113053676A (en) * | 2021-03-18 | 2021-06-29 | 合肥工业大学 | Composite film electrode material, electrode and preparation method thereof |
| CN115116764A (en) * | 2022-07-12 | 2022-09-27 | 安徽大学 | Zinc ion mixed super capacitor positive electrode material CZIF-67-CNTs, preparation method and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112017869A (en) * | 2020-08-19 | 2020-12-01 | 五邑大学 | Self-supporting flexible composite film and preparation method thereof |
| CN113053676A (en) * | 2021-03-18 | 2021-06-29 | 合肥工业大学 | Composite film electrode material, electrode and preparation method thereof |
| CN113053676B (en) * | 2021-03-18 | 2022-07-29 | 合肥工业大学 | Preparation method of NH 2-rGO/CNT/alpha-MnO 2NWs composite film electrode material and electrode |
| CN115116764A (en) * | 2022-07-12 | 2022-09-27 | 安徽大学 | Zinc ion mixed super capacitor positive electrode material CZIF-67-CNTs, preparation method and application |
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