CN111640586B - Wood-based flexible electrode and preparation method and application thereof - Google Patents

Wood-based flexible electrode and preparation method and application thereof Download PDF

Info

Publication number
CN111640586B
CN111640586B CN202010494292.4A CN202010494292A CN111640586B CN 111640586 B CN111640586 B CN 111640586B CN 202010494292 A CN202010494292 A CN 202010494292A CN 111640586 B CN111640586 B CN 111640586B
Authority
CN
China
Prior art keywords
veneer
wood
loaded
flexible electrode
graphene oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010494292.4A
Other languages
Chinese (zh)
Other versions
CN111640586A (en
Inventor
孙德林
孙振宇
余先纯
陈浩伟
张传艳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University of Forestry and Technology
Original Assignee
Central South University of Forestry and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University of Forestry and Technology filed Critical Central South University of Forestry and Technology
Priority to CN202010494292.4A priority Critical patent/CN111640586B/en
Publication of CN111640586A publication Critical patent/CN111640586A/en
Application granted granted Critical
Publication of CN111640586B publication Critical patent/CN111640586B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES 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

Abstract

The invention discloses a wood-based flexible electrode, which takes a rotary-cut or sliced veneer as a base material, wherein the pores of the base material are loaded with graphene oxide, and the surface and the pores of the base material are loaded with nano MnO2And the outermost side of the surface of the base material is encapsulated with a graphite layer. The invention also provides a preparation method of the wood-based flexible electrode, which comprises the following steps: taking the graphene oxide aqueous solution as a filtrate, and taking rotary-cut or sliced sheet veneer as a filter membrane for suction filtration treatment; after drying, a graphite rod is used as a packaging material, and a graphite layer is uniformly packaged on one surface of the veneer; impregnating the veneer in KMnO at room temperature4Drying the aqueous solution, and soaking in H2O2In alkaline solution, nano MnO is loaded through oxidation-reduction reaction2(ii) a And uniformly packaging the graphite layer on the other surface of the veneer to obtain the wood-based flexible electrode. The invention has the advantages of environmental protection, simplicity and easy operation.

Description

Wood-based flexible electrode and preparation method and application thereof
Technical Field
The invention relates to the technical field of new energy super capacitors, in particular to a wood-based flexible electrode and a preparation method and application thereof.
Background
With the rapid development of electronic technology, flexible portable electronic products are widely applied, and especially in the fields of medical instruments, sports equipment and the like, the flexible super capacitor plays a very important role as a power source: high energy and power density, fast charge and discharge, high cycle times and safe use are important performance indexes. Meanwhile, due to the great unpredictability of the environment and manner of use of portable electronic products, the requirements for flexible electrode materials in capacitors are also increasing.
Supercapacitors, also known as electric double layer capacitors. A common flexible super capacitor mainly comprises a flexible electrode, electrolyte and a diaphragm, wherein the quality of a flexible electrode material directly influences the comprehensive performance of the flexible electrode material. At present, the electrodes of the flexible supercapacitor are mainly prepared by loading porous carbon-based materials, metal oxides, nano materials with high specific capacitance and the like on a flexible substrate. However, when one material is used alone, there are limitations that the energy density of the carbon-based material is difficult to increase, part of the metal oxide has a higher theoretical specific capacitance, but is easy to fall off on the flexible substrate, and the manufacturing cost of part of the high specific capacitance nano material is higher. Therefore, research and development of the flexible electrode can be focused on the aspects of exerting the synergistic function of a plurality of materials when the materials are matched with each other, reducing the manufacturing cost and the like.
The flexible substrate is one of key materials for preparing the flexible supercapacitor electrode. At present, carbon fiber cloth, nano cellulose paper, conductive polymer fabric and the like are mostly used as flexible substrates. The carbon fiber cloth and the nano cellulose paper are expensive, and a large amount of wood and alkali are consumed during the preparation of the nano cellulose paper, so that the pollution is serious; the metal plating layer on the surface of the conductive polymer fabric is easy to oxidize when the electrode is charged and discharged quickly, so that the service life is influenced.
Regarding the research on the wood-based flexible electrode, in the chinese patent application "a method for preparing a wood flexible supercapacitor and a wood flexible porous electrode thereof" (CN 107742583A), wood is sliced along a direction perpendicular to an axial direction to obtain a wood sheet with a cross section, then soaked with a monomer of a conductive polymer, and then subjected to oxidative polymerization in an inorganic acid in the presence of an oxidant to obtain the wood-based flexible electrode. In the chinese patent application "a method for preparing a transparent and electrically conductive flexible wood composite" (CN 109049215A), a composite material is obtained by slicing and delignifying wood and placing it in an electrically conductive solution. In the Chinese patent application for' a wood-based flexible composite electrode materialThe preparation method (CN 110164715A) also comprises removing lignin from cross-section wood substrate, freeze drying, self-assembling carbon nanotubes, and performing KMnO4And K2SO4Load MnO for reduction reaction in mixed solution2Thereby obtaining the wood-based flexible electrode.
These studies all have some drawbacks: if a cross-section wood sheet (wood) is used as a substrate, the substrate is easily damaged, and the flexibility of the electrode is greatly reduced. After lignin is removed from the wood sheet, the shrinkage rate is large during freeze drying, so that the original form is difficult to maintain to a great extent, the assembly of the capacitor is influenced, and further the energy and power density are influenced. If the cross-section sheet (wood) is delignified, it is more difficult to maintain the original shape, and the bending properties are greatly affected.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a green, environment-friendly, simple and feasible wood-based flexible electrode and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a wood-based flexible electrode is prepared from rotary-cut or sliced wood as substrate, graphene oxide in the pores of said substrate, and nano MnO in the surface and pores of said substrate2And the outermost side of the surface of the base material is encapsulated with a graphite layer.
As a general inventive concept, the present invention also provides a method of manufacturing a wood-based flexible electrode, including the steps of:
s1, taking the graphene oxide aqueous solution as a filtrate, taking rotary-cut or sliced sheet-shaped veneer as a suction filtration membrane for suction filtration treatment, loading the graphene oxide in pores of the veneer, and drying to obtain the graphene oxide-loaded veneer;
s2, uniformly packaging a graphite layer on one surface of the graphene oxide loaded veneer obtained in the step S1 by taking a graphite rod as a packaging material to obtain a veneer with a single-side packaged graphite layer;
s3, soaking the veneer of the single-side packaging graphite layer obtained in the step S2 in KMnO at normal temperature4Aqueous solutionMedium-load KMnO4Drying, and soaking in H at room temperature2O2In alkaline solution, nano MnO is loaded through oxidation-reduction reaction2Washing the veneer with water until the washed washing liquid is neutral, and drying to obtain the loaded nano MnO2The veneer of (2);
s4, taking a graphite rod as a packaging material, and adding the loaded nano MnO obtained in the step S32And uniformly packaging a graphite layer on the other surface of the veneer to obtain the wood-based flexible electrode.
As a further improvement to the above technical solution:
step S2 specifically includes: rubbing a stone grinding rod on one surface of the graphene oxide loaded veneer obtained in the step S1 to enable a graphite layer to be attached to the surface of the veneer, repeatedly bending the veneer, and removing graphite floating powder on the surface of the veneer to obtain the veneer with a single-side packaged graphite layer.
And after removing the graphite floating powder on the surface of the veneer, repeating the step of removing by friction bending for 1-2 times.
In the step S1, the mass fraction of the graphene oxide aqueous solution is 2-5%.
In step S1, after drying, graphene floating powder on the surface of the veneer needs to be removed.
In the step S3, the KMnO4The mass concentration of the aqueous solution is 10-20%, and the loaded KMnO4The time is 20-60 min.
In the step S3, the H2O2The mass concentration of the alkaline solution is 8-12%, the pH value is 9-11, and the supported nano MnO is2The time of the reaction is 2-24 hours.
The step S3 is reacted under normal pressure.
The invention also provides an application of the wood-based flexible electrode or the wood-based flexible electrode prepared by the preparation method in a super capacitor as a general inventive concept.
The super capacitor uses a wood-based flexible electrode as a working electrode.
Compared with the prior art, the invention has the advantages that:
1) the wood veneer is used as a base material, so that the wood veneer is light in weight, low in price and wide in source. Meanwhile, natural pores of the wood are fully utilized, chemical delignification is not needed, and the requirements of environmental protection are met.
2) The invention uses rotary cutting and slicing veneer as the base material, the base material can be repeatedly bent and twisted, and compared with the cross section veneer, the invention has better flexibility.
3) The method adopts a suction filtration method to assemble the graphene oxide on the substrate, and is convenient, rapid and environment-friendly.
4) The invention can lead the graphite, the graphene oxide and the nano MnO to be mixed at normal temperature and normal pressure2The assembly together does not need high temperature and high pressure equipment, and can greatly reduce the manufacturing cost.
5) The invention adopts graphite packaging on the surface of the veneer, which not only can reduce graphene oxide and nano MnO2And graphite also has an energy storage function as a carbon material. Meanwhile, the graphite has an excellent conductive function, and the flexible capacitor can be directly assembled without using a metal current collector.
6) The wood-based flexible electrode has good flexibility, can be applied to assembling a super capacitor, has the characteristic of pseudo capacitance as can be seen from a volt ampere cycle curve in an attached figure 3, and can greatly improve the specific capacitance.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention.
Fig. 2 is a real image of the wood-based flexible electrode according to embodiment 1 of the present invention.
FIG. 3 is a voltammetry cyclic curve diagram of the wood-based flexible electrode obtained in example 1 of the present invention at a scan rate of 10-400 mV/s.
Detailed Description
The invention will be described in further detail below with reference to the drawings and specific examples. Unless otherwise specified, the instruments or materials employed in the present invention are commercially available.
Example 1
A wood-based flexible electrode is prepared from sliced beech as substrate, graphene oxide loaded in pores of the substrate, and surface and pores of the substrateInternally loaded with nano MnO2And the outermost side of the surface of the base material is encapsulated with a graphite layer.
As shown in fig. 1, the method for manufacturing a wood-based flexible electrode of this embodiment includes the following steps:
1) cutting the beech wood sliced veneer which is 0.2 mm in thickness and washed and dried by deionized water into 60 mm multiplied by 60 mm to be a filtering membrane, placing the filtering membrane on a filtering funnel, and pouring a graphene oxide aqueous solution with the mass fraction of 2% as a filtrate for suction filtration. In the process, the solution is made to penetrate through the veneer and repeated for 3 times, so that the graphene oxide is loaded in the pores of the veneer. And flattening the veneer, drying at 60 ℃ until the water content is 10%, and removing graphene floating powder on the surface of the veneer by using a brush to obtain the graphene oxide-loaded veneer.
2) Repeatedly rubbing one surface of the veneer obtained in the step 1) by using a high-purity graphite rod to enable a layer of graphite layer to be uniformly attached to the surface of the veneer, repeatedly bending the veneer for 10 times, and removing graphite floating powder on the surface by using a brush.
The invention loads nano MnO2The graphite layer is packaged on one surface of the veneer in advance, compared with the method for loading nano MnO2Then, the graphite layers are packaged on the two surfaces of the veneer, so that the load of nano MnO can be reduced2The number of times of later friction is reduced to load nano MnO2And (4) falling off.
3) And (3) repeating the step 2) once to obtain the beech wood sliced veneer with a single surface firmly packaged with the high-purity graphite layer.
4) Completely immersing the veneer obtained in the step 3) in KMnO with the mass concentration of 10% at normal temperature and normal pressure4Taking out the solution, drying at 60 deg.C to water content of 10% to obtain loaded KMnO4The veneer of (2).
5) Loading KMnO in the step 4) at normal temperature and normal pressure4The veneer is completely immersed in H with the mass concentration of 8%2O2KMnO in wood veneer 2 h in alkaline solution (pH = 9)4And H2O2MnO formed by the reaction2And deposited and attached on the surface and in the pores of the veneer to realize nanometerMnO2When no air bubble emerges, the loaded nano MnO is obtained2The veneer of (2).
Graphene oxide and nano MnO2All have higher theoretical specific capacitance, can promote the energy storage effect of electrode, increase specific capacitance.
6) Repeatedly washing the veneer obtained in the step 5) with deionized water until the washing liquid becomes neutral, and drying until the water content is 10%.
7) According to the method in the step 2), the graphite layer is firmly attached to the other surface of the veneer without the graphite layer, and the nano MnO deposited in the veneer matrix2And packaging with graphene oxide to obtain the beech-based flexible electrode.
Fig. 2 is a diagram of an embodiment of the wood-based flexible electrode of the present invention, in which the wood-based flexible electrode of fig. 2a is in a twisted state, and the wood-based flexible electrode of fig. 2b is in a bent state, and it can be seen from the diagram that the wood-based flexible electrode of the present invention has good flexibility.
At 3 mol/L of Na2SO4The solution is electrolyte, the beech-based flexible electrode, the saturated calomel electrode and the platinum sheet electrode are respectively used as a working electrode, a reference electrode and a counter electrode, and the specific capacitance at 200 mV/s is 281.3F/g; the specific capacitance in the bent state is 279.7F/g; the specific capacitance retention rate after 2000 cycles is 92.5%, and the electrochemical performance is excellent.
FIG. 3 is a voltammetry cyclic curve diagram of the wood-based flexible electrode obtained in example 1 of the present invention at a scan rate of 10-400 mV/s, wherein the protruding redox peaks indicate the feature of pseudocapacitance.
Example 2
A wood-based flexible electrode is prepared by using rotary cut fraxinus mandshurica as base material, loading graphene oxide in pores of the base material, and loading nano MnO on surface and in pores of the base material2And the outermost side of the surface of the base material is encapsulated with a graphite layer.
The preparation method of the wood-based flexible electrode of the embodiment comprises the following steps:
1) the method comprises the steps of cutting a rotary cut veneer of a fraxinus mandshurica wood which is 0.5 mm in thickness, washed by deionized water and dried into 60 mm multiplied by 60 mm sheets, placing the sheets on filter paper of a suction filtration funnel, and pouring a graphene oxide aqueous solution with the mass fraction of 3% as a suction filtration liquid for suction filtration. In the process, the solution is made to penetrate through the veneer and repeated for 3 times, so that the graphene oxide is loaded in the pores of the veneer. And flattening the veneer, drying at 60 ℃ until the water content is 10%, and removing graphene floating powder on the surface of the veneer by using a brush to obtain the graphene oxide-loaded veneer.
2) Repeatedly rubbing one surface of the veneer obtained in the step 1) by using a high-purity graphite rod to enable a layer of graphite layer to be uniformly attached to the surface of the veneer, repeatedly bending the veneer for 10 times, and removing graphite floating powder on the surface by using a brush.
3) And (3) repeating the step 2) once to obtain the fraxinus mandshurica wood sliced veneer with a single surface firmly packaged with the high-purity graphite layer.
4) Completely immersing the veneer obtained in the step 3) in KMnO with the mass concentration of 12% at normal temperature and normal pressure4Taking out the solution for 40 min, drying at 60 deg.C until the water content is 10%, to obtain the loaded KMnO4The veneer of (2).
5) Immersing the product of step 4) in KMnO at normal temperature and pressure4The veneer is completely immersed in H with the mass concentration of 10%2O2KMnO in wood veneer in alkaline solution for 8 h (pH = 11)4And H2O2MnO formed by the reaction2And deposited and attached on the surface and in the pores of the veneer to realize the nano MnO2When no bubble emerges, the reaction is complete to obtain the loaded nano MnO2The veneer of (2).
6) Repeatedly washing the veneer obtained in the step 5) with deionized water until the washing liquid becomes neutral, and drying until the water content is 10%.
7) According to the method in the step 2), the graphite layer is firmly attached to the other surface of the veneer without the graphite layer, and the nano MnO deposited in the veneer matrix2And packaging with graphene oxide to obtain the fraxinus mandshurica-based flexible electrode.
At 3 mol/L of Na2SO4The solution is electrolyte, flexible electrode of northeast China ash root, saturated calomelThe electrode and the platinum sheet electrode are respectively used as a working electrode, a reference electrode and a counter electrode, and the specific capacitance at 0.400 mV/s is 262.6F/g; the specific capacitance in the bent state was 259.4F/g; the specific capacitance retention rate after 2000 cycles is 90.8%, and the electrochemical performance is excellent.
Example 3
A wood-based flexible electrode is prepared from sliced red oak as substrate, graphene oxide loaded in the pores of said substrate, and nano MnO loaded on the surface and in the pores of said substrate2And the outermost side of the surface of the base material is encapsulated with a graphite layer.
The preparation method of the wood-based flexible electrode of the embodiment comprises the following steps:
1) cutting 0.8 mm-thick red oak sliced veneer which is washed by deionized water and dried into 60 mm multiplied by 60 mm sheets, placing the sheets on filter paper of a suction filtration funnel, and pouring 3% of graphene oxide aqueous solution serving as suction filtration liquid for suction filtration. In this process, the solution was allowed to permeate through the veneer and repeated 3 times, so that the graphene oxide was loaded in the pores of the veneer. And flattening the veneer, drying at 60 ℃ until the water content is 10%, and removing graphene floating powder on the surface of the veneer by using a brush to obtain the graphene oxide-loaded veneer.
2) Repeatedly rubbing one surface of the veneer obtained in the step 1) by using a high-purity graphite rod to enable a layer of graphite layer to be uniformly attached to the surface of the veneer, repeatedly bending the veneer for 10 times, and removing graphite floating powder on the surface by using a brush.
3) And (3) repeating the step 2) once to obtain the red oak sliced veneer with a single surface firmly packaged with the high-purity graphite layer.
4) Completely immersing the veneer obtained in the step 3) in KMnO with the mass concentration of 15% at normal temperature and normal pressure4Taking out the solution, drying at 60 deg.C to water content of 10% to obtain loaded KMnO4The veneer of (2).
5) Immersing the product of step 4) in KMnO at normal temperature and pressure4The veneer is completely immersed in H with the mass concentration of 12%2O2KMnO in wood veneer 14 h (pH = 10) in alkaline solution4And H2O2MnO formed by the reaction2And deposited and attached on the surface and in the pores of the veneer to realize the nano MnO2When no bubble emerges, the reaction is complete to obtain the loaded nano MnO2The veneer of (2).
6) Repeatedly washing the veneer obtained in the step 5) with deionized water until the washing liquid becomes neutral, and drying until the water content is 10%.
7) According to the method in the step 2, the graphite layer is firmly attached to the other surface of the veneer without the graphite layer, and the nano MnO deposited in the veneer matrix2And packaging with graphene oxide to obtain the red oak-based flexible electrode.
At 3 mol/L of Na2SO4The solution is electrolyte, the red oak-based flexible electrode, the saturated calomel electrode and the platinum sheet electrode are respectively used as a working electrode, a reference electrode and a counter electrode, and the specific capacitance at 250 mV/s is 270.2F/g; the specific capacitance in the bent state is 267.8F/g; the specific capacitance retention rate after 2000 cycles is 93.2%, and the electrochemical performance is excellent.
Example 4
A wood-based flexible electrode is prepared from rotary-cut white oak veneer as substrate, graphene oxide loaded in pores of the substrate, and nano MnO loaded on surface and in pores of the substrate2And the outermost side of the surface of the base material is encapsulated with a graphite layer.
The preparation method of the wood-based flexible electrode of the embodiment comprises the following steps:
1) cutting a white oak rotary-cut veneer which is 0.4 mm thick and washed and dried by deionized water into 50 mm multiplied by 50 mm sheets, placing the sheets on a filter paper of a suction filtration funnel, pouring a graphene oxide aqueous solution with the mass fraction of 5%, and carrying out suction filtration. In this process, the solution was allowed to permeate through the veneer and repeated 3 times, so that the graphene oxide was loaded in the pores of the veneer. Flattening the veneer, drying at 60 ℃ until the water content is 10%, and removing graphene floating powder on the surface of the veneer by using a brush to obtain the graphene oxide loaded veneer.
2) Repeatedly rubbing one surface of the veneer in the step 1) by using a high-purity graphite rod to enable a layer of graphite layer to be uniformly attached to the surface of the veneer, repeatedly bending the veneer for 10 times, and removing graphite floating powder on the surface by using a brush.
3) And (3) repeating the step 2) once to obtain the white oak rotary-cut veneer with a single surface firmly packaged with the high-purity graphite layer.
4) Completely immersing the veneer obtained in the step 3) in KMnO with the mass concentration of 14% at normal temperature and normal pressure4Taking out the solution, drying at 60 deg.C to water content of 10% to obtain loaded KMnO4The veneer of (2).
5) Soaking in KMnO at normal temperature and pressure4The veneer is completely immersed in H with the mass concentration of 12%2O2KMnO in wood veneer 14 h in alkaline solution (pH = 11)4And H2O2MnO formed by the reaction2And deposited and attached on the surface and in the pores of the veneer to realize the nano MnO2When no bubble emerges, the reaction is complete to obtain the loaded nano MnO2The veneer of (2).
6) Repeatedly washing the veneer obtained in the step 5) with deionized water until the washing liquid becomes neutral, and drying until the water content is 10%.
7) According to the method in the step 2), the graphite layer is firmly attached to the other surface of the veneer without the graphite layer, and MnO deposited in the veneer matrix2And packaging with graphene oxide to obtain the bamboo-based flexible electrode.
At 3 mol/L of Na2SO4The solution is electrolyte, the bamboo-based flexible electrode, the saturated calomel electrode and the platinum sheet electrode are respectively used as a working electrode, a reference electrode and a counter electrode, and the specific capacitance at 300 mV/s is 283.6F/g; the specific capacitance in the bent state was 297.5F/g; the specific capacitance retention rate after 2000 cycles is 95.7%, and the electrochemical performance is excellent.
Example 5
A wood-based flexible electrode is prepared from sliced beech as substrate, graphene oxide loaded in the pores of the substrate, and nano MnO loaded on the surface and in the pores of the substrate2And the outermost side of the surface of the base material is encapsulated with a graphite layer.
The preparation method of the wood-based flexible electrode of the embodiment comprises the following steps:
1) cutting 1.2 mm thick, deionized water washed and dried beech wood sliced veneer into 60 mm pieces, placing on the filter paper of a suction filtration funnel, pouring 5% graphene oxide aqueous solution as a filtrate, and performing suction filtration. In the process, the solution penetrates through the veneer and is repeated for 3 times, the graphene oxide is loaded in pores of the veneer, the veneer is flattened, the veneer is dried at 60 ℃ until the water content is 10%, and graphene floating powder on the surface of the veneer is removed by a brush, so that the graphene oxide-loaded veneer is obtained.
2) Repeatedly rubbing one surface of the veneer obtained in the step 1) by using a high-purity graphite rod to enable a layer of graphite layer to be uniformly attached to the surface of the veneer, repeatedly bending the veneer for 10 times, and removing graphite floating powder on the surface by using a brush.
3) And (3) repeating the step 2) once to obtain the beech wood sliced veneer with a single surface firmly packaged with the high-purity graphite layer.
4) Completely immersing the veneer obtained in the step 3) in KMnO with the mass concentration of 20% at normal temperature and normal pressure4Taking out the solution, drying at 60 deg.C to water content of 10% to obtain loaded KMnO4The veneer of (2).
5) Soaking in KMnO at normal temperature and pressure4The veneer is completely immersed in H with the mass concentration of 12%2O2KMnO in wood veneer 24h in alkaline solution (pH = 10)4And H2O2MnO formed by the reaction2And deposited and attached on the surface and in the pores of the veneer to realize the nano MnO2When no bubble emerges, the reaction is complete to obtain the loaded nano MnO2The veneer of (2).
6) Repeatedly washing the veneer obtained in the step 5) with deionized water until the washing liquid becomes neutral, and drying until the water content is 10%.
7) According to the method in the step 2), the graphite layer is firmly attached to the other surface of the veneer without the graphite layer, and the nano MnO deposited in the veneer matrix2And graphene oxide encapsulationThus, a beech-based flexible electrode was obtained.
At 3 mol/L of Na2SO4The solution is electrolyte, the beech-based flexible electrode, the saturated calomel electrode and the platinum sheet electrode are respectively used as a working electrode, a reference electrode and a counter electrode, and the specific capacitance at 100 mV/s is 296.8F/g; the specific capacitance in the bent state was 291.5F/g; the specific capacitance retention rate after 2000 cycles is 95.7%, and the electrochemical performance is excellent.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments to equivalent variations, without departing from the scope of the invention, using the teachings disclosed above. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.

Claims (8)

1. A preparation method of a wood-based flexible electrode is characterized by comprising the following steps: the method comprises the following steps:
s1, taking the graphene oxide aqueous solution as a filtrate, taking rotary-cut or sliced sheet-shaped veneer as a filtering membrane for suction filtration treatment, loading the graphene oxide in pores of the veneer, and drying to obtain the graphene oxide-loaded veneer;
s2, taking a graphite rod as a packaging material, rubbing the graphite rod on one surface of the graphene oxide loaded veneer obtained in the step S1 to enable a graphite layer to be uniformly attached to the surface of the veneer, repeatedly bending the veneer, and removing graphite floating powder on the surface of the veneer to obtain the veneer with the single-side packaged graphite layer;
s3, soaking the veneer of the single-side packaging graphite layer obtained in the step S2 in KMnO at normal temperature4KMnO loaded in aqueous solution4Drying, and soaking in H at room temperature2O2In alkaline solution, nano MnO is loaded through oxidation-reduction reaction2Flushing the veneer with water until the flushed liquor is neutral,drying to obtain the loaded nano MnO2The veneer of (2);
s4, taking the graphite rod as a packaging material, and loading the nano MnO obtained in the step S3 according to the method in the step S22And uniformly packaging a graphite layer on the other surface of the veneer to obtain the wood-based flexible electrode.
2. The method of claim 1, wherein: and after removing the graphite floating powder on the surface of the veneer, repeating the step of removing by friction bending for 1-2 times.
3. The production method according to claim 1 or 2, characterized in that: in the step S1, the mass fraction of the graphene oxide aqueous solution is 2-5%.
4. The production method according to claim 3, characterized in that: in step S1, after drying, graphene floating powder on the surface of the veneer needs to be removed.
5. The production method according to claim 1 or 2, characterized in that: in the step S3, the KMnO4The mass concentration of the aqueous solution is 10-20%, and the loaded KMnO4The time is 20-60 min.
6. The method of claim 5, wherein: in the step S3, the H2O2The mass concentration of the alkaline solution is 8-12%, the pH value is 9-11, and the supported nano MnO is2The time of the reaction is 2-24 hours.
7. Use of the wood-based flexible electrode prepared according to the preparation method of any one of claims 1 to 6 in a supercapacitor.
8. Use according to claim 7, characterized in that: the super capacitor uses a wood-based flexible electrode as a working electrode.
CN202010494292.4A 2020-06-03 2020-06-03 Wood-based flexible electrode and preparation method and application thereof Active CN111640586B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010494292.4A CN111640586B (en) 2020-06-03 2020-06-03 Wood-based flexible electrode and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010494292.4A CN111640586B (en) 2020-06-03 2020-06-03 Wood-based flexible electrode and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111640586A CN111640586A (en) 2020-09-08
CN111640586B true CN111640586B (en) 2022-01-25

Family

ID=72331334

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010494292.4A Active CN111640586B (en) 2020-06-03 2020-06-03 Wood-based flexible electrode and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111640586B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112582244B (en) * 2020-12-14 2022-07-05 中南林业科技大学 Non-porous TEM grid-supported supporting film based on wood slices and preparation method and application thereof
CN112635202A (en) * 2020-12-29 2021-04-09 北京化工大学 Nickel cobaltate @ graphene @ China fir composite material electrode and preparation method and application thereof
CN114589781B (en) * 2022-03-04 2022-08-09 浙江大学 Wood-based wet gas generator and preparation method thereof
CN114613617A (en) * 2022-03-25 2022-06-10 北京林业大学 Preparation method of wood-based micro supercapacitor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107742583A (en) * 2017-09-28 2018-02-27 中国林业科学研究院木材工业研究所 A kind of wooden based combined electrode material and preparation method thereof
CN108492997A (en) * 2018-03-15 2018-09-04 南通纺织丝绸产业技术研究院 Silk base flexible electrode material and preparation method thereof
CN109087822A (en) * 2018-10-15 2018-12-25 南京邮电大学 A kind of flexible-paper-base graphene supercapacitor preparation method
CN110164715A (en) * 2019-05-30 2019-08-23 北京林业大学 A kind of preparation method of wooden base flexible composite electrode material
CN111362250A (en) * 2020-03-16 2020-07-03 四川大学 High specific capacitance super-thick biochar, biochar monolithic electrode and biochar composite electrode

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11440214B2 (en) * 2017-04-03 2022-09-13 University Of Maryland, College Park Flexible wood structures and devices, and methods for fabricating and use thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107742583A (en) * 2017-09-28 2018-02-27 中国林业科学研究院木材工业研究所 A kind of wooden based combined electrode material and preparation method thereof
CN108492997A (en) * 2018-03-15 2018-09-04 南通纺织丝绸产业技术研究院 Silk base flexible electrode material and preparation method thereof
CN109087822A (en) * 2018-10-15 2018-12-25 南京邮电大学 A kind of flexible-paper-base graphene supercapacitor preparation method
CN110164715A (en) * 2019-05-30 2019-08-23 北京林业大学 A kind of preparation method of wooden base flexible composite electrode material
CN111362250A (en) * 2020-03-16 2020-07-03 四川大学 High specific capacitance super-thick biochar, biochar monolithic electrode and biochar composite electrode

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Synthesis of porous graphitic carbon from biomass by one-step method And its role in the electrode for supercapacitor;Zhang Xiaohua;《Journal of Applied Electrochemistry》;20181231;全文 *

Also Published As

Publication number Publication date
CN111640586A (en) 2020-09-08

Similar Documents

Publication Publication Date Title
CN111640586B (en) Wood-based flexible electrode and preparation method and application thereof
CN110164715B (en) Preparation method of wood-based flexible composite electrode material
CN105118688B (en) A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film material
KR100649092B1 (en) Metal oxide supercapacitor having metal oxide electrode coated onto the titanium dioxide ultrafine and its fabrication method
CN105175761B (en) A kind of preparation method and applications of bacteria cellulose/polyaniline/graphene film material
CN110256733B (en) Preparation method of cellulose network polyaniline composite material and supercapacitor
CN108520830B (en) Preparation method of sheath-core porous graphene fiber and supercapacitor
CN110060885A (en) A kind of flexible fabric electrode and the preparation method and application thereof
CN107195906A (en) A kind of porous carbon cloth, preparation method and applications
CN104231623B (en) A kind of metal ion mixing is prepared the method for different-shape graphene oxide/polyaniline composite electrode material
Yang et al. High Mass‐Loading Biomass‐Based Porous Carbon Electrodes for Supercapacitors: Review and Perspectives
CN104716335B (en) A kind of flow battery electrode and preparation and application
CN109003840A (en) A kind of preparation method of compound paper base flexible electrode material
Li et al. Enhancing the supercapacitor performance of flexible MXene/carbon cloth electrodes by oxygen plasma and chemistry modification
CN114030046B (en) Preparation method of isotropic conductive paper
Thielke et al. Sustainable electrodes for the next generation of redox flow batteries
CN105788884A (en) Preparation method of manganese dioxide/carbon paper composite electrode for super capacitor
CN114486010A (en) Flexible piezoresistive sensor and preparation method thereof
CN105513834B (en) A kind of preparation method and applications of bacteria cellulose graphene paper supported cobaltosic oxide flexible electrode material
CN108492997B (en) Silk base flexible electrode material and preparation method thereof
CN111747409A (en) Preparation method of phosphotungstic acid catalyzed hemp stem core hydrothermal carbon material
CN109741970A (en) A kind of preparation method of lignin modification active carbon high-performance energy storage material
EP3761331B1 (en) Electrochemical element separator and electrochemical element
CN113096969A (en) Polymer gel electrolyte-electrode and preparation method thereof, super capacitor and preparation method thereof
CN102268690B (en) Diaphragm for electrochemical synthesis of dinitrogen pentoxide and preparation method thereof

Legal Events

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