CN109721048B - Preparation method of three-dimensional spherical conductive graphene/carbon nanotube composite material - Google Patents
Preparation method of three-dimensional spherical conductive graphene/carbon nanotube composite material Download PDFInfo
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- CN109721048B CN109721048B CN201910058171.2A CN201910058171A CN109721048B CN 109721048 B CN109721048 B CN 109721048B CN 201910058171 A CN201910058171 A CN 201910058171A CN 109721048 B CN109721048 B CN 109721048B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 93
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 71
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000003860 storage Methods 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 18
- 239000000017 hydrogel Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
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Abstract
The invention relates to a preparation method of a three-dimensional spherical conductive graphene/carbon nanotube composite material, which comprises the following steps: firstly, preparing a graphene oxide dispersion liquid I by using a graphite sheet; then ZrO is mixed2Ball-milling the grinding balls, the graphene oxide dispersion liquid I and the carbon nano tubes in a hydrazine hydrate solution to obtain graphene oxide/carbon nano tube dispersion liquid II; then adjusting the pH value to obtain a mixed dispersion liquid III; and then carrying out hydrothermal reaction to obtain the three-dimensional spherical conductive graphene/carbon nano tube composite material. The composite material can be applied to hydrogen storage batteries, the maximum hydrogen storage capacity can reach 1.68 wt%, and the hydrogen storage capacity can still be kept above 80% after 50 times of circulation. Meanwhile, under the condition of a discharge current density of 1000mA/g, the discharge capacity of the lithium ion battery is still kept above 65%. Can be used in the field of hydrogen storage of nickel-hydrogen batteries. The invention solves the technical problems of complex preparation method and high cost of the existing three-dimensional spherical conductive graphene/carbon nano tube.
Description
Technical Field
The invention relates to a preparation method of a graphene composite material, and belongs to the field of electrochemical hydrogen storage materials.
Background
The hydrogen has abundant reserves in nature, the highest energy-quality ratio and cleanness without pollution, so that the development and storage of hydrogen energy become important contents for coping with energy crisis and solving environmental problems in various countries.
Three-dimensional graphene and carbon nanotube materials are important structural and functional materials, and three-dimensional graphene, carbon nanotubes and composite materials thereof with different morphologies have potential application values in the aspect of hydrogen storage, and have attracted wide attention. Theoretically, the two-dimensional graphene/carbon nanotube composite material has the advantages of ultrahigh specific surface area, larger charge transfer rate, excellent mechanical strength and the like, but in practical application, due to pi-pi interaction between two-dimensional graphene sheets, aggregation and stacking between the sheets are easy to occur, so that the hydrogen storage performance is greatly reduced. In order to overcome this drawback, the morphology and structure of the three-dimensional composite material need to be designed. As is well known, a three-dimensional spherical composite material has a spherical structure, graphene sheets of the three-dimensional spherical composite material are not closely arranged together through van der waals force like a graphite structure, but the distance between each two graphene sheets exceeds the acting range of van der waals force, the arrangement between the layers is relatively loose, and the three-dimensional spherical composite material is supported by carbon nanotubes, so that the problems of graphene stacking and agglomeration can be effectively solved. Therefore, the preparation of the graphene/carbon nanotube composite material into a three-dimensional spherical structure has become one of the best ways to improve the hydrogen storage performance.
At present, the method for preparing the three-dimensional spherical graphene mainly comprises a template-assisted method, an aerogel-based self-assembly method and a water-in-oil emulsion method. However, the existing method has the disadvantages of complex equipment, complex process, high cost and the like, so that the development of a preparation method of the three-dimensional spherical conductive graphene/carbon nano tube with low cost and simple process is a problem to be solved urgently.
Disclosure of Invention
The invention provides a preparation method of a three-dimensional spherical conductive graphene/carbon nanotube composite material, aiming at solving the technical problems of complex preparation method and high cost of the existing three-dimensional spherical conductive graphene/carbon nanotube.
The preparation method of the three-dimensional spherical conductive graphene/carbon nanotube composite material comprises the following steps:
firstly, graphite flakes are used as raw materials, and the Hummer method is adopted to prepare the graphite flakes with the concentration of 1.25-1.75 mg ml-1A graphene oxide dispersion liquid I;
di, according to ZrO2The mass ratio of the grinding balls to the carbon nano tubes to the graphene oxide is (5-8) to 1:1, and ZrO is added2ZrO is filled with grinding balls, carbon nano tubes and graphene oxide dispersion liquid I2Adding a hydrazine hydrate solution into the ball milling tank with the lining, introducing high-purity argon, and carrying out ball milling for 48-60 h under the condition that the rotating speed of the ball mill is 1050-1100 rpm to obtain a graphene oxide/carbon nano tube dispersion liquid II;
thirdly, using 10mol L-1The pH value of the graphene oxide dispersion liquid II is adjusted to 13.55-13.85 by using NaOH solution to obtain the graphene oxide dispersion liquidTo mixed dispersion III;
and fourthly, preserving the temperature of the mixed dispersion liquid III in a hydrothermal kettle at 160-180 ℃ for 12-13 h to obtain the three-dimensional spherical conductive graphene/carbon nano tube composite material.
Particularly, the concentration of the graphene oxide dispersion liquid I in the step one can be 1.45-1.55 mg ml-1。
Particularly, the mass percentage concentration of the hydrazine hydrate solution in the second step can be 2-4%; and/or the volume ratio of the hydrazine hydrate solution to the graphene oxide dispersion liquid I is 1: (30-50).
Particularly, the mass percentage concentration of the high-purity argon in the step two is more than or equal to 99.999%.
In another aspect, the invention also relates to a three-dimensional spherical conductive graphene/carbon nanotube composite material prepared by the method.
In another aspect, the present invention also relates to a hydrogen storage electrode prepared using the three-dimensional spherical conductive graphene/carbon nanotube composite material.
In another aspect, the invention also relates to a battery comprising said hydrogen storage electrode.
According to the invention, a high-energy ball milling assisted hydrothermal method is adopted, the graphene oxide can be fully stripped into few layers of graphene oxide at a high rotating speed, the internal energy is rapidly increased by a high-speed grinding ball under the condition of high rotating speed, the graphene oxide is reduced, but the few-layer structure is maintained due to the input of high energy, and the few-layer graphene/carbon nanotube system has large surface energy after ball milling, so that a foundation is provided for later-stage composite material agglomeration and balling. The strong alkaline condition of the hydrothermal process improves the surface tension of the solution, and is beneficial to the formation of a spherical three-dimensional product under the condition of limiting proper concentration in the invention, and the material is spherical hydrogel. The hydrogen storage performance of the three-dimensional spherical conductive graphene/carbon nanotube composite material obtained after the three-dimensional spherical conductive graphene hydrogel material is freeze-dried is greatly improved. The composite material can be used for preparing hydrogen storage electrodes, is applied to energy systems such as nickel-metal hydride batteries and the like, has the maximum hydrogen storage capacity of 1.68wt percent and excellent electrochemical hydrogen storage performance. After 50 times of circulation, the hydrogen storage capacity of the catalyst is still kept above 80%. Meanwhile, under the condition of a discharge current density of 1000mA/g, the discharge capacity of the lithium ion battery is still kept above 65%. Can be used in the field of hydrogen storage. The preparation process is simple, high in safety and low in equipment investment, and the cost of the product is further reduced. The material can be used in the field of batteries.
Drawings
Fig. 1 is a photograph of a three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in example 1;
FIG. 2 is a high-power scanning electron micrograph of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in example 1
Fig. 3 is an XRD spectrum of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in example 1;
fig. 4 is a graph of cycle performance of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in example 1;
fig. 5 is a rate performance curve diagram of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in example 1;
fig. 6 is a photograph of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in example 2;
fig. 7 is a high-power scanning electron micrograph of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in example 2;
fig. 8 is an XRD spectrum of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in example 2;
fig. 9 is a graph of cycle performance of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in example 2;
fig. 10 is a rate performance curve diagram of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in example 2.
Detailed Description
The following examples, in which devices, methods, etc. conventional in the art are employed unless otherwise specified, are used to demonstrate the beneficial effects of the present invention.
Example 1: the preparation method of the three-dimensional spherical conductive graphene/carbon nanotube composite material of the embodiment comprises the following steps:
firstly, graphite flakes purchased from Alfa-Elisa (China) chemical Co., Ltd are used as raw materials, and the Hummer method is adopted to prepare the graphite flakes with the concentration of 1.5mg ml-1The graphene oxide dispersion liquid I;
secondly, 0.36 g of ZrO is added2Charging mill balls, 0.06 g of carbon nanotubes and 40ml of the graphene oxide dispersion I prepared in the first step into a solution containing ZrO2Adding 1.2ml of hydrazine hydrate solution with the mass percentage concentration of 3% into a ball milling tank with an inner liner, filling high-purity argon with the mass percentage purity of 99.999%, fixing the ball milling tank in a ball mill, carrying out ball milling for 50 hours under the condition that the rotating speed of the ball mill is 1050rpm, and cooling the ball milling tank to room temperature after ball milling is finished to obtain graphene oxide/carbon nanotube dispersion liquid II;
thirdly, adding 40ml of the graphene oxide/carbon nano tube dispersion liquid II obtained in the second step into a 100ml beaker, and then using 10mol L of the graphene oxide/carbon nano tube dispersion liquid II-1Adjusting the pH value of the mixed dispersion liquid II to 13.7 by using the NaOH solution to obtain a mixed dispersion liquid III;
and fourthly, adding the mixed dispersion liquid III into a hydrothermal kettle, and keeping the temperature in an oven at 180 ℃ for 12 hours to obtain the three-dimensional spherical conductive graphene/carbon nano tube composite material, wherein the material is spherical hydrogel.
Fig. 1 is a photograph of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in this example 1, and as can be seen from fig. 1, the composite material has a solid sphere structure, the diameter of the composite material is 13mm, and the sphericity of the composite material is good.
Fig. 2 is a high-power scanning electron microscope photograph of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in this example 1, and it can be seen from fig. 2 that a large number of micropores exist in the material, which are similar to a spongy structure, and are formed by stacking reduced graphene oxide sheets with a carbon nanotube as a skeleton.
Fig. 3 is an XRD spectrum of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in this example 1; as can be seen from fig. 3, the composite material is composed of graphene and carbon nanotubes.
After the three-dimensional spherical conductive graphene/carbon nano tube composite hydrogel material is subjected to freeze drying for 48 hours, hydrogen storage electrodes are prepared and form a battery, and an electrochemical performance test is performed, so that an obtained cycle performance curve is shown in fig. 4. As can be seen from fig. 4, the maximum hydrogen storage capacity of the three-dimensional spherical conductive graphene/carbon nanotube composite material is 1.68 wt%, and the electrochemical hydrogen storage performance is excellent. After 50 times of circulation, the hydrogen storage capacity of the catalyst is still kept above 80%. The rate performance curve of the material is shown in FIG. 5, and it can be seen from FIG. 5 that the discharge capacity of the material is still maintained above 65% under the condition of a discharge current density of 1000 mA/g.
In this embodiment, a three-dimensional spherical conductive graphene/carbon nanotube composite hydrogel material is prepared by using a common apparatus and a simple method. Low cost and good performance.
Example 2: the preparation method of the three-dimensional spherical conductive graphene/carbon nanotube composite material of the embodiment comprises the following steps:
firstly, using graphite flake purchased from Alfa-Elisa (China) chemical Co., Ltd as raw material, and adopting Hummer method to prepare 1.7mg ml-1The graphene oxide dispersion liquid I;
secondly, 0.408 g of ZrO is added2Grinding balls, 0.068 g of carbon nanotubes and 40ml of graphene oxide dispersion liquid I prepared in the first step, then adding 1.0ml of hydrazine hydrate solution with the mass percentage concentration of 4%, filling high-purity argon with the mass percentage purity of 99.999%, finally fixing a ball milling tank in the ball mill, carrying out ball milling for 60 hours under the condition that the rotating speed of the ball mill is 1100rpm, and cooling the ball milling tank to room temperature after the ball milling is finished, thus obtaining graphene oxide/carbon nanotube dispersion liquid II;
thirdly, adding 40ml of the graphene oxide/carbon nano tube dispersion liquid II obtained in the second step into a 100ml beaker, and then using 10mol L of the graphene oxide/carbon nano tube dispersion liquid II-1Regulating the p H value of the mixed dispersion liquid II to be 13.8 by using the NaOH solution to obtain a mixed dispersion liquid III;
and fourthly, adding the mixed dispersion liquid III into a hydrothermal kettle, and keeping the temperature in an oven at 170 ℃ for 12 hours to obtain the three-dimensional spherical conductive graphene/carbon nano tube composite material, wherein the material is spherical hydrogel.
Fig. 6 is a photograph of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in this example 2, and as can be seen from fig. 6, the composite material has a solid sphere structure, the diameter of the composite material is 14mm, and the sphericity of the composite material is good.
Fig. 7 is a high-power scanning electron micrograph of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in this example 2, and it can be seen from fig. 7 that a large number of micropores are present in the material, which are similar to a spongy structure, and are formed by stacking reduced graphene oxide sheets with a carbon nanotube as a skeleton.
Fig. 8 is an XRD spectrum of the three-dimensional spherical conductive graphene/carbon nanotube composite material prepared in this example 2; as can be seen from fig. 8, the composite material is composed of graphene and carbon nanotubes.
The three-dimensional spherical conductive graphene/carbon nanotube composite hydrogel material prepared in this embodiment 2 is freeze-dried to prepare a hydrogen storage electrode, and a battery is formed, and an electrochemical performance test is performed, so that an obtained charge-discharge curve is shown in fig. 9. As can be seen from fig. 9, the maximum hydrogen storage capacity of the three-dimensional spherical conductive graphene material is 1.66 wt%, and the electrochemical hydrogen storage performance is excellent. After 50 times of circulation, the hydrogen storage capacity of the catalyst is still kept above 80%. The high rate performance curve of the material is shown in FIG. 10, and it can be seen from FIG. 10 that the discharge capacity of the material is still maintained above 65% under the condition of a discharge current density of 1000 mA/g.
In this embodiment, a three-dimensional spherical conductive graphene/carbon nanotube composite hydrogel material is prepared by using a common apparatus and a simple method. Low cost and good performance.
Claims (7)
1. A preparation method of a three-dimensional spherical conductive graphene/carbon nanotube composite material is characterized by comprising the following steps:
firstly, graphite flakes are used as raw materials, and the Hummer method is adopted to prepare the graphite flakes with the concentration of 1.25-1.75 mg ml-1A graphene oxide dispersion liquid I;
di, according to ZrO2The mass ratio of the grinding balls to the carbon nano tubes to the graphene oxide is (5-8) to 1:1, and ZrO is added2ZrO is filled with grinding balls, carbon nano tubes and graphene oxide dispersion liquid I2Ball milling tank with liningAdding a hydrazine hydrate solution, introducing high-purity argon, and performing ball milling for 48-60 hours at the rotating speed of a ball mill of 1050-1100 rpm to obtain a graphene oxide/carbon nano tube dispersion liquid II;
thirdly, using 10mol L-1Adjusting the pH value of the graphene oxide dispersion liquid II to 13.55-13.85 by using the NaOH solution to obtain a mixed dispersion liquid III;
and fourthly, adding the mixed dispersion liquid III into a hydrothermal kettle, and keeping the temperature in an oven at 160-180 ℃ for 12-13 h to obtain the three-dimensional spherical conductive graphene/carbon nano tube composite material.
2. The method for preparing the three-dimensional spherical conductive graphene/carbon nanotube composite material according to claim 1, wherein the concentration of the graphene oxide dispersion liquid I in the step one is 1.45-1.55 mg ml-1。
3. The method for preparing the three-dimensional spherical conductive graphene/carbon nanotube composite material according to claim 1 or 2, wherein the mass percentage concentration of the hydrazine hydrate solution in the second step is 2-4%; the volume ratio of the hydrazine hydrate solution to the graphene oxide dispersion liquid I is 1: (30-50).
4. The preparation method of the three-dimensional spherical conductive graphene/carbon nanotube composite material according to claim 1 or 2, wherein the mass percentage concentration of the high-purity argon gas in the step two is not less than 99.999%.
5. A three-dimensional spherical conductive graphene/carbon nanotube composite material, wherein it is prepared according to the method of any one of claims 1 to 4.
6. A hydrogen storage electrode, wherein the hydrogen storage electrode is prepared using the three-dimensional spherical conductive graphene/carbon nanotube composite material according to claim 5.
7. A battery comprising the hydrogen storage electrode according to claim 6.
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