CN110610817A - Based on Mn3O4Supercapacitor made of graphene composite material and preparation method of supercapacitor - Google Patents
Based on Mn3O4Supercapacitor made of graphene composite material and preparation method of supercapacitor Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a supercapacitor based on a Mn3O 4/graphene composite material and a preparation method thereof, and belongs to the technical field of batteries and capacitors. The supercapacitor based on the Mn3O 4/graphene composite material is composed of a positive plate, a negative plate, a diaphragm between the positive plate and the negative plate and a water system electrolyte with ionic conductivity, and is characterized in that the positive plate comprises a positive plate current collector and a positive electrode mixed material deposited on the surface of the positive plate current collector, and the negative plate comprises a negative plate current collector and a negative electrode mixed material deposited on the surface of the negative plate current collector; the cathode mixed material comprises a Mn3O 4/graphene composite material, and the anode mixed material comprises an anode active material. The invention has the advantages of low cost, long cycle life and the like.
Description
Technical Field
The invention belongs to the technical field of batteries and capacitors, and particularly relates to a supercapacitor based on a Mn3O 4/graphene composite material and a preparation method thereof.
Background
With the development of economy and society, non-renewable energy sources such as petroleum and coal are gradually exhausted, and the use of the non-renewable energy sources causes environmental pollution and aggravation of greenhouse effect. The human society urgently needs to develop clean energy, renewable energy and corresponding energy-saving and environment-friendly technology. As a novel energy storage device between a storage battery and a conventional capacitor, a super capacitor has the advantages of high specific capacity, high power density, long cycle life, wide working temperature range, maintenance-free property and the like, and has attracted great attention as a novel energy storage device in recent years. Since supercapacitors have a higher power density than batteries, this provides a wide space for the development and application of supercapacitors.
According to different energy storage mechanisms, supercapacitors are divided into three categories: electric double layer capacitors, faraday pseudocapacitors and hybrid supercapacitors. One who has utilized the storage of large amounts of electrical energy on surfaces of matter, such as batteries, for practical purposes is Becker, who applied the first such patent in 1957. Electric double layer capacitors having farad capacity and capable of being rapidly charged and discharged have been developed by NEC electric company of japan in the 70 th 20 th century. Conway developed a pseudocapacitance system based on the redox reaction of a substance to store charge in ottawa in 1975 to 1981 with the support of a continuous Group and d.craig et al, which is another type of charge storage system. Commercial supercapacitors are the gold capacitors of Matsushita Electric Industrial Co. (Osaka, Japan) and the military capacitor products of Pinnacle Research.
With the application and development of electric vehicles, various countries have invested capital to participate in the development of the super capacitors for vehicles from the 90 s in the 20 th century. At present, mature super capacitor products are matched with storage batteries to be applied to a hybrid power system of a vehicle. Due to the unique advantages of the super capacitor, the super capacitor has wide application in the fields of military aerospace, communication, power supply, electric power, vehicle manufacturing and the like.
However, the conventional super capacitor has low cycle life and high cost, and cannot meet the increasing requirements. Therefore, the super capacitor with long cycle life and low cost is developed and has wide market.
Disclosure of Invention
The first object of the present invention is to solve the above problems in the prior art, and to provide a supercapacitor based on Mn3O 4/graphene composite material; the second purpose of the invention is to provide a preparation method for preparing the supercapacitor based on the Mn3O 4/graphene composite material.
The first object of the present invention can be achieved by the following technical solutions: a supercapacitor based on a Mn3O 4/graphene composite material is composed of a positive plate, a negative plate, a diaphragm between the positive plate and the negative plate and an aqueous electrolyte with ionic conductivity, and is characterized in that the positive plate comprises a positive plate current collector and a positive electrode mixed material deposited on the surface of the positive plate current collector, and the negative plate comprises a negative plate current collector and a negative electrode mixed material deposited on the surface of the negative plate current collector; the positive electrode mixture material includes Mn3O4The negative electrode mixed material comprises a negative electrode active material.
Preferably, the negative active material is one or more of a porous carbon material, a transition metal oxide and a conductive polymer.
Preferably, the positive electrode mixture material and the negative electrode mixture material each further include a conductive agent and a binder.
Preferably, the composition and weight percentage of the positive electrode mixed material are Mn3O450-90% of graphene composite material, 5-20% of conductive agent and 1-20% of binder。
Preferably, the composition and weight percentage of the positive electrode mixed material are Mn3O480% of/graphene composite material, 10% of conductive agent and 10% of binder; or the composition and the weight percentage of the positive electrode mixed material are Mn3O490% of/graphene composite material, 5% of conductive agent and 5% of binder, or the composition and weight percentage of the anode mixed material are Mn3O470% of/graphene composite material, 15% of conductive agent and 15% of binder.
Preferably, the composition and weight percentage of the negative electrode mixed material are 50-90% of negative electrode active material, 5-20% of conductive agent and 1-20% of binder.
Preferably, the composition and weight percentage of the negative electrode mixed material are 80% of negative electrode active material, 10% of conductive agent and 10% of binder; the composition and weight percentage of the negative electrode mixed material are 90 percent of negative electrode active material, 5 percent of conductive agent and 5 percent of binder; the composition and weight percentage of the negative electrode mixed material are 70 percent of negative electrode active material, 15 percent of conductive agent and 15 percent of binder.
Preferably, the diaphragm is one of polypropylene non-woven fabrics, porous glass fibers, polyethylene microporous membranes and composite membranes of PP and PE.
Preferably, the porous carbon material is one or a mixture of more than one of activated carbon, mesoporous carbon, carbon nanotubes, graphene, template carbon, carbon aerogel and carbon fibers.
Preferably, the conductive agent is one or any combination of conductive carbon black (super-p), conductive graphite (KS-6), conductive graphite (SFG-6), acetylene black, carbon fiber (VGCF), Carbon Nanotubes (CNTs), Ketjen black, nickel powder and cobalt powder.
Preferably, the binder is one or any combination of polytetrafluoroethylene, sodium carboxymethylcellulose and styrene butadiene rubber.
Preferably, the electrolyte is one or a mixture of two of a salt solution and an alkaline solution.
The salt solution is one or any combination of lithium chloride, lithium sulfate, sodium chloride, sodium sulfate, potassium chloride, potassium sulfate and sodium acetate.
The alkaline solution is one or a mixture of potassium hydroxide and sodium hydroxide.
The second object of the present invention can be achieved by the following technical solutions: a preparation method for preparing the supercapacitor based on the Mn3O 4/graphene composite material comprises the following steps:
S01，Mn3O4preparation of graphene composite material:
(1) weighing 98% sulfuric acid, placing in a reaction bottle, cooling the sulfuric acid liquid to 0 ℃, adding potassium permanganate while stirring, maintaining the temperature of a solvent below 20 ℃, adding deionized water while stirring after maintaining stirring for 100-140 min, maintaining the temperature of a reaction system between 30 ℃ and 40 ℃, and continuing to stir for 20-40 min; finally, adding deionized water and hydrogen peroxide to terminate the system reaction, standing at room temperature for 20-28h, centrifugally cleaning the reaction product with hydrochloric acid solution until BaCl is used in the cleaning solution2Drying the solid matter obtained after centrifugal separation of sulfate ions in a drying oven at 40-60 ℃ to obtain graphite oxide;
(2) placing graphite oxide in deionized water, performing ultrasonic dispersion, respectively weighing 1.0,2.0,3.0 and 4.0mmol of manganese acetate, adding the manganese acetate into a parallel ultrasonic graphite oxide solution, respectively adding ethanolamine, stirring at room temperature for 0.5-1.5h, transferring each mixed solution into a hydrothermal kettle, sealing, placing the sealed hydrothermal kettle in an oven at the temperature of 110-130 ℃ for 10-14h, taking out the hydrothermal kettle, and naturally cooling to room temperature; the product is centrifugally separated and is respectively washed three times by deionized water and ethanol; drying in an oven at 50-70 deg.C for 20-28h to obtain Mn3O4A graphene composite material.
SO2, preparation of positive plate: weighing Mn3O4The graphene/graphene composite material and the conductive agent are uniformly mixed and ground, the binder is weighed and added, the mixture is dispersed in ethanol, and ultrasonic uniform dispersion is carried out. Uniformly dripping the mixed solution on 1cm2And manufacturing a pole piece on the foam current collector. Drying the pole piece at 60-130 ℃, and tabletting under the pressure of 5-15 MPa. Soaking the pressed pole piece in a salt solution for 12h-20 days;
SO3, negative plateThe preparation of (1): weighing the negative electrode active material and the conductive agent, mixing and grinding uniformly, weighing the binder, adding the binder into the mixture, dispersing the mixture into ethanol, and performing ultrasonic uniform dispersion. Uniformly dripping the mixed solution on 1cm2And pole pieces are manufactured on the foam current collector. Drying the pole piece at 60-130 ℃, and tabletting under the pressure of 5-15 MPa. Soaking the pressed pole piece in an alkaline solution for 2-48 h;
the positive electrode sheet and the negative electrode sheet are immersed in an aqueous electrolyte having ionic conductivity, and a separator is interposed between the positive electrode sheet and the negative electrode sheet.
Compared with the prior art, the invention has the following advantages:
1. the super-hybrid capacitor disclosed by the invention has the advantages of low cost of the Mn-based material, good safety performance of the aqueous electrolyte and long cycle life.
2. According to the invention, the anode and the cathode are made of mixed materials, so that on one hand, the cost of the pole piece is reduced, and the good performance of the pole piece is maintained; on the other hand, the Mn is fully exerted3O4The excellent performance of the graphene composite material and the activated carbon finally improves the overall performance of the hybrid capacitor.
3. In different Ag-1The positive electrode active material is Mn3O4The hybrid supercapacitor made of the graphene composite material and taking the active substance as the negative electrode of the active carbon has higher rate capability.
4. The positive electrode active material is Mn3O4The hybrid supercapacitor with the active substance of the negative electrode being active carbon is high in specific capacitance and good in cycle life in a salt solution.
Drawings
FIG. 1 shows Mn as the positive electrode active material3O4The negative active material of the graphene composite material is a charge-discharge curve of a mixed super capacitor of active carbon in a salt solution.
FIG. 2 shows Mn as the positive electrode active material3O4The negative active material of the graphene composite material is a charge-discharge curve of a mixed super capacitor with a carbon nano tube in a salt solution.
FIG. 3 shows Mn as the positive electrode active material3O4GrapheneThe circulation stability curves of the composite material and the hybrid supercapacitor taking the active carbon as the negative active substance in the salt solution and the alkali solution respectively.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the drawings, but the present invention is not limited to these embodiments.
Mn in the invention3O4Preparation of graphene composite material:
firstly, preparing graphite oxide: firstly, measuring 46ml of 98% sulfuric acid, placing the sulfuric acid in a reaction bottle, cooling sulfuric acid liquid to 0 ℃, slowly adding 6g of potassium permanganate under the conditions of stirring and cooling, maintaining the temperature of a solvent below 20 ℃ in the whole operation process, slowly adding 140ml of deionized water after maintaining stirring for 120min, raising the temperature of a reaction system to 98 ℃ after adding the deionized water, maintaining stirring until the temperature of the reaction system is reduced to 35 +/-3 ℃, and then continuing stirring for 30 min. Finally, 800ml of deionized water and 30ml of 30% hydrogen peroxide are added to terminate the reaction of the system. After 24 hours of standing at room temperature, the reaction product was centrifugally washed with a 5% hydrochloric acid solution until the washing solution was washed with BaCl2No sulfate ion was detected. The solid material obtained after centrifugation, i.e. graphite oxide, was dried in an oven at 50 ℃ for 4 days.
Mn3O4Preparation of graphene composite material:
weighing 50mg of graphite oxide, placing the graphite oxide in 30ml of deionized water, carrying out ultrasonic treatment for 90min so that the graphite oxide can be uniformly dispersed, respectively weighing 1.0,2.0,3.0 and 4.0mmol of manganese acetate, adding the manganese acetate into a parallel ultrasonic graphite oxide solution, adding 10ml of ethanolamine into the solutions respectively, stirring the solutions at room temperature for 1h, transferring the mixed solutions into a hydrothermal kettle with a teflon material inner container for sealing, placing the sealed hydrothermal kettle in a 120-DEG C oven for maintaining for 12h, taking out the hydrothermal kettle, and naturally cooling the hydrothermal kettle to the room temperature. The reaction product was centrifuged and washed three times with deionized water and ethanol. And drying the reacted solid product in an oven at 60 ℃ for 24h to obtain black powder, namely the Mn3O4@ graphene composite material.
Example 1
Manufacturing a positive plate: weighing Mn3O4Mixing and grinding 80% of/graphene composite material and 10% of acetylene black uniformly, weighing 10% of polytetrafluoroethylene, adding the polytetrafluoroethylene into the mixture, dispersing the mixture into a certain amount of ethanol, and ultrasonically and uniformly dispersing the mixed solution. Uniformly dripping the mixed solution on 1cm2And manufacturing a pole piece on the Ni foam current collector. The pole piece is dried (80 ℃) and pressed into tablets under 10 MPa. The pressed pole piece is soaked in sodium sulfate solution with electrolyte of 1mol/L for 3 days.
And (3) manufacturing a negative plate: weighing 80% of active carbon and 10% of acetylene black, uniformly mixing and grinding, weighing 10% of polytetrafluoroethylene, adding the polytetrafluoroethylene, dispersing the mixture in a certain amount of ethanol, and uniformly dispersing the mixed solution by ultrasonic. Uniformly dripping the mixed solution on 1cm2And manufacturing a pole piece on the Ni foam current collector. The pole piece is dried (80 ℃) and pressed into tablets under 10 MPa. The pressed pole piece is soaked in a potassium hydroxide solution with 6mol/L electrolyte for 1 day.
Example 2
Manufacturing a positive plate: weighing Mn3O4Mixing and grinding 90% of the graphene composite material and 5% of acetylene black uniformly, weighing 5% of polytetrafluoroethylene, adding the polytetrafluoroethylene into the mixture, dispersing the mixture into a certain amount of ethanol, and ultrasonically and uniformly dispersing the mixed solution. Uniformly dripping the mixed solution on 1cm2And (4) manufacturing a pole piece on a Cu foam current collector. The pole piece is dried (60 ℃) and pressed into tablets under 12 MPa. The pressed pole piece is soaked in a sodium chloride salt solution with 1mol/L of electrolyte for 6 days.
And (3) manufacturing a negative plate: weighing 90% of active carbon and 5% of acetylene black, uniformly mixing and grinding, weighing 5% of polytetrafluoroethylene, adding the polytetrafluoroethylene, dispersing the mixture in a certain amount of ethanol, and uniformly dispersing the mixed solution by ultrasonic. Uniformly dripping the mixed solution on 1cm2And (4) manufacturing a pole piece on a Cu foam current collector. The pole piece is dried (60 ℃) and pressed into tablets under 12 MPa. The pressed pole piece is soaked in a potassium hydroxide solution with 6mol/L electrolyte for 12 hours.
Example 3
Manufacturing a positive plate: weighing Mn3O4Graphene compositeMixing and grinding 70% of the material and 15% of acetylene black uniformly, weighing and adding 15% of polytetrafluoroethylene, dispersing the mixture in a certain amount of ethanol, and ultrasonically and uniformly dispersing the mixed solution. Uniformly dripping the mixed solution on 1cm2And manufacturing a pole piece on the Al foam current collector. The pole piece is dried (100 ℃) and pressed into tablets under 8 MPa. The pressed pole piece is soaked in a potassium chloride salt solution with 1mol/L of electrolyte for 10 days.
And (3) manufacturing a negative plate: weighing 70% of active carbon and 15% of acetylene black, uniformly mixing and grinding, weighing 15% of polytetrafluoroethylene, adding the polytetrafluoroethylene, dispersing the mixture in a certain amount of ethanol, and uniformly dispersing the mixed solution by ultrasonic. Uniformly dripping the mixed solution on 1cm2And manufacturing a pole piece on the Al foam current collector. The pole piece is dried (100 ℃) and pressed into tablets under 8 MPa. The pressed pole piece is soaked in a potassium hydroxide solution with 6mol/L electrolyte for 2 hours.
As the current collector material, a porous mesh metal material such as (Cu, Ni, Al) or a stainless steel mesh can be used.
As can be seen from a comparison of FIGS. 1 and 2, the Ag concentration in the different Ag layers-1The positive electrode active material is Mn3O4The hybrid supercapacitor made of the graphene composite material and taking the active substance as the negative electrode of the active carbon has higher rate capability. Ag-1Is determined by the current set/mass of active material. Is a preset value.
As can be seen from FIG. 3, the positive electrode active material was Mn3O4The hybrid supercapacitor with the active substance of the negative electrode being active carbon is high in specific capacitance and good in cycle life in a salt solution.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. Based on Mn3O4Supercapacitor made of graphene composite materialThe lithium ion battery comprises a positive plate, a negative plate, a diaphragm between the positive plate and the negative plate and an aqueous electrolyte with ionic conductivity, and is characterized in that the positive plate comprises a positive plate current collector and a positive electrode mixed material deposited on the surface of the positive plate current collector, and the negative plate comprises a negative plate current collector and a negative electrode mixed material deposited on the surface of the negative plate current collector; the cathode mixed material comprises a Mn3O 4/graphene composite material, and the anode mixed material comprises an anode active material.
2. An Mn-based according to claim 13O4The supercapacitor made of the graphene composite material is characterized in that the negative active material is one or a mixture of a porous carbon material, a transition metal oxide and a conductive polymer.
3. An Mn-based according to claim 13O4The supercapacitor made of the graphene composite material is characterized in that the positive electrode mixed material and the negative electrode mixed material both further comprise a conductive agent and a binder.
4. An Mn-based according to claim 13O4The supercapacitor made of the/graphene composite material is characterized in that the positive electrode mixed material comprises 50-90 wt% of Mn3O 4/graphene composite material, 5-20 wt% of a conductive agent and 1-20 wt% of a binder.
5. An Mn-based according to claim 43O4The supercapacitor made of the/graphene composite material is characterized in that the composition and the weight percentage of the positive electrode mixed material are 80% of Mn3O 4/graphene composite material, 10% of conductive agent and 10% of binder; or the composition and the weight percentage of the positive electrode mixed material are 90% of Mn3O 4/graphene composite material, 5% of conductive agent and 5% of binder, or the composition and the weight percentage of the positive electrode mixed material are 70% of Mn3O 4/graphene composite material, 15% of conductive agent and 15% of binder.
6. An Mn-based according to claim 13O4The supercapacitor made of the graphene composite material is characterized in that the negative electrode mixed material comprises, by weight, 50-90% of a negative electrode active material, 5-20% of a conductive agent and 1-20% of a binder.
7. An Mn-based according to claim 13O4The supercapacitor made of the graphene composite material is characterized in that the negative electrode mixed material comprises 80% of a negative electrode active material, 10% of a conductive agent and 10% of a binder in percentage by weight; the composition and weight percentage of the negative electrode mixed material are 90 percent of negative electrode active material, 5 percent of conductive agent and 5 percent of binder; the composition and weight percentage of the negative electrode mixed material are 70 percent of negative electrode active material, 15 percent of conductive agent and 15 percent of binder.
8. An Mn-based according to claim 13O4The supercapacitor made of the graphene composite material is characterized in that the diaphragm is one of polypropylene non-woven fabrics, porous glass fibers, polyethylene microporous films and PP and PE composite films.
9. An Mn-based according to claim 13O4The supercapacitor made of the/graphene composite material is characterized in that the porous carbon material is one or a mixture of more than one of activated carbon, mesoporous carbon, carbon nanotubes, graphene, template carbon, carbon aerogel and carbon fibers.
10. A method for preparing an Mn-based alloy as claimed in any of claims 1 to 93O4The preparation method of the supercapacitor made of the graphene composite material is characterized by comprising the following steps:
s01, preparation of Mn3O 4/graphene composite material:
(1) weighing 98% sulfuric acid, placing in a reaction bottle, cooling the sulfuric acid liquid to 0 ℃, adding potassium permanganate while stirring, maintaining the temperature of a solvent below 20 ℃, adding deionized water while stirring after maintaining stirring for 100-140 min, maintaining the temperature of a reaction system between 30 ℃ and 40 ℃, and continuing to stir for 20-40 min; finally, adding deionized water and hydrogen peroxide to terminate the system reaction, standing at room temperature for 20-28h, centrifugally cleaning the reaction product with a hydrochloric acid solution until no sulfate ions are detected in the cleaning solution by BaCl2, and drying the obtained solid matter in a drying oven at 40-60 ℃ to obtain graphite oxide;
(2) placing graphite oxide in deionized water, performing ultrasonic dispersion, respectively weighing 1.0,2.0,3.0 and 4.0mmol of manganese acetate, adding the manganese acetate into a parallel ultrasonic graphite oxide solution, respectively adding ethanolamine, stirring at room temperature for 0.5-1.5h, transferring each mixed solution into a hydrothermal kettle, sealing, placing the sealed hydrothermal kettle in an oven at the temperature of 110-130 ℃ for 10-14h, taking out the hydrothermal kettle, and naturally cooling to room temperature; the product is centrifugally separated and is respectively washed three times by deionized water and ethanol; and drying in an oven at 50-70 ℃ for 20-28h to obtain the Mn3O 4/graphene composite material.
SO2, preparation of positive plate: weighing the Mn3O 4/graphene composite material and the conductive agent, mixing and grinding uniformly, weighing the binder, adding the binder into the mixture, dispersing the mixture into ethanol, and performing ultrasonic uniform dispersion. The mixed solution was uniformly dropped on a 1cm2 foam current collector to make a pole piece. Drying the pole piece at 60-130 ℃, and tabletting under the pressure of 5-15 MPa. Soaking the pressed pole piece in a salt solution for 12h-20 days;
SO3, preparation of negative electrode plate: weighing the negative electrode active material and the conductive agent, mixing and grinding uniformly, weighing the binder, adding the binder into the mixture, dispersing the mixture into ethanol, and performing ultrasonic uniform dispersion. The mixed solution was uniformly dropped on a 1cm2 foam current collector to make a pole piece. Drying the pole piece at 60-130 ℃, and tabletting under the pressure of 5-15 MPa. Soaking the pressed pole piece in an alkaline solution for 2-48 h;
the positive electrode sheet and the negative electrode sheet are immersed in an aqueous electrolyte having ionic conductivity, and a separator is interposed between the positive electrode sheet and the negative electrode sheet.
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| CN111986931A (en) * | 2020-07-24 | 2020-11-24 | 华南理工大学 | Manganese oxide nano-structure electrode material and preparation method and application thereof |
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| CN111986931A (en) * | 2020-07-24 | 2020-11-24 | 华南理工大学 | Manganese oxide nano-structure electrode material and preparation method and application thereof |
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