CN102229425B - Method for preparing cobalt/graphene composite material by alcohol thermal method - Google Patents
Method for preparing cobalt/graphene composite material by alcohol thermal method Download PDFInfo
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- CN102229425B CN102229425B CN 201110077569 CN201110077569A CN102229425B CN 102229425 B CN102229425 B CN 102229425B CN 201110077569 CN201110077569 CN 201110077569 CN 201110077569 A CN201110077569 A CN 201110077569A CN 102229425 B CN102229425 B CN 102229425B
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Abstract
The invention relates to a method for preparing a cobalt/graphene composite material by an alcohol thermal method. The method comprises the following steps of: (1) dispersing graphite oxide into glycol solution at room temperature to obtain mixed solution with concentration of 0.5 to 2 mg/mL, ultrasonically dispersing the mixed solution for 30 to 60 minutes, adding cobalt salt, anhydrous sodium acetate and polyethylene glycol, and stirring for 1 to 2 hours to obtain reaction solution; and (2) adding the reaction solution into a reaction kettle, heating the reaction kettle to 180 to 210 DEG C, reacting for 8 to 16 hours, cooling the obtained product to room temperature, centrifugally collecting the product, washing the product with deionized water and absolute ethanol, and drying to obtain the cobalt/graphene composite material. The method is simple in process and suitable for industrialized production. The prepared cobalt/graphene composite material has a pure cobalt crystalline phase, high complex property with graphene, high dispersibility on the surface of the graphene and in the layer, low resistivity, high magnetization intensity and a good application prospect.
Description
Technical field
The invention belongs to cobalt/graphene composite material field, particularly the method for the standby cobalt/graphene composite material of the hot legal system of a kind of alcohol.
Background technology
Graphene be a kind of by carbon atom by sp
2Carbon lattice close-packed arrays forms the stratified material that is similar to polynuclear plane, is subject in recent years the extensive concern of scientific circles.The electronic movement velocity of Graphene reaches 1/300 of the light velocity, that is to say considerably beyond the movement velocity of electronics in general conductor, and many research expectations are by compound to reach the purpose that improves the material electrical property with Graphene.In addition, it also has a lot of good performances: good heat-conductive characteristic, mechanical property, chemical stability, large surface-to-volume ratio, this is so that it has huge application prospect at many sciemtifec and technical spheres such as nanoelectronics, sensor, nano composite material, battery, ultracapacitor and hydrogen storages.
Recent study person's discovery, graphene-based matrix material can significantly improve the performances such as raw-material specific conductivity, thermal conductivity, physical strength.Haegyeom Kim etc. have reported that at Carbon 49 (2011) 326-332 stirring reduction under the low temperature makes Co
3O
4/ graphene complex material, the approximately Co of 5.5nm
3O
4Particle is attached on the graphene film, has not only greatly improved the specific conductivity of electrode, has also avoided electrode because of Co in the charge and discharge process
3O
4It is cracked that volume change is brought.Zhong-Shuai Wu etc. have reported at ACSNano 4 (2010) 3187-3194 and have utilized Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and ammoniacal liquor effect to obtain Co (OH)
2/ graphene complex, then calcining obtains Co
3O
4/ graphene complex shows good electrical property.Hongkun He and Chao Gao have reported at ACS ApplMater Inter 2 (2010) 3201-3210 and have passed through FeCl
3Synthesize Fe with GO pyroreaction in NaOH/DEG
3O
4/ graphene complex, its particle diameter distribution are at 1.2～6.3nm, and matrix material demonstrates good electrical property and magnetic property.
The investigator has also carried out broad research to the matrix material of metal simple-substance and Graphene.Yaojuan Hu etc. have reported with the plating legal system at Electrochimica Acta 56 (2010) 491-500 and have got Au/ graphene nano structural composite material, the activity of its catalytic activity during apparently higher than single use Au or Graphene.Ki-Seok Kim etc. have reported by hydrazine reduction Silver Nitrate, graphite oxide, PVP and APTMS mixing solutions at Synthetic Metals 160 (2010) 2355-2360 and have prepared silver-colored doped graphene matrix material, prepare the Ag-GR/PPy matrix material, test result shows that the Ag nano particle has significantly improved the chemical property of polypyrrole/ graphene complex.Sheng Liu etc. has reported in Journal of Power Sources 195 (2010) 4628-4633 by electrochemical reducing and has prepared Pt/ expansible black lead alkene nanometer sheet, the Pt uniform particles that diameter is about 15nm is dispersed in the graphene layer, improved the electrocatalysis characteristic of graphene nanometer sheet, good stability.Shubin Yang etc. has reported that at ChemSusChem 3 (2010) 236-239 employing flush type metallorganics molecule such as Cobalt Phthalocyanine (CoPc) obtain organo-metallic/graphene complex, obtained the Co/ graphene complex by the hydrazine solution reduction again, the particle diameter of Co is about 7nm.
Mainly there is following defective in the method for preparing at present metal/graphite alkene mixture: processing step is more, cost is higher.Therefore the focus that seek that the single stage method preparation cost is low, advantages of good crystallization, the metal/graphite alkene matrix material that is difficult for reuniting becomes research.Have no at present the report that adopts the standby cobalt/graphene composite material of pure hot legal system.
Summary of the invention
Technical problem to be solved by this invention provides the method for the standby cobalt/graphene composite material of the hot legal system of a kind of alcohol, and the method technique is simple, is easy to suitability for industrialized production; The cobalt crystalline phase is pure in prepared cobalt/graphene composite material, and is compound good with Graphene, good dispersity in Graphene surface and layer, and the composite material resistance rate is little, and the specific magnetising moment is high, has a good application prospect.
The method of the standby cobalt/graphene composite material of the hot legal system of a kind of alcohol of the present invention comprises:
(1) under the room temperature graphite oxide is scattered in the ethylene glycol solution, gets the mixed solution that concentration is 0.5～2mg/mL, behind mixed solution ultra-sonic dispersion 30～60min, add cobalt salt, anhydrous sodium acetate and polyoxyethylene glycol, stir 1～2h, form reaction solution; Wherein, the mass ratio of cobalt salt and graphite oxide is 1: 1～5: 1, and the mass ratio of anhydrous sodium acetate and cobalt salt is 10: 1～12: 1, and the volume ratio of polyoxyethylene glycol and ethylene glycol is 1: 110～1: 550;
(2) above-mentioned reaction solution is added in the reactor, be warming up to 180～210 ℃, reaction 8～16h; Products therefrom is cooled to room temperature, and centrifugal collection product with deionized water and absolute ethanol washing, is dried and be get final product.
Cobalt salt in the described step (1) is Cobaltous nitrate hexahydrate.
The mass concentration of the ethylene glycol in the described step (1) is 98%～99.5%.
The molecular weight of the polyoxyethylene glycol in the described step (1) is 200～1000.
Deionized water wash number of times in the described step (2) is 6～8 times, and the absolute ethanol washing number of times is 3～5 times.
Bake out temperature in the described step (2) is 40～80 ℃, and the time is 12～24h.
By regulating the ratio of graphite oxide, cobalt salt, obtain the different cobalt/graphene composite materials that form.
This preparation method is with respect to common liquid phase method, and magnetic nanoparticle is more stable in organic phase, is difficult for generating impurity phase.Because in liquid phase, magnetic nano-particle is very easily reunited because of the effect that is subject to the strong electrostatic attraction of solion, so present method selects electrostatic stabilization good anhydrous sodium acetate adds as alkaline reagents, to prevent the extensive reunion of cobalt.
Beneficial effect
(1) technique of the present invention is simple, and is low to the production unit requirement, is easy to suitability for industrialized production;
(2) cobalt good crystallinity in prepared cobalt/graphene composite material, compound good with Graphene, good dispersity in Graphene surface and layer, the composite material resistance rate is little, and the specific magnetising moment is high, has a good application prospect.
Description of drawings
Fig. 1 is the X-ray diffractogram of matrix material;
Fig. 2 is the stereoscan photograph of matrix material;
Fig. 3 is the magnetic hysteresis loop figure of matrix material.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Take by weighing the 55mg graphite oxide under the room temperature and be scattered in the 28mL ethylene glycol solution, behind the gained mixed solution ultra-sonic dispersion 45min, add 110mg Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, 1200mg anhydrous sodium acetate and 0.2mL Macrogol 200, stir 1.5h, form reaction solution.Reaction solution is added in the reactor, be warming up to 200 ℃, reaction 12h.Reaction finishes, and centrifugal collection product is used deionized water wash 6 times, uses absolute ethanol washing 3 times, then with product dry 18h under 60 ℃, obtains cobalt/graphene composite material.Fig. 1 is the X-ray diffractogram of the present embodiment resulting materials, can find out that the nano particle in this matrix material is cobalt, and graphite oxide is reduced to Graphene.Fig. 2 is the stereoscan photograph of the present embodiment resulting materials, and cobalt and Graphene are compound good, good dispersity in Graphene surface and layer.Fig. 3 is the magnetic hysteresis loop figure of the present embodiment resulting materials, can find out that resulting materials has good magnetic property; Resistivity measurement is the result show: the resistivity of this matrix material is 0.493 Ω cm, and it has good conductivity.
Take by weighing the 55mg graphite oxide under the room temperature and be scattered in the 110mL ethylene glycol solution, behind the gained mixed solution ultra-sonic dispersion 30min, add 55mg Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, 550mg anhydrous sodium acetate and 1mL cetomacrogol 1000, stir 1h, form reaction solution.Reaction solution is added in the reactor, be warming up to 180 ℃, reaction 16h.Reaction finishes, and centrifugal collection product is used deionized water wash 8 times, uses absolute ethanol washing 5 times, then with product dry 24h under 40 ℃, obtains cobalt/graphene composite material.X-ray diffraction analysis shows that the nano particle in the present embodiment synthetic materials is cobalt.The magnetic hysteresis loop test shows: resulting materials has good magnetic property.Resistivity measurement is the result show: this matrix material has good conductivity.
Embodiment 3
Take by weighing the 55mg graphite oxide under the room temperature and be scattered in the 55mL ethylene glycol solution, behind the gained mixed solution ultra-sonic dispersion 60min, add 165mg Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, 1980mg anhydrous sodium acetate and 0.1mL poly(oxyethylene glycol) 400, stir 2h, form reaction solution.Reaction solution is added in the reactor, be warming up to 210 ℃, reaction 8h.Reaction finishes, and centrifugal collection product with deionized water, absolute ethanol washing product, then with product dry 12h under 80 ℃, obtains cobalt/graphene composite material.X-ray diffraction analysis shows that the nano particle in the present embodiment synthetic materials is cobalt.The magnetic hysteresis loop test shows: resulting materials has good magnetic property.Resistivity measurement is the result show: this matrix material has good conductivity.
Claims (6)
1. the method for the standby cobalt/graphene composite material of the hot legal system of alcohol comprises:
(1) under the room temperature graphite oxide is scattered in the ethylene glycol solution, gets the mixed solution that concentration is 0.5～2mg/mL, behind mixed solution ultra-sonic dispersion 30～60min, add cobalt salt, anhydrous sodium acetate and polyoxyethylene glycol, stir 1～2h, form reaction solution; Wherein, the mass ratio of cobalt salt and graphite oxide is 1: 1～5: 1, and the mass ratio of anhydrous sodium acetate and cobalt salt is 10: 1～12: 1, and the volume ratio of polyoxyethylene glycol and ethylene glycol is 1: 110～1: 550;
(2) above-mentioned reaction solution is added in the reactor, be warming up to 180～210 ℃, reaction 8～16h; Products therefrom is cooled to room temperature, and centrifugal collection product with deionized water and absolute ethanol washing, is dried and be get final product.
2. the hot legal system of a kind of alcohol according to claim 1 is for the method for cobalt/graphene composite material, and it is characterized in that: the cobalt salt in the described step (1) is Cobaltous nitrate hexahydrate.
3. the hot legal system of a kind of alcohol according to claim 1 is for the method for cobalt/graphene composite material, and it is characterized in that: the mass concentration of the ethylene glycol in the described step (1) is 98%～99.5%.
4. the hot legal system of a kind of alcohol according to claim 1 is for the method for cobalt/graphene composite material, and it is characterized in that: the molecular weight of the polyoxyethylene glycol in the described step (1) is 200～1000.
5. the hot legal system of a kind of alcohol according to claim 1 is for the method for cobalt/graphene composite material, and it is characterized in that: the deionized water wash number of times in the described step (2) is 6～8 times, and the absolute ethanol washing number of times is 3～5 times.
6. the hot legal system of a kind of alcohol according to claim 1 is for the method for cobalt/graphene composite material, and it is characterized in that: the bake out temperature in the described step (2) is 40～80 ℃, and the time is 12～24h.
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| WO2012155196A1 (en) * | 2011-05-13 | 2012-11-22 | University Of Wollongong | Spray pyrolysis method for in situ production of graphene oxide based composites |
| CN102886276A (en) * | 2012-10-12 | 2013-01-23 | 东华大学 | Preparation method of Co/graphene-PAN (polyacrylonitrile) composite material |
| CN103400967B (en) * | 2013-07-18 | 2016-04-13 | 上海交通大学 | Three-dimensional porous cobalt-based/graphene composite material and preparation method thereof |
| CN106970116B (en) * | 2017-03-20 | 2019-09-10 | 中国石油大学(华东) | The sensitive polyhedral cobaltosic oxide of a kind of pair of acetone-three-dimensional porous Graphene gel composite material film |
| CN107626931B (en) * | 2017-09-12 | 2020-12-08 | 四川大学 | Preparation and application of cobalt-graphene composite material for absorbing electromagnetic waves |
| CN110627108A (en) * | 2019-09-27 | 2019-12-31 | 东华大学 | Zinc oxide/reduced graphene oxide composite material and preparation method and application thereof |
| CN113634744A (en) * | 2021-07-13 | 2021-11-12 | 中北大学 | Preparation method of graphene surface cobalt-plated reinforced cobalt-based alloy composite powder for selective laser melting forming |
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| CN101837971A (en) * | 2010-05-14 | 2010-09-22 | 东华大学 | Method for preparing graphene/Fe3O4 composite powder by alcohol thermal method |
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