CN105645381A - Method for preparing graphene/carbon nanotube composite material by intensive microwave process - Google Patents
Method for preparing graphene/carbon nanotube composite material by intensive microwave process Download PDFInfo
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- CN105645381A CN105645381A CN201610018438.1A CN201610018438A CN105645381A CN 105645381 A CN105645381 A CN 105645381A CN 201610018438 A CN201610018438 A CN 201610018438A CN 105645381 A CN105645381 A CN 105645381A
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Abstract
The invention relates to a method for preparing a graphene/carbon nanotube composite material by an intensive microwave process. The method is based on a microwave irradiation process, and comprises the following steps: putting graphite oxide into a microwave oven, and carrying out microwave irradiation for 2-5 minutes to obtain the reduced and stripped graphite oxide; and mixing the reduced and stripped graphite oxide with ferrocene, and carrying out secondary microwave treatment under identical conditions, thereby finally obtaining the graphene/carbon nanotube composite material. The method has the advantages of simple technique and low cost. The produced Gr/CNTs (carbon nanotubes) composite material has favorable electric conductivity and magnetism.
Description
Technical field
The present invention relates to a kind of nano carbon composite material, particularly relate to a kind of method that potent microwave method prepares graphene carbon nanometer tube composite materials.
Background technology
Electrochemical capacitor, as a kind of novel energy-storing device, due to advantages such as its charge-discharge velocity are fast, power density is high, have extended cycle life, is the energy storage device of another great application potential and Development volue after lithium ion battery. But the relatively low key factor being restriction ultracapacitor and developing and apply of energy density, explore the emphasis that the energy density how improving ultracapacitor is this area research at present. Computing formula according to energy density improves energy density and mainly starts with from two aspects, improves the voltage window of electrochemical capacitor on the one hand; Still further aspect is to improve the specific capacity of electrode material, and the raising of these two aspects all can bring the raising of energy density.
Graphene is as a kind of two dimension monolayer material, there is higher specific surface area and higher electrical conductivity, it it is a kind of desirably electrochemical capacitor electrode material, but the method complex process of tradition preparation graphene carbon nanometer tube composite materials, relatively costly and reduced graphene use the toxic reagent such as hydrazine hydrate, therefore for a long time, the production of graphene carbon nanometer tube composite materials is always up a problem demanding prompt solution.
Summary of the invention
Subject matter to be solved by this invention is: for producing the graphene carbon nanometer tube composite materials that a kind of cost is low, production method simple and fast, safety non-toxic are harmful, invented a kind of method that potent microwave method produces graphene carbon nanometer tube composite materials. The method simple and fast, whole preparation process will not be used any to the virulent reagent raw material of human body, safety non-toxic evil.
The present invention implements by following technical solution:
Potent microwave method prepares the method for graphene carbon nanometer tube composite materials, comprises the steps:
1) at ambient temperature 2��4g graphite is equipped with in the beaker of 100��120mL concentrated sulphuric acid, then after being slowly added to 15��20g potassium permanganate under condition of ice bath, reactant liquor is transferred to the stirred in water bath reaction 20��50min of 28��33 DEG C, reaction adds the frozen water of 300��450mL and is diluted after terminating, drip H2O2Solution, until bubble-free produces, carries out sucking filtration and is rinsed with a large amount of clear water by the golden yellow filter cake obtained, and the powder obtained is dried overnight in vacuum drying oven;
2) graphite oxide powder step 1 prepared is put in vial, is placed in microwave oven, 1000W microwave 20��50s, obtains MRGO;
3) take 13��18mgMRGO and 20��35mg ferrocene and jointly put into grinding 15min in agate mortar, after mix homogeneously, the black powder of mix homogeneously is transferred in vial, 1000W microwave 20��50s, the uniform Gr/CNTs composite of pattern can be obtained.
Specifically, described step 1) the middle H dripped2O2The mass fraction of solution is 13��18%.
Specifically, described step 1) in utilize vacuum drying oven that graphite oxide powder is dried temperature to be set as 30��45 DEG C.
Beneficial effects of the present invention: (1) preparation process will not use the toxic reagent such as hydrazine hydrate, and safe production process is reliably pollution-free; (2) whole preparation process can reach requirement only with twice microwave, does not need the extreme environment experiments such as High Temperature High Pressure, therefore extremely suitable industrialization large-scale production.
Detailed description of the invention:
The following is specific embodiments of the invention, technical scheme is described further, but protection scope of the present invention is not limited to these embodiments. Every change without departing substantially from present inventive concept or equivalent replacement are included within protection scope of the present invention.
Embodiment 1
1) at ambient temperature 2.2 graphite are equipped with in the beaker of 105mL concentrated sulphuric acid, then after being slowly added to 16g potassium permanganate under condition of ice bath, reactant liquor is transferred to the stirred in water bath reaction 23min of 29 DEG C, reaction adds after the frozen water of 430mL is diluted after terminating, dropping mass fraction is 14%H2O2Solution is until bubble-free produces. Carrying out sucking filtration and rinsed with a large amount of clear water by the golden yellow filter cake obtained, the powder obtained is dried overnight in the vacuum drying oven of 32 DEG C;
2) graphite oxide powder step 1 prepared is put in vial, is placed in microwave oven, 1000W microwave 30s, obtains MRGO;
3) take 16mgMRGO and 33mg ferrocene and jointly put into grinding 15min in agate mortar, after mix homogeneously, the black powder of mix homogeneously is transferred in vial, 1000W microwave 44s, obtain the uniform Gr/CNTs composite of black pattern.
Embodiment 2
1) at ambient temperature 3.6g graphite is equipped with in the beaker of 112mL concentrated sulphuric acid, then after being slowly added to 18g potassium permanganate under condition of ice bath, reactant liquor is transferred to the stirred in water bath reaction 44min of 30 DEG C, reaction adds after the frozen water of 390mL is diluted after terminating, dropping mass fraction is 16%H2O2Solution is until bubble-free produces. Carrying out sucking filtration and rinsed with a large amount of clear water by the golden yellow filter cake obtained, the powder obtained is dried overnight in the vacuum drying oven of 42 DEG C;
2) graphite oxide powder step 1 prepared is put in vial, is placed in microwave oven, 1000W microwave 35s, obtains MRGO;
3) take 16mgMRGO and 25mg ferrocene and jointly put into grinding 15min in agate mortar, after mix homogeneously, the black powder of mix homogeneously is transferred in vial, 1000W microwave 29s, the uniform Gr/CNTs composite of pattern can be obtained.
Embodiment 3
1) at ambient temperature 3.2g graphite is equipped with in the beaker of 114mL concentrated sulphuric acid, then after being slowly added to 16g potassium permanganate under condition of ice bath, reactant liquor is transferred to the stirred in water bath reaction 42min of 31 DEG C, reaction adds after the frozen water of 340mL is diluted after terminating, dropping mass fraction is 17.3%H2O2Solution is until bubble-free produces.Carrying out sucking filtration and rinsed with a large amount of clear water by the golden yellow filter cake obtained, the powder obtained is dried overnight in the vacuum drying oven of 42 DEG C;
2) graphite oxide powder step 1 prepared is put in vial, is placed in microwave oven, 1000W microwave 38s, obtains MRGO;
3) take 15mgMRGO and 26mg ferrocene and jointly put into grinding 15min in agate mortar, after mix homogeneously, the black powder of mix homogeneously is transferred in vial, 1000W microwave 39s, the uniform Gr/CNTs composite of pattern can be obtained.
Embodiment 4
1) at ambient temperature 2g graphite is equipped with in the beaker of 100mL concentrated sulphuric acid, then after being slowly added to 15g potassium permanganate under condition of ice bath, reactant liquor is transferred to the stirred in water bath reaction 50min of 33 DEG C, reaction adds after the frozen water of 300mL is diluted after terminating, dropping mass fraction is 13%H2O2Solution is until bubble-free produces. Carrying out sucking filtration and rinsed with a large amount of clear water by the golden yellow filter cake obtained, the powder obtained is dried overnight in the vacuum drying oven of 45 DEG C;
2) graphite oxide powder step 1 prepared is put in vial, is placed in microwave oven, 1000W microwave 50s, obtains MRGO;
3) take 13mgMRGO and 20mg ferrocene and jointly put into grinding 15min in agate mortar, after mix homogeneously, the black powder of mix homogeneously is transferred in vial, 1000W microwave 20s, the uniform Gr/CNTs composite of pattern can be obtained.
Embodiment 5
1) at ambient temperature 4g graphite is equipped with in the beaker of 120mL concentrated sulphuric acid, then after being slowly added to 20g potassium permanganate under condition of ice bath, reactant liquor is transferred to the stirred in water bath reaction 20min of 28 DEG C, reaction adds after the frozen water of 450mL is diluted after terminating, dropping mass fraction is 18%H2O2Solution is until bubble-free produces. Carrying out sucking filtration and rinsed with a large amount of clear water by the golden yellow filter cake obtained, the powder obtained is dried overnight in the vacuum drying oven of 30 DEG C;
2) graphite oxide powder step 1 prepared is put in vial, is placed in microwave oven, 1000W microwave 20s, obtains MRGO;
3) take 18mgMRGO and 35mg ferrocene and jointly put into grinding 15min in agate mortar, after mix homogeneously, the black powder of mix homogeneously is transferred in vial, 1000W microwave 50s, the uniform Gr/CNTs composite of pattern can be obtained.
Claims (3)
1. the method that potent microwave method prepares graphene carbon nanometer tube composite materials, it is characterised in that comprise the steps:
1) at ambient temperature 2��4g graphite is equipped with in the beaker of 100��120mL concentrated sulphuric acid, then after being slowly added to 15��20g potassium permanganate under condition of ice bath, reactant liquor is transferred to the stirred in water bath reaction 20��50min of 28��33 DEG C, reaction adds the frozen water of 300��450mL and is diluted after terminating, drip H2O2Solution, until bubble-free produces, carries out sucking filtration and is rinsed with a large amount of clear water by the golden yellow filter cake obtained, and the powder obtained is dried overnight in vacuum drying oven;
2) graphite oxide powder step 1 prepared is put in vial, is placed in microwave oven, 1000W microwave 20��50s, obtains MRGO;
3) take 13��18mgMRGO and 20��35mg ferrocene and jointly put into grinding 15min in agate mortar, after mix homogeneously, the black powder of mix homogeneously is transferred in vial, 1000W microwave 20��50s, the uniform Gr/CNTs composite of pattern can be obtained.
2. the method that potent microwave method according to claim 1 prepares graphene carbon nanometer tube composite materials, it is characterised in that described step 1) the middle H dripped2O2The mass fraction of solution is 13��18%.
3. the method that potent microwave method according to claim 1 prepares graphene carbon nanometer tube composite materials, it is characterised in that described step 1) in utilize vacuum drying oven that graphite oxide powder is dried temperature to be set as 30��45 DEG C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106882798A (en) * | 2017-02-09 | 2017-06-23 | 广东派勒智能纳米科技股份有限公司 | The preparation technology of Graphene, carbon nano tube compound material |
| CN107895653A (en) * | 2017-10-27 | 2018-04-10 | 西安理工大学 | Method that microwave prepares cigarette filter/graphene composite material and application thereof |
| CN108039499A (en) * | 2017-10-23 | 2018-05-15 | 广东工业大学 | A kind of N doping peels off the preparation method of carbon nanotube loaded cobaltosic oxide material |
| CN108511760A (en) * | 2018-06-13 | 2018-09-07 | 天合光能股份有限公司 | Conductive agent for lithium battery and preparation method thereof |
| CN108726515A (en) * | 2018-05-31 | 2018-11-02 | 西北师范大学 | Preparation method with three-dimensional structure redox graphene-ferrocene composite material |
| CN109231190A (en) * | 2018-11-02 | 2019-01-18 | 重庆大学 | Prepare redox graphene method and its redox graphene obtained |
| CN111302328A (en) * | 2020-02-24 | 2020-06-19 | 西北工业大学 | Carbon nanotube/graphene hybrid material and preparation method and application thereof |
| CN116535124A (en) * | 2023-05-09 | 2023-08-04 | 青岛理工大学 | CNTs@microbead core-shell filler, cement-based composite material, preparation method and application |
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| CN103384007A (en) * | 2013-07-23 | 2013-11-06 | 深圳清华大学研究院 | Carbon nano tube/graphene composite negative pole material, preparation method thereof and lithium battery |
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| CN103832996A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/carbon nano-tube composite material, preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106882798A (en) * | 2017-02-09 | 2017-06-23 | 广东派勒智能纳米科技股份有限公司 | The preparation technology of Graphene, carbon nano tube compound material |
| CN108039499A (en) * | 2017-10-23 | 2018-05-15 | 广东工业大学 | A kind of N doping peels off the preparation method of carbon nanotube loaded cobaltosic oxide material |
| CN108039499B (en) * | 2017-10-23 | 2023-10-03 | 广东工业大学 | Preparation method of nitrogen-doped exfoliated carbon nanotube loaded cobaltosic oxide material |
| CN107895653A (en) * | 2017-10-27 | 2018-04-10 | 西安理工大学 | Method that microwave prepares cigarette filter/graphene composite material and application thereof |
| CN108726515A (en) * | 2018-05-31 | 2018-11-02 | 西北师范大学 | Preparation method with three-dimensional structure redox graphene-ferrocene composite material |
| CN108511760A (en) * | 2018-06-13 | 2018-09-07 | 天合光能股份有限公司 | Conductive agent for lithium battery and preparation method thereof |
| CN109231190A (en) * | 2018-11-02 | 2019-01-18 | 重庆大学 | Prepare redox graphene method and its redox graphene obtained |
| CN111302328A (en) * | 2020-02-24 | 2020-06-19 | 西北工业大学 | Carbon nanotube/graphene hybrid material and preparation method and application thereof |
| CN116535124A (en) * | 2023-05-09 | 2023-08-04 | 青岛理工大学 | CNTs@microbead core-shell filler, cement-based composite material, preparation method and application |
| CN116535124B (en) * | 2023-05-09 | 2024-04-12 | 青岛理工大学 | CNTs@microbead core-shell filler, cement-based composite material, preparation method and application |
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Effective date of registration: 20210106 Address after: 276624 Room 608, 6th floor, Zhongxing business enterprise development center, Pingshang Town, Lingang Economic Development Zone, Linyi City, Shandong Province Patentee after: Linyi Xinghuo Intellectual Property Service Co.,Ltd. Address before: A506, comprehensive building, University Science Park, 750 Shunhua Road, high tech Zone, Jinan City, Shandong Province Patentee before: SHANDONG LIANXING ENERGY GROUP Co.,Ltd. |