CN110853934A - Three-dimensional dual-function carbon micron tube/nitrogen-doped reduced graphene oxide composite biomass material and preparation method and application thereof - Google Patents

Three-dimensional dual-function carbon micron tube/nitrogen-doped reduced graphene oxide composite biomass material and preparation method and application thereof Download PDF

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CN110853934A
CN110853934A CN201911144408.5A CN201911144408A CN110853934A CN 110853934 A CN110853934 A CN 110853934A CN 201911144408 A CN201911144408 A CN 201911144408A CN 110853934 A CN110853934 A CN 110853934A
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graphene oxide
nitrogen
dimensional
doped reduced
oxide composite
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熊传银
李冰冰
段超
李萌瑞
杨祺
党伟华
赵伟
戴磊
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Shaanxi University of Science and Technology
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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
    • 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
    • H01G11/24—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 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
    • 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
    • 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

Abstract

The invention relates to a three-dimensional dual-function carbon micron tube/nitrogen-doped reduced graphene oxide composite biomass material and a preparation method and application thereof, wherein the preparation method of the biomass material comprises the following steps of 1, immersing fluff into a graphene oxide aqueous solution to obtain the graphene oxide solution loaded with the fluff; and 2, reacting the oxidized graphene solution loaded with the fluff for 3-6 hours at the temperature of 850 ℃ under the protection of the gas containing the nitrogen element to obtain the three-dimensional dual-function carbon micron tube/nitrogen-doped reduced oxidized graphene composite biomass material. The material can be mixed with acetylene black and polytetrafluoroethylene in ethanol to form paste, and the paste is coated on one surface of the foamed nickel and dried to obtain the corresponding electrode material. The material is used as a bifunctional material of a high-performance super capacitor and a high-efficiency ORR catalyst, and can open up a general way for designing and preparing a biomass material with multiple excellent functions such as electrochemical performance, redox reaction performance and the like.

Description

Three-dimensional dual-function carbon micron tube/nitrogen-doped reduced graphene oxide composite biomass material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of biomass materials, and particularly relates to a three-dimensional dual-functional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material and a preparation method and application thereof.
Background
Green energy and electrocatalysts are of great interest to researchers worldwide as two areas of life affecting people today and even in the future. The key to charge storage performance and electrocatalysis remains the material. In addition, with the development of flight technology and the acceleration of life rhythm of people, the requirements of people on the energy storage and catalysis efficiency of materials are higher and higher. As resource and environmental issues become more prominent, it is necessary to combine these two functions.
Graphene (abbreviated as GR) is widely used in supercapacitors, batteries, catalysis, sensors, portable electronics, flexible electronics, foldable displays, and computer chips due to its large specific surface area, low density, and good electrical conductivity. Due to the strong van der waals force existing between the graphene sheet layers, the graphene sheet layers are easy to reassemble, the excellent performance of the graphene is severely limited, and the application of the graphene is further hindered. Thus, making three-dimensional GR is a common consensus that hinders GR sheet reassembly. At present, a plurality of methods are used for preparing pure three-dimensional GR or three-dimensional GR-based hybrid, such as an oriented self-assembly method, a template orientation method, a freezing technology, an electrochemical method, a chemical etching method, a photoetching technology and the like, but the performances of the pure three-dimensional GR material prepared by the methods are limited and single in the aspects of energy storage or electrocatalysts, and the increasing demands of people cannot be met. Therefore, by introducing other components as spacers to prevent the re-fragmentation of the GR, it is a good choice to achieve good functionality with the synergy of both parties.
Researchers often use gaskets such as various metal oxides, conductive polymers or inorganic species, among others, where metal oxides and conductive polymers are unstable and prone to deformation during energy storage or electrocatalysis. There are also some environmental problems. Thus, while inorganic spacers are somewhat functionally inferior to metal oxides and conductive polymers, inorganic spacers are certainly a better choice from an environmental standpoint. The biomass resource is a renewable resource and needs to be changed into an inorganic substance after high-temperature carbonization, and the resource can be utilized for a long time on the premise of reasonable protection and utilization, so that how to use the biomass as a spacer to prevent GR from being broken again is an urgent problem to be solved by utilizing the synergistic effect of the biomass resource and the GR to realize good energy storage and catalytic function utilization.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material, and a preparation method and application thereof.
The invention is realized by the following technical scheme:
a preparation method of a three-dimensional difunctional carbon micron tube/nitrogen-doped reduced graphene oxide composite biomass material comprises the following steps,
step 1, immersing fluff into a graphene oxide aqueous solution to obtain a graphene oxide solution loaded with the fluff;
and 2, reacting the oxidized graphene solution loaded with the fluff for 3-6 hours at the temperature of 850 ℃ under the protection of the gas containing the nitrogen element to obtain the three-dimensional dual-function carbon micron tube/nitrogen-doped reduced oxidized graphene composite biomass material.
Preferably, in step 1, the ratio of the mass of the fluff to the concentration of the graphene oxide aqueous solution is (0.5-1) g: (1-3) g/mL.
Preferably, in step 1, the fluff is immersed in the graphene oxide aqueous solution and then is subjected to ultrasonic treatment for 3-48 hours to obtain the graphene oxide solution loaded with the fluff.
Preferably, the gas containing nitrogen in step 2 is NH3。
Preferably, the villi in step 1 are extracted from poplar seed, phoenix tree seed or willow seed.
The three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material is prepared by the preparation method of the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material.
A preparation method of a three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass electrode material is based on the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass electrode material and comprises the following steps,
step 1, according to (85-95): (22-26): (5-6) mixing the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material according to claim 6, acetylene black and polytetrafluoroethylene in ethanol to form a paste;
and 2, uniformly coating the paste obtained in the step 1 on one surface of the foamed nickel, and then drying the foamed nickel containing the paste to obtain the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass electrode material.
Further, in step 2, the foamed nickel containing paste is dried at 70-90 ℃ for 6-18 h.
The three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass electrode material is prepared by the preparation method of the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass electrode material.
A capacitor containing the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass electrode material.
Compared with the prior art, the invention has the following beneficial technical effects:
the preparation method of the three-dimensional difunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material comprises the steps of soaking to obtain a graphene oxide solution loaded with fluff, and then carrying out high-temperature reaction under the protection of nitrogen-containing gas to obtain a CMT/N-RGO hybrid, wherein the CMT/N-RGO hybrid has a rich porous interlayer structure and is beneficial to the transmission of ions and charges. The improvement of the capacitive and electrocatalytic performances of the hybrid material is mainly related to three factors, firstly, the CMT is used as an isolating agent for RGO re-fracturing, so that the accumulation of N-RGO can be effectively prevented, and the large specific surface area of the N-RGO is fully utilized to obtain large capacitance; secondly, N atoms are introduced to obtain N-RGO, so that the conductivity and wettability of the CMT/N-RGO hybrid can be improved, the high-capacity and good electrocatalyst performance can be provided, additional capacitance can be provided, and the catalytic efficiency of the composite material can be greatly improved; thirdly, the cross-linked CMT in the N-RGO can be used as a bridge for transmitting electrons between N-RGO layers, contributes to a part of the whole capacitance, and is beneficial to fully utilizing the larger specific surface area of GR to store energy, so that the CMT/N-RGO mixed material has huge application potential as a dual-function material of a high-performance super capacitor and a high-efficiency ORR catalyst, and a universal way is opened for designing and preparing various nano composite material-based biomass materials with multiple excellent functions such as electrochemical performance, excellent oxidation-reduction reaction performance and the like.
Furthermore, CMT made of poplar, phoenix tree or willow filler not only can realize sustainable utilization of waste resources, but also can solve some environmental problems caused by fluff,
the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material can be used for preparing a high-performance super capacitor, can be used as a high-efficiency oxidation-reduction reaction catalyst, has high coulombic efficiency, good capacitance performance and high reversible Faraday reaction, and has wide application prospects in super capacitors and electrocatalysts; the application of the biomass material obviously improves the energy density and the cycle stability of the battery.
The invention relates to a preparation method of a three-dimensional bifunctional carbon micron tube/nitrogen-doped reduced graphene oxide composite biomass electrode material. Common electrocatalytic oxygen reduction (ORR) catalysts are divided into platinum-based noble metal catalysts and non-noble metal catalysts in terms of components, and the materials adopt catalytic electrode materials prepared from biomass materials, so that the cost is reduced, and the problems of cost and pollution caused by using excessive noble metals are avoided.
The composite biomass electrode material has excellent supercapacitor performance, and a symmetrical supercapacitor can be constructed by taking the mixed material as an electrode, so that the composite biomass electrode material has the characteristics of high charging and discharging speed, good speed performance, 95% of capacitance retention rate and 65% -77% of energy efficiency.
Drawings
FIG. 1 is a flow chart of the preparation of the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material of the present invention.
FIG. 2 is an SEM photograph of CMT prepared in example 1 of the present invention at a magnification of 10 μm.
FIG. 3 is an SEM photograph of CMT prepared in example 1 of the present invention at a magnification of 1 μm.
FIG. 4 is an SEM photograph of CMT/N-RGO prepared in example 1 of the present invention at a magnification of 10 μm.
FIG. 5 is an SEM photograph of CMT/N-RGO prepared in example 1 of the present invention at a magnification of 1 μm.
FIG. 6 is a graph showing a spectrum test of CMT/N-RGO prepared in example 1 of the present invention.
FIG. 7a is a graph of voltage versus current density for CMT/N-RGO prepared in example 1 of the present invention at various scan rates.
FIG. 7b is a charge and discharge curve of CMT/N-RGO prepared in example 1 of the present invention at different current densities.
FIG. 7c is a graph of specific capacitance and energy efficiency for CMT/N-RGO prepared in example 1 of the present invention at different current densities.
FIG. 8 is a CMT polarization curve for CMT/N-RGO prepared in example 1 of the present invention and conventional Pt/C, comparative example.
FIG. 9 shows the CMT/N-RGO at O prepared in example 1 of the present invention2With N in saturated KOH (0.1M) solution2Is shown by comparison of the electrocatalytic redox activity curves of saturated KOH (0.1M) solution (A).
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention combines an impregnation method and a chemical vapor deposition method to prepare a novel environment-friendly sustainable-development three-dimensional dual-functional carbon nanotube/nitrogen-doped reduced graphene oxide (CMT/N-RGO) composite biomass material, which comprises the following steps,
step 1, extracting graphene oxide from natural graphite by adopting an improved Hummers method, wherein due to the fact that oxygen-containing functional groups are added to the graphene oxide, agglomeration among graphene sheets is reduced, and a premise is provided for uniform mixing with fluff, then 0.5-1g of the fluff is immersed into a graphene oxide aqueous solution with the concentration of 1-3g/mL for ultrasonic immersion for 3-48h, and the color of the fluff is changed from white to yellow, so that the graphene oxide solution is successfully loaded on the fluff, and the fluff can be extracted from poplar seed, phoenix tree seed and willow seed;
step 2, adding 0.5-1.5g of the graphene oxide solution loaded with the fluff into a CVD tube furnace, and introducing NH with the flow rate of 400-3As the ammonia gas contains N element, CMT/N-RGO hybrid products can be obtained after reaction for 3-6 h.
Then, the CMT/N-RGO hybrid product can be further made into a biomass electrode, comprising the following steps,
step 3, weighing 85-95mg of CMT/N-RGO hybrid sample, 22-26mg of acetylene black and 5-6mg of polytetrafluoroethylene respectively, mixing in an agate tank, adding ethanol into the mixture to grind the mixture into paste by taking the polytetrafluoroethylene as a binder;
step 4, cutting the foamed nickel into round sheets with the diameter of 1-1.2cm, uniformly coating the paste on one surface of the foamed nickel, taking the foamed nickel as a collecting agent, and covering the foamed nickel with CMT/N-
The nickel foam of RGO is dried in a vacuum drying oven at 70-90 deg.C for 6-18h, and then the sample prepared as the electrode material is taken out.
For comparison, the CMT/N-RGO in step 4 was replaced with pure CMT obtained by reacting fluff directly in a CVD tube furnace at 800-850 ℃ for 3-6h, nickel foam covered with pure CMT was dried in a vacuum drying oven at 70-90 ℃ for 6-18h, and the prepared sample was then taken out.
The two different covers have two considerations, the first is to compare the performance, the second is to assemble a symmetrical electrode capacitor and an asymmetrical electrode capacitor, wherein the symmetry and the asymmetry mean that the two electrode materials are the same or different, the assembly of the capacitor is simple, and a diaphragm is placed between the electrode materials of the same material or different component materials.
Example 1
A preparation method of a nitrogen-doped reduced graphene oxide biomass-coated carbon nanotube is shown in figure 1 and comprises the following steps,
step 1, extracting villus from poplar catkins, extracting graphene oxide from natural graphite by adopting an improved Hummers method, then immersing 1g of villus into a graphene oxide aqueous solution with the concentration of 2mg/mL for ultrasonic soaking for 48 hours, wherein the color of the villus is changed from white to yellow, which indicates that the graphene oxide solution is successfully loaded on the villus;
step 2, adding 1g of the graphene oxide solution loaded with fluff into a CVD (chemical vapor deposition) tube furnace, and introducing NH with the flow rate of 600ml/min at 800 DEG C3Reacting for 4h to obtain a CMT/N-RGO hybrid product;
step 3, weighing 90mg of CMT/N-RGO hybrid sample, 24mg of acetylene black and 6mg of polytetrafluoroethylene respectively, mixing in an agate tank, taking the polytetrafluoroethylene as a binder, adding ethanol, and grinding into paste;
and 4, cutting the foamed nickel into circular sheets with the diameter of 1cm, uniformly coating the paste on one surface of the foamed nickel, taking the foamed nickel as a collecting agent, drying the nickel foam covered with the CMT/N-RGO in a vacuum drying oven at 80 ℃ for 15 hours, and taking out a sample.
For comparison, the CMT/N-RGO in step 4 was replaced with pure CMT, which was obtained by reacting fluff directly in a CVD tube furnace at 800 ℃ for 4h, and the nickel foam covered with pure CMT was dried in a vacuum drying oven at 80 ℃ for 15h, after which the prepared sample was taken out.
Fig. 2 shows the microtubes in the graph, fig. 3 shows the specific microtubes, fig. 4 shows that the sheet-shaped reduced graphene oxide is interwoven with the carbon microtubes, fig. 5 shows the reduced graphene oxide with folds on the surface, and fig. 6 shows that the material element contains C, N, O through the energy spectrum test, and the material is successfully doped with N element, which indicates that the carbon microtube composite material doped with N element is successfully prepared.
FIG. 7a CMT/N-RGO Material at 10mV s-1At different scan rates, the current density-voltage curve is substantially rectangular, indicating good cycling stability, up to 200mV s-1The curve is still substantially rectangular, indicating that it has good cycling stability over a range of scans. FIG. 7b shows from the charge and discharge curves that the charge and discharge time of the CMT/N-RGO material is substantially the same as the charge and discharge time at different charge and discharge rates, and both have faster charge and discharge rates, and when the charge and discharge rates are increased within the voltage range of 0-1V, the corresponding charge and discharge times are proportionally reduced, which indicates that the material has good charge and discharge cycle stability and is suitable for working at different charge and discharge rates. FIG. 7c is a plot of specific capacitance versus current density versus energy efficiency versus current density, showing that the CMT/N-RGO material is at 8Ag-1The specific capacitance of the capacitor can reach 200F g at the current density of-1While the energy efficiency was 56%, when the current density was increased to 40Ag-1When the specific capacitance is 140F g-1The corresponding energy efficiency is changed from 65 percent to 65 percent, the material has good speed performance, and the figure shows that the energy efficiency of the material is basically kept near 60 percent, and the material shows higher energy efficiency, which shows that the material has higher reversible Faraday reaction in the charge-discharge process, and the process of storing charges not only includesIncluding storage on the electric double layer and including storage of charge in the electrode by redox reactions of ions in the electrolyte in the electrode active material.
In FIG. 8, the CMT/N-RGO hybrid product as a high efficiency electrocatalyst for oxidation-reduction reaction has a positive initial potential of-0.12V and a half-wave potential of-0.21V, which is comparable to industrial Pt/C (-0.05V and-0.1V) electrodes and can be used as a high efficiency electrocatalyst for oxidation-reduction reaction.
The SSA value of the nitrogen-doped reduced graphene oxide-coated biomass material CMT/N-RGO hybrid product obtained in the embodiment is 418m2g-1270m higher than CMT2g-1It shows that the SSA value of the CMT/N-RGO hybrid product is greatly improved, which is beneficial to charge storage. When the scanning rate is from 10mV s-1Increase to 200mV s-1In the process, the capacitance retention rate of the CMT/N-RGO is still 93 percent higher than that of 75 percent CMT during the test, which shows that the material has good capacitance performance.
FIG. 9 detection of CMT/N-RGO Material at O Using polarization curves2With N in saturated KOH (0.1M) solution2The electrocatalytic redox activity of the saturated KOH (0.1M) solution of (A) was compared and the results showed that the activity was reduced to O2The saturated KOH (0.1M) solution has obvious O in the range of-0.35V to-0.4V2Decrease in peak value, accounting for CMT/N-RGO electrolyzed water and reduced O2Mixed catalytic properties of (2).
For the electrocatalytic oxygen reduction (ORR) test method and means in FIG. 9, the ORR test working electrode was prepared by dispersing CMT/N-RGO in 2.0mL of mixed solution with a water to ethanol volume ratio of 1: 3. In the presence of 1.5M Li2SO4In the aqueous electrolyte and the solid electrolyte composed of PVA and KOH, electrochemical performance test is carried out on the synthesized hybrid product. And (3) ultrasonically dispersing the mixed solution, adding 100 mu L of electrolyte solution until the mixed solution is uniformly suspended, and then treating the mixed solution by ultrasonic waves for 60 minutes to obtain final uniform ink, wherein the ink is formed by uniformly dispersing carbon black and an additive. Then, 10. mu.L of uniform ink was dropped onto the surface of the glassy carbon electrodeDrying at room temperature. A0.1M KOH aqueous solution is used as an electrolyte, a platinum wire and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, and the counter electrode is connected with a working electrode and a counter electrode during testing, wherein the working electrode is connected with a material, the counter electrode is connected with the platinum wire (similar to a positive electrode and a negative electrode), and the reference electrode and the working electrode are connected with the material together and used as a reference. All potentials were normalized to Reversible Hydrogen Electrode (RHE) according to equation 1:
E(RHE)＝E(SCE)+0.998 V (1)
example 2
A preparation method of a nitrogen-doped reduced graphene oxide coated biomass carbon nanotube comprises the following steps,
step 1, extracting villus from phoenix tree batting, extracting graphene oxide from natural graphite by adopting an improved Hummers method, and then soaking 0.5g of villus in a graphene oxide aqueous solution with the concentration of 1mg/mL for 3 hours in an ultrasonic mode, wherein the color of the villus is changed from white to yellow, which indicates that the graphene oxide solution is successfully loaded on the villus;
step 2, adding 0.5g of the chorionic graphene oxide solution into a CVD (chemical vapor deposition) tube furnace, and introducing NH with the flow rate of 400ml/min at 850 DEG C3Reacting for 3h to obtain a CMT/N-RGO hybrid product;
step 3, weighing 85mg of CMT/N-RGO hybrid sample, 22mg of acetylene black and 5mg of polytetrafluoroethylene respectively, mixing in an agate tank, taking the polytetrafluoroethylene as a binder, adding ethanol, and grinding into paste;
and 4, cutting the foamed nickel into circular sheets with the diameter of 1.1cm, uniformly coating the paste on one surface of the foamed nickel, taking the foamed nickel as a collecting agent, drying the nickel foam covered with the CMT/N-RGO in a vacuum drying oven at 70 ℃ for 6 hours, and taking out a sample.
Example 3
A preparation method of a nitrogen-doped reduced graphene oxide coated biomass carbon nanotube comprises the following steps,
step 1, extracting villus from catkin, extracting graphene oxide from natural graphite by adopting an improved Hummers method, then immersing 0.6g of villus into a graphene oxide aqueous solution with the concentration of 3mg/mL for 10 hours by ultrasonic immersion, wherein the color of the villus is changed from white to yellow, which indicates that the graphene oxide solution is successfully loaded on the villus;
step 2, adding 1.5g of the graphene oxide solution loaded with fluff into a CVD (chemical vapor deposition) tube furnace, and introducing NH with the flow rate of 500ml/min at 810 DEG C3Reacting for 5h to obtain a CMT/N-RGO hybrid product;
step 3, respectively weighing 95mg of CMT/N-RGO hybrid sample, 23mg of acetylene black and 6mg of polytetrafluoroethylene, mixing in an agate tank, taking the polytetrafluoroethylene as a binder, adding ethanol, and grinding into paste;
and 4, cutting the foamed nickel into circular sheets with the diameter of 1.2cm, uniformly coating the paste on one surface of the foamed nickel, taking the foamed nickel as a collecting agent, drying the nickel foam covered with the CMT/N-RGO in a vacuum drying oven at 90 ℃ for 8 hours, and taking out a sample.
Example 4
A preparation method of a nitrogen-doped reduced graphene oxide coated biomass carbon nanotube comprises the following steps,
step 1, extracting villus from poplar catkins, extracting graphene oxide from natural graphite by adopting an improved Hummers method, then soaking 0.8g of villus in a graphene oxide aqueous solution with the concentration of 1.5mg/mL for 20 hours by ultrasonic waves, wherein the color of the villus is changed from white to yellow, which indicates that the graphene oxide solution is successfully loaded on the villus;
step 2, adding 0.8g of the chorionic graphene oxide solution into a CVD (chemical vapor deposition) tube furnace, and introducing NH with the flow rate of 450ml/min at 820 DEG C3Reacting for 6h to obtain a CMT/N-RGO hybrid product;
step 3, weighing 92mg of CMT/N-RGO hybrid sample, 24mg of acetylene black and 5mg of polytetrafluoroethylene respectively, mixing in an agate tank, taking the polytetrafluoroethylene as a binder, adding ethanol, and grinding into paste;
and 4, cutting the foamed nickel into circular sheets with the diameter of 1cm, uniformly coating the paste on one surface of the foamed nickel, taking the foamed nickel as a collecting agent, drying the nickel foam covered with the CMT/N-RGO in a vacuum drying oven at 75 ℃ for 10 hours, and taking out a sample.
Example 5
A preparation method of a nitrogen-doped reduced graphene oxide coated biomass carbon nanotube comprises the following steps,
step 1, extracting villus from catkin, extracting graphene oxide from natural graphite by adopting an improved Hummers method, and then soaking 0.9g of villus in a graphene oxide aqueous solution with the concentration of 2.5mg/mL for 30 hours in an ultrasonic mode, wherein the color of the villus is changed from white to yellow, which indicates that the graphene oxide solution is successfully loaded on the villus;
step 2, adding 1.2g of the chorionic graphene oxide solution into a CVD (chemical vapor deposition) tube furnace, and introducing NH with the flow rate of 550ml/min at 830 DEG C3Reacting for 5.5h to obtain a CMT/N-RGO hybrid product;
step 3, weighing 88mg of CMT/N-RGO hybrid sample, 25mg of acetylene black and 5.5mg of polytetrafluoroethylene respectively, mixing in an agate tank, adding ethanol into the mixture to grind the mixture into paste, wherein the polytetrafluoroethylene is used as a binder;
and 4, cutting the foamed nickel into circular sheets with the diameter of 1.1cm, uniformly coating the paste on one surface of the foamed nickel, taking the foamed nickel as a collecting agent, drying the nickel foam covered with the CMT/N-RGO in a vacuum drying oven at 85 ℃ for 18h, and taking out a sample.
Example 6
A preparation method of a nitrogen-doped reduced graphene oxide coated biomass carbon nanotube comprises the following steps,
step 1, extracting villus from phoenix tree batting, extracting graphene oxide from natural graphite by adopting an improved Hummers method, and then soaking 1g of villus in a graphene oxide aqueous solution with the concentration of 2mg/mL for 40 hours in an ultrasonic mode, wherein the color of the villus is changed from white to yellow, which indicates that the graphene oxide solution is successfully loaded on the villus;
step 2, adding 0.6g of the chorionic graphene oxide solution into a CVD (chemical vapor deposition) tube furnace, and introducing NH with the flow rate of 580ml/min at 840 DEG C3Reacting for 4.5h to obtain a CMT/N-RGO hybrid product;
step 3, weighing 90mg of CMT/N-RGO hybrid sample, 26mg of acetylene black and 5.5mg of polytetrafluoroethylene respectively, mixing in an agate tank, adding ethanol into the mixture to grind the mixture into paste, wherein the polytetrafluoroethylene is used as a binder;
and 4, cutting the foamed nickel into circular sheets with the diameter of 1.2cm, uniformly coating the paste on one surface of the foamed nickel, taking the foamed nickel as a collecting agent, drying the nickel foam covered with the CMT/N-RGO in a vacuum drying oven at 88 ℃ for 18h, and taking out a sample.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principles of the present invention are intended to be included within the scope of the embodiments of the present invention.

Claims (10)

1. A preparation method of a three-dimensional difunctional carbon micron tube/nitrogen-doped reduced graphene oxide composite biomass material is characterized by comprising the following steps of,
step 1, immersing fluff into a graphene oxide aqueous solution to obtain a graphene oxide solution loaded with the fluff;
and 2, reacting the oxidized graphene solution loaded with the fluff for 3-6 hours at the temperature of 850 ℃ under the protection of the gas containing the nitrogen element to obtain the three-dimensional dual-function carbon micron tube/nitrogen-doped reduced oxidized graphene composite biomass material.
2. The preparation method of the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material according to claim 1, wherein in the step 1, the ratio of the mass of the fluff to the concentration of the graphene oxide aqueous solution is (0.5-1) g: (1-3) g/mL.
3. The preparation method of the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material according to claim 1, wherein in the step 1, the fluff is immersed in the graphene oxide aqueous solution and then subjected to ultrasonic treatment for 3-48h to obtain the graphene oxide solution loaded with the fluff.
4. The method for preparing the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material according to claim 1, wherein the nitrogen-containing gas in the step 2 is NH3。
5. The method for preparing the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material according to claim 1, wherein the villus in the step 1 is extracted from poplar seed, phoenix tree seed or willow seed.
6. The three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material is prepared by the preparation method of the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material according to any one of claims 1 to 5.
7. A preparation method of a three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass electrode material is characterized by comprising the following steps based on claim 6,
step 1, according to (85-95): (22-26): (5-6) mixing the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass material according to claim 6, acetylene black and polytetrafluoroethylene in ethanol to form a paste;
and 2, uniformly coating the paste obtained in the step 1 on one surface of the foamed nickel, and then drying the foamed nickel containing the paste to obtain the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass electrode material.
8. The preparation method of the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass electrode material according to claim 7, wherein in the step 2, the foamed nickel containing the paste is dried at 70-90 ℃ for 6-18 h.
9. The three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass electrode material is prepared by the preparation method of the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass electrode material according to any one of claims 7 to 8.
10. A capacitor comprising the three-dimensional bifunctional carbon nanotube/nitrogen-doped reduced graphene oxide composite biomass electrode material of claim 9.
CN201911144408.5A 2019-11-20 2019-11-20 Three-dimensional dual-function carbon micron tube/nitrogen-doped reduced graphene oxide composite biomass material and preparation method and application thereof Pending CN110853934A (en)

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