CN107393730A - A kind of preparation method of graphene/cobalt nickel bimetal hydroxide - Google Patents
A kind of preparation method of graphene/cobalt nickel bimetal hydroxide Download PDFInfo
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- CN107393730A CN107393730A CN201710574021.8A CN201710574021A CN107393730A CN 107393730 A CN107393730 A CN 107393730A CN 201710574021 A CN201710574021 A CN 201710574021A CN 107393730 A CN107393730 A CN 107393730A
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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
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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
- 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
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Abstract
The present invention discloses a kind of preparation method of graphene/cobalt nickel bimetal hydroxide, comprises the following steps：Choose the powdered graphite of certain particle size, oxidation processes are carried out to it, filtering cleaning obtains powdered graphite, then after carrying out microwave bulking to powdered graphite, obtain expansion worm powdered graphite, and put it into N methyl pyrrolidone solvents, through ultrasonic vibration, centrifuge, take upper strata suspension, the cobalt salt of certain mol proportion and nickel salt are added thereto, obtain certain density presoma, and presoma is put into autoclave heated sealed, reaction product is filtered after cooling, washed, graphene/cobalt nickel bimetal hydroxide is obtained after drying.The features such as composite of the present invention there is raw material to be easy to get, inexpensively, and cost is low, and electrode energy storage characteristic effect is good, can apply in terms of electrode material for super capacitor and electrochemical catalysis.
Description
Technical field
The present invention relates to function and service functional material preparation field, it is directed primarily to that a kind of production cost is low, in light weight, storage
Can the good composite nano materials preparation method of effect.
Background technology
If ultracapacitor divides from energy storage mechnism, ultracapacitor is divided into double layer capacitor and pseudocapacitors.It is
A kind of novel energy storage apparatus, it has, and power density is high, the charging interval is short, service life is long, good temp characteristic, save the energy and
The features such as green.It can be divided into electric double layer type ultracapacitor and fake capacitance type ultracapacitor by its energy storage mechnism, it is double
Electric layer type ultracapacitor mainly uses activated carbon, and carbon fiber, carbon aerogels, CNT or graphene are as electrode material
, pass through the mechanism of electric field adsorption charge storage energy.Fake capacitance type ultracapacitor include metal oxide electrode material with
Polymer electrode material, metal oxide include NiOx, MnO2、V2O5Deng positive electrode is used as, activated carbon is used as negative material system
Electrode is produced in standby ultracapacitor, the conducting polymer materials doping such as including PPY, PTH, PANi.Wherein newly discovered tool
There is the hydrotalcite-based compound of high energy storage characteristic, its main body is typically made up of the hydroxide of two kinds of metals, and also known as stratiform is double
Hydroxy composite metal oxide or double-metal hydroxide, they are a kind of compounds with high electrochemical energy storage characteristic.
But double-metal hydroxide self-conductive characteristic is poor so that its cyclical stability and high rate performance can under
Drop, the method that one effective to improve disadvantages mentioned above are exactly it is compound with the material with highly conductive characteristic, such as carbon nanometer
Pipe, graphene etc., a kind of composite is obtained, the characteristic of the high energy storage of hydroxide can not only be played, can also carried by carbon material
Its high electrical conductivity, realizes high combination property.
The content of the invention
For problem and shortage existing for electrode material for super capacitor, it is an object of the invention to provide one kind to have high storage
The preparation method of the combination electrode material of energy characteristic and electrochemical stability, from cobalt-nickel bimetal with hydrotalcite structure
Hydroxide and graphene In-situ reaction, combination is realized by chemical one-step method, provided for high-performance super capacitor
High-quality electrode material.
A kind of preparation method of graphene/cobalt-nickel bimetal hydroxide, comprises the following steps：
(1) powdered graphite that granularity is 1~100 micron is chosen, it is carried out at concentrated nitric acid and potassium permanganate oxidation successively
Reason, powdered graphite is cleaned after filtering with a large amount of water；
(2) after and then the powdered graphite of gained in (1) being put into micro-wave oven microwave bulking, expansion worm graphite powder is obtained
End；
(3) expanded graphite powder in (2) is put into 1-METHYLPYRROLIDONE solvent, shaken through more than 2 hours ultrasonic waves
Swing and centrifuge, it is 1~10mg/mL upper stratas suspension to take concentration, is used as multi-layer graphene；
(4) 1:9-9:The cobalt salt and nickel salt of 1 mol ratio are added in the multi-layer graphene suspension obtained in (3), cobalt
The integral molar quantity of salt and nickel salt is 0.01~0.1mol, is stirred at room temperature, that is, obtains 0.1~1mol/L presomas；
(5) by the presoma in (4) be put into polytetrafluoroethylene (PTFE) be liner autoclave in, filling rate be 70%~
85%, after sealing reactor, it is heated to 180~200 degree and reacts 1~2 hour；
(6) after the reactor in (5) being naturally cooled into room temperature, take out reaction product by filtering, wash, dry after i.e.
Obtain graphene/cobalt-nickel bimetal hydroxide.
Further, described cobalt salt is four hydration cobalt acetates and one kind in cabaltous nitrate hexahydrate or their mixing
Thing.
Further, described nickel salt is four hydration nickel acetates and one kind in Nickelous nitrate hexahydrate or their mixing
Thing.
Graphene/cobalt-nickel bimetal hydroxide prepared by the present invention has advantages below：
(1) raw material sources are wide, cheap, and product specific capacitance is high, good cycling stability；
(2) composite one-time process obtains, and technique is simple, with short production cycle；
(3) low is required to Preparation equipment, is easy to mass prepare with scale.
Embodiment
Embodiment 1
The natural high purity graphite powder of 5 microns of average grain diameter is chosen, concentrated nitric acid and potassium permanganate oxidation are carried out to it successively
Processing, powdered graphite is cleaned after filtering with a large amount of water；Then after powdered graphite being put into micro-wave oven microwave bulking, it is compacted to obtain expansion
Worm powdered graphite；After adding ultrasonic vibration ultrasonic oscillation in 1-METHYLPYRROLIDONE and centrifuging, 5mg/mL upper stratas are taken out
Suspension 100mL, add 0.025mol tetra- and be hydrated cobalt acetate and the hydration nickel acetates of 0.075mol tetra-, after stirring, load total
In volume 120mL reactor, by 180 degree react 1 hour after, cool down, filter, washing, dry after obtain graphene/cobalt-
Nickel bimetal hydroxide.In the 2mol/L KOH aqueous solution, it is 1185F/g that single electrode, which tests its specific capacitance, by 10000 times
After charge and discharge cycles, specific capacitance retention rate is 92%.
Embodiment 2
The natural high purity graphite powder of 1 micron of average grain diameter is chosen, concentrated nitric acid and potassium permanganate oxidation are carried out to it successively
Processing, powdered graphite is cleaned after filtering with a large amount of water；Then after powdered graphite being put into micro-wave oven microwave bulking, it is compacted to obtain expansion
Worm powdered graphite；After adding ultrasonic vibration ultrasonic oscillation in 1-METHYLPYRROLIDONE and centrifuging, 1mg/mL upper stratas are taken out
Suspension 100mL, 0.001mol cabaltous nitrate hexahydrates and 0.009mol Nickelous nitrate hexahydrates are added, after stirring, loaded total
In volume 140mL reactor, by 200 degree reaction 2 hours after, cool down, filter, washing, dry after obtain graphene/cobalt-
Nickel bimetal hydroxide.In the 2mol/L KOH aqueous solution, it is 1476F/g that single electrode, which tests its specific capacitance, by 5000 times
After charge and discharge cycles, specific capacitance retention rate is 95%.
Embodiment 3
The natural high purity graphite powder of 100 microns of average grain diameter is chosen, concentrated nitric acid and potassium permanganate oxygen are carried out to it successively
Change is handled, and powdered graphite is cleaned with a large amount of water after filtering；Then after powdered graphite being put into micro-wave oven microwave bulking, expanded
Worm powdered graphite；After adding ultrasonic vibration ultrasonic oscillation in 1-METHYLPYRROLIDONE and centrifuging, 10mg/mL is taken out
Upper suspension 100mL, add 0.009mol tetra- and be hydrated cobalt acetate and the hydration nickel acetates of 0.001mol tetra-, after stirring, dress
In the reactor for entering cumulative volume 125mL, by 200 degree reaction 2 hours after, cool down, filter, washing, dry after obtain graphene/
Cobalt-nickel bimetal hydroxide.In the 2mol/L KOH aqueous solution, it is 1064F/g that single electrode, which tests its specific capacitance, is passed through
After 10000 charge and discharge cycles, specific capacitance retention rate is 97%.
Claims (3)
1. a kind of preparation method of graphene/cobalt-nickel bimetal hydroxide, comprises the following steps：
(1) powdered graphite that granularity is 1~100 micron is chosen, carries out concentrated nitric acid and potassium permanganate oxidation processing, mistake successively to it
After filter powdered graphite is cleaned with a large amount of water；
(2) after and then the powdered graphite of gained in (1) being put into micro-wave oven microwave bulking, expansion worm powdered graphite is obtained；
(3) expanded graphite powder in (2) is put into 1-METHYLPYRROLIDONE solvent, through more than 2 hours ultrasonic oscillations, simultaneously
Centrifuge, it is 1~10mg/mL upper stratas suspension to take concentration, is used as multi-layer graphene；
(4) 1:9~9:The cobalt salt and nickel salt of 1 mol ratio are added in the multi-layer graphene suspension obtained in (3), cobalt salt and
The integral molar quantity of nickel salt is 0.01~0.1mol, is stirred at room temperature, that is, obtains 0.1~1mol/L presomas.
(5) presoma in (4) being put into the autoclave that polytetrafluoroethylene (PTFE) is liner, filling rate is 70%~85%,
After sealing reactor, it is heated to 180~200 degree and reacts 1~2 hour；
(6) after the reactor in (5) being naturally cooled into room temperature, take out reaction product and obtained by filtering, wash, after drying
Graphene/cobalt-nickel bimetal hydroxide.
2. preparation method as claimed in claim 1, it is characterised in that the cobalt salt described in step (4) is four hydration cobalt acetates
With one kind in cabaltous nitrate hexahydrate or their mixture.
3. preparation method as claimed in claim 1, it is characterised in that the nickel salt described in step (4) is four hydration nickel acetates
With one kind in Nickelous nitrate hexahydrate or their mixture.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109513440A (en) * | 2018-11-12 | 2019-03-26 | 上海今海新材料科技有限公司 | A kind of preparation method for the oxidation copper composite powders that flower-shaped graphene supports |
| CN110289178A (en) * | 2019-05-13 | 2019-09-27 | 江苏大学 | Two-step method prepares nickel oxide/cobaltosic oxide/N doping carbon dots ultrathin nanometer plate electrode material and its application |
| CN110676069A (en) * | 2019-10-15 | 2020-01-10 | 西华大学 | Graphene-metal oxide/nitride composite energy storage material and preparation method thereof |
| CN111001375A (en) * | 2019-12-29 | 2020-04-14 | 福建工程学院 | Preparation method of layered double-hydroxide composite adsorption material |
| CN111199834A (en) * | 2020-01-08 | 2020-05-26 | 杭州电子科技大学 | Cobalt sulfide/multilayer graphene composite material and preparation method thereof |
| CN113231023A (en) * | 2021-05-17 | 2021-08-10 | 黑龙江省科学院高技术研究院 | Preparation method and application of expanded graphite-based cobalt-indium bimetal hydroxide interlayer composite material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109513440A (en) * | 2018-11-12 | 2019-03-26 | 上海今海新材料科技有限公司 | A kind of preparation method for the oxidation copper composite powders that flower-shaped graphene supports |
| CN110289178A (en) * | 2019-05-13 | 2019-09-27 | 江苏大学 | Two-step method prepares nickel oxide/cobaltosic oxide/N doping carbon dots ultrathin nanometer plate electrode material and its application |
| CN110676069A (en) * | 2019-10-15 | 2020-01-10 | 西华大学 | Graphene-metal oxide/nitride composite energy storage material and preparation method thereof |
| CN111001375A (en) * | 2019-12-29 | 2020-04-14 | 福建工程学院 | Preparation method of layered double-hydroxide composite adsorption material |
| CN111001375B (en) * | 2019-12-29 | 2023-03-14 | 福建工程学院 | Preparation method of layered double-hydroxide composite adsorption material |
| CN111199834A (en) * | 2020-01-08 | 2020-05-26 | 杭州电子科技大学 | Cobalt sulfide/multilayer graphene composite material and preparation method thereof |
| CN113231023A (en) * | 2021-05-17 | 2021-08-10 | 黑龙江省科学院高技术研究院 | Preparation method and application of expanded graphite-based cobalt-indium bimetal hydroxide interlayer composite material |
| CN113231023B (en) * | 2021-05-17 | 2022-06-28 | 黑龙江省科学院高技术研究院 | Preparation method and application of expanded graphite-based cobalt-indium bimetal hydroxide interlayer composite material |
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