CN110379646B - Preparation method of asymmetric supercapacitor based on molybdenum diselenide/charcoal - Google Patents

Preparation method of asymmetric supercapacitor based on molybdenum diselenide/charcoal Download PDF

Info

Publication number
CN110379646B
CN110379646B CN201910679107.6A CN201910679107A CN110379646B CN 110379646 B CN110379646 B CN 110379646B CN 201910679107 A CN201910679107 A CN 201910679107A CN 110379646 B CN110379646 B CN 110379646B
Authority
CN
China
Prior art keywords
charcoal
molybdenum diselenide
temperature
solution
preparing
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
CN201910679107.6A
Other languages
Chinese (zh)
Other versions
CN110379646A (en
Inventor
万才超
魏松
吴义强
张陆雨
田文燕
刘心怡
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 CN201910679107.6A priority Critical patent/CN110379646B/en
Publication of CN110379646A publication Critical patent/CN110379646A/en
Application granted granted Critical
Publication of CN110379646B publication Critical patent/CN110379646B/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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

A preparation method of an asymmetric super capacitor based on molybdenum diselenide/charcoal relates to a preparation method of an asymmetric super capacitor. The invention solves the problems of high preparation cost and low specific capacitance of the existing carbon material. The preparation method comprises the following steps: firstly, removing lignin; secondly, preparing molybdenum diselenide powder; thirdly, preparing wood chips loaded with molybdenum diselenide; fourthly, preparing the molybdenum diselenide/charcoal composite material; fifthly, preparing charcoal; sixthly, preparing a manganese dioxide/charcoal composite material; and seventhly, preparing the asymmetric super capacitor. The method is used for preparing the asymmetric supercapacitor based on the molybdenum diselenide/charcoal.

Description

Preparation method of asymmetric supercapacitor based on molybdenum diselenide/charcoal
Technical Field
The invention relates to a preparation method of an asymmetric supercapacitor.
Background
With the rapid consumption of traditional fossil resources and the increasing severity of environmental pollution, the demand for new energy materials, which are green and sustainable, and low-cost and high-performance energy storage systems is urgent. The development of more environmentally friendly and more efficient energy storage and conversion technologies is the key to achieving global energy sustainability. The development of supercapacitors offers the possibility of sustainable use of energy. The super capacitor has the advantages of high specific capacitance, high power density, high charging and discharging speed, long service life, wide applicable temperature range, high safety and the like, and is widely applied to the fields of military affairs, aviation, hybrid electric vehicles, mobile communication and the like. Currently, research on supercapacitors is mainly focused on developing new electrode materials, such as carbon materials, conductive polymers, transition metal oxides, and transition metal sulfur/selenides. Among them, molybdenum diselenide is a transition metal selenide having a graphene-like layered structure and a plurality of oxidation states coexisting, has a narrower energy band gap (1.33-1.72eV) and a larger interlayer distance (0.65nm) than other transition metal sulfur/selenides, has a more stable structure at the edge of unsaturated selenium and provides more electrochemically active sites, which makes the material itself have a higher faraday capacitance and a lower internal resistance, and is receiving wide attention in the field of electrochemical energy storage. However, in the actual preparation process, due to intermolecular forces, the layered molybdenum diselenide nanosheets are easily aggregated and have poor cycle stability, so the layered molybdenum diselenide nanosheets are usually designed into a composite nanostructure with a carbon material as a substrate to enhance the electrochemical performance, and the currently ideal carbon materials include graphene, carbon nanotubes, carbon fibers and the like, but have high cost. The charcoal is a carbon material which takes natural wood as a raw material and has the performances of high specific surface area, high porosity, high conductivity and the like after high-temperature carbonization, and the layered porous structure of the charcoal, such as vertical wood tube holes, micropores and nanopores, is favorable for ion diffusion and rapid migration of electrons. In addition, compared with the traditional mineral carbon material, the charcoal has the advantages of being renewable, environment-friendly, simple in process and the like, and the cost of the charcoal is far lower than that of carbon materials such as graphene, carbon nanotubes and carbon fibers. However, for the electrode material of the supercapacitor, the application of the supercapacitor with high specific capacitance cannot be satisfied only by realizing charge storage by using an electric double layer generated by net charge adsorption on the surface of the carbon material, the preparation cost is high, the specific capacitance is low, and the specific capacitance is only 30F/g-120F/g by using the carbon material as a negative electrode.
Disclosure of Invention
The invention provides a preparation method of an asymmetric supercapacitor based on molybdenum diselenide/charcoal, aiming at solving the problems of high preparation cost and low specific capacitance of the existing carbon material.
A preparation method of an asymmetric supercapacitor based on molybdenum diselenide/charcoal is carried out according to the following steps:
firstly, delignification:
cutting a wood raw material into square thin slices along the growth direction of trees to obtain wood chips with the thickness of 1-10 mm;
② thickeningWood chips with the degree of 1 mm-10 mm are dipped in NaOH and Na2SO3Heating the mixed solution for 1 to 10 hours in a water bath kettle at the temperature of between 50 and 100 ℃, and then pouring out waste liquid to obtain NaOH and Na2SO3Treated wood;
the NaOH and the Na2SO3The mixed solution is NaOH solution with the concentration of 0.01mmol/L to 10mmol/L and Na with the concentration of 0.01mmol/L to 10mmol/L2SO3The solution is prepared by mixing (0.1-10) by volume ratio of 1;
③ mixing NaOH and Na2SO3Boiling the treated wood with deionized water for 0.1-10 h, and then pouring out waste liquid;
fourthly, replacing deionized water, repeating the step one until waste liquid is colorless, then washing the waste liquid at normal temperature by using the deionized water as washing liquid until the washing liquid is neutral, and finally freeze-drying the waste liquid to obtain the wood chips without lignin;
secondly, preparing molybdenum diselenide powder:
reacting NaBH4Adding into water to obtain NaBH4Adding Se powder to NaBH4Magnetically stirring for 0.1-10 hr to obtain solution A, adding Na2MoO4·2H2Dissolving O in deionized water to obtain a solution B, mixing the solution A and the solution B, stirring for 0.1-10 h to obtain a homogeneous reddish brown solution C, placing the homogeneous reddish brown solution C in a high-pressure reaction kettle, carrying out hydrothermal reaction for 10-100 h at the temperature of 60-250 ℃, collecting dark gray precipitate, carrying out vacuum filtration, and finally carrying out vacuum drying to obtain molybdenum diselenide powder;
the NaBH4The mass ratio of the (0.01-1) to the volume of the water is 10 mL; the amount of Se powder is equal to that of NaBH4The mass ratio of (1) to (0.01-1) g; said Na2MoO4·2H2The volume ratio of the O substance to the deionized water is (0.01-20) mmol:60 mL; the volume ratio of the solution A to the solution B is 1 (0.1-10);
thirdly, preparing the molybdenum diselenide loaded wood chip:
adding molybdenum diselenide powder into water under the condition that the power is 100W-1000W, carrying out ultrasonic treatment for 0.1 h-10 h in an ice bath to obtain molybdenum diselenide suspension with the concentration of 0.1 mg/mL-10 mg/mL, soaking the wood chips with the lignin removed into the molybdenum diselenide suspension with the concentration of 0.1 mg/mL-10 mg/mL, carrying out ultrasonic treatment for 1 min-60 min under the condition that the power is 100W-1000W, and carrying out freeze drying to obtain the wood chips loaded with molybdenum diselenide;
fourthly, preparing the molybdenum diselenide/charcoal composite material:
placing the wood chip loaded with molybdenum diselenide into a high-temperature pyrolysis device, heating to 200-500 ℃ at a heating rate of 0.1-20 ℃/min under the condition of inert gas, preserving heat for 1-10 h at a temperature of 200-500 ℃, then heating to 800-2000 ℃ at a heating rate of 0.1-20 ℃/min, preserving heat for 1-10 h at a temperature of 800-2000 ℃, then cooling to 200-800 ℃ at a cooling rate of 0.1-20 ℃/min, and finally naturally cooling to room temperature to obtain the molybdenum diselenide/charcoal composite material;
fifthly, preparing charcoal:
putting the wood chips without the lignin into a high-temperature pyrolysis device, heating to 200-500 ℃ at a heating rate of 0.1-20 ℃/min under the condition of inert gas, preserving heat for 1-10 h at the temperature of 200-500 ℃, then heating to 800-2000 ℃ at a heating rate of 0.1-20 ℃/min, preserving heat for 1-10 h at the temperature of 800-2000 ℃, then cooling to 200-800 ℃ at a cooling rate of 0.1-20 ℃/min, and finally naturally cooling to room temperature to obtain charcoal;
sixthly, preparing the manganese dioxide/charcoal composite material:
soaking charcoal in 0.01-10 wt% potassium permanganate solution, heating at 40-250 deg.c for 0.1-100 hr, washing with deionized water, and vacuum drying to obtain composite manganese dioxide/charcoal material;
the mass ratio of the potassium permanganate to the charcoal in the potassium permanganate solution with the mass percentage of 0.01-10% is 1 (0.1-10);
seventhly, preparing an asymmetric super capacitor:
the molybdenum diselenide/charcoal composite material is used as a negative electrode, the manganese dioxide/charcoal composite material is used as a positive electrode, a KOH solution with the concentration of 3mol/L is used as an electrolyte, a cellulose filter membrane is used as a diaphragm, a gold foil is used as a current collector, then the molybdenum diselenide/charcoal composite material, the manganese dioxide/charcoal composite material and the cellulose filter membrane are soaked in the electrolyte for 0.1-100 h, and finally the asymmetric supercapacitor based on the molybdenum diselenide/charcoal is obtained through assembly.
The invention has the beneficial effects that:
firstly, the molybdenum diselenide/charcoal composite material prepared by the invention is at 1mA/cm2The area specific capacitance under the current density can reach 1043mF/cm2。
Secondly, the manganese dioxide/charcoal composite material prepared by the invention is at 0.2mA/cm2The area specific capacitance under the current density can reach 216.5mF/cm2。
Thirdly, the asymmetric super capacitor based on molybdenum diselenide/charcoal prepared by the invention is at 1mA/cm2The area specific capacitance under the current density can reach 307.8F/cm2At 40mA/cm2The capacity retention rate is 81.46% after 1000 times of cyclic charge and discharge under high current density.
And fourthly, the preparation method provided by the invention is simple and feasible, expensive equipment is not required, and most raw materials are wide in source, low in cost and renewable.
The invention relates to a preparation method of an asymmetric supercapacitor based on molybdenum diselenide/charcoal.
Drawings
FIG. 1 is a scanning electron micrograph of charcoal prepared according to step five of the example;
FIG. 2 is a scanning electron micrograph of a molybdenum diselenide/charcoal composite prepared according to step four of the example;
FIG. 3 is an X-ray diffraction diagram, 1 is a molybdenum diselenide/charcoal composite prepared in one step four of the example, and 2 is an X-ray diffraction standard card for molybdenum diselenide;
FIG. 4 is a drawing showingConstant current charge-discharge diagram, 1 is the manganese dioxide/charcoal composite material prepared in the sixth step of the example at 0.2mA/cm2A charge-discharge curve under current density, 2 is that the molybdenum diselenide/charcoal composite material prepared in the fourth step of the embodiment is at 1mA/cm2A charge-discharge curve at current density;
FIG. 5 shows the asymmetric supercapacitor based on molybdenum diselenide/charcoal prepared in the first example at 1mA/cm2A charge-discharge plot at current density;
FIG. 6 shows the asymmetric supercapacitor made of molybdenum diselenide/charcoal based at 40mA/cm prepared in accordance with example one2Cycle life diagram of 1000 times of cyclic charge and discharge under current density.
Detailed Description
The first embodiment is as follows: the preparation method of the asymmetric supercapacitor based on molybdenum diselenide/charcoal in the embodiment is carried out according to the following steps:
firstly, delignification:
cutting a wood raw material into square thin slices along the growth direction of trees to obtain wood chips with the thickness of 1-10 mm;
② soaking wood chips with thickness of 1 mm-10 mm in NaOH and Na2SO3Heating the mixed solution for 1 to 10 hours in a water bath kettle at the temperature of between 50 and 100 ℃, and then pouring out waste liquid to obtain NaOH and Na2SO3Treated wood;
the NaOH and the Na2SO3The mixed solution is NaOH solution with the concentration of 0.01mmol/L to 10mmol/L and Na with the concentration of 0.01mmol/L to 10mmol/L2SO3The solution is prepared by mixing (0.1-10) by volume ratio of 1;
③ mixing NaOH and Na2SO3Boiling the treated wood with deionized water for 0.1-10 h, and then pouring out waste liquid;
fourthly, replacing deionized water, repeating the step one until waste liquid is colorless, then washing the waste liquid at normal temperature by using the deionized water as washing liquid until the washing liquid is neutral, and finally freeze-drying the waste liquid to obtain the wood chips without lignin;
secondly, preparing molybdenum diselenide powder:
reacting NaBH4Adding into water to obtain NaBH4Adding Se powder to NaBH4Magnetically stirring for 0.1-10 hr to obtain solution A, adding Na2MoO4·2H2Dissolving O in deionized water to obtain a solution B, mixing the solution A and the solution B, stirring for 0.1-10 h to obtain a homogeneous reddish brown solution C, placing the homogeneous reddish brown solution C in a high-pressure reaction kettle, carrying out hydrothermal reaction for 10-100 h at the temperature of 60-250 ℃, collecting dark gray precipitate, carrying out vacuum filtration, and finally carrying out vacuum drying to obtain molybdenum diselenide powder;
the NaBH4The mass ratio of the (0.01-1) to the volume of the water is 10 mL; the amount of Se powder is equal to that of NaBH4The mass ratio of (1) to (0.01-1) g; said Na2MoO4·2H2The volume ratio of the O substance to the deionized water is (0.01-20) mmol:60 mL; the volume ratio of the solution A to the solution B is 1 (0.1-10);
thirdly, preparing the molybdenum diselenide loaded wood chip:
adding molybdenum diselenide powder into water under the condition that the power is 100W-1000W, carrying out ultrasonic treatment for 0.1 h-10 h in an ice bath to obtain molybdenum diselenide suspension with the concentration of 0.1 mg/mL-10 mg/mL, soaking the wood chips with the lignin removed into the molybdenum diselenide suspension with the concentration of 0.1 mg/mL-10 mg/mL, carrying out ultrasonic treatment for 1 min-60 min under the condition that the power is 100W-1000W, and carrying out freeze drying to obtain the wood chips loaded with molybdenum diselenide;
fourthly, preparing the molybdenum diselenide/charcoal composite material:
placing the wood chip loaded with molybdenum diselenide into a high-temperature pyrolysis device, heating to 200-500 ℃ at a heating rate of 0.1-20 ℃/min under the condition of inert gas, preserving heat for 1-10 h at a temperature of 200-500 ℃, then heating to 800-2000 ℃ at a heating rate of 0.1-20 ℃/min, preserving heat for 1-10 h at a temperature of 800-2000 ℃, then cooling to 200-800 ℃ at a cooling rate of 0.1-20 ℃/min, and finally naturally cooling to room temperature to obtain the molybdenum diselenide/charcoal composite material;
fifthly, preparing charcoal:
putting the wood chips without the lignin into a high-temperature pyrolysis device, heating to 200-500 ℃ at a heating rate of 0.1-20 ℃/min under the condition of inert gas, preserving heat for 1-10 h at the temperature of 200-500 ℃, then heating to 800-2000 ℃ at a heating rate of 0.1-20 ℃/min, preserving heat for 1-10 h at the temperature of 800-2000 ℃, then cooling to 200-800 ℃ at a cooling rate of 0.1-20 ℃/min, and finally naturally cooling to room temperature to obtain charcoal;
sixthly, preparing the manganese dioxide/charcoal composite material:
soaking charcoal in 0.01-10 wt% potassium permanganate solution, heating at 40-250 deg.c for 0.1-100 hr, washing with deionized water, and vacuum drying to obtain composite manganese dioxide/charcoal material;
the mass ratio of the potassium permanganate to the charcoal in the potassium permanganate solution with the mass percentage of 0.01-10% is 1 (0.1-10);
seventhly, preparing an asymmetric super capacitor:
the molybdenum diselenide/charcoal composite material is used as a negative electrode, the manganese dioxide/charcoal composite material is used as a positive electrode, a KOH solution with the concentration of 3mol/L is used as an electrolyte, a cellulose filter membrane is used as a diaphragm, a gold foil is used as a current collector, then the molybdenum diselenide/charcoal composite material, the manganese dioxide/charcoal composite material and the cellulose filter membrane are soaked in the electrolyte for 0.1-100 h, and finally the asymmetric supercapacitor based on the molybdenum diselenide/charcoal is obtained through assembly.
The specific implementation is that molybdenum diselenide nanosheets are effectively assembled on the surface of a charcoal three-dimensional porous structure through a simple method, the pure charcoal electrode material is improved compared with a capacitor, and meanwhile, the circulation stability of a transition metal active substance is enhanced, so that a high-performance super capacitor is constructed.
The beneficial effects of the embodiment are as follows:
firstly, the molybdenum diselenide/charcoal composite material prepared by the embodiment is 1mA/cm2The area specific capacitance under the current density can reach 1043mF/cm2。
Secondly, the manganese dioxide/charcoal composite material prepared by the embodiment is at 0.2mA/cm2The area specific capacitance under the current density can reach 216.5mF/cm2。
Thirdly, the asymmetric supercapacitor based on molybdenum diselenide/charcoal prepared by the embodiment is at 1mA/cm2The area specific capacitance under the current density can reach 307.8F/cm2At 40mA/cm2The capacity retention rate is 81.46% after 1000 times of cyclic charge and discharge under high current density.
And fourthly, the preparation method provided by the embodiment is simple and feasible, expensive equipment is not needed, and most raw materials are wide in source, low in cost and renewable.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the wood raw material in the step one is hardwood. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the wood raw material in the step one is balsa wood. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: step one, wood chips with the thickness of 2 mm-10 mm are soaked in NaOH and Na2SO3Heating the mixed solution for 6 to 10 hours in a water bath kettle at the temperature of between 80 and 100 ℃, and then pouring out waste liquid to obtain NaOH and Na2SO3Treated wood; NaOH and Na in the step one2SO3The mixed solution is NaOH solution with the concentration of 1.25 mmol/L-10 mmol/L and Na with the concentration of 0.2 mmol/L-10 mmol/L2SO3The solution is prepared by mixing the components according to the volume ratio of 1 (1-10). The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: step two, NaBH is added4Adding into water to obtain NaBH4Adding Se powder to NaBH4Magnetically stirring the solution A for 1 to 10 hours to obtain a solution A, and adding Na2MoO4·2H2Dissolving O in deionized water to obtain a solution B, mixing the solution A and the solution B, stirring for 1-10 h to obtain a homogeneous reddish brown solution C, placing the homogeneous reddish brown solution C in a high-pressure reaction kettle, carrying out hydrothermal reaction for 24-100 h at the temperature of 200-250 ℃, collecting dark gray precipitate, carrying out vacuum filtration, and finally carrying out vacuum drying to obtain molybdenum diselenide powder; NaBH described in step two4The mass ratio of the (0.2-1) g to the volume of the water is 10 mL; the amount of Se powder is equal to that of NaBH4The mass ratio of (1 mmol), (0.01-0.5) g; said Na2MoO4·2H2The volume ratio of the O substance to the deionized water is (5-20) mmol:60 mL; the volume ratio of the solution A to the solution B is 1 (6-10). The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: in the third step, under the condition that the power is 500W-1000W, adding molybdenum diselenide powder into water, carrying out ultrasonic treatment for 0.5 h-10 h in ice bath to obtain molybdenum diselenide suspension with the concentration of 2 mg/mL-10 mg/mL, soaking the wood chips with the lignin removed into the molybdenum diselenide suspension with the concentration of 2 mg/mL-10 mg/mL, carrying out ultrasonic treatment for 15 min-60 min under the condition that the power is 500W-1000W, and carrying out freeze drying to obtain the wood chips loaded with molybdenum diselenide. The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: in the fourth step, the wood chip loaded with molybdenum diselenide is placed in a high-temperature pyrolysis device, the temperature is raised to 300-500 ℃ at the heating rate of 2-20 ℃/min under the condition of inert gas, the temperature is kept for 1-5 h under the condition of 300-500 ℃, then the temperature is raised to 800-1000 ℃ at the heating rate of 5-20 ℃/min, the temperature is kept for 2-10 h under the condition of 800-1000 ℃, then the temperature of the high-temperature pyrolysis device is lowered to 200-500 ℃ at the cooling rate of 5-20 ℃/min, and finally the temperature is naturally lowered to the room temperature, so that the molybdenum diselenide/charcoal composite material is obtained. The others are the same as the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: putting the wood chips without the lignin into a high-temperature pyrolysis device, heating to 300-500 ℃ at a heating rate of 2-20 ℃/min under the condition of inert gas, preserving the heat for 1-5 h at the temperature of 300-500 ℃, then heating to 800-1000 ℃ at a heating rate of 5-20 ℃/min, preserving the heat for 2-10 h at the temperature of 800-1000 ℃, then cooling to 200-500 ℃ at a cooling rate of 5-20 ℃/min, and finally naturally cooling to room temperature to obtain the charcoal. The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: step six, soaking the charcoal in a potassium permanganate solution with the mass percent of 0.03-10%, heating for 12-100 h at the temperature of 60-250 ℃, then washing with deionized water, and finally performing vacuum drying to obtain a manganese dioxide/charcoal composite material; the mass ratio of the potassium permanganate to the charcoal in the potassium permanganate solution with the mass percentage of 0.03-10% in the sixth step is 1 (4-10). The other points are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and step seven, soaking the molybdenum diselenide/charcoal composite material, the manganese dioxide/charcoal composite material and the cellulose filter membrane in the electrolyte for 6-100 hours. The other points are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a preparation method of an asymmetric supercapacitor based on molybdenum diselenide/charcoal is carried out according to the following steps:
firstly, delignification:
firstly, cutting a wood raw material into square thin slices along the growth direction of trees to obtain wood chips with the thickness of 2 mm;
② soaking wood chips with the thickness of 2mm in NaOH and Na2SO3Heating in 100 deg.C water bath for 6 hr, and discharging waste liquid to obtain NaOH and Na2SO3Treated wood;
the NaOH and the Na2SO3The mixed solution of (1) and (2) is NaOH solution with a concentration of 1.25mmol/L and Na solution with a concentration of 0.2mmol/L2SO3The solution is mixed according to the volume ratio of 1: 1;
③ mixing NaOH and Na2SO3Boiling the treated wood with deionized water for 30min, and then pouring out waste liquid;
fourthly, replacing deionized water, repeating the step one until waste liquid is colorless, then washing the waste liquid at normal temperature by using the deionized water as washing liquid until the washing liquid is neutral, and finally freeze-drying the waste liquid to obtain the wood chips without lignin;
secondly, preparing molybdenum diselenide powder:
0.2g of NaBH4Added to 10mL of water to give NaBH4To 12mmol of Se powder is added to NaBH4Magnetically stirring for 1h to obtain solution A, adding 5mmol Na2MoO4·2H2Dissolving O in 60mL of deionized water to obtain a solution B, mixing 10mL of the solution A with 60mL of the solution B, stirring for 1h to obtain a homogeneous reddish brown solution C, placing the homogeneous reddish brown solution C in a high-pressure reaction kettle, carrying out hydrothermal reaction for 24h at the temperature of 200 ℃, collecting dark gray precipitate, carrying out vacuum filtration, and finally carrying out vacuum drying to obtain molybdenum diselenide powder;
thirdly, preparing the molybdenum diselenide loaded wood chip:
adding molybdenum diselenide powder into water under the condition that the power is 500W, carrying out ultrasonic treatment on the molybdenum diselenide powder in ice bath for 30min to obtain a molybdenum diselenide suspension liquid with the concentration of 2mg/mL, soaking the wood chip with the lignin removed in the molybdenum diselenide suspension liquid with the concentration of 2mg/mL, carrying out ultrasonic treatment for 15min under the condition that the power is 500W, and carrying out freeze drying to obtain a wood chip loaded with molybdenum diselenide;
fourthly, preparing the molybdenum diselenide/charcoal composite material:
placing the wood chip loaded with molybdenum diselenide into a high-temperature pyrolysis device, heating to 500 ℃ at a heating rate of 2 ℃/min under the condition of inert gas, preserving heat for 1h at the temperature of 500 ℃, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h at the temperature of 800 ℃, cooling to 500 ℃ from 800 ℃ at a cooling rate of 5 ℃/min, and naturally cooling to room temperature to obtain the molybdenum diselenide/charcoal composite material;
fifthly, preparing charcoal:
putting the wood chips without the lignin in a high-temperature pyrolysis device, heating to 500 ℃ at a heating rate of 2 ℃/min under the condition of inert gas, preserving heat for 1h at the temperature of 500 ℃, then heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h at the temperature of 800 ℃, then reducing the temperature of the high-temperature pyrolysis device from 800 ℃ to 500 ℃ at a cooling rate of 5 ℃/min, and finally naturally cooling to room temperature to obtain charcoal;
sixthly, preparing the manganese dioxide/charcoal composite material:
soaking charcoal in 0.03 mass percent potassium permanganate solution, heating for 12 hours at the temperature of 60 ℃, then washing with deionized water, and finally drying in vacuum to obtain a manganese dioxide/charcoal composite material;
the mass ratio of potassium permanganate to charcoal in the potassium permanganate solution with the mass percent of 0.03% is 1: 4;
seventhly, preparing an asymmetric super capacitor:
taking a molybdenum diselenide/charcoal composite material as a negative electrode, a manganese dioxide/charcoal composite material as a positive electrode, a KOH solution with the concentration of 3mol/L as an electrolyte, a cellulose filter membrane as a diaphragm and a gold foil as a current collector, then soaking the molybdenum diselenide/charcoal composite material, the manganese dioxide/charcoal composite material and the cellulose filter membrane in the electrolyte for 6 hours, and finally assembling to obtain the asymmetric supercapacitor based on the molybdenum diselenide/charcoal;
the side length of the molybdenum diselenide/charcoal composite material and the side length of the manganese dioxide/charcoal composite material are both 10mm multiplied by 10mm, and the thickness of the composite material is 2.0 mm;
the side lengths of the cellulose filter membrane and the gold foil are both 12mm multiplied by 12 mm;
the wood raw material in the step one is balsa wood.
FIG. 1 is a scanning electron micrograph of charcoal prepared according to step five of the example; as can be seen, the charcoal has a layered porous network structure, which is favorable for the diffusion of ions and the rapid transport of electrons.
FIG. 2 is a scanning electron micrograph of a molybdenum diselenide/charcoal composite prepared according to step four of the example; from the figure, it can be observed that a large amount of nano petal-shaped molybdenum diselenide is uniformly adsorbed on the surface of the charcoal network structure.
FIG. 3 is an X-ray diffraction diagram, 1 is a molybdenum diselenide/charcoal composite prepared in one step four of the example, and 2 is an X-ray diffraction standard card for molybdenum diselenide; as can be seen from the figure, by comparing the X-ray diffraction standard card of molybdenum diselenide, the molybdenum diselenide/charcoal composite material contains a molybdenum diselenide component.
An electrochemical workstation with the model number of CS3104 is adopted to perform constant current charge and discharge tests on positive and negative electrode materials, the test voltage ranges are respectively 0-0.5V, -0.3V-0.8V, and 3mol/L KOH solution is prepared as electrolyte.
An electrochemical workstation with the model number of CS3104 is adopted to carry out constant current charge and discharge and cycle life test on the asymmetric super capacitor, and the test voltage range is 0-1.6V.
According to the constant current charging and discharging data, the electrode material and the capacitor area specific capacitance (C) are calculated by the following formula:
C＝(I·Δt)/(S·ΔU)
wherein I is current density, Deltat is discharge time, S is sample test area, and DeltaU is test voltage range.
FIG. 4 is a constant current charge-discharge diagram, wherein 1 shows that manganese dioxide/charcoal composite material prepared in the sixth step of the example is at 0.2mA/cm2A charge-discharge curve under current density, 2 is the molybdenum diselenide/charcoal composite prepared in the fourth step of the exampleThe material is at 1mA/cm2Charge and discharge curves at current density. As can be seen, the manganese dioxide/charcoal composite material prepared in the sixth step of the example was 0.2mA/cm2Charging and discharging under current density, and the area specific capacitance is 216.5mF/cm2The mass specific capacitance is 43F/g; example four step preparation of a molybdenum diselenide/charcoal composite at 1mA/cm2Charging and discharging at current density, and area specific capacitance of 1043mF/cm2The mass specific capacitance was 208.65F/g.
FIG. 5 shows the asymmetric supercapacitor based on molybdenum diselenide/charcoal prepared in the first example at 1mA/cm2A charge-discharge plot at current density; as can be seen from the figure, the area specific capacitance is 307.8F/cm2The mass specific capacitance was 30.4F/g.
FIG. 6 shows the asymmetric supercapacitor made of molybdenum diselenide/charcoal based at 40mA/cm prepared in accordance with example one2A cycle life chart of 1000 times of cyclic charge and discharge under current density; as can be seen, the capacity retention was 81.46%.

Claims (10)

1. A preparation method of an asymmetric supercapacitor based on molybdenum diselenide/charcoal is characterized by comprising the following steps:
firstly, delignification:
cutting a wood raw material into square thin slices along the growth direction of trees to obtain wood chips with the thickness of 1-10 mm;
② soaking wood chips with thickness of 1 mm-10 mm in NaOH and Na2SO3Heating the mixed solution for 1 to 10 hours in a water bath kettle at the temperature of between 50 and 100 ℃, and then pouring out waste liquid to obtain NaOH and Na2SO3Treated wood;
the NaOH and the Na2SO3The mixed solution is NaOH solution with the concentration of 0.01mmol/L to 10mmol/L and Na with the concentration of 0.01mmol/L to 10mmol/L2SO3The solution is prepared by mixing (0.1-10) by volume ratio of 1;
③ mixing NaOH and Na2SO3Boiling the treated wood with deionized water for 0.1-10 h, and then pouring out waste liquid;
fourthly, replacing deionized water, repeating the step one until waste liquid is colorless, then washing the waste liquid at normal temperature by using the deionized water as washing liquid until the washing liquid is neutral, and finally freeze-drying the waste liquid to obtain the wood chips without lignin;
secondly, preparing molybdenum diselenide powder:
reacting NaBH4Adding into water to obtain NaBH4Adding Se powder to NaBH4Magnetically stirring for 0.1-10 hr to obtain solution A, adding Na2MoO4·2H2Dissolving O in deionized water to obtain a solution B, mixing the solution A and the solution B, stirring for 0.1-10 h to obtain a homogeneous reddish brown solution C, placing the homogeneous reddish brown solution C in a high-pressure reaction kettle, carrying out hydrothermal reaction for 10-100 h at the temperature of 60-250 ℃, collecting dark gray precipitate, carrying out vacuum filtration, and finally carrying out vacuum drying to obtain molybdenum diselenide powder;
the NaBH4The mass ratio of the (0.01-1) to the volume of the water is 10 mL; the amount of Se powder is equal to that of NaBH4The mass ratio of (1) to (0.01-1) g; said Na2MoO4·2H2The volume ratio of the O substance to the deionized water is (0.01-20) mmol:60 mL; the volume ratio of the solution A to the solution B is 1 (0.1-10);
thirdly, preparing the molybdenum diselenide loaded wood chip:
adding molybdenum diselenide powder into water under the condition that the power is 100W-1000W, carrying out ultrasonic treatment for 0.1 h-10 h in an ice bath to obtain molybdenum diselenide suspension with the concentration of 0.1 mg/mL-10 mg/mL, soaking the wood chips with the lignin removed into the molybdenum diselenide suspension with the concentration of 0.1 mg/mL-10 mg/mL, carrying out ultrasonic treatment for 1 min-60 min under the condition that the power is 100W-1000W, and carrying out freeze drying to obtain the wood chips loaded with molybdenum diselenide;
fourthly, preparing the molybdenum diselenide/charcoal composite material:
placing the wood chip loaded with molybdenum diselenide into a high-temperature pyrolysis device, heating to 200-500 ℃ at a heating rate of 0.1-20 ℃/min under the condition of inert gas, preserving heat for 1-10 h at a temperature of 200-500 ℃, then heating to 800-2000 ℃ at a heating rate of 0.1-20 ℃/min, preserving heat for 1-10 h at a temperature of 800-2000 ℃, then cooling to 200-800 ℃ at a cooling rate of 0.1-20 ℃/min, and finally naturally cooling to room temperature to obtain the molybdenum diselenide/charcoal composite material;
fifthly, preparing charcoal:
putting the wood chips without the lignin into a high-temperature pyrolysis device, heating to 200-500 ℃ at a heating rate of 0.1-20 ℃/min under the condition of inert gas, preserving heat for 1-10 h at the temperature of 200-500 ℃, then heating to 800-2000 ℃ at a heating rate of 0.1-20 ℃/min, preserving heat for 1-10 h at the temperature of 800-2000 ℃, then cooling to 200-800 ℃ at a cooling rate of 0.1-20 ℃/min, and finally naturally cooling to room temperature to obtain charcoal;
sixthly, preparing the manganese dioxide/charcoal composite material:
soaking charcoal in 0.01-10 wt% potassium permanganate solution, heating at 40-250 deg.c for 0.1-100 hr, washing with deionized water, and vacuum drying to obtain composite manganese dioxide/charcoal material;
the mass ratio of the potassium permanganate to the charcoal in the potassium permanganate solution with the mass percentage of 0.01-10% is 1 (0.1-10);
seventhly, preparing an asymmetric super capacitor:
the molybdenum diselenide/charcoal composite material is used as a negative electrode, the manganese dioxide/charcoal composite material is used as a positive electrode, a KOH solution with the concentration of 3mol/L is used as an electrolyte, a cellulose filter membrane is used as a diaphragm, a gold foil is used as a current collector, then the molybdenum diselenide/charcoal composite material, the manganese dioxide/charcoal composite material and the cellulose filter membrane are soaked in the electrolyte for 0.1-100 h, and finally the asymmetric supercapacitor based on the molybdenum diselenide/charcoal is obtained through assembly.
2. The method for preparing an asymmetric supercapacitor based on molybdenum diselenide/charcoal as claimed in claim 1, wherein the wood raw material in the step one is hardwood.
3. The method for preparing an asymmetric supercapacitor based on molybdenum diselenide/charcoal according to claim 1, wherein the wood raw material in the step one is balsa wood.
4. The method as claimed in claim 1, wherein the step of impregnating wood chips with a thickness of 2mm to 10mm with NaOH and Na is performed in step one2SO3Heating the mixed solution for 6 to 10 hours in a water bath kettle at the temperature of between 80 and 100 ℃, and then pouring out waste liquid to obtain NaOH and Na2SO3Treated wood; NaOH and Na in the step one2SO3The mixed solution is NaOH solution with the concentration of 1.25 mmol/L-10 mmol/L and Na with the concentration of 0.2 mmol/L-10 mmol/L2SO3The solution is prepared by mixing the components according to the volume ratio of 1 (1-10).
5. The method for preparing an asymmetric supercapacitor based on molybdenum diselenide/charcoal as claimed in claim 1, wherein NaBH is added in the second step4Adding into water to obtain NaBH4Adding Se powder to NaBH4Magnetically stirring the solution A for 1 to 10 hours to obtain a solution A, and adding Na2MoO4·2H2Dissolving O in deionized water to obtain a solution B, mixing the solution A and the solution B, stirring for 1-10 h to obtain a homogeneous reddish brown solution C, placing the homogeneous reddish brown solution C in a high-pressure reaction kettle, carrying out hydrothermal reaction for 24-100 h at the temperature of 200-250 ℃, collecting dark gray precipitate, carrying out vacuum filtration, and finally carrying out vacuum drying to obtain molybdenum diselenide powder; NaBH described in step two4The mass ratio of the (0.2-1) g to the volume of the water is 10 mL; the amount of Se powder is equal to that of NaBH4The mass ratio of (1 mmol), (0.01-0.5) g; said Na2MoO4·2H2The volume ratio of the O substance to the deionized water is (5-20) mmol:60 mL; the volume ratio of the solution A to the solution B is 1 (6-10).
6. The method for preparing the asymmetric supercapacitor based on molybdenum diselenide/charcoal according to claim 1, wherein in the third step, under the condition that the power is 500W-1000W, molybdenum diselenide powder is added into water, ice bath ultrasonic treatment is carried out for 0.5 h-10 h to obtain molybdenum diselenide suspension with the concentration of 2 mg/mL-10 mg/mL, the wood chips with lignin removed are soaked in the molybdenum diselenide suspension with the concentration of 2 mg/mL-10 mg/mL, under the condition that the power is 500W-1000W, ultrasonic treatment is carried out for 15 min-60 min, and freeze drying is carried out to obtain the wood chips loaded with molybdenum diselenide.
7. The method for preparing the asymmetric supercapacitor based on molybdenum diselenide/charcoal according to claim 1, characterized in that in the fourth step, the wood chips loaded with molybdenum diselenide are placed in a high-temperature pyrolysis device, the temperature is raised to 300-500 ℃ at a heating rate of 2-20 ℃/min under the condition of inert gas, the temperature is kept at 300-500 ℃ for 1-5 h, then the temperature is raised to 800-1000 ℃ at a heating rate of 5-20 ℃/min, the temperature is kept at 800-1000 ℃ for 2-10 h at a temperature of 800-1000 ℃, then the temperature of the high-temperature pyrolysis device is lowered to 200-500 ℃ from 800-1000 ℃ at a cooling rate of 5-20 ℃/min, and finally the temperature is naturally lowered to room temperature, so that the molybdenum diselenide/charcoal composite material is obtained.
8. The preparation method of the asymmetric supercapacitor based on molybdenum diselenide/charcoal according to claim 1, characterized in that in the fifth step, the wood chips without lignin are placed in a high temperature pyrolysis device, the temperature is raised to 300-500 ℃ at a heating rate of 2-20 ℃/min under the condition of inert gas, the temperature is kept at 300-500 ℃ for 1-5 h, then the temperature is raised to 800-1000 ℃ at a heating rate of 5-20 ℃/min, the temperature is kept at 800-1000 ℃ for 2-10 h at a temperature of 800-1000 ℃, then the temperature of the high temperature pyrolysis device is lowered to 200-500 ℃ from 800-1000 ℃ at a cooling rate of 5-20 ℃/min, and finally the temperature is naturally lowered to room temperature to obtain the charcoal.
9. The preparation method of the asymmetric supercapacitor based on molybdenum diselenide/charcoal according to claim 1, characterized in that in the sixth step, charcoal is immersed in 0.03% -10% by mass potassium permanganate solution, heated for 12-100 h at 60-250 ℃, then washed with deionized water, and finally vacuum-dried to obtain manganese dioxide/charcoal composite material; the mass ratio of the potassium permanganate to the charcoal in the potassium permanganate solution with the mass percentage of 0.03-10% in the sixth step is 1 (4-10).
10. The method for preparing an asymmetric supercapacitor based on molybdenum diselenide/charcoal as claimed in claim 1, wherein in step seven, the molybdenum diselenide/charcoal composite material, the manganese dioxide/charcoal composite material and the cellulose filter membrane are soaked in the electrolyte for 6-100 h.
CN201910679107.6A 2019-07-25 2019-07-25 Preparation method of asymmetric supercapacitor based on molybdenum diselenide/charcoal Active CN110379646B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910679107.6A CN110379646B (en) 2019-07-25 2019-07-25 Preparation method of asymmetric supercapacitor based on molybdenum diselenide/charcoal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910679107.6A CN110379646B (en) 2019-07-25 2019-07-25 Preparation method of asymmetric supercapacitor based on molybdenum diselenide/charcoal

Publications (2)

Publication Number Publication Date
CN110379646A CN110379646A (en) 2019-10-25
CN110379646B true CN110379646B (en) 2021-04-02

Family

ID=68256179

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910679107.6A Active CN110379646B (en) 2019-07-25 2019-07-25 Preparation method of asymmetric supercapacitor based on molybdenum diselenide/charcoal

Country Status (1)

Country Link
CN (1) CN110379646B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931266B (en) * 2019-11-12 2021-04-20 陕西科技大学 3D flowering rod-shaped nickel sulfide/wood electrode material and preparation method and application thereof
CN111362250B (en) * 2020-03-16 2023-08-01 四川大学 High specific capacitance super-thick biochar, biochar single-chip electrode and biochar composite electrode
CN111640584B (en) * 2020-04-20 2021-11-26 北京邮电大学 Method for preparing supercapacitor electrode material from two-dimensional transition metal selenide composite carbon material
CN112397850B (en) * 2020-11-12 2022-04-05 同济大学 Modified lignocellulose diaphragm for lithium ion battery and preparation method and application thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101429975B1 (en) * 2007-12-21 2014-08-18 재단법인 포항산업과학연구원 Method for heat treatment of activated carbons for electrodes
CN101944396B (en) * 2010-07-29 2013-01-02 兰州理工大学 Method for preparing porous mold charcoal/metal oxide composite material for super capacitor electrode
CN101964258A (en) * 2010-07-29 2011-02-02 兰州理工大学 Method for preparing porous molding charcoal for super capacitor electrode
CN104356430B (en) * 2014-11-17 2016-06-01 武汉理工大学 The preparation method of a kind of carbon point/chitosan in situ matrix material
TWI606631B (en) * 2016-03-08 2017-11-21 Institute Of Unclear Energy Res Rocaec Method for manufacturing lead carbon bonding, structure of lead carbon electrode sheet, and structure of lead carbon battery
CN105742074B (en) * 2016-03-31 2018-07-20 复旦大学 Selenizing molybdenum composite material of a kind of porous carbon fiber based on poly-dopamine/bis- and preparation method thereof
CN106207125B (en) * 2016-08-23 2018-10-26 东华大学 Sulfur doping selenizing molybdenum/graphene-graphene nanobelt aeroge and its preparation
CN107958791B (en) * 2017-02-23 2020-04-28 中国科学院深圳先进技术研究院 Three-dimensional material, preparation method thereof and electrode for supercapacitor
WO2019006044A1 (en) * 2017-06-28 2019-01-03 Massachusetts Institute Of Technology Nearly 2d electronic microparticles

Also Published As

Publication number Publication date
CN110379646A (en) 2019-10-25

Similar Documents

Publication Publication Date Title
CN110379646B (en) Preparation method of asymmetric supercapacitor based on molybdenum diselenide/charcoal
CN109037704B (en) Nitrogen-doped 3D porous carbon material and preparation method and application thereof
CN105869912A (en) Preparation method of starch-based uniformly-dispersed activated carbon microsphere material and application thereof
CN107221454B (en) A kind of all-solid-state flexible supercapacitor and preparation method thereof based on porous carbon fiber cloth
CN111453726A (en) Nitrogen-doped porous carbon material and preparation method and application thereof
CN105152170A (en) Preparation method for cicada slough based porous carbon material used for electrochemical capacitor
CN109767924B (en) LDH-based supercapacitor composite electrode material, and preparation method and application thereof
CN109019598A (en) A kind of mixing biomass prepares the method and manufactured three-dimensional porous carbon material and its application of the three-dimensional porous carbon material of high specific capacitance
CN108899530B (en) Silicon-carbon composite material and preparation method and application thereof
AU2020101283A4 (en) Method for Manufacturing Straw-Based Activated Carbon Electrode Material for Super Capacitor with Energy Storage Efficiency Enhanced Through Acid Mine Drainage
CN111422865B (en) Nitrogen-containing carbon material for supercapacitor and preparation method and application thereof
CN104701496A (en) SnO2/CMK-3 nanometer composite lithium-ion battery negative electrode material preparation method
CN112079352B (en) Preparation method and application of biomass-based porous nitrogen-doped carbon material
CN111128562A (en) Activated carbon fiber paper and preparation method and application thereof
CN108963237B (en) Preparation method of sodium ion battery negative electrode material
CN106409528B (en) A kind of ZnFe2O4Nano particle/Carbon fibe hybrid supercapacitor electrode material and preparation method thereof
CN107154498B (en) Preparation method and application of microporous carbon structure electrode material prepared from plant material
CN103578772B (en) Electrode for capacitors active material and preparation method thereof
CN108010734A (en) A kind of micro super capacitor production method based on graphene/carbon nano-tube aeroge
CN114300276B (en) Ni-Fe-S@NiCo 2 O 4 Nano-NF composite material and preparation method and application thereof
CN114360918B (en) Preparation method of electrode material of high-performance supercapacitor heterostructure
CN103839691A (en) Nitrogen-doped graphene composite material, preparation method thereof, electrode plate and supercapacitor
CN111341567B (en) 3D poplar catkin derived carbon-supported NiCo-LDH nanosheet supercapacitor and preparation method thereof
CN113788473B (en) Ultrasound-assisted method for preparing nitrogen-sulfur co-doped squid ink derived carbon/graphene composite material and application of nitrogen-sulfur co-doped squid ink derived carbon/graphene composite material in potassium storage field
CN109786723A (en) A kind of preparation method of the carbon composite of three-dimensional porous low metal doping

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