CN105632787A - Preparation method of cobaltosic oxide/graphene nano composite electrode material for super capacitor - Google Patents
Preparation method of cobaltosic oxide/graphene nano composite electrode material for super capacitor 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
- H01G11/84—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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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- 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
The invention relates to a preparation method of a cobaltosic oxide/graphene nano composite electrode material for a super capacitor. The method comprises the following steps: adding cobalt nitrate hexahydrate to deionized water, and stirring the cobalt nitrate hexahydrate to completely dissolve; adding ethanol amine to the solution and stirring the ethanol amine to fully mix the ethanol amine and the solution evenly; carrying out hydrothermal reaction on the obtained solution, naturally cooling the solution to a room temperature, collecting a solid substance, cleaning the solid substance with the deionized water and ethanol respectively and then putting the product into an oven for drying; grinding the product, carrying out high-temperature reaction, and then carrying out natural cooling to obtain an amorphous porous cobaltosic oxide nanosheet; adding the amorphous porous cobaltosic oxide nanosheet to a graphene oxide solution, and carrying out ultrasonic stirring treatment to obtain the mixed solution; carrying out hydrothermal reduction treatment; and carrying out centrifugal separation, carrying out freeze drying on the product and collecting the obtained product. The cobaltosic oxide is evenly distributed on the /graphene nanosheet in a form of the amorphous porous nanosheet, so that the specific surface area is increased; the specific capacitance is improved; the current impedance is reduced; and the cycling stability is strengthened.
Description
Technical field
The present invention relates to electrode material for super capacitor field, the preparation method being specifically related to the nano combined electrode material for super capacitor of a kind of cobalt oxide/graphene.
Background technology
Ultracapacitor, also referred to as electrochemical capacitor, is a kind of novel energy-storing device between traditional capacitor and accumulator, has excellent pulse charge-discharge performance and Large Copacity energy-storage property. As high in power density, have extended cycle life, charging rate is fast, can instantaneous high-current discharge, green non-pollution, be the novel energy-storing equipment that gets up of development in recent years. Now, the development of ultracapacitor is all extremely paid close attention in countries in the world, puts into substantial amounts of manpower and materials respectively and it is researched and developed.
The aspects such as Cobalto-cobaltic oxide is a kind of typical metal-oxide, and it is at lithium ion battery, accumulator, catalyst have potential using value.
C-base composte material has the performance of very superior electrode material for super capacitor, huge specific surface area, good chemical stability, outstanding chemical property etc. Graphene, as new a member of carbon-based material, since within 2004, finding, has become very popular material and has been used in lithium ion battery, field-effect transistor, gas sensor, the field such as absorbing material and catalyst. In the recent period, scientists finds that the redox graphene prepared by chemical method and the composite based on it have the electrode of super capacitor performance of excellence. Such as Zhangetal. (J.Electroanal.Chem., 2009,634,68) is at graphenic surface load zinc oxide; Yuetal. (NanoLetters, 2011,11,4438) are at graphenic surface load manganese dioxide; Lietal. (J.Mater.Chem., 2011,21,5069) are at graphenic surface load ferroso-ferric oxide; Wangetal. (Electrochim.Acta, 2010,55,6812) to aoxidize three in graphenic surface load four violent etc. These composites based on Graphene all show good electrode of super capacitor performance. Graphene and Co3O4Much research, Zhouetal. (Phys.Chem.Chem.Phys., 2011,13,14462) is had to adopt two step surfactant auxiliary laws to prepare Graphene and Co before the electrode that composite is applied to ultracapacitor3O4Composite; Wangetal. (J.AlloysCompd., 2011,509,7778) adopt original flavor solution circumfluence method to prepare Graphene and Co3O4Composite; Yanetal. (Electrochim.Acta, 2010.55,6973) and Parketal. (Electrochim.Acta, 2013,89,516) adopt microwave assisting method to prepare Graphene and Co3O4Composite; Xiangetal. (J.PowerSources, 2013,226,65) adopt one step hydro thermal method synthesizing graphite alkene and Co3O4Nano particle composite material etc. But first synthesize amorphous porous C o3O4Nanometer sheet, then be have not been reported at the composite being prepared Graphene and Cobalto-cobaltic oxide by hydrothermal reduction method.
Summary of the invention
It is an object of the invention to: the preparation method providing the nano combined electrode material for super capacitor of a kind of cobalt oxide/graphene, the method is easy, and environmental protection, cost is low, and material has good electrode of super capacitor performance.
For achieving the above object, the technical solution used in the present invention is as follows:
The preparation method of the nano combined electrode material for super capacitor of a kind of cobalt oxide/graphene, comprises the following steps:
(1) adding in deionized water by cabaltous nitrate hexahydrate, stirring is completely dissolved to it;
(2) adding ethanolamine under magnetic stirring in the solution of step (1), stirring makes it fully mix;
(3) gained solution in step (2) is poured into politef for the reactor of liner, carry out hydro-thermal reaction;
(4) reaction naturally cools to room temperature after terminating, and collects solid matter in reactor, and respectively with deionized water and ethanol purge, is then placed in baking oven and is dried;
(5) put into after dry gained solid matter being ground after tube furnace carries out pyroreaction, then natural cooling obtains amorphous porous cobaltosic oxide nano sheet;
(6) amorphous porous cobaltosic oxide nano sheet is added in graphene oxide water solution, and in addition ultrasonic agitation processes, and obtains mixed solution;
(7) mixed solution in step (6) is put into baking oven hydrothermal reduction process;
(8), by product centrifugation in step (7), and by its lyophilization, after end to be dried, products therefrom is collected.
Preferably, in described step (3), the temperature of hydro-thermal reaction is 180-220 DEG C, and the time is 22-26h.
Preferably, temperature dry in described step (4) is 55-65 DEG C, and the time is 11-13h.
Preferably, in described step (5), pyroreaction is to carry out in atmosphere, is incubated 1-3h after being warmed up to 350-550 DEG C with the programming rate of 1-5 DEG C/min.
Preferably, in described step (6), graphene oxide water solution concentration is 6-10mg/mL, and the described graphene oxide in graphene oxide water solution and Cobalto-cobaltic oxide mass ratio are 1:8-12, and the ultrasonic disperse time is 0.5-3h.
Preferably, in described step (7), the temperature of hydrothermal reduction reaction is 120-180 DEG C, and the response time is 3-8h.
Preferably, in described step (8), cryodesiccated temperature is-30 DEG C��-50 DEG C, and the time is 22-26h.
Preferably, the concrete preparation method of described graphene oxide water solution is:
Concentrated sulphuric acid and strong phosphoric acid are separately added in beaker, beaker are put into and is warmed in the water-bath of 45-55 DEG C, and continuously stirred with magnetic stirring apparatus;
White carbon black and potassium permanganate are slowly added in beaker successively, in the process added, ensure that mixeding liquid temperature is 45-55 DEG C, after waiting to add, continuously stirred 5-7h;
It is the hydrogen peroxide of 1.5% by mass fraction, is slowly injected in mixed liquor, mixed liquor color now be can be observed by black purpling, until when mixed liquor color becomes bright yellow and no longer has bubble to emerge, stopping adding hydrogen peroxide; Gained mixed liquor continuously stirred 2.5-3.5h again under 45-55 DEG C of condition, product naturally cools to room temperature;
Above-mentioned mixed liquor is centrifuged and is washed with water for several times, and lower floor's jelly is graphene oxide water solution, and being diluted with water to concentration is 6-10mg/mL.
Preferably, described concentrated sulphuric acid, strong phosphoric acid, hydrogen peroxide volume ratio are 9:1:10, and the mass ratio of described white carbon black and potassium permanganate is 1:6.
The present invention has the beneficial effects that: the present invention is prepared for the nano combined electrode material for super capacitor of cobalt oxide/graphene when hydrothermal reduction. Cobalto-cobaltic oxide is that amorphous porous nano lamellar is evenly distributed on graphene nanometer sheet, increases specific surface area, improves specific capacitance, reduce current impedance, strengthens cyclical stability. In the present invention, the nano combined electrode material for super capacitor of cobalt oxide/graphene of preparation, when sweep current is 1A/g, this composite has the specific capacitance of 894F/g. And this composite is when sweep current 5A/g, carries out 3000 circulations, specific capacitance only loss 4.7%, present extremely strong stability. Each performance has all fully met the requirement of electrode material for super capacitor.
Accompanying drawing explanation
Fig. 1 is the Raman figure of the nano combined electrode material for super capacitor of cobalt oxide/graphene of example 1 preparation.
Fig. 2 is the nano combined electrode material for super capacitor SEM figure of cobalt oxide/graphene of example 1 preparation.
Fig. 3 is the nano combined electrode material for super capacitor TEM figure of cobalt oxide/graphene of example 1 preparation.
Fig. 4 is the nano combined electrode material for super capacitor of cobalt oxide/graphene of example 1 preparation charging and discharging curve figure under different scanning rates.
Fig. 5 be example 1 preparation the nano combined electrode material for super capacitor of cobalt oxide/graphene when sweep current 5A/g, carry out 3000 cyclic curve figure.
Detailed description of the invention
In order to further appreciate that the present invention, below in conjunction with specific embodiment, the present invention is described further, it will be appreciated that these embodiments are merely to illustrate the present invention and are not limited to the scope of the present invention.
Embodiment 1
The preparation method of the nano combined electrode material for super capacitor of a kind of cobalt oxide/graphene, comprises the following steps:
(1) weigh the cabaltous nitrate hexahydrate of 0.58g, put in 24mL deionized water, and continue stirring until it and be completely dissolved;
(2) weigh in the solution that 8mL ethanolamine adds step (1), stir 1h;
(3) gained solution in step (2) is poured into politef for the reactor of liner, hydro-thermal reaction 24h at 200 DEG C.
(4) reaction naturally cools to room temperature after terminating, and collects solid matter in reactor, and respectively with deionized water and ethanol purge, is then placed in baking oven 60 DEG C of dry 12h;
(5) put into after dry gained solid matter being ground after tube furnace carries out pyroreaction, then natural cooling obtains amorphous porous cobaltosic oxide nano sheet; Wherein, pyroreaction is to carry out in atmosphere, is incubated 2h after being warmed up to 450 DEG C with the programming rate of 2 DEG C/min.
(6) being added in graphene oxide water solution by amorphous porous cobaltosic oxide nano sheet, and in addition ultrasonic agitation processes 2h, obtains mixed solution, wherein, the graphene oxide in graphene oxide water solution and Cobalto-cobaltic oxide mass ratio are 1:8;
(7) mixed solution in step (6) being put into baking oven hydrothermal reduction process, wherein, the temperature of hydrothermal reduction reaction is 160 DEG C, and the response time is 5h.
(8), by product centrifugation in step (7), and by it in-30 DEG C of lyophilization 24h, after end to be dried, products therefrom is collected.
The preparation method of graphene oxide water solution is as follows:
The Hummers method improved is adopted to prepare graphene oxide, as the presoma of hybrid supercapacitor electrode material.
Concrete preparation method is: the concentrated sulphuric acid of 180mL and the strong phosphoric acid of 20mL are separately added in the beaker of 500mL, are put into by beaker in the water-bath being warmed to 50 DEG C, and continuously stirred with magnetic stirring apparatus; The white carbon black of 1.5g is slowly added in mixed liquor, is also added slowly in beaker by the potassium permanganate of 9g afterwards, ensures that mixeding liquid temperature is at 50 DEG C in the process added, after waiting to add, and continuously stirred 6h; Then it is that 1.5% hydrogen peroxide is slowly injected in mixed liquor by the 200mL mass fraction after dilution, mixed liquor color now be can be observed by black purpling, until mixed liquor color is when becoming bright yellow and no longer have bubble to emerge, stop adding hydrogen peroxide; Gained mixed liquor continuously stirred 3h again under 50 DEG C of conditions, product naturally cools to room temperature; Above-mentioned mixed liquor is centrifuged and is washed with water for several times, and lower floor's jelly is graphene oxide water solution, and being diluted with water to concentration is 8mg/mL.
Embodiment 2
The preparation method of the nano combined electrode material for super capacitor of a kind of cobalt oxide/graphene, comprises the following steps:
(1) weigh the cabaltous nitrate hexahydrate of 0.58g, put in 24mL deionized water, and continue stirring until it and be completely dissolved;
(2) weigh in the solution that 8mL ethanolamine adds step (1), stir 1h;
(3) gained solution in step (2) is poured into politef for the reactor of liner, hydro-thermal reaction 26h at 180 DEG C.
(4) reaction naturally cools to room temperature after terminating, and collects solid matter in reactor, and respectively with deionized water and ethanol purge, is then placed in baking oven 55 DEG C of dry 11h;
(5) put into after dry gained solid matter being ground after tube furnace carries out pyroreaction, then natural cooling obtains amorphous porous cobaltosic oxide nano sheet; Wherein, pyroreaction is to carry out in atmosphere, is incubated 3h after being warmed up to 400 DEG C with the programming rate of 3 DEG C/min.
(6) being added in graphene oxide water solution by amorphous porous cobaltosic oxide nano sheet, and in addition ultrasonic agitation processes 1.5h, obtains mixed solution, wherein, the graphene oxide in graphene oxide water solution and Cobalto-cobaltic oxide mass ratio are 1:10;
(7) mixed solution in step (6) being put into baking oven hydrothermal reduction process, wherein, the temperature of hydrothermal reduction reaction is 150 DEG C, and the response time is 6h.
(8), by product centrifugation in step (7), and by it in-40 DEG C of lyophilization 24h lyophilization 25h, after end to be dried, products therefrom is collected.
Wherein, the preparation process of graphene oxide water solution is with example 1.
Embodiment 3
The preparation method of the nano combined electrode material for super capacitor of a kind of cobalt oxide/graphene, comprises the following steps:
(1) weigh the cabaltous nitrate hexahydrate of 0.58g, put in 24mL deionized water, and continue stirring until it and be completely dissolved;
(2) weigh in the solution that 8mL ethanolamine adds step (1), stir 1h;
(3) gained solution in step (2) is poured into politef for the reactor of liner, hydro-thermal reaction 226h at 220 DEG C.
(4) reaction naturally cools to room temperature after terminating, and collects solid matter in reactor, and respectively with deionized water and ethanol purge, is then placed in baking oven 65 DEG C of dry 13h;
(5) put into after dry gained solid matter being ground after tube furnace carries out pyroreaction, then natural cooling obtains amorphous porous cobaltosic oxide nano sheet; Wherein, pyroreaction is to carry out in atmosphere, is incubated 2.5h after being warmed up to 450 DEG C with the programming rate of 4 DEG C/min.
(6) being added in graphene oxide water solution by amorphous porous cobaltosic oxide nano sheet, and in addition ultrasonic agitation processes 1h, obtains mixed solution, wherein, the graphene oxide in graphene oxide water solution and Cobalto-cobaltic oxide mass ratio are 1:12;
(7) mixed solution in step (6) being put into baking oven hydrothermal reduction process, wherein, the temperature of hydrothermal reduction reaction is 170 DEG C, and the response time is 4h.
(8), by product centrifugation in step (7), and by it in-50 DEG C of lyophilization 24h lyophilization 22h, after end to be dried, products therefrom is collected.
Wherein, the preparation process of graphene oxide water solution is with example 1.
In conjunction with accompanying drawing 1-5, the invention will be further described:
Fig. 1 is the Raman figure of the nano combined electrode material for super capacitor of cobalt oxide/graphene of example 1 preparation, as can be seen from Figure 1: products therefrom is the complex of Cobalto-cobaltic oxide and Graphene.
Fig. 2 is the nano combined electrode material for super capacitor SEM figure of cobalt oxide/graphene of example 1 preparation, Fig. 3 is the cobalt oxide/graphene nano combined electrode material for super capacitor TEM figure of example 1 preparation, from Fig. 2,3 it can be seen that Cobalto-cobaltic oxide is amorphous porous nano lamellar is evenly distributed on graphene nanometer sheet.
Fig. 4 is the nano combined electrode material for super capacitor of cobalt oxide/graphene of example 1 preparation charging and discharging curve figure under different scanning rates, as can be seen from Figure 4: the nano combined electrode material for super capacitor of cobalt oxide/graphene of preparation, when sweep current is 1A/g, this composite has the specific capacitance of 894F/g.
Fig. 5 is that the nano combined electrode material for super capacitor of cobalt oxide/graphene of example 1 preparation is when sweep current 5A/g, carry out 3000 cyclic curve figure, as can be seen from Figure 5: the composite of the present invention is when sweep current 5A/g, carry out 3000 circulations, specific capacitance only loss 4.7%, presents extremely strong stability.
Claims (9)
1. the preparation method of the nano combined electrode material for super capacitor of cobalt oxide/graphene, it is characterised in that: comprise the following steps:
(1) adding in deionized water by cabaltous nitrate hexahydrate, stirring is completely dissolved to it;
(2) adding ethanolamine under magnetic stirring in the solution of step (1), stirring makes it fully mix;
(3) gained solution in step (2) is poured into politef for the reactor of liner, carry out hydro-thermal reaction;
(4) reaction naturally cools to room temperature after terminating, and collects solid matter in reactor, and respectively with deionized water and ethanol purge, is then placed in baking oven and is dried;
(5) put into after dry gained solid matter being ground after tube furnace carries out pyroreaction, then natural cooling obtains amorphous porous cobaltosic oxide nano sheet;
(6) amorphous porous cobaltosic oxide nano sheet is added in graphene oxide water solution, and in addition ultrasonic agitation processes, and obtains mixed solution;
(7) mixed solution in step (6) is put into baking oven hydrothermal reduction process;
(8), by product centrifugation in step (7), and by its lyophilization, after end to be dried, products therefrom is collected.
2. the preparation method of the nano combined electrode material for super capacitor of cobalt oxide/graphene according to claim 1, it is characterised in that: in described step (3), the temperature of hydro-thermal reaction is 180-220 DEG C, and the time is 22-26h.
3. the preparation method of the nano combined electrode material for super capacitor of cobalt oxide/graphene according to claim 1, it is characterised in that: temperature dry in described step (4) is 55-65 DEG C, and the time is 11-13h.
4. the preparation method of the nano combined electrode material for super capacitor of cobalt oxide/graphene according to claim 1, it is characterized in that: in described step (5), pyroreaction is to carry out in atmosphere, after being warmed up to 350-550 DEG C with the programming rate of 1-5 DEG C/min, be incubated 1-3h.
5. the preparation method of the nano combined electrode material for super capacitor of cobalt oxide/graphene according to claim 1, it is characterized in that: in described step (6), graphene oxide water solution concentration is 6-10mg/mL, the described graphene oxide in graphene oxide water solution and Cobalto-cobaltic oxide mass ratio are 1:8-12, and the ultrasonic disperse time is 0.5-3h.
6. the preparation method of the nano combined electrode material for super capacitor of cobalt oxide/graphene according to claim 1, it is characterised in that: in described step (7), the temperature of hydrothermal reduction reaction is 120-180 DEG C, and the response time is 3-8h.
7. the preparation method of the nano combined electrode material for super capacitor of cobalt oxide/graphene according to claim 1, it is characterised in that: in described step (8), cryodesiccated temperature is-30 DEG C��-50 DEG C, and the time is 22-26h.
8. the preparation method of the nano combined electrode material for super capacitor of cobalt oxide/graphene according to claim 1, it is characterised in that: the concrete preparation method of described graphene oxide water solution is:
Concentrated sulphuric acid and strong phosphoric acid are separately added in beaker, beaker are put into and is warmed in the water-bath of 45-55 DEG C, and continuously stirred with magnetic stirring apparatus;
White carbon black and potassium permanganate are slowly added in beaker successively, in the process added, ensure that mixeding liquid temperature is 45-55 DEG C, after waiting to add, continuously stirred 5-7h;
It is the hydrogen peroxide of 1.5% by mass fraction, is slowly injected in mixed liquor, mixed liquor color now be can be observed by black purpling, until when mixed liquor color becomes bright yellow and no longer has bubble to emerge, stopping adding hydrogen peroxide; Gained mixed liquor continuously stirred 2.5-3.5h again under 45-55 DEG C of condition, product naturally cools to room temperature;
Above-mentioned mixed liquor is centrifuged and is washed with water for several times, and lower floor's jelly is graphene oxide water solution, and being diluted with water to concentration is 6-10mg/mL.
9. the preparation method of the nano combined electrode material for super capacitor of cobalt oxide/graphene according to claim 8, it is characterized in that: described concentrated sulphuric acid, strong phosphoric acid, hydrogen peroxide volume ratio are 9:1:10, the mass ratio of described white carbon black and potassium permanganate is 1:6.
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| CN106816316A (en) * | 2017-03-15 | 2017-06-09 | 苏州海凌达电子科技有限公司 | A kind of ultracapacitor preparation method of manganese cobalt nickel base electrode |
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| CN106816316A (en) * | 2017-03-15 | 2017-06-09 | 苏州海凌达电子科技有限公司 | A kind of ultracapacitor preparation method of manganese cobalt nickel base electrode |
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| CN109468709A (en) * | 2018-10-29 | 2019-03-15 | 宿州学院 | A kind of graphene doping Co3O4The preparation method of hollow fibre |
| CN109556705A (en) * | 2018-10-29 | 2019-04-02 | 苏州佳世达电通有限公司 | Ultrasound scanner head and preparation method thereof |
| CN109468709B (en) * | 2018-10-29 | 2021-07-16 | 宿州学院 | Preparation method of graphene-doped Co3O4 mesoporous fiber |
| CN111410855A (en) * | 2019-12-31 | 2020-07-14 | 宁波德泰化学有限公司 | Preparation method of high-surface-activity/high-hydrophilicity dispersion type carbon black |
| CN112700904A (en) * | 2020-11-09 | 2021-04-23 | 扬州鑫鸿电子有限公司 | Preparation method of graphene nano material composite flexible electrode |
| CN116443956A (en) * | 2023-04-28 | 2023-07-18 | 天能电池集团股份有限公司 | Preparation method of nano nickel oxide/graphene composite electrode material |
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