CN104591118B - A kind of preparation method of three-dimensional shape graphene/carbon nano-tube compounded microbeads - Google Patents
A kind of preparation method of three-dimensional shape graphene/carbon nano-tube compounded microbeads Download PDFInfo
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- CN104591118B CN104591118B CN201510001489.9A CN201510001489A CN104591118B CN 104591118 B CN104591118 B CN 104591118B CN 201510001489 A CN201510001489 A CN 201510001489A CN 104591118 B CN104591118 B CN 104591118B
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Abstract
The preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads, it relates to the preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads.The present invention is to solve that prior art is preparing the problem that during three-dimensional grapheme/carbon nano tube compound material occurs, operation is complicated, post processing is difficult, Particle dispersity is bigger.Method: graphene oxide water solution mixed with the CNT after acid treatment, sonicated is configured to dispersion phase solution.With dimethicone as flowing phase, obtain monodispersed drop by syringe pump, and be collected in the container of polypropylene material.60 DEG C of drying baker are put in Muffle furnace after solidification and calcines, thus obtain three-dimensional shape graphene/carbon nano-tube compounded microbeads.The present invention is used for preparing three-dimensional shape graphene/carbon nano-tube compounded microbeads.
Description
Technical field
The present invention relates to the preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads.
Background technology
Graphene, has the two-dimensional structure of monoatomic layer thickness, has big theoretical specific surface area, high electronic conductivity, good
Good chemical stability and relatively low production cost.It is by mechanically pulling off since preparing first by Geim from it, owing to it is only
Special characteristic, has been extensively studied at aspects such as catalysis, energy conversion, storage and sensors and has applied.CNT is then
It is a kind of One-dimensional Quantum material with special construction, the cylinder that flake graphite alkene is rolled into can be regarded in theory as, have solely
Special hollow-core construction, nano-scale, the highest abnormal aspect ratio and bigger specific surface area, have single wall and many walls point.From
It is since 1991 are found by Iijima, due to its outstanding physical and chemical performance, mechanical property and heat stability so that
It is at numerous areas such as electronic equipment, solaode, and catalysis, environmental area and biotechnology industry etc. have various
Application.Graphene/carbon nanotube composite material combines the advantage of the two, by the cooperative effect between them so that it is performance
Go out the performance more excellent than any one homogenous material, such as isotropism thermal conductance, electrochemical capacitance etc..Based on this, graphite
Alkene/carbon nano tube compound material has broad application prospects at aspects such as ultracapacitor, display, biological detection.
Three-dimensional Graphene/carbon nanotube composite material, as a kind of novel aggregated structure, has caused the extensive of scientific circles
Pay close attention to.By in-situ chemical vapour phase reduction sedimentation, Chen etc. prepares the graphene/carbon nano-tube of tridimensional network and is combined
Material；By gentle phase-change method, Xiaowei Ma etc. prepares flower shape β-Ni (OH) of three-dimensional2/ GO/CNTs is combined
Material；The method reduced by in-situ chemical, Yang etc. selects ethylene glycol to make reducing agent, reduction difference under the conditions of ice-water bath
The graphene/carbon nano-tube compound aqueous solution of ratio, the graphene/carbon nano-tube obtaining having hierarchy after filtering drying is multiple
Condensation material.Laifa Shen etc. use liquid phase method to synthesize the TiO of three-dimensional2-GNS-CNT nano composite material, makes ultra-fine
TiO2Nanocrystal growth is in two-dimentional Graphene and one-dimensional carbon nano tube surface, and this material can be used for the preparation of lithium battery；
Du etc. are by inserting the CNT of growth of vertical arrangement, preparation in the pyrolysis phthalocyanine dyestuffs orderly pyrolytic graphite of thermotropism expansion height
Go out adjustable three-dimensional column Graphene/carbon nanotube structure；Seok-Hu Bae etc. are 3D stone by microblogging self assembly
Ink alkene-CNT-nickel nanostructured, can be used as high-capacity cathode material in lithium ion battery；Alfred T.Chidembo
Deng having obtained the isotropic graphene-carbon nano tube-nickel oxide ternary structural of self assembly with spray heating decomposition, wherein comprise
Part spherical structure.In the prior art, the preparation of three dimensional structure graphene/carbon nano-tube mostly exist preparation process complicated,
The problems such as post processing difficulty are especially in terms of preparation graphene/carbon nano-tube complex microsphere, simple and effectively the most prominent
Method.
Summary of the invention
The present invention is to solve prior art prepare operation during three-dimensional grapheme/carbon nano tube compound material occurs complicated,
Post processing difficulty, the problem that Particle dispersity is bigger, and the preparation of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads is provided
Method.
The preparation method of the present invention a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads is to sequentially include the following steps:
One, being placed in nitration mixture by CNT, back flow reaction 2h～3h under the conditions of temperature is 80 DEG C～85 DEG C, after centrifuge washing
Carry out dialysis, then be placed in the baking oven that temperature is 60 DEG C～70 DEG C and be dried, the carbon nanotube powder after being processed；
The quality of described CNT and the volume ratio of nitration mixture are 1:(90～100)；Described nitration mixture is concentrated nitric acid with concentrated sulphuric acid by body
Long-pending than being 1:(2～4) mixture that mixes, wherein the mass fraction of concentrated sulphuric acid is 98%, and the mass fraction of concentrated nitric acid is 65%；
Two, the carbon nanotube powder after process step one obtained mixes with graphene oxide water solution, and low whipping speed is
300r/min～400r/min and supersonic frequency are process 5h～10h under conditions of 40KHz～50KHz, obtain dispersion phase solution；
The solid content of described graphene oxide water solution is 1%～1.5%；
Carbon nanotube powder after the process that described step one obtains is 1 with the mass ratio of graphene oxide water solution:
(0.01～0.5)；
Three, dispersion phase solution step 2 obtained is poured in No. 1 syringe, is poured into by dimethicone in No. 2 syringes,
Use syringe pump that the dimethicone in the dispersion phase solution in No. 1 syringe and No. 2 syringes is advanced to PP material to receive
In device, obtain graphene/carbon nano-tube compounded microbeads to be oxidized；
Described No. 1 syringe and No. 2 syringes are injected delivery side of pump and are connected to one end of same PTFE tube；Described PTFE
The other end of pipe is connected with PP material receptor；
The volume ratio of the dispersion phase solution in described No. 1 syringe and the dimethicone in No. 2 syringes is 1:(5～20)；
The propelling speed of described No. 1 syringe is 0.5:(110～130 with the ratio of the propelling speed of No. 2 syringes)；
Four, it is 60 DEG C～the drying baker of 70 DEG C that the graphene/carbon nano-tube compounded microbeads to be oxidized step 3 obtained is placed in temperature
Middle solidification 12h～24h, then with normal hexane wash 4～6 times, then be placed in baking oven employing substep intensification heating dry
Pre-oxidation, graphene/carbon nano-tube compounded microbeads after being pre-oxidized；
Described employing substep intensification heating carries out drying preoxidation process: dry under conditions of temperature is 140 DEG C～160 DEG C
Intervene oxidation 6h～9h, under conditions of temperature is 270 DEG C～290 DEG C, then dries pre-oxidation 1.5h～2h；
Five, under nitrogen atmosphere, after the pre-oxidation obtaining step 4, graphene/carbon nano-tube compounded microbeads carries out carbonization treatment,
Obtain three-dimensional shape graphene/carbon nano-tube compounded microbeads；
Described carbonization treatment process is: be 700 DEG C with the heating rate of 4 DEG C/min～6 DEG C/min by room temperature to temperature
～800 DEG C, and at temperature is 700 DEG C～800 DEG C, it is incubated 1.5h～2.5h.
Beneficial effects of the present invention:
Acid-treated CNT is mixed sonicated obtaining and has certain viscosity by the present invention with graphene oxide water solution
Dispersion phase solution, by micro fluidic device, using dimethicone as flowing phase, mixed solution is prepared as dispersion phase
Graphene/carbon nano-tube compounded microbeads, then carry out solidifying and pre-oxidizing by microballon, after calcination processing, finally give three-dimensional shape
Graphene/carbon nano-tube compounded microbeads.The method novelty is unique, simple to operate, and post processing is easy, and process safety is reliably to ring
Border is friendly, and the bead size obtained is controlled, uniform particle diameter, pattern are peculiar.It is that material with carbon element skilled person prepares three-dimensional stone
Ink alkene/CNT compounded microbeads one compares method easily.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the carbon nanotube powder after the process that step one obtains；
Fig. 2 is the SEM figure of graphene oxide water solution described in step 2；
Fig. 3 is 100 times of SEM figures of three-dimensional shape graphene/carbon nano-tube compounded microbeads；
Fig. 4 is 40000 times of SEM figures of three-dimensional shape graphene/carbon nano-tube compounded microbeads；
Fig. 5 is 40000 times of SEM figures within three-dimensional shape graphene/carbon nano-tube compounded microbeads.
Detailed description of the invention
Detailed description of the invention one: the preparation method of present embodiment a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads be by with
Lower step is carried out:
One, being placed in nitration mixture by CNT, back flow reaction 2h～3h under the conditions of temperature is 80 DEG C～85 DEG C, after centrifuge washing
Carry out dialysis, then be placed in the baking oven that temperature is 60 DEG C～70 DEG C and be dried, the carbon nanotube powder after being processed；
The quality of described CNT and the volume ratio of nitration mixture are 1:(90～100)；Described nitration mixture is concentrated nitric acid with concentrated sulphuric acid by body
Long-pending than being 1:(2～4) mixture that mixes, wherein the mass fraction of concentrated sulphuric acid is 98%, and the mass fraction of concentrated nitric acid is 65%；
Two, the carbon nanotube powder after process step one obtained mixes with graphene oxide water solution, and low whipping speed is
300r/min～400r/min and supersonic frequency are process 5h～10h under conditions of 40KHz～50KHz, obtain dispersion phase solution；
The solid content of described graphene oxide water solution is 1%～1.5%；
Carbon nanotube powder after the process that described step one obtains is 1 with the mass ratio of graphene oxide water solution:
(0.01～0.5)；
Three, dispersion phase solution step 2 obtained is poured in No. 1 syringe, is poured into by dimethicone in No. 2 syringes,
Use syringe pump that the dimethicone in the dispersion phase solution in No. 1 syringe and No. 2 syringes is advanced to PP material to receive
In device, obtain graphene/carbon nano-tube compounded microbeads to be oxidized；
Described No. 1 syringe and No. 2 syringes are injected delivery side of pump and are connected to one end of same PTFE tube；Described PTFE
The other end of pipe is connected with PP material receptor；
The volume ratio of the dispersion phase solution in described No. 1 syringe and the dimethicone in No. 2 syringes is 1:(5～20)；
The propelling speed of described No. 1 syringe is 0.5:(110～130 with the ratio of the propelling speed of No. 2 syringes)；
Four, it is 60 DEG C～the drying baker of 70 DEG C that the graphene/carbon nano-tube compounded microbeads to be oxidized step 3 obtained is placed in temperature
Middle solidification 12h～24h, then with normal hexane wash 4～6 times, then be placed in baking oven employing substep intensification heating dry
Pre-oxidation, graphene/carbon nano-tube compounded microbeads after being pre-oxidized；
Described employing substep intensification heating carries out drying preoxidation process: dry under conditions of temperature is 140 DEG C～160 DEG C
Intervene oxidation 6h～9h, under conditions of temperature is 270 DEG C～290 DEG C, then dries pre-oxidation 1.5h～2h；
Five, under nitrogen atmosphere, after the pre-oxidation obtaining step 4, graphene/carbon nano-tube compounded microbeads carries out carbonization treatment,
Obtain three-dimensional shape graphene/carbon nano-tube compounded microbeads；
Described carbonization treatment process is: be 700 DEG C with the heating rate of 4 DEG C/min～6 DEG C/min by room temperature to temperature
～800 DEG C, and at temperature is 700 DEG C～800 DEG C, it is incubated 1.5h～2.5h.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: nitration mixture described in step one is dense nitre
The mixture that acid mixes for 1:3 by volume with concentrated sulphuric acid.Other are identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is unlike detailed description of the invention one or two: step one described in step 2
Carbon nanotube powder after the process obtained is 1:0.1 with the mass ratio of graphene oxide water solution.Other and detailed description of the invention
One or two is identical.
Detailed description of the invention four: present embodiment is unlike one of detailed description of the invention one to three: described in step 31
The volume ratio of the dispersion phase solution in number syringe and the dimethicone in No. 2 syringes is 1:10.Other be embodied as
One of mode one to three is identical.
Detailed description of the invention five: present embodiment is unlike one of detailed description of the invention one to four: described in step 31
Number propelling speed of syringe is 0.5:120 with the ratio of the propelling speed of No. 2 syringes.Other are with detailed description of the invention one to four
One of identical.
Detailed description of the invention six: present embodiment is unlike one of detailed description of the invention one to five: dry described in step 4
Dry case is air dry oven or vacuum drying oven.Other are identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: present embodiment is unlike one of detailed description of the invention one to six: adopt described in step 4
Carry out drying preoxidation process by substep intensification heating and be: under conditions of temperature is 150 DEG C, dry pre-oxidation 9h, then
Pre-oxidation 2h is dried under conditions of temperature is 280 DEG C.Other are identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: present embodiment is unlike one of detailed description of the invention one to seven: described in step 5
Carbonization treatment process is: be 750 DEG C with the heating rate of 5 DEG C/min by room temperature to temperature, and at temperature is 750 DEG C
Insulation 2h.Other are identical with one of detailed description of the invention one to seven.
Effect by following example checking present invention:
Embodiment one: the preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads is to sequentially include the following steps:
One, CNT is placed in nitration mixture, back flow reaction 3h under the conditions of temperature is 80 DEG C, after centrifuge washing, carries out dialysis,
It is placed in again in the baking oven that temperature is 70 DEG C and is dried, the carbon nanotube powder after being processed；
Described nitration mixture is that the mass fraction of the mixture wherein concentrated sulphuric acid that concentrated nitric acid mixes for 1:3 by volume with concentrated sulphuric acid is
98%, the mass fraction of concentrated nitric acid is 65%；
Two, the carbon nanotube powder after process 0.1g step one obtained mixes with 0.05g graphene oxide water solution,
Mixing speed is 300r/min～400r/min and supersonic frequency is process 5h～10h under conditions of 40KHz～50KHz, is divided
Dephasing solution；The solid content of described graphene oxide water solution is 1%；
Three, the dispersion phase solution that 10mL step 2 obtains is poured in No. 1 syringe, pour 50mL dimethicone into 2
In number syringe, syringe pump is used to be advanced by the dimethicone in the dispersion phase solution in No. 1 syringe and No. 2 syringes
In PP material receptor, obtain graphene/carbon nano-tube compounded microbeads to be oxidized；
Described No. 1 syringe and No. 2 syringes are injected delivery side of pump and are connected to one end of same PTFE tube；Described PTFE
The other end of pipe is connected with PP material receptor；
The propelling speed of described No. 1 syringe is 0.5:120 with the ratio of the propelling speed of No. 2 syringes；
Four, the graphene/carbon nano-tube compounded microbeads to be oxidized step 3 obtained is placed in the drying baker that temperature is 60 DEG C solidification
24h, then with normal hexane wash 6 times, then be placed in baking oven employing substep intensification heating carry out dry pre-oxidation, obtain pre-
Graphene/carbon nano-tube compounded microbeads after oxidation；
Described employing substep intensification heating is dried preoxidation process and is: dry pre-oxidation 9h under conditions of temperature is 150 DEG C,
Then under conditions of temperature is 280 DEG C, dry pre-oxidation 2h；
Five, under nitrogen atmosphere, after the pre-oxidation obtaining step 4, graphene/carbon nano-tube compounded microbeads carries out carbonization treatment,
Obtain three-dimensional shape graphene/carbon nano-tube compounded microbeads；
Described carbonization treatment process is: be 750 DEG C with the heating rate of 5 DEG C/min by room temperature to temperature, and in temperature
It is insulation 2h at 750 DEG C.
Fig. 1 is the SEM figure of the carbon nanotube powder after the process that step one obtains；The pipe of CNT as we can see from the figure
Shape structure and a large amount of CNT are mutually wound around；
Fig. 2 is the SEM figure of graphene oxide water solution described in step 2；As can be seen from the figure thin specific to Graphene
Thin lamella fold pattern；
Fig. 3 is 100 times of SEM figures of three-dimensional shape graphene/carbon nano-tube compounded microbeads；As can be seen from the figure complex microsphere
The peculiar pattern of three-dimensional, there is rough, wrinkled surface, the most also existence of tubular structure, particle diameter is relatively uniform,
At about 150nm.
Fig. 4 is 40000 times of SEM figures of three-dimensional shape graphene/carbon nano-tube compounded microbeads；Figure demonstrates graphene sheet layer
Fold pattern and the tubular structure of CNT, in a large amount of fold lamellas, be interspersed with CNT.
Fig. 5 is 40000 times of SEM figures within three-dimensional shape graphene/carbon nano-tube compounded microbeads；SEM within compounded microbeads
Figure demonstrates that a large amount of CNT being mutually wound around is present in graphene film interlayer, shows that the graphene sheet layer of two dimension is with one-dimensional
CNT is combined the Graphene/carbon nanotube composite material having obtained three dimensional structure.
Claims (8)
1. the preparation method of a three-dimensional shape graphene/carbon nano-tube compounded microbeads, it is characterised in that three-dimensional shape graphene/carbon is received
The preparation method of mitron compounded microbeads is to sequentially include the following steps:
One, being placed in nitration mixture by CNT, back flow reaction 2h～3h under the conditions of temperature is 80 DEG C～85 DEG C, after centrifuge washing
Carry out dialysis, then be placed in the baking oven that temperature is 60 DEG C～70 DEG C and be dried, the carbon nanotube powder after being processed；
The quality of described CNT and the volume ratio of nitration mixture are 1:(90～100)；Described nitration mixture is concentrated nitric acid with concentrated sulphuric acid by body
Long-pending than being 1:(2～4) mixture that mixes, wherein the mass fraction of concentrated sulphuric acid is 98%, and the mass fraction of concentrated nitric acid is 65%；
Two, the carbon nanotube powder after process step one obtained mixes with graphene oxide water solution, and low whipping speed is
300r/min～400r/min and supersonic frequency are process 5h～10h under conditions of 40KHz～50KHz, obtain dispersion phase solution；
The solid content of described graphene oxide water solution is 1%～1.5%；
Carbon nanotube powder after the process that described step one obtains is 1 with the mass ratio of graphene oxide water solution:
(0.01～0.5)；
Three, dispersion phase solution step 2 obtained is poured in No. 1 syringe, is poured into by dimethicone in No. 2 syringes,
Use syringe pump that the dimethicone in the dispersion phase solution in No. 1 syringe and No. 2 syringes is advanced to PP material to receive
In device, obtain graphene/carbon nano-tube compounded microbeads to be oxidized；
The outlet of described No. 1 syringe and No. 2 syringes is connected to one end of same PTFE tube；Described PTFE tube another
One end is connected with PP material receptor；
The volume ratio of the dispersion phase solution in described No. 1 syringe and the dimethicone in No. 2 syringes is 1:(5～20)；
The propelling speed of described No. 1 syringe is 0.5:(110～130 with the ratio of the propelling speed of No. 2 syringes)；
Four, it is 60 DEG C～the drying baker of 70 DEG C that the graphene/carbon nano-tube compounded microbeads to be oxidized step 3 obtained is placed in temperature
Middle solidification 12h～24h, then with normal hexane wash 4～6 times, then be placed in baking oven employing substep intensification heating dry
Pre-oxidation, graphene/carbon nano-tube compounded microbeads after being pre-oxidized；
Described employing substep intensification heating carries out drying preoxidation process: dry under conditions of temperature is 140 DEG C～160 DEG C
Intervene oxidation 6h～9h, under conditions of temperature is 270 DEG C～290 DEG C, then dries pre-oxidation 1.5h～2h；
Five, under nitrogen atmosphere, after the pre-oxidation obtaining step 4, graphene/carbon nano-tube compounded microbeads carries out carbonization treatment,
Obtain three-dimensional shape graphene/carbon nano-tube compounded microbeads；
Described carbonization treatment process is: be 700 DEG C with the heating rate of 4 DEG C/min～6 DEG C/min by room temperature to temperature
～800 DEG C, and at temperature is 700 DEG C～800 DEG C, it is incubated 1.5h～2.5h.
The preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads the most according to claim 1, its feature
It is that nitration mixture described in step one is the mixture that concentrated nitric acid mixes for 1:3 by volume with concentrated sulphuric acid.
The preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads the most according to claim 1, its feature
It is that the carbon nanotube powder after the process that step one described in step 2 obtains with the mass ratio of graphene oxide water solution is
1:0.1。
The preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads the most according to claim 1, its feature
The volume ratio of the dimethicone in the dispersion phase solution being described in step 3 in No. 1 syringe and No. 2 syringes is
1:10。
The preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads the most according to claim 1, its feature
It is that the propelling speed of No. 1 syringe described in step 3 is 0.5:120 with the ratio of the propelling speed of No. 2 syringes.
The preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads the most according to claim 1, its feature
It is that drying baker described in step 4 is air dry oven or vacuum drying oven.
The preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads the most according to claim 1, its feature
It is described in step 4 that using substep intensification heating to carry out drying preoxidation process is: under conditions of temperature is 150 DEG C
Dry pre-oxidation 9h, under conditions of temperature is 280 DEG C, then dries pre-oxidation 2h.
The preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads the most according to claim 1, its feature
The carbonization treatment process described in step 5 that is is: be 750 DEG C with the heating rate of 5 DEG C/min by room temperature to temperature,
And at temperature is 750 DEG C, it is incubated 2h.
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| CN108091878B (en) * | 2017-12-05 | 2020-06-09 | 四川华昆能源有限责任公司 | Preparation method of graphene carbon nanotube composite conductive framework for lithium-sulfur battery |
| CN110465317A (en) * | 2018-10-18 | 2019-11-19 | 黑龙江大学 | A kind of photochemical catalyst g-C3N4/ GO/ magnetic particle and preparation method thereof |
| CN109830382A (en) * | 2019-04-01 | 2019-05-31 | 黑龙江东方学院 | A kind of preparation method and application of the graphene/carbon nano-tube compounded microbeads with core-shell structure |
| CN111204741B (en) * | 2020-01-15 | 2021-12-03 | 北京科技大学 | Preparation method of three-dimensional graphene/carbon nanotube cross-linked composite material |
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| CN102915854A (en) * | 2012-11-20 | 2013-02-06 | 黑龙江大学 | Preparation method of electrode material for super-capacitor |
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