Carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode and its preparation method and application

Abstract

The present invention discloses a carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode and its preparation method and application. The preparation method comprises the following steps: using bamboo powder and bamboo fiber as base materials, using a thermosetting water-based phenolic resin as an adhesive, adding carbon fiber, and obtaining a core layer material through pressing; using bamboo veneer as an interlayer material, alternately stacking one layer of interlayer material and one layer of core layer material in sequence to form a laminated structure, and obtaining a carbon fiber composite bamboo-based laminated structure wood ceramic matrix material through hot pressing and vacuum sintering; then assembling carbon nanotubes and graphene through vacuum pressure impregnation deposition to obtain a polypyrrole-anchored carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode. The carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode of the present invention has the advantages of being green and environmentally friendly, having stable chemical properties, long cycle service life, large specific capacitance, etc., and has good practical value.

Description

Technical Field

[0001] The present invention belongs to the technical field of new energy supercapacitors, and particularly relates to a carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode, a preparation method thereof, and an application thereof. Background Art

[0002] As a renewable resource, biomass materials are widely sourced and inexpensive, and the use of biomass materials for electrode materials has a long history. In recent years, intelligent electronic products have developed rapidly, and the requirements for energy storage electrodes for mobile terminals, intelligent wearable devices, etc. have been developing towards high energy and high power density. At present, the use of the hierarchical pore structure of biomass materials to prepare advanced energy storage materials through artificial coupling has attracted much attention in the energy field. However, using biomass materials as raw materials, the biomass bulk carbon-based electrodes prepared by existing preparation methods have deficiencies such as high brittleness and small specific capacitance. Therefore, how to obtain an electrode material that is safe, efficient, inexpensive, stable, and has a large specific capacitance is of great practical significance for realizing clean, low-carbon, and green and efficient energy storage and conversion. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode that is green and environmentally friendly, has stable chemical properties, a long cycle service life, and a large specific capacitance, a preparation method thereof, and an application thereof.

[0004] To solve the above technical problems, the present invention adopts the following technical solutions.

[0005] A preparation method of a carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode includes the following steps:

[0006] (1) Using bamboo powder and bamboo fiber as base materials, using thermosetting water-based phenolic resin as an adhesive, adding carbon fiber, and then obtaining a core layer material through pressing; the length of the carbon fiber is <5 mm;

[0007] (2) Using bamboo veneer as an interlayer material, alternately stacking one layer of interlayer material and one layer of core layer material in sequence to form a laminated structure, and obtaining a blank through hot pressing;

[0008] (3) Vacuum sintering the blank obtained in step (2) at 850 °C to 1200 °C to obtain a carbon fiber composite bamboo-based laminated structure wood ceramic matrix material;

[0009] (4) Mixing a conductive polymer monomer, ethanol, and water to obtain a mixed solution A; the conductive polymer monomer is pyrrole; mixing carbon nanotubes and graphene to obtain a mixture; mixing the mixture, the mixed solution A, and a dispersant, and obtaining a mixed solution B through dispersion;

[0010] (5) Immerse the carbon fiber composite bamboo-based laminated structural wood ceramic matrix material obtained in step (3) into the mixed solution B obtained in step (4), and perform vacuum pressure impregnation to obtain a wood ceramic sample;

[0011] (6) Immerse the wood ceramic sample obtained in step (5) into water, add hydrogen peroxide dropwise, stir, wash, and dry to obtain a polypyrrole-anchored carbon nanotube / graphene assembled carbon fiber composite laminated structural wood ceramic electrode.

[0012] In the above preparation method, preferably, in step (4), the mass ratio of water, ethanol, and the conductive polymer monomer is 100∶20∶1 - 10.

[0013] In the above preparation method, preferably, in step (4), the mass ratio of carbon nanotubes and graphene is 1∶1, the mass ratio of the mixture, mixed solution A, and the dispersant is 10∶100∶0.5, and the dispersant is sodium dodecylbenzenesulfonate.

[0014] In the above preparation method, preferably, in step (2), the thickness of the core layer material is 0.5 mm - 2 mm, and the thickness of the bamboo veneer is 0.3 mm - 0.6 mm.

[0015] In the above preparation method, preferably, in step (5), the specific process of the vacuum pressure impregnation is as follows:

[0016] S1. Place the carbon fiber composite bamboo-based laminated structural wood ceramic matrix material in an impregnation device, evacuate to -0.09 MPa, and hold for 30 min;

[0017] S2. Add the mixed solution B to the impregnation device, hold for 60 min, then pressurize to 0.7 MPa, continue to hold for 60 min, and take out the matrix material;

[0018] S3. Repeat steps S1 and S2 to perform repeated treatment on the matrix material; the number of repetitions is 2 times.

[0019] In the above preparation method, preferably, in step (1), the particle size of the bamboo powder < 40 mesh, the length of the bamboo fiber < 20 mm, the mass ratio of carbon fiber to the base material is 2∶100, the pressing temperature is 60 °C, and the density of the core layer material is 0.5 g / cm 3 .

[0020] In the above preparation method, preferably, in step (2), the hot pressing temperature is 135 °C, and the density of the blank is 0.6 g / cm 3; Before use, the bamboo veneer includes the following treatments: immersing the bamboo veneer in a thermosetting aqueous phenolic resin for 30 min, taking it out, and draining; the mass concentration of the thermosetting aqueous phenolic resin is 50%;

[0021] And / or, in step (3), the time of the vacuum sintering is 2 h;

[0022] And / or, in step (4), the time of the dispersion is 30 min, and the dispersion is ultrasonic dispersion.

[0023] For the above preparation method, preferably, in step (6), the mass ratio of water to hydrogen peroxide is 10:1, the mass concentration of the hydrogen peroxide is 10%, the pH value of the hydrogen peroxide is 4.5, stirring is continuously carried out during the dropping of the hydrogen peroxide, the dropping rate of the hydrogen peroxide is 20 drops / min, and the rotation speed of the stirring is 100 r / min.

[0024] As a general technical concept, the present invention also provides a carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode prepared by the above preparation method.

[0025] As a general technical concept, the present invention also provides an application of the above carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode in a supercapacitor.

[0026] Compared with the prior art, the advantages of the present invention are:

[0027] (1) The present invention provides a preparation method of a carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode. A mixture of bamboo powder (particle size < 40 mesh), bamboo fiber (length < 20 mm), carbon fiber (length < 5 mm) and thermosetting waterborne phenolic resin is used as the core layer material, and bamboo veneer is used as the interlayer material. They are alternately stacked in sequence (one layer of bamboo veneer and one layer of core layer material) to form a laminated structure. After hot pressing and vacuum sintering, a carbon fiber composite bamboo-based laminated structure wood ceramic matrix material is obtained. Then, carbon nanotubes (CNTs) and graphene (Gr) are assembled by vacuum pressure impregnation deposition, and the conductive polymer polypyrrole (PPy) is used to anchor the carbon nanotubes and graphene to prevent them from falling off, thereby obtaining a bulk carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode. The carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode of the present invention uses the laminated structure wood ceramic bracket as the charge and discharge platform, graphene and carbon nanotubes as the energy storage active substances, and at the same time uses the conductive polymer polypyrrole to anchor them to prevent them from falling off, jointly constructing a carbon fiber composite laminated structure wood ceramic electrode, which will give full play to the multiple synergistic energy storage functions of the laminated structure, biomass porous carbon, graphene and carbon nanotubes, effectively improving the specific capacitance. Specifically, on the one hand, the matrix material of the laminated structure is a new type of layered porous carbon-based material made of sheet-like biomass materials as the basic structural unit, which preserves the multi-level pore structure of the biomass substrate to a certain extent, and also has the characteristics of light weight and good chemical corrosion resistance. It can be used as the carrier of the energy storage electrode material active substance, and the laminated structure has unique advantages in preparing energy storage electrodes. Its layered structure can be regarded as the superposition of multiple electrode sheets, which can improve the specific capacitance. More importantly, the addition of short carbon fibers can not only enhance the matrix material, but also further improve its conductivity; on the other hand, as new carbon-based materials, graphene and carbon nanotubes are light in weight, good in electrical conductivity and excellent in mechanical properties. The assembly of carbon nanotubes and graphene can not only improve the pore structure of the matrix material, but also increase the specific surface area of the matrix material, thereby ultimately improving the energy and power density of the electrode. In addition, in the present invention, the waste bamboo powder and fiber are used as the core layer, which is low in price and wide in source, meeting the national industrial development direction. The preparation method of the present invention has the advantages of simple process, low cost, safety, high efficiency, etc.; the obtained carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode does not require a metal current collector and can be directly used as an electrode material, having the advantages of environmental protection, stable chemical properties, long cycle service life, large specific capacitance, etc., and having good practical value.

[0028] (2) The preparation method of the present invention optimizes the mass ratio of water, ethanol, and the conductive polymer monomer to 100∶20∶1 - 10. By optimizing the ratio of the three, the cost can be effectively controlled, and at the same time, the performance of the electrode can be improved. When the amount of the conductive polymer monomer is too low, a continuous polymer cannot be formed, and the anchoring effect on the carbon nanotubes is small, which easily leads to the shedding of the carbon nanotubes during use and affects the service life. When the amount of the conductive polymer monomer is large, on the one hand, it is easy to cause waste, and on the other hand, it is easy to accumulate and form a relatively thick polymer film during polymerization. Although it can play a good anchoring role, the conductivity of the conductive polymer is far worse than that of the laminated structure wood ceramic, which will increase the resistance of the electrode and is not conducive to the high-speed transmission of electrons, thereby affecting the energy storage performance of the electrode.

[0029] (3) The preparation method of the present invention optimizes the thickness of the core layer material to 0.5 mm - 2 mm and the thickness of the bamboo veneer to 0.3 mm - 0.6 mm, making the energy storage performance of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode more excellent. The specific reason is that two sandwich layers and one core layer form a structural unit. Since the pore structure and specific surface area of the core layer material are superior to those of the sandwich layer material, it plays a greater role in energy storage. However, too thick core layer and sandwich layer will increase the storage and transmission distance of electrons and ions, which is not conducive to their high-speed movement, especially when the sandwich layer is relatively thick. Description of the Drawings

[0030] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.

[0031] Figure 1 It is the microstructural diagram of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode prepared in Example 1 of the present invention.

[0032] Figure 2 It is the CV and GCD curve diagrams of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode prepared in Example 2 of the present invention. Detailed Embodiments

[0033] The following further describes the present invention with reference to the accompanying drawings of the specification and specific preferred embodiments, but does not limit the protection scope of the present invention thereby. The materials and instruments used in the following embodiments are all commercially available.

[0034] Example 1:

[0035] A preparation method of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode of the present invention includes the following steps:

[0036] (1) Bamboo powder and bamboo fiber of equal mass were used as the base material, thermosetting water-based phenolic resin was used as the adhesive, and short carbon fiber with a mass fraction of 2% was added based on the mass of the base material. The mixture was pressed at 60°C into a film with a thickness of 0.5 mm and a density of 0.5 g / cm 3 The thin sheet is the core layer material; wherein the particle size of bamboo powder is less than 40 mesh, the length of bamboo fiber is less than 20 mm, and the length of short carbon fiber is less than 5 mm.

[0037] (2) Cutting bamboo veneer with a thickness of 0.3 mm into the same size as the core layer, and then immersing it in a thermosetting water-based phenolic resin with a mass concentration of 50%, taking it out after 30 minutes, draining it, and obtaining a sandwich material.

[0038] (3) A layer of sandwich material and a layer of core material are alternately stacked and assembled, and hot pressed at 135°C for 10 minutes to obtain a blank with a laminated structure, the density of which is 0.6 g / cm 3 .

[0039] (4) The blank obtained in step (3) is sintered at 850° C. for 2 h under vacuum to obtain a short carbon fiber composite bamboo-based laminated structure wood ceramic matrix material.

[0040] (5) Water, ethanol and pyrrole monomers are mixed at a mass ratio of 100:20:1 to prepare a water-ethanol-pyrrole solution; carbon nanotubes and graphene are fully mixed at a mass ratio of 1:1 to obtain a low-dimensional carbon material mixture; 10 g of the low-dimensional carbon material mixture is added to 100 g of the water-ethanol-pyrrole mixed solution, and then 0.5 g of sodium dodecylbenzene sulfonate is added as a dispersant, and ultrasonic dispersion is performed for 30 minutes to obtain a mixed solution B.

[0041] In this step, the carbon nanotubes and graphene are effectively dispersed by using a dispersant, which can reduce agglomeration, thereby facilitating the carbon nanotubes and graphene to be evenly distributed in the matrix during subsequent assembly.

[0042] (6) placing the short carbon fiber composite bamboo-based laminated structure wood ceramic matrix material obtained in step (4) in an impregnation tank, evacuating to -0.09 MPa, maintaining for 30 min, and sucking in the mixed solution B obtained in step (5), maintaining for 60 min; then pressurizing to 0.7 MPa, maintaining for 60 min, and then releasing the mixed solution B from the impregnation tank.

[0043] (7) After repeating step (6) twice, the matrix material is taken out to obtain a laminated structure wood ceramic sample loaded with pyrrole, graphene and carbon nanotubes.

[0044] (8) Immerse the sample obtained in step (7) into a magnetic stirring reactor with a separating device, add 200 g of distilled water to submerge the sample, turn on the magnetic stirring device with a rotation speed of 100 r / min, dropwise add 20 g of hydrogen peroxide with a mass concentration of 10% and a pH value of 4.5 at a dropping rate of 20 drops / min, and continue stirring for 2 h after the dropping is completed.

[0045] The magnetic stirring reactor with a separating device means that the magnetic stirring rotor is separated from the sample, so that the stirring rotor does not contact the sample.

[0046] In this step, by first immersing the sample in water and then dropwise adding hydrogen peroxide for impregnation, the pyrrole monomers in the sample polymerize to form polypyrrole, thereby anchoring carbon nanotubes and graphene.

[0047] (9) Then take out the sample in step (8), rinse it with clear water until neutral, and after drying, obtain a polypyrrole-anchored carbon nanotube / graphene-assembled carbon fiber composite laminated structure wood ceramic electrode.

[0048] In this embodiment, the mass specific capacitance of the carbon nanotube / graphene-assembled carbon fiber composite laminated structure wood ceramic electrode was tested. Specifically: using the carbon nanotube / graphene-assembled carbon fiber composite laminated structure wood ceramic electrode prepared in this embodiment as the working electrode, Pt as the counter electrode, and 6 mol·L -1 KOH solution as the electrolyte, at a scanning rate of 5 mV·s -1 , its mass specific capacitance is 209.8 F·g -1 .

[0049] Figure 1 is the micrograph of the carbon nanotube / graphene-assembled carbon fiber composite laminated structure wood ceramic electrode prepared in Example 1 of the present invention. Figure 1 In it, (a) is the end face of the laminated structure. From (b), carbon fibers distributed in the core layer structure can be seen. From (c), graphene and carbon nanotubes attached to the surface of the carbon fibers can be seen. From (d), granular polypyrrole anchoring the carbon nanotubes can be seen.

[0050] Example 2:

[0051] A preparation method of a carbon nanotube / graphene-assembled carbon fiber composite laminated structure wood ceramic electrode of the present invention includes the following steps:

[0052] (1) Using bamboo powder and bamboo fiber as the base materials, and thermosetting water-based phenolic resin as the adhesive, add 2% of short carbon fibers by the mass of the base materials, and press them into a thin sheet with a thickness of 2 mm and a density of 0.5 g / cm 3 at 60 °C, that is, the core layer material; wherein, the particle size of the bamboo powder is <40 mesh, the length of the bamboo fiber is <20 mm, and the length of the short carbon fiber is <5 mm.

[0053] (2) Cut the bamboo veneer with a thickness of 0.6 mm into the same size as the core layer, then soak it in the thermosetting waterborne phenolic resin with a mass concentration of 50%, take it out and drain it after 30 min to obtain the sandwich material.

[0054] (3) Stack one layer of sandwich material and one layer of core layer material alternately in sequence to form a blank, and perform hot pressing at 135 °C for 10 min to obtain a blank with a laminated structure, and its density is 0.6 g / cm 3 .

[0055] (4) Sinter the blank obtained in step (3) under vacuum at 1200 °C for 2 h to obtain a short carbon fiber composite bamboo-based laminated structure wood ceramic matrix material.

[0056] (5) Mix water, ethanol and pyrrole monomer according to a mass ratio of 100:20:10 to prepare a water-ethanol-pyrrole solution; fully mix carbon nanotubes and graphene according to a mass ratio of 1:1 of carbon nanotubes to graphene to obtain a low-dimensional carbon material mixture; add 10 g of the low-dimensional carbon material mixture to 100 g of the water-ethanol-pyrrole mixed solution, and then add 0.5 g of sodium dodecylbenzenesulfonate as a dispersant, and disperse it ultrasonically for 30 min to obtain a mixed solution B.

[0057] (6) Place the short carbon fiber composite bamboo-based laminated structure wood ceramic matrix material obtained in step (4) in an impregnation tank, evacuate to -0.09 MPa and keep it for 30 min, inhale the mixed solution B obtained in step (5), and keep it for 60 min; then pressurize to 0.7 MPa, keep it for 60 min and then release the mixed solution B from the impregnation tank.

[0058] (7) Repeat step (6) twice and then take out the matrix material to obtain a laminated structure wood ceramic sample loaded with pyrrole, graphene and carbon nanotubes.

[0059] (8) Place the sample obtained in step (7) in a magnetic stirring reactor with a separation device, add 200 g of distilled water to submerge the sample, turn on the magnetic stirring device with a rotation speed of 100 r / min, drop 20 g of hydrogen peroxide with a mass concentration of 10% and a pH value of 4.5, and the dropping rate of hydrogen peroxide is 20 drops / min. After the dropping is completed, continue to stir for 2 h.

[0060] The magnetic stirring reactor with a separation device means that the magnetic stirring rotor is separated from the sample so that the stirring rotor does not contact the sample.

[0061] (9) Then take out the sample in step (8), rinse it with clean water until neutral, and after drying, obtain a polypyrrole-anchored carbon nanotube / graphene-assembled carbon fiber composite laminated structure wood ceramic electrode.

[0062] In this embodiment, the specific capacitance per unit mass of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode was tested. Specifically, the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode prepared in this embodiment was used as the working electrode, Pt was used as the counter electrode, and a 6 mol·L -1 KOH solution was used as the electrolyte. At a scanning rate of 5 mV·s -1 , its specific capacitance per unit mass was 386.5 F·g -1 .

[0063] Figure 2 The CV and GCD curves of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode prepared in Example 2 of the present invention are shown in Figure 2 . In

[0064] , (a) is the CV curve and (b) is the GCD curve. It can be seen from the figure that the CV curve in (a) is approximately rectangular and there is no redox peak, indicating that the capacitance of the supercapacitor is mainly double-layer capacitance. Moreover, the curve has a large coverage area, indicating a high specific capacitance; the GCD curve in (b) is approximately an isosceles triangle, indicating that the sample has good electric double-layer capacitance performance and good charge-discharge efficiency.

[0064] Example 3:

[0065] A preparation method of a carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode of the present invention includes the following steps:

[0066] (1) Using bamboo powder and bamboo fiber as the base materials and thermosetting waterborne phenolic resin as the adhesive, 2% short carbon fiber was added according to the mass of the base materials, and it was pressed at 60 °C to form a sheet with a thickness of 0.8 mm and a density of 0.5 g / cm 3 , that is, the core layer material; wherein, the particle size of the bamboo powder is <40 mesh, the length of the bamboo fiber is <20 mm, and the length of the short carbon fiber is <5 mm.

[0067] (2) Cut the bamboo veneer with a thickness of 0.4 mm into the same size as the core layer, then soak it in thermosetting waterborne phenolic resin with a mass concentration of 50%, take it out and drain it after 30 min to obtain the interlayer material.

[0068] (3) Stack one layer of interlayer material and one layer of core layer material alternately to form a blank, and perform hot pressing at 135 °C for 10 min to obtain a blank with a laminated structure, and its density is 0.6 g / cm 3 .

[0069] (4) Sinter the blank obtained in step (3) at 900 °C for 2 h under vacuum to obtain a short carbon fiber composite bamboo-based laminated structure wood ceramic matrix material.

[0070] (5) Water, ethanol and pyrrole monomers are mixed at a mass ratio of 100:20:3 to prepare a water-ethanol-pyrrole solution; carbon nanotubes and graphene are fully mixed at a mass ratio of 1:1 to obtain a low-dimensional carbon material mixture; 10 g of the low-dimensional carbon material mixture is added to 100 g of the water-ethanol-pyrrole mixed solution, and then 0.5 g of sodium dodecylbenzene sulfonate is added as a dispersant, and ultrasonic dispersion is performed for 30 minutes to obtain a mixed solution B.

[0071] (6) placing the short carbon fiber composite bamboo-based laminated structure wood ceramic matrix material obtained in step (4) in an impregnation tank, evacuating to -0.09 MPa, maintaining for 30 min, and sucking in the mixed solution B obtained in step (5), maintaining for 60 min; then pressurizing to 0.7 MPa, maintaining for 60 min, and then releasing the mixed solution B from the impregnation tank.

[0072] (7) After repeating step (6) twice, the matrix material is taken out to obtain a laminated structure wood ceramic sample loaded with pyrrole, graphene and carbon nanotubes.

[0073] (8) The sample obtained in step (7) is placed in a magnetic stirring reactor with a separator, 200 g of distilled water is added to immerse the sample, the magnetic stirring device is turned on, the rotation speed is 100 r / min, 20 g of hydrogen peroxide with a mass concentration of 10% and a pH value of 4.5 is added dropwise, and the hydrogen peroxide is added at a rate of 20 drops / min. After the addition is completed, stirring is continued for 2 h.

[0074] The magnetic stirring reactor is provided with a separation device, that is, the magnetic stirring rotor is separated from the sample, so that the stirring rotor does not contact the sample.

[0075] (9) Then, the sample in step (8) is taken out, rinsed with clean water until it is neutral, and dried to obtain a polypyrrole-anchored carbon nanotube / graphene-assembled carbon fiber composite laminated structure wood ceramic electrode.

[0076] This example tests the mass specific capacitance of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode. Specifically, the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode prepared in this example is used as the working electrode, Pt is used as the counter electrode, and 6 mol·L -1 The KOH solution was used as electrolyte and the scan rate was 5 mV·s -1 When the mass specific capacitance is 238.6F·g -1 .

[0077] Embodiment 4:

[0078] A method for preparing a carbon nanotube / graphene-assembled carbon fiber composite laminated structure wood ceramic electrode of the present invention comprises the following steps:

[0079] (1) Bamboo powder and bamboo fiber are used as the base material, thermosetting water-based phenolic resin is used as the adhesive, and 2% of short carbon fiber is added according to the mass of the base material. The mixture is pressed at 60°C into a film with a thickness of 1.2 mm and a density of 0.5 g / cm 3 The thin sheet is the core layer material; wherein the particle size of bamboo powder is less than 40 mesh, the length of bamboo fiber is less than 20 mm, and the length of short carbon fiber is less than 5 mm.

[0080] (2) Cutting bamboo veneer with a thickness of 0.5 mm into the same size as the core layer, and then immersing it in a thermosetting water-based phenolic resin with a mass concentration of 50%, taking it out after 30 minutes, draining it, and obtaining a sandwich material.

[0081] (3) A layer of sandwich material and a layer of core material are alternately stacked and assembled, and hot pressed at 135°C for 10 minutes to obtain a blank with a laminated structure, the density of which is 0.6 g / cm 3 .

[0082] (4) The blank obtained in step (3) is sintered at 1000° C. for 2 h under vacuum to obtain a short carbon fiber composite bamboo-based laminated structure wood ceramic matrix material.

[0083] (5) Water, ethanol and pyrrole monomers are mixed at a mass ratio of 100:20:5 to prepare a water-ethanol-pyrrole solution; carbon nanotubes and graphene are fully mixed at a mass ratio of 1:1 to obtain a low-dimensional carbon material mixture; 10 g of the low-dimensional carbon material mixture is added to 100 g of the water-ethanol-pyrrole mixed solution, and then 0.5 g of sodium dodecylbenzene sulfonate is added as a dispersant, and ultrasonic dispersion is performed for 30 minutes to obtain a mixed solution B.

[0084] (6) placing the short carbon fiber composite bamboo-based laminated structure wood ceramic matrix material obtained in step (4) in an impregnation tank, evacuating to -0.09 MPa, maintaining for 30 min, and sucking in the mixed solution B obtained in step (5), maintaining for 60 min; then pressurizing to 0.7 MPa, maintaining for 60 min, and then releasing the mixed solution B from the impregnation tank.

[0085] (7) After repeating step (6) twice, the matrix material is taken out to obtain a laminated structure wood ceramic sample loaded with pyrrole, graphene and carbon nanotubes.

[0086] (8) The sample obtained in step (7) is placed in a magnetic stirring reactor with a separator, 200 g of distilled water is added to immerse the sample, the magnetic stirring device is turned on, the rotation speed is 100 r / min, 20 g of hydrogen peroxide with a mass concentration of 10% and a pH value of 4.5 is added dropwise, and the hydrogen peroxide is added at a rate of 20 drops / min. After the addition is completed, stirring is continued for 2 h.

[0087] A magnetic stirring reactor with a separation device, that is, the magnetic stirring rotor is separated from the sample, so that the stirring rotor does not contact the sample.

[0088] (9) Then take out the sample in step (8), rinse it with clean water until neutral, and after drying, obtain a polypyrrole-anchored carbon nanotube / graphene-assembled carbon fiber composite laminated wood ceramic electrode.

[0089] In this example, the mass specific capacitance of the carbon nanotube / graphene-assembled carbon fiber composite laminated wood ceramic electrode was tested. Specifically: using the carbon nanotube / graphene-assembled carbon fiber composite laminated wood ceramic electrode prepared in this example as the working electrode, Pt as the counter electrode, and 6 mol·L -1 of KOH solution as the electrolyte, at a scanning rate of 5 mV·s -1 , its mass specific capacitance is 321.6 F·g -1 .

[0090] Example 5:

[0091] A preparation method of a carbon nanotube / graphene-assembled carbon fiber composite laminated wood ceramic electrode of the present invention includes the following steps:

[0092] (1) Using bamboo powder and bamboo fiber as the base materials, and thermosetting water-based phenolic resin as the adhesive, add 2% short carbon fibers by the mass of the base materials, and press them at 60 °C to form a sheet with a thickness of 1.5 mm and a density of 0.5 g / cm 3 , which is the core layer material; among them, the particle size of the bamboo powder is <40 mesh, the length of the bamboo fiber is <20 mm, and the length of the short carbon fiber is <5 mm.

[0093] (2) Cut the bamboo veneer with a thickness of 0.6 mm into the same size as the core layer, then soak it in thermosetting water-based phenolic resin with a mass concentration of 50%, take it out and drain it after 30 min to obtain the interlayer material.

[0094] (3) Stack one layer of interlayer material and one layer of core layer material alternately to form a blank, and perform hot pressing at 135 °C for 10 min to obtain a blank with a laminated structure, and its density is 0.6 g / cm 3 .

[0095] (4) Keep the blank obtained in step (3) sintered at 1100 °C for 2 h under vacuum to obtain a short carbon fiber composite bamboo-based laminated wood ceramic matrix material.

[0096] (5) Mix water, ethanol, and pyrrole monomer in a mass ratio of 100∶20∶6 to prepare a water-ethanol-pyrrole solution; fully mix carbon nanotubes and graphene according to a mass ratio of 1∶1 to obtain a low-dimensional carbon material mixture; add 10 g of the low-dimensional carbon material mixture to 100 g of the water-ethanol-pyrrole mixed solution, then add 0.5 g of sodium dodecylbenzenesulfonate as a dispersant, and disperse ultrasonically for 30 min to obtain mixed solution B.

[0097] (6) Place the short carbon fiber composite bamboo-based laminated structure wood ceramic matrix material obtained in step (4) in an impregnation tank, evacuate to -0.09 MPa and maintain for 30 min, suck in the mixed solution B obtained in step (5), and maintain for 60 min; then pressurize to 0.7 MPa, and after maintaining for 60 min, release the mixed solution B from the impregnation tank.

[0098] (7) After repeating step (6) twice, take out the matrix material to obtain a laminated structure wood ceramic sample loaded with pyrrole, graphene, and carbon nanotubes.

[0099] (8) Place the sample obtained in step (7) in a magnetic stirring reactor with a separation device, add 200 g of distilled water to submerge the sample, turn on the magnetic stirring device with a rotation speed of 100 r / min, dropwise add 20 g of hydrogen peroxide with a mass concentration of 10% and a pH value of 4.5 at a dropping rate of 20 drops / min, and continue stirring for 2 h after the dropping is completed.

[0100] The magnetic stirring reactor with a separation device means that the magnetic stirring rotor is separated from the sample so that the stirring rotor does not contact the sample.

[0101] (9) Then take out the sample in step (8), rinse it with clean water until neutral, and after drying, obtain a polypyrrole-anchored carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode.

[0102] In this example, the mass specific capacitance of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode was tested. Specifically: using the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode prepared in this example as the working electrode, Pt as the counter electrode, and 6 mol·L -1 of KOH solution as the electrolyte, at a scanning rate of 5 mV·s -1 its mass specific capacitance was 352.5 F·g -1 .

[0103] Example 6:

[0104] A preparation method of a carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode of the present invention includes the following steps:

[0105] (1) Using bamboo powder and bamboo fiber as the base materials, and thermosetting water-based phenolic resin as the adhesive, 2% short carbon fiber is added based on the mass of the base materials, and it is pressed at 60 °C to form a sheet with a thickness of 1.8 mm and a density of 0.5 g / cm 3 , which is the core layer material; among them, the particle size of the bamboo powder is <40 mesh, the length of the bamboo fiber is <20 mm, and the length of the short carbon fiber is <5 mm.

[0106] (2) Cut the bamboo veneer with a thickness of 0.4 mm into the same size as the core layer, then soak it in the thermosetting water-based phenolic resin with a mass concentration of 50%, take it out and drain it after 30 min to obtain the sandwich material.

[0107] (3) Stack one layer of sandwich material and one layer of core layer material alternately in sequence to form a blank, and perform hot pressing at 135 °C for 10 min to obtain a blank with a laminated structure, and its density is 0.6 g / cm 3 .

[0108] (4) Sinter the blank obtained in step (3) under vacuum at 1150 °C for 2 h to obtain a short carbon fiber composite bamboo-based laminated structure wood ceramic matrix material.

[0109] (5) Mix water, ethanol and pyrrole monomer according to a mass ratio of 100∶20∶8 to prepare a water-ethanol-pyrrole solution; fully mix carbon nanotubes and graphene according to a mass ratio of carbon nanotubes to graphene of 1∶1 to obtain a low-dimensional carbon material mixture; add 10 g of the low-dimensional carbon material mixture to 100 g of the water-ethanol-pyrrole mixed solution, and then add 0.5 g of sodium dodecylbenzenesulfonate as a dispersant, and disperse it ultrasonically for 30 min to obtain a mixed solution B.

[0110] (6) Place the short carbon fiber composite bamboo-based laminated structure wood ceramic matrix material obtained in step (4) in an impregnation tank, evacuate to -0.09 MPa and keep it for 30 min, suck in the mixed solution B obtained in step (5), and keep it for 60 min; then pressurize to 0.7 MPa, keep it for 60 min and then release the mixed solution B from the impregnation tank.

[0111] (7) Repeat step (6) twice and then take out the matrix material to obtain a laminated structure wood ceramic sample loaded with pyrrole, graphene and carbon nanotubes.

[0112] (8) Place the sample obtained in step (7) in a magnetic stirring reactor with a separating device, add 200 g of distilled water to submerge the sample, turn on the magnetic stirring device with a rotation speed of 100 r / min, drop 20 g of hydrogen peroxide with a mass concentration of 10% and a pH value of 4.5, the dropping speed of the hydrogen peroxide is 20 drops / min, and continue to stir for 2 h after the dropping is completed.

[0113] A magnetic stirring reactor with a separation device, that is, the magnetic stirring rotor is separated from the sample so that the stirring rotor does not contact the sample.

[0114] (9) Then take out the sample in step (8), rinse it with clear water until neutral, and after drying, obtain a polypyrrole-anchored carbon nanotube / graphene-assembled carbon fiber composite laminated structure wood ceramic electrode.

[0115] In this embodiment, the specific capacitance of the carbon nanotube / graphene-assembled carbon fiber composite laminated structure wood ceramic electrode was tested. Specifically: using the carbon nanotube / graphene-assembled carbon fiber composite laminated structure wood ceramic electrode prepared in this embodiment as the working electrode, Pt as the counter electrode, and 6 mol·L -1 of KOH solution as the electrolyte, at a scanning rate of 5 mV·s -1 , its specific capacitance was 295.3 F·g -1 .

[0116] The above is only a preferred embodiment of the present invention, and it does not impose any form of limitation on the present invention. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make many possible changes and modifications to the technical solution of the present invention by using the methods and technical contents disclosed above, or modify it into an equivalent embodiment with equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the technical solution of the present invention still fall within the scope of the protection of the technical solution of the present invention.

Claims

1. A preparation method of a carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode, Characterized in that, Comprising the following steps: (1) Using bamboo powder and bamboo fiber as base materials, thermosetting water-based phenolic resin as an adhesive, adding carbon fiber, and obtaining a core layer material through pressing; the length of the carbon fiber < 5 mm; (2) Using bamboo veneer as an interlayer material, alternately stacking one layer of interlayer material and one layer of core layer material in sequence to form a laminated structure, and obtaining a blank through hot pressing; (3) Sintering the blank obtained in step (2) under vacuum at 850 °C to 1200 °C to obtain a carbon fiber composite bamboo-based laminated structure wood ceramic matrix material; (4) Mixing a conductive polymer monomer, ethanol, and water to obtain a mixed solution A; the conductive polymer monomer is pyrrole; mixing carbon nanotubes and graphene to obtain a mixture; mixing the mixture, the mixed solution A, and a dispersant, and dispersing to obtain a mixed solution B; the mass ratio of water, ethanol, and the conductive polymer monomer is 100∶20∶1 to 10; the mass ratio of carbon nanotubes and graphene is 1∶1, and the mass ratio of the mixture, the mixed solution A, and the dispersant is 10∶100∶0.5; (5) Immersing the carbon fiber composite bamboo-based laminated structure wood ceramic matrix material obtained in step (3) into the mixed solution B obtained in step (4), and performing vacuum pressure impregnation to obtain a wood ceramic sample; (6) Immersing the wood ceramic sample obtained in step (5) into water, dropping hydrogen peroxide, stirring, washing, and drying to obtain a polypyrrole-anchored carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode.

2. The preparation method of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode according to claim 1, Characterized in that, In step (4), the dispersant is sodium dodecylbenzenesulfonate.

3. The preparation method of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode according to claim 1, Characterized in that, In step (2), the thickness of the core layer material is 0.5 mm to 2 mm, and the thickness of the bamboo veneer is 0.3 mm to 0.6 mm.

4. The preparation method of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode according to claim 1, Characterized in that, In step (5), the specific process of the vacuum pressure impregnation is: S1. Placing the carbon fiber composite bamboo-based laminated structure wood ceramic matrix material in an impregnation device, evacuating to -0.09 MPa, and maintaining for 30 min; S2. Adding the mixed solution B to the impregnation device, maintaining for 60 min, then pressurizing to 0.7 MPa, and continuing to maintain for 60 min, and taking out the matrix material; S3. Repeating steps S1 and S2 to perform repeated treatment on the matrix material; the number of repetitions is 2 times.

5. The preparation method of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode according to any one of claims 1 to 4, Characterized in that, In step (1), the particle size of the bamboo powder is < 40 mesh, the length of the bamboo fiber is < 20 mm, the mass ratio of the carbon fiber to the base material is 2:100, the pressing temperature is 60 °C, and the density of the core layer material is 0.5 g / cm 3 .

6. The preparation method of the carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode according to any one of claims 1 to 4, Characterized in that, In step (2), the temperature of the hot pressing is 135°C, and the density of the blank is 0.6 g / cm 3 ; Before use, the bamboo veneer includes the following treatment: immersing the bamboo veneer in a thermosetting waterborne phenolic resin for 30 min, taking it out and draining; the mass concentration of the thermosetting waterborne phenolic resin is 50%; And / or, in step (3), the time of the vacuum sintering is 2 h; And / or, in step (4), the time of the dispersion is 30 min, and the dispersion is ultrasonic dispersion.

7. The method for preparing a carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode according to any one of claims 1 to 4, characterized in that In step (6), the mass ratio of water to hydrogen peroxide is 10:1, the mass concentration of the hydrogen peroxide is 10%, the pH value of the hydrogen peroxide is 4.5, continuous stirring is carried out during the dropping of the hydrogen peroxide, the dropping rate of the hydrogen peroxide is 20 drops / min, and the rotation speed of the stirring is 100 r / min.

8. A carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode prepared by the preparation method according to any one of claims 1 to 7.

9. Application of a carbon nanotube / graphene assembled carbon fiber composite laminated structure wood ceramic electrode according to claim 8 in a supercapacitor.

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