CN110942926B - Bagasse-based activated carbon layered structure electrode material, preparation method thereof and application thereof in supercapacitor - Google Patents

Bagasse-based activated carbon layered structure electrode material, preparation method thereof and application thereof in supercapacitor Download PDF

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CN110942926B
CN110942926B CN201911324744.8A CN201911324744A CN110942926B CN 110942926 B CN110942926 B CN 110942926B CN 201911324744 A CN201911324744 A CN 201911324744A CN 110942926 B CN110942926 B CN 110942926B
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宋雪萍
樊晗晗
柴新宇
康希恒
何辉
吴敏
王双飞
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Guangxi University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract

The invention provides a supercapacitor electrode material and a preparation method and application thereof2Preparation of composite alpha-MnO2@ ZAC and freeze drying in alpha-MnO2Loading CNT on the surface of @ ZAC to build up network structure, and electrochemical deposition of delta-MnO2The layered structure electrode material (AMCM) is prepared as the electrode material of the supercapacitor. The layered structure electrode material (AMCM) has larger specific capacitance and good cyclicity in a three-electrode system, and is assembled into an asymmetric supercapacitor MnZAC/CNT/MnO2the/ZAC has good rate performance, is an ideal electrode material and has wide application prospect in the field of super capacitors.

Description

Bagasse-based activated carbon layered structure electrode material, preparation method thereof and application thereof in supercapacitor
Technical Field
The invention belongs to the technical field of preparation of electrode materials of supercapacitors, and particularly relates to alpha-MnO loaded after activated carbon is prepared by using zinc chloride activated bagasse2Post-deposition of delta-MnO with post-loaded CNT2A method for preparing an electrode material with a layered structure.
Background
With the continuous deepening of the industrialization process of the 21 st century, energy and environmental problems become two important challenges in the world today, and ensuring the safety and stability of national energy is a major problem facing all countries in the world. The electric energy is a clean, efficient and stable energy source, but the energy storage technology still needs to be developed, and the preparation of a high-performance energy storage device with high power density, high energy density and long service life and capable of realizing rapid charge and discharge is a development direction with great potential. As a new energy storage device, the super capacitor has important potential in the fields of national defense and military industry, urban public transport, intelligent electronic products, new energy power vehicles, flexible wearable equipment and the like, and compared with the traditional iron-manganese battery, the super capacitor has the advantages of high power density, high charging speed, long service life, suitability for various environments and the like. However, the current commercialized super capacitor still has the defect of low energy density (usually less than 10Wh/kg), which makes it unable to meet the requirement of industrial enterprises and social development for energy, therefore, increasing the energy density of super capacitor becomes the primary task of capacitor energy storage technology. The electrode materials forming the super capacitor are key factors influencing the capacitive performance of the super capacitor, at present, the further improvement of the performance of the electrode materials and the design of composite electrode materials become important ways for the capacity expansion of the super capacitor, and with the deepening of research, researchers think that different materials are compounded, and the development of novel electrode materials with better performance by mutually compensating the respective defects and achieving a synergistic effect is the electrochemical performance improvement with the most potential.
Environmental concerns have also raised concerns from researchers around the world, particularly as renewable resources have become the most potential source of resources in the future due to the increasing consumption of fossil resources. In the selection of electrode materials of energy storage devices, agricultural wastes are abundant in raw material sources and green and cheap in price, so that the preparation of carbon electrode materials by using the agricultural wastes attracts the attention of many researchers. The bagasse is biomass waste with Guangxi characteristics, and has regional advantages of high yield, concentrated production places, complete industrial chain and the like. Before, the bagasse is usually used as a fuel for power generation or used as a paper making raw material for producing various paper products, and the added value of the product still has a large space for improvement. Therefore, the method for preparing the activated carbon by using the bagasse as the carbon source and applying the activated carbon to the super capacitor is a promising biomass high-value utilization mode. In the electrode material, the activated carbon has natural advantages, and the abundant pore structure and the large specific surface area can provide mass transfer channels and adsorption sites for free diffusion and energy storage of electrolyte ions. Currently, preparing an activated carbon electrode material with a higher specific surface area, a more reasonable pore size distribution, and a richer surface functional group is a major development direction of current research. In addition, the electrode material achieves better electrochemical performance behavior through compounding, so that the performance of the activated carbon can be optimized, and the effect of complementing and perfecting the electrode material can be achieved.
Disclosure of Invention
In order to realize the aim, the invention provides alpha-MnO loaded after activated carbon is prepared by using zinc chloride activated bagasse2Post-deposition of delta-MnO with post-loaded CNT2The method for preparing the electrode material with the layered structure provides the electrode material of the super capacitor with high specific capacitance, good cycle performance and good rate performance, and has wide application prospect.
The above purpose of the invention is realized by the following technical scheme:
a bagasse-based active carbon layered structure electrode material is prepared by using bagasse as a raw material and activating the bagasse by using zinc chloride to prepare mesoporous active carbon ZAC; reuse of KMnO4alpha-MnO of nano linear structure is loaded on the surface of active carbon ZAC under hydrothermal condition2Preparation of composite alpha-MnO2@ ZAC; then the CNT is loaded in alpha-MnO by a freeze drying method2Preparation of composite material alpha-MnO on @ ZAC2@ ZAC/CNT to build up network structures; finally in (CH)3COO)2In Mn electrolyte solution in alpha-MnO2@ ZAC/CNT surface electrochemical deposition of delta-MnO2Obtaining bagasse-based active carbon layered structure electrode material alpha-MnO2@ZAC/CNT/δ-MnO2(ii) a The bagasse-based active carbon layered structure electrode material is delta-MnO from outside to inside in sequence2Carbon nano-meterTube CNT, alpha-MnO2And active carbon ZAC.
The carbon nano tube CNT is a multi-wall carbon nano tube with the inner diameter of 3-5 nm.
The bagasse-based active carbon layered structure electrode material is prepared by the following steps:
(1) bagasse is used as a raw material, and zinc chloride is utilized to prepare active carbon ZAC by a two-step hydrothermal method: mixing bagasse with H2O2Mixing the water solution, placing the mixture in a high-temperature high-pressure reaction kettle for hydrothermal reaction to obtain a first-step hydrothermal product, drying the first-step hydrothermal product, and then mixing the dried first-step hydrothermal product with ZnCl2Mixing the mixture in ultrapure water, placing the mixture in a high-temperature high-pressure reaction kettle for further hydrothermal reaction to obtain a second hydrothermal product, drying the second hydrothermal product, and placing the dried second hydrothermal product in a tubular furnace for further carbonization: heating the hydrothermal product of the second step in high-purity nitrogen, and then adding CO2After reaction in the gas, switching to nitrogen, cooling to room temperature, washing to neutrality by using HCl solution and deionized water, and drying to obtain active carbon ZAC;
(2) mixing the active carbon ZAC prepared in the step (1) with KMnO4In CH3Mixing the COOH solution, putting the mixture into a high-temperature high-pressure reaction kettle for hydrothermal reaction to prepare the composite material alpha-MnO2@ ZAC, repeatedly washing with deionized water to neutrality, and drying;
(3) alpha-MnO prepared in the step (2)2Mixing the @ ZAC with the CNT solution of the carbon nano tube, and preparing the composite material alpha-MnO by a freeze drying method2@ ZAC/CNT, followed by (CH)3COO)2Electrochemical deposition of delta-MnO in Mn electrolyte solution2Obtaining bagasse-based active carbon layered structure electrode material alpha-MnO2@ZAC/CNT/δ-MnO2Washing with deionized water to neutrality, and drying.
Bagasse and H in the step (1)2O2The ratio of the aqueous solution was 15g:90mL, H2O2The mass concentration of the aqueous solution is 10 wt%; the first step hydrothermal product is reacted with ZnCl2The mass ratio of (A) to (B) is 2: 1; the first step hydrothermal product and ZnCl2The volume ratio of the total mass of the ultrapure water to the ultrapure water is 1g:6 mL; the reaction conditions of the two-step hydrothermal method are as follows: at a rate of 3.7 deg.C/minHeating to 200 deg.C and maintaining for 20 min; the temperature rise in the high-purity nitrogen is carried out at the speed of 10 ℃/min to 800 ℃, the nitrogen flow rate is 50mL/min, and the temperature rise in CO is carried out2The reaction in gas is carried out with CO at a flow rate of 40mL/min2Reacting for 2 hours in the gas.
CH in the step (2)3The concentration of the COOH solution was 0.4M; the active carbon ZAC and KMnO4、CH3The ratio of the COOH solution was 0.625g:0.5g:30 mL; the hydrothermal reaction is carried out under the condition that the temperature is heated to 140 ℃ from room temperature in a reaction kettle, and the temperature is kept constant at 140 ℃ for 12 hours.
The mass concentration of the CNT solution of the carbon nano tube in the step (3) is 0.3 wt%, and the CNT solution of the carbon nano tube and the alpha-MnO are2The mass ratio of @ ZAC is 0.015: 0.3; the freeze-drying method is to freeze-dry for 3 days at the temperature of minus 20 ℃; said (CH)3COO)2The concentration of Mn electrolyte is 1M, and the conditions of electrochemical deposition are as follows: cycling between 0.4V and 1.0V for 1 cycle at a scan rate of 2mV/s, 10mV/s, 30mV/s, 50 mV/s.
The bagasse-based activated carbon layered structure electrode material can be used as an electrode material of a supercapacitor, has excellent electrochemical properties such as high specific capacitance, good cycle performance and good rate capability, and is applied to the supercapacitor within the protection range of the invention.
The invention provides alpha-MnO loaded after preparation of active carbon ZAC by using zinc chloride activated bagasse2Post-deposition of delta-MnO with post-loaded CNT2A method for preparing an electrode material with a layered structure. alpha-MnO loaded on active carbon ZAC2The specific capacitance is improved by adding a metal oxide to an electric double layer electrode material to increase the pseudo capacitance. Pure activated carbon as an electrode material provides only a double electric layer capacitance of physical adsorption between an electrolyte and electrostatic charges on the surface of the electrode material, and supports a metal oxide alpha-MnO2A pseudocapacitance of the interaction stored energy of the faraday electrochemical activation reaction may be provided. The natural pore structure advantage and high specific surface area of the activated carbon as a traditional carbon-based material enable the activated carbon to be used as a better conductive material, and the pore structure advantage and high specific surface area of the activated carbon can be in a nanowire typealpha-MnO of2Providing growth nucleation sites by making composite material alpha-MnO2@ ZAC is intended to enhance the electrochemical properties of activated carbon by synergistic effect and to exert MnO2The electrochemical performance of the activated carbon is optimized while the pseudocapacitance is maintained, so that the overall electrochemical performance is improved. In the alpha-MnO2Carrying CNT on @ ZAC and depositing delta-MnO2The function of the method is to further prepare the composite electrode material so as to further improve the performance of the super capacitor. By loading the CNT (carbon nano-tube) which is a one-dimensional material on the surface of the activated carbon substrate material, on one hand, the activated carbon substrate material can be used as a conductive substrate material and provides more sites for delta-MnO2Growth, with less impact on the activated carbon substrate material, configuration for delta-MnO2A new surface of the load; on the other hand, MnO is relatively thinned2Thickness of layer, MnO2The theoretical specific capacitance can be fully exerted, not only can a new surface be constructed, but also a lower layer material can not be covered, so that the performance of the super capacitor is further improved.
The invention has the beneficial effects that: the invention provides alpha-MnO loaded after preparation of active carbon ZAC by using zinc chloride activated bagasse2Post-deposition of delta-MnO with post-loaded CNT2Preparation of layered electrode material alpha-MnO2@ZAC/CNT/δ-MnO2The method can obtain the electrode material with the laminated structure and excellent electrochemical properties such as high specific capacitance, good cycle performance, good multiplying power performance and the like, and has the following advantages compared with the traditional electrode material active carbon: 1) the specific capacitance of the super capacitor is greatly increased; 2) the prepared electrode material with the laminated structure is alpha-MnO2@ZAC/CNT/δ-MnO2The external specific surface area of the activated carbon can be increased; 3) adding MnO at the same time2A nucleation site of, MnO2Theoretical specific capacitance of (2).
Drawings
FIG. 1 is a flow chart of a process for preparing the bagasse-based activated carbon layered structure electrode material of the present invention.
Detailed Description
Example 1
Preparation of activated carbon ZAC:
(1) first, in a first step hydrothermalIn the process, 15g of dried bagasse and 90mL of 10% by weight H2O2Mixing the aqueous solutions, placing the solid-liquid mixture in a high-temperature high-pressure reaction kettle, heating to 200 ℃ at the speed of 3.7 ℃/min, preserving heat for 20min, then quickly cooling the reaction kettle to room temperature by utilizing cooling circulating water washing, and drying the obtained solid-liquid mixture at 105 ℃ for 12h to obtain dry solid;
(2) then, in the second hydrothermal process, the solid product obtained in the first hydrothermal process is mixed with ZnCl2Mixing the solid in a mass ratio of 2:1, uniformly mixing the solid with ultrapure water in a high-temperature high-pressure reaction kettle in a solid-liquid ratio of 1g:6mL, obtaining a second-step hydrothermal product under the same hydrothermal temperature rise program, and drying the product for later use;
(3) finally, carbonizing the obtained hydrothermal product solid in the second step, putting the sample in a nickel boat, and adding high-purity N2Under protection, the temperature is raised to 800 ℃ at the speed of 10 ℃/min, wherein N2The flow rate was 50 mL/min. Then, protective gas N is added2Switching to the reaction gas CO2The sample was brought to 40mL/min CO2Reacting in gas for 2h, and after the reaction is finished, adding CO as reaction gas2Switching to protective gas N2The sample was taken out after the temperature was lowered to room temperature under an inert atmosphere. Washing the sample obtained by carbonization with 0.1mol/LHCl solution at 80 ℃ for 60s, washing with deionized water to neutrality, and drying at 105 ℃ for 24h to obtain the active carbon ZAC.
As a result: the obtained ZAC specific surface area of the activated carbon is 1419.08m2G, maximum pore volume 0.65cm3G, pore size distribution of phi<5nm mesoporous activated carbon with high graphitization degree, wherein the ZAC surface of the activated carbon contains a certain amount of different oxygen-containing functional groups; ZAC mesoporous activated carbon is used as an electrode material, and the double-layer capacitance of the assembled symmetrical super capacitor ZAC// ZAC in a three-electrode system is represented by high specific capacitance 282F/g, excellent rate performance (190F/g, kept at 10A/g), and good cycle stability (98.5% of specific capacitance is kept in 1000 cycles) in the formed symmetrical double-layer super capacitor; the maximum energy density at 4756.85W/kg is 29.4Wh/kg, which is far superior to the energy density of a common commercial electrode material (<3Wh/kg)。
Example 2
Using KMnO4Hydrothermal method of one-dimensional nano-linear alpha-MnO of ZAC obtained in example 12The load of (2):
(1) before hydrothermal reaction, 0.5g of KMnO was accurately weighed4The powder was placed in an Erlenmeyer flask, to which was added 30mL of 0.4M CH3Stirring the COOH solution at room temperature until the COOH solution is dissolved;
(2) then 0.625g of ZAC is weighed and mixed with the solution, and then the mixture is transferred into a 100mL polytetrafluoroethylene lining type reaction kettle for hydrothermal reaction;
(3) when the hydrothermal reaction is carried out, the reaction kettle is placed in an oven, heated to 140 ℃ from room temperature, and kept at the 140 ℃ for 12 hours. After the reaction is finished, rapidly cooling the reaction kettle in cold water to room temperature to rapidly terminate the hydrothermal reaction;
(4) repeatedly pumping and filtering the solid product obtained in the step (3) by using distilled water, washing to be neutral, and drying in a drying oven at the temperature of 60 ℃ for 12 hours to obtain alpha-MnO2@ ZAC composite, this composite being designated as MnZAC.
As a result: the MnZAC surface of the obtained composite material is successfully doped with 15.23 wt% of Mn element, and a hydrothermal method mainly forms alpha-MnO of a nano structure taking a nano rod shape with a one-dimensional tunnel structure as a main crystal phase on the ZAC surface2The composite material MnZAC has a specific capacitance of 327F/g, and the performance is better than that of 282F/g of ZAC. The assembled asymmetric super capacitor MnZAC// ZAC is 1M Na2SO4The electrolyte can still maintain the specific capacitance retention rate of 88.2 percent after being circulated for 1000 times; and the electrochemical resistance is small.
Example 3
Bagasse-based active carbon layered structure electrode material alpha-MnO2@ZAC/CNT/δ-MnO2The preparation of (1):
on the basis of the composite material MnZAC in the embodiment 2, MnO is deposited after a layered network structure is constructed on the MnZAC by utilizing a freeze drying-electrochemical deposition two-step method2Preparation of alpha-MnO2@ZAC/CNT/δ-MnO2The method comprises the following specific operation steps:
(1) firstly, preparing a CNT solution with the mass concentration ratio of 0.3 wt%, then measuring 5mL of the CNT solution and mixing with 0.3g of MnZAC, wherein the mass ratio of mCNT to mMnZAC is 0.015:0.3, carrying out ultrasonic treatment for 20min under the condition of 60kW power, then placing the mixture in a refrigerator at the temperature of-20 ℃ for freezing, and then carrying out freeze drying for 3 days to obtain solid powder of the MnZAC/CNT composite material;
(2) next, electrochemical deposition of the surface of the MnZAC/CNT composite is carried out at 1M (CH)3COO)2The method is carried out in Mn electrolyte solution, and the deposition conditions are as follows: circulating at a certain scanning rate (2mV/s, 10mV/s, 30mV/s, 50mV/s) for 1 period between 0.4V and 1.0V (compared with Ag/AgCl), repeatedly washing the sample with deionized water for 3 times, and drying at room temperature to obtain the electrode material (alpha-MnO) with a laminated structure2@ZAC/CNT/δ-MnO2) The sample of (2) is named AMCM.
The obtained electrode material AMCM with the layered structure takes MnZAC as a substrate material, a network structure is built on the surface of the substrate material by loading CNT, and delta-MnO is electrochemically deposited on the CNT network structure2Designing and preparing electrode material delta-MnO of laminated structure2@ZAC/CNT/δ-MnO2The electrode material is delta-MnO from outside to inside in sequence2、CNT、α-MnO2And ZAC activated carbon.
Competition mechanism of CNT ability to fit holes and hide holes on MnZAC surface: when the loading capacity of the CNT is low, the multi-walled carbon nanotubes with the inner diameter of 5nm and the length of 50 μm are loosely parallel to and intersect with the surface of the substrate material MnZAC to form a network structure, so that part of the pore structure of the MnZAC is shielded, meanwhile, the formed network structure can increase part of the mesoporous structure, and the hole lapping capacity of the CNT is higher than the hole shielding capacity. When the loading capacity of the CNT reaches a certain value (0.015g), the CNT can be densely wound and distributed on the surface of the MnZAC, and the parallel and crossed mesoporous structure is converted into a microporous structure, so that most of the pore structure can be shielded, a microporous structure (2-5nm) mainly formed by winding and building the CNT and a partial mesoporous structure (5-10nm) are formed, a part of pore volume brought by a 5nm inner diameter structure of the CNT is also existed, and the hole shielding capacity is larger than the hole building capacity; meanwhile, the material AMCM (2-10 nm) with the most prominent pore structure is subjected to electrochemical performance testThe obtained mass specific capacitance is 346F/g, the ratio ZAC and alpha-MnO2The electrochemical performance of the @ ZAC is more excellent, and the asymmetric supercapacitor AMCM// ZAC assembled by the capacitor still has 79% of specific capacitance retention rate after 1000 cycles.

Claims (3)

1. A bagasse-based active carbon layered structure electrode material is characterized in that bagasse is used as a raw material, and mesoporous active carbon ZAC is prepared by activating the bagasse with zinc chloride; reuse of KMnO4Loading alpha-MnO on the ZAC surface of active carbon under hydrothermal condition2Preparation of alpha-MnO2@ ZAC; then the CNT is loaded in alpha-MnO by a freeze drying method2Preparation of alpha-MnO on @ ZAC2@ ZAC/CNT; finally in (CH)3COO)2In Mn electrolyte solution in alpha-MnO2@ ZAC/CNT surface electrochemical deposition of delta-MnO2Obtaining the bagasse-based active carbon layered structure electrode material; the bagasse-based active carbon layered structure electrode material is delta-MnO from outside to inside in sequence2Carbon nanotube CNT and alpha-MnO2Activated carbon ZAC; the preparation method comprises the following steps:
(1) bagasse is used as a raw material, and zinc chloride is utilized to prepare active carbon ZAC by a two-step hydrothermal method: mixing bagasse with H2O2Mixing the water solution, placing the mixture in a high-temperature high-pressure reaction kettle for hydrothermal reaction to obtain a first-step hydrothermal product, drying the first-step hydrothermal product, and then mixing the dried first-step hydrothermal product with ZnCl2Mixing the mixture in ultrapure water, placing the mixture in a high-temperature high-pressure reaction kettle for further hydrothermal reaction to obtain a second hydrothermal product, heating the second hydrothermal product in high-purity nitrogen, and then adding CO2After reaction in the gas, switching to nitrogen gas, cooling to room temperature, washing, and drying to obtain active carbon ZAC;
(2) mixing the active carbon ZAC prepared in the step (1) with KMnO4In CH3Mixing the COOH solution, putting the mixture into a high-temperature high-pressure reaction kettle for hydrothermal reaction to prepare the composite material alpha-MnO2@ ZAC, washing, drying;
(3) alpha-MnO prepared in the step (2)2Mixing the @ ZAC with the CNT solution of the carbon nano tube, and preparing the composite material alpha-MnO by a freeze drying method2@ZAC/CNT, followed by (CH)3COO)2Electrochemical deposition of delta-MnO in Mn electrolyte2Obtaining bagasse-based active carbon layered structure electrode material alpha-MnO2@ZAC/CNT/δ-MnO2Washing and drying;
bagasse and H in the step (1)2O2The ratio of the aqueous solution was 15g:90mL, H2O2The mass concentration of the aqueous solution is 10 wt%; the first step hydrothermal product is reacted with ZnCl2The mass ratio of (A) to (B) is 2: 1; the first step hydrothermal product and ZnCl2The volume ratio of the total mass of the ultrapure water to the ultrapure water is 1g:6 mL; the reaction conditions of the two-step hydrothermal method are as follows: heating to 200 deg.C at a rate of 3.7 deg.C/min and maintaining for 20 min; the temperature rise in the high-purity nitrogen is carried out at the speed of 10 ℃/min to 800 ℃, the nitrogen flow rate is 50mL/min, and the temperature rise in CO is carried out2The reaction in gas is carried out with CO at a flow rate of 40mL/min2Reacting for 2 hours in gas;
CH in the step (2)3The concentration of the COOH solution was 0.4M; the active carbon ZAC and KMnO4、CH3The ratio of the COOH solution was 0.625g:0.5g:30 mL; the hydrothermal reaction is carried out under the condition that the temperature is heated to 140 ℃ from room temperature in a reaction kettle, and the temperature is kept constant at 140 ℃ for 12 hours;
the mass concentration of the carbon nano tube CNT solution in the step (3) is 0.3 wt%, and the carbon nano tube CNT and the composite material alpha-MnO are2The mass ratio of @ ZAC is 0.015: 0.3; the freeze-drying method is to freeze-dry for 3 days at the temperature of minus 20 ℃; said (CH)3COO)2The concentration of the Mn electrolyte solution is 1M, and the conditions of electrochemical deposition are as follows: cycling between 0.4V and 1.0V for 1 period at a scan rate of 2mV/s, 10mV/s, 30mV/s, or 50 mV/s.
2. The bagasse-based activated carbon layered structure electrode material as described in claim 1, wherein the carbon nanotube CNT is a multi-walled carbon nanotube having an inner diameter of 3 to 5 nm.
3. Use of the bagasse-based activated carbon layered structure electrode material as described in any one of claims 1 to 2 in a supercapacitor.
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