CN109721048A - A kind of preparation method of three-dimensional globular conductive graphene/carbon nano tube compound material - Google Patents
A kind of preparation method of three-dimensional globular conductive graphene/carbon nano tube compound material Download PDFInfo
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- CN109721048A CN109721048A CN201910058171.2A CN201910058171A CN109721048A CN 109721048 A CN109721048 A CN 109721048A CN 201910058171 A CN201910058171 A CN 201910058171A CN 109721048 A CN109721048 A CN 109721048A
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Abstract
The present invention relates to a kind of preparation methods of three-dimensional globular conductive graphene/carbon nano tube compound material, comprising the following steps: first prepares graphene oxide dispersion I with graphite flake；Then by ZrO2Abrading-ball, graphene oxide dispersion I and the carbon nanotube ball milling together in hydrazine hydrate solution, obtain graphene oxide/carbon nano tube dispersion liquid II；Then it adjusts pH value and obtains mixed dispersion liquid III；Hydro-thermal reaction is carried out later, obtains three-dimensional globular conductive graphene/carbon nano tube compound material.The composite material can be applied in hydrogen storage battery, and maximum hydrogen storage capability is up to 1.68wt%, and after circulation 50 times, hydrogen storage ability remains at 80% or more.Simultaneously under the conditions of the discharge current density of 1000mA/g, discharge capability remains at 65% or more.It can be used for nickel-metal hydride battery hydrogen storage field.The present invention solves the preparation method complexity of existing three-dimensional globular conductive graphene/carbon nanotube, technical problem at high cost.
Description
Technical field
The present invention relates to the preparation methods of graphene composite material, belong to electrochemical hydrogen bearing material field.
Background technique
The reserves of hydrogen in nature are extremely abundant, have highest energy matter ratio, cleanliness without any pollution, therefore, Hydrogen Energy are developed
Various countries' reply energy crisis is had become with storage, solves the important content of environmental problem.
Three-dimensional grapheme and carbon nano-tube material are a kind of important structure and function material, the three-dimensional graphite of different-shape
Alkene, carbon nanotube and its composite material have potential application value in terms of hydrogen storage, have caused extensive concern.It is theoretical
On, two-dimensional graphene/carbon nano tube compound material has specific surface area, the biggish electric charge transfer rate, excellent machine of superelevation
The advantages that tool intensity, but caused between lamella due to the π-π interaction between two-dimensional graphene lamella in practical applications
It is easy to happen reunion and stacking, so that hydrogen storage property is had a greatly reduced quality.In order to overcome this disadvantage, need to design three-dimensional composite material
Pattern and structure.It is well known that three-dimensional globular composite material has chondritic, graphene film interlayer is not image-stone ink knot
It is closely arranged together between structure is every layer such by Van der Waals force, but the distance between each graphene sheet layer is above
The sphere of action of Van der Waals force, arrangement relative loose between layers, and have the support of carbon nanotube, can effectively it overcome
Graphene stacks and agglomeration traits.Therefore, Graphene/carbon nanotube composite material three-dimensional globular structure is made into have become
Improve one of the optimal path of hydrogen storage property.
Currently, the method that can prepare three-dimensional globular graphene mainly has template auxiliary law, airsetting matrix self-assembly method, You Bao
Aqueous emulsion method.But there is the disadvantages of the device is complicated, and technique is cumbersome, at high cost in existing method, therefore, developing low-cost, technique
The preparation method of simple three-dimensional globular conductive graphene/carbon nanotube becomes urgent problem to be solved.
Summary of the invention
The present invention is the preparation method complexity in order to solve above-mentioned existing three-dimensional globular conductive graphene/carbon nanotube,
Technical problem at high cost, and a kind of preparation method of three-dimensional globular conductive graphene/carbon nano tube compound material is provided.
Three-dimensional globular conductive graphene/carbon nano tube compound material preparation method of the invention, comprising the following steps:
One, using graphite flake as raw material, use Hummer method preparation concentration for 1.25~1.75mg ml-1Graphite oxide
Alkene dispersion liquid I；
Two, ZrO is pressed2The mass ratio of abrading-ball, carbon nanotube and graphene oxide is (5~8): the ratio of 1:1, by ZrO2Mill
Ball, carbon nanotube and graphene oxide dispersion I, which are packed into, has ZrO2In the ball grinder of liner, hydrazine hydrate solution is added, is filled
Enter high-purity argon gas, 48~60h of ball milling under conditions of drum's speed of rotation is 1050~1100rpm obtains graphene oxide/carbon and receives
Mitron dispersion liquid II；
Three, with 10mol L-1NaOH solution the pH value of graphene oxide dispersion II is adjusted to 13.55~13.85,
Obtain mixed dispersion liquid III；
Four, mixed dispersion liquid III is kept the temperature at 160~180 DEG C to 12~13h in water heating kettle, obtains three-dimensional globular conduction
Graphene/carbon nanotube composite material.
Particularly, the concentration of the graphene oxide dispersion I can be 1.45~1.55mg in the above step 1
ml-1。
Particularly, the mass percentage concentration of hydrazine hydrate solution can be 2%~4% in above-mentioned steps two；And/or hydration
The volume ratio of hydrazine solution and graphene oxide dispersion I is 1:(30~50).
Particularly, mass percentage concentration >=99.999% of the high-purity argon gas described in above-mentioned steps two.
On the other hand, the invention further relates to the three-dimensional globular prepared by the above method conductive graphene/carbon nanotube is compound
Material.
On the other hand, the invention further relates to use three-dimensional globular conductive graphene/carbon nano tube compound material preparation storage
Hydrogen electrode.
On the other hand, the invention further relates to a kind of battery, which includes the hydrogen-storage electrode.
The present invention uses high-energy ball milling assisting alcohol-hydrothermal method, and higher revolving speed enables graphene oxide to be fully stripped into
Few layer graphene oxide, under high speed conditions, the abrading-ball of high speed increases internal energy sharply, and graphene oxide occurs also
Original, but due to the input of high-energy, and remain few layer of structure, after ball milling few layer graphene/carbon nano-tube system have compared with
Big surface energy, provides the foundation for the reunion balling-up of later period composite material.The strong alkaline condition of water-heat process, improves solution
Surface tension, is conducive to the formation of spherical three-dimensional product in the case where the present invention limits debita spissitudo, which is spherical hydrogel.It should
Gained three-dimensional globular conductive graphene/carbon nano tube compound material after the freeze-drying of three-dimensional globular conductive graphene hydrogel material
Hydrogen storage property greatly improve.The composite material can prepare hydrogen-storage electrode, be applied in the energy resource systems such as nickel-metal hydride battery, maximum
Hydrogen storage capability is had excellent performance up to 1.68wt%, electrochemical hydrogen storage.Circulation 50 times after, hydrogen storage ability remain at 80% with
On.Simultaneously under the conditions of the discharge current density of 1000mA/g, discharge capability remains at 65% or more.It can be used for hydrogen storage neck
Domain.Preparation process of the invention is simple, highly-safe, and equipment investment is small, further decreases the cost of product.The material is available
In field of batteries.
Detailed description of the invention
Fig. 1 is three-dimensional globular conductive graphene/carbon nano tube compound material photo prepared by embodiment 1；
Fig. 2 is that three-dimensional globular conductive graphene/carbon nano tube compound material high power scanning electron microscope prepared by embodiment 1 is shone
Piece
Fig. 3 is three-dimensional globular conductive graphene/carbon nano tube compound material XRD spectra prepared by embodiment 1；
Fig. 4 is three-dimensional globular conductive graphene/carbon nano tube compound material cycle performance curve prepared by embodiment 1
Figure；
Fig. 5 is three-dimensional globular conductive graphene/carbon nano tube compound material high rate performance curve prepared by embodiment 1
Figure；
Fig. 6 is three-dimensional globular conductive graphene/carbon nano tube compound material photo prepared by embodiment 2；
Fig. 7 is that three-dimensional globular conductive graphene/carbon nano tube compound material high power scanning electron microscope prepared by embodiment 2 is shone
Piece；
Fig. 8 is three-dimensional globular conductive graphene/carbon nano tube compound material XRD spectra prepared by embodiment 2；
Fig. 9 is three-dimensional globular conductive graphene/carbon nano tube compound material cycle performance curve prepared by embodiment 2
Figure；
Figure 10 is three-dimensional globular conductive graphene/carbon nano tube compound material high rate performance curve prepared by embodiment 2
Figure.
Specific embodiment
It is used in the embodiment of the present invention unless otherwise specified with the following examples verifying beneficial effects of the present invention
It is equipment, the method etc. of this field routine.
Embodiment 1: three-dimensional globular conductive graphene/carbon nano tube compound material preparation method of the present embodiment, by with
Lower step carries out:
One, it to be purchased from AlfaAesar (China) Chemical Co., Ltd.'s graphite flake as raw material, is prepared using Hummer method
Concentration is 1.5mg ml-1Graphene oxide dispersion I；
Two, by 0.36 gram of ZrO2The graphene oxide dispersion I of abrading-ball, 0.06 gram of carbon nanotube and the preparation of 40ml step 1
Being packed into has ZrO2In the ball grinder of liner, the hydrazine hydrate solution that 1.2ml mass percentage concentration is 3% is added, quality is filled with
Ball grinder, is finally fixed in ball mill, is in drum's speed of rotation by the high-purity argon gas that percent purity is 99.999%
Ball milling 50h under conditions of 1050rpm, to the end of ball milling, ball grinder is cooled to room temperature, and obtains graphene oxide/carbon nanotube point
Dispersion liquid II；
Three, 40ml graphene oxide/carbon nano tube dispersion liquid II that step 2 obtains is added in the beaker of 100ml,
Reuse 10mol L-1NaOH solution adjust mixed dispersion liquid II pH value be 13.7, obtain mixed dispersion liquid III；
Four, mixed dispersion liquid III is added in water heating kettle, keeps the temperature 12h in 180 DEG C of baking oven, obtained three-dimensional globular and lead
Graphene/carbon nano tube compound material, the material are spherical hydrogels.
Fig. 1 is three-dimensional globular conductive graphene/carbon nano tube compound material photo prepared by the present embodiment 1, can from Fig. 1
To find out, which is solid spherical structure, and a diameter of 13mm, sphericity is good.
Fig. 2 is three-dimensional globular conductive graphene/carbon nano tube compound material high power scanning electron microscope prepared by the present embodiment 1
Photo is similar to spongy tissue, using carbon nanotube as bone figure it is seen that there are a large amount of microcellular structures for the material internal
Frame is stacked by redox graphene lamella and is formed.
Fig. 3 is three-dimensional globular conductive graphene/carbon nano tube compound material XRD spectra prepared by the present embodiment 1；From figure
3 as can be seen that the composite material is made of graphene and carbon nanotube.
After three-dimensional globular conductive graphene/carbon nanotube compound hydrogel material is freeze-dried 48 hours, it is prepared into storage
Hydrogen electrode and composition battery, carry out electrochemical property test, and obtained cycle performance curve is as shown in Figure 4.It can from Fig. 4
Out, the maximum hydrogen storage capability of three-dimensional globular conductive graphene/carbon nano tube compound material is 1.68wt%, electrochemical hydrogen storage performance
It is excellent.After circulation 50 times, hydrogen storage ability remains at 80% or more.The high rate performance curve of the material as shown in figure 5, from
Fig. 5 can be seen that under the conditions of the discharge current density of 1000mA/g, and discharge capability remains at 65% or more.
The present embodiment is prepared for three-dimensional globular conductive graphene/carbon nanotube using common equipment and simple method
Compound hydrogel material.At low cost, performance is good.
Embodiment 2: three-dimensional globular conductive graphene/carbon nano tube compound material preparation method of the present embodiment, by with
Lower step carries out:
One, to be purchased from the graphite flake of AlfaAesar (China) Chemical Co., Ltd. as raw material, using Hummer method system
Standby concentration is 1.7mg ml-1Graphene oxide dispersion I；
Two, by 0.408 gram of ZrO2The graphene oxide of abrading-ball, 0.068 gram of carbon nanotube and the preparation of 40ml step 1 disperses
Liquid I, add 1.0ml mass percentage concentration be 4% hydrazine hydrate solution, be filled with quality percent purity be 99.999% it is high-purity
Ball grinder is finally fixed in ball mill by argon gas, ball milling 60h under conditions of drum's speed of rotation is 1100rpm, to ball milling knot
Beam, ball grinder are cooled to room temperature, and obtain graphene oxide/carbon nano tube dispersion liquid II；
Three, 40ml graphene oxide/carbon nano tube dispersion liquid II that step 2 obtains is added in the beaker of 100ml,
Reuse 10mol L-1NaOH solution adjust mixed dispersion liquid II p H value be 13.8, obtain mixed dispersion liquid III；
Four, mixed dispersion liquid III is added in water heating kettle, keeps the temperature 12h in 170 DEG C of baking oven, obtained three-dimensional globular and lead
Graphene/carbon nano tube compound material, the material are spherical hydrogels.
Fig. 6 is three-dimensional globular conductive graphene/carbon nano tube compound material photo prepared by the present embodiment 2, can from Fig. 6
To find out, which is solid spherical structure, and a diameter of 14mm, sphericity is good.
Fig. 7 is three-dimensional globular conductive graphene/carbon nano tube compound material high power scanning electron microscope prepared by the present embodiment 2
Photo is similar to spongy tissue, using carbon nanotube as bone from figure 7 it can be seen that there are a large amount of microcellular structures for the material internal
Frame is stacked by redox graphene lamella and is formed.
Fig. 8 is three-dimensional globular conductive graphene/carbon nano tube compound material XRD spectra prepared by the present embodiment 2；From figure
8 as can be seen that the composite material is made of graphene and carbon nanotube.
After three-dimensional globular conductive graphene prepared by the present embodiment 2/carbon nanotube compound hydrogel material freeze-drying
It is prepared into hydrogen-storage electrode, and forms battery, carries out electrochemical property test, obtained charging and discharging curve is as shown in Figure 9.From Fig. 9
As can be seen that the maximum hydrogen storage capability of three-dimensional globular conductive graphene material is 1.66wt%, electrochemical hydrogen storage is had excellent performance.?
After circulation 50 times, hydrogen storage ability remains at 80% or more.The high rate capability curve of the material is as shown in Figure 10, from Figure 10
As can be seen that discharge capability remains at 65% or more under the conditions of the discharge current density of 1000mA/g.
The present embodiment is prepared for three-dimensional globular conductive graphene/carbon nanotube using common equipment and simple method
Compound hydrogel material.At low cost, performance is good.
Claims (7)
1. a kind of preparation method of three-dimensional globular conductive graphene/carbon nano tube compound material, it is characterised in that this method includes
Following steps:
One, using graphite flake as raw material, use Hummer method preparation concentration for 1.25~1.75mg ml-1Graphene oxide point
Dispersion liquid I；
Two, ZrO is pressed2The mass ratio of abrading-ball, carbon nanotube and graphene oxide is (5~8): the ratio of 1:1, by ZrO2Abrading-ball, carbon
Nanotube and graphene oxide dispersion I, which are packed into, has ZrO2In the ball grinder of liner, hydrazine hydrate solution is added, is filled with high-purity
Argon gas, 48~60h of ball milling under conditions of drum's speed of rotation is 1050~1100rpm obtain graphene oxide/carbon nanotube point
Dispersion liquid II；
Three, with 10mol L-1NaOH solution the pH value of graphene oxide dispersion II is adjusted to 13.55~13.85, obtain
Mixed dispersion liquid III；
Four, mixed dispersion liquid III is added in water heating kettle, 12~13h is kept the temperature in 160~180 DEG C of baking oven, obtains three-dimensional
Spherical conductive graphene/carbon nano tube compound material.
2. a kind of preparation method of three-dimensional globular conductive graphene/carbon nano tube compound material according to claim 1,
The concentration for being characterized in that graphene oxide dispersion I described in step 1 is 1.45~1.55mg ml-1。
3. a kind of preparation side of three-dimensional globular conductive graphene/carbon nano tube compound material according to claim 1 or 2
Method, it is characterised in that the mass percentage concentration of hydrazine hydrate solution is 2%~4% in step 2；Hydrazine hydrate solution and graphite oxide
The volume ratio of alkene dispersion liquid I is 1:(30~50).
4. a kind of preparation side of three-dimensional globular conductive graphene/carbon nano tube compound material according to claim 1 or 2
Method, it is characterised in that mass percentage concentration >=99.999% of high-purity argon gas described in step 2.
5. a kind of three-dimensional globular conductive graphene/carbon nano tube compound material, wherein it is according to claim 1 to any one of 4 institutes
The method preparation stated.
6. a kind of hydrogen-storage electrode, wherein the hydrogen-storage electrode be using the three-dimensional globular conductive graphene described in claim 5/
Carbon nano tube compound material preparation.
7. a kind of battery, which includes hydrogen-storage electrode as claimed in claim 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112456479A (en) * | 2020-11-17 | 2021-03-09 | 安徽理工大学 | Preparation method of uniformly dispersed graphene/carbon nanotube composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105590757A (en) * | 2014-11-18 | 2016-05-18 | 中国科学院宁波材料技术与工程研究所 | Carbon nanotube/graphene composite gel and preparation method thereof |
| CN107512041A (en) * | 2017-07-17 | 2017-12-26 | 青岛超碳新材料科技有限公司 | A kind of preparation method of copper foil graphene/carbon nano-tube or copper foil graphene/carbon nano-tube copper foil heat conduction film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105590757A (en) * | 2014-11-18 | 2016-05-18 | 中国科学院宁波材料技术与工程研究所 | Carbon nanotube/graphene composite gel and preparation method thereof |
| CN107512041A (en) * | 2017-07-17 | 2017-12-26 | 青岛超碳新材料科技有限公司 | A kind of preparation method of copper foil graphene/carbon nano-tube or copper foil graphene/carbon nano-tube copper foil heat conduction film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112456479A (en) * | 2020-11-17 | 2021-03-09 | 安徽理工大学 | Preparation method of uniformly dispersed graphene/carbon nanotube composite material |
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