CN109817917B - Three-dimensional spherical conductive graphene/Co1-xPreparation method of S composite material - Google Patents
Three-dimensional spherical conductive graphene/Co1-xPreparation method of S composite material Download PDFInfo
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Abstract
Three-dimensional spherical conductive graphene/Co1‑xThe invention discloses a preparation method of an S composite material, and relates to a preparation method of a graphene composite material. The preparation method aims to solve the technical problems of complex preparation method and high cost of the existing three-dimensional spherical graphene composite material. The method comprises the following steps: preparing graphene oxide dispersion liquid by using graphite flakes, and then carrying out ball milling treatment; adding CoCl into the graphene oxide dispersion liquid2·6H2O, after dispersing evenly and adjusting the pH value, adding Na2S·9H2O, dispersing uniformly; finally, carrying out hydrothermal reaction on the mixed solution to obtain the three-dimensional spherical conductive graphene/Co1‑xAnd (3) an S composite material. The material is freeze dried to prepare the hydrogen storage alloy electrode, the maximum hydrogen storage capacity of the hydrogen storage alloy electrode reaches 2.14 wt%, and the hydrogen storage capacity is still kept above 76% 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 kept above 64 percent. Can be used in the field of hydrogen storage batteries.
Description
Technical Field
The invention relates to a preparation method of a graphene composite material.
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.
The three-dimensional graphene material is an important structural and functional material, and the three-dimensional graphene with different morphologies and the composite material thereof have potential application values in the aspect of hydrogen storage, and have attracted wide attention. Theoretically, two-dimensional graphene has the advantages of ultra-high specific surface area, large charge transfer rate, excellent mechanical strength and the like, but in practical application, due to pi-pi interaction between two-dimensional graphene sheet layers, aggregation and stacking between the sheet layers are easy to occur, and the hydrogen storage performance is greatly reduced. In order to overcome this drawback, the morphology and structure of the graphene material need to be designed. As is well known, a three-dimensional spherical graphene material has a spherical structure, graphene sheets are not closely arranged together through van der waals force between each layer like a graphite structure, but the distance between each graphene sheet exceeds the acting range of van der waals force, and the arrangement between layers is relatively loose, so that the problems of graphene stacking and aggregation can be effectively overcome. Therefore, making graphene into a three-dimensional spherical structure is 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 defects of complex equipment, complex process, high cost and the like.
Disclosure of Invention
The invention aims to solve the problem of the existing three-dimensional spherical graphene/Co1-xThe preparation method of the S composite material is complex and has high cost, and the three-dimensional spherical conductive graphene/Co is provided1-xA preparation method of the S composite material.
The invention relates to three-dimensional spherical conductive graphene/Co1-xThe preparation method of the S composite material comprises the following steps:
firstly, graphite flakes are used as raw materials, and the preparation method is adopted to prepare the graphite flakes with the concentration of 1.25-1.75 mg mL by the Hummer method-1A graphene oxide dispersion liquid I;
di, according to ZrO2The mass ratio of the grinding balls to the graphene oxide is (5-8): 1, and ZrO is added2ZrO is filled with grinding balls and graphene oxide dispersion liquid I2Adding hydrazine hydrate into the ball milling tank with the lining, filling high-purity argon, fixing the ball milling tank in a ball mill, performing ball milling for 48-60 hours under the condition that the rotating speed of the ball mill is 1050-1100 rpm, and cooling the ball milling tank to room temperature to obtain graphene oxide dispersion liquid II;
thirdly, adding CoCl into the graphene oxide dispersion liquid II2·6H2O, wherein the graphene oxide and CoCl in the graphene oxide dispersion liquid II2·6H2The mass ratio of O is 1: (3.5-9.5), ultrasonically dispersing for 5-10 min, and then using 10mol L-1Adjusting the pH value of the mixed dispersion liquid II to 13.55-13.85 by using the NaOH solution to obtain a mixed dispersion liquid III;
fourthly, adding Na into the mixed dispersion liquid III2S·9H2O, wherein Na2S·9H2O and CoCl2·6H2The molar ratio of O is 1: (0.5-0.7), ultrasonically dispersing for 20-30 min to obtain a mixed dispersion liquid IV;
fifthly, adding the mixed dispersion liquid IV 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/Co1-xAnd (3) an S composite material.
The invention adopts a high-energy ball milling assisted hydrothermal method, and the graphene oxide can be fully stripped into few layers at a high rotating speedUnder the condition of high rotating speed, the high-speed grinding ball enables the internal energy to be increased rapidly, the graphene oxide is reduced, but due to the input of high energy, a few-layer structure is kept, and a few-layer graphene system has larger surface energy after ball milling, so that a foundation is provided for later-stage graphene agglomeration and balling. The strong alkaline condition of the hydrothermal process improves the surface tension of the solution, and is beneficial to forming a spherical three-dimensional product under the proper concentration defined by the invention, and the three-dimensional spherical conductive graphene/Co1-xThe S composite material is hydrogel, and the hydrogen storage performance of the three-dimensional spherical material is greatly improved. Conducting three-dimensional spherical graphene/Co1- xThe S composite hydrogel material is freeze-dried to prepare a hydrogen storage alloy electrode, the hydrogen storage alloy electrode is applied to energy systems such as nickel-metal hydride batteries, the maximum hydrogen storage capacity can reach 2.14 wt%, the electrochemical hydrogen storage performance is excellent, and after 50 times of circulation, three-dimensional spherical graphene/Co1-xThe hydrogen storage capacity of the S composite material is still kept above 76%. Meanwhile, under the condition of a discharge current density of 1000mA/g, the discharge capacity of the lithium ion battery is still kept above 64 percent. Can be used in the field of hydrogen storage. The preparation method has the advantages of simple process, high safety and low cost.
Drawings
FIG. 1 shows three-dimensional spherical conductive graphene/Co prepared in experiment 11-xS a photograph of the composite;
FIG. 2 shows three-dimensional spherical conductive graphene/Co prepared in experiment 11-xS, high-power scanning electron microscope photos of the composite material;
FIG. 3 shows three-dimensional spherical conductive graphene/Co prepared in experiment 11-xAn XRD spectrum of the S composite material;
FIG. 4 shows three-dimensional spherical conductive graphene/Co prepared in experiment 11-xS, a cycle performance curve of the composite material;
FIG. 5 shows three-dimensional spherical conductive graphene/Co prepared in experiment 11-xS, a rate performance curve of the composite material;
FIG. 6 shows three-dimensional spherical conductive graphene/Co prepared in experiment 21-xS a photograph of the composite;
FIG. 7 shows three-dimensional spherical conductive graphene/Co prepared in experiment 21-xS compositeHigh power scanning electron microscope photograph of material
FIG. 8 shows three-dimensional spherical conductive graphene/Co prepared in experiment 21-xAn XRD spectrum of the S composite material;
FIG. 9 shows three-dimensional spherical conductive graphene/Co prepared in experiment 21-xS, a cycle performance curve of the composite material;
FIG. 10 shows three-dimensional spherical conductive graphene/Co prepared in experiment 21-xRate performance curve of S composite.
Detailed Description
The first embodiment is as follows: three-dimensional spherical conductive graphene/Co of the present embodiment1-xThe preparation method of the S composite material comprises the following steps:
firstly, graphite flakes are used as raw materials, and the preparation method is adopted to prepare the graphite flakes with the concentration of 1.25-1.75 mg mL by the Hummer method-1A graphene oxide dispersion liquid I;
di, according to ZrO2The mass ratio of the grinding balls to the graphene oxide is (5-8): 1, and ZrO is added2ZrO is filled with grinding balls and graphene oxide dispersion liquid I2Adding hydrazine hydrate into the ball milling tank with the lining, filling high-purity argon, fixing the ball milling tank in a ball mill, performing ball milling for 48-60 hours under the condition that the rotating speed of the ball mill is 1050-1100 rpm, and cooling the ball milling tank to room temperature to obtain graphene oxide dispersion liquid II;
thirdly, adding CoCl into the graphene oxide dispersion liquid II2·6H2O, wherein the graphene oxide and CoCl in the graphene oxide dispersion liquid II2·6H2The mass ratio of O is 1: (3.5-9.5), ultrasonically dispersing for 5-10 min, and then using 10mol L-1Adjusting the p H value of the mixed dispersion liquid II to be 13.55-13.85 by using the NaOH solution to obtain a mixed dispersion liquid III;
fourthly, adding Na into the mixed dispersion liquid III2S·9H2O, wherein Na2S·9H2O and CoCl2·6H2The molar ratio of O is 1: (0.5-0.7), ultrasonically dispersing for 20-30 min to obtain a mixed dispersion liquid IV;
fifthly, adding the mixed dispersion liquid IV into a hydrothermal kettle, and keeping the temperature of the hydrothermal kettle at 160-180 ℃ in an oven at 12-13 DEG Ch, obtaining the three-dimensional spherical conductive graphene/Co1-xAnd (3) an S composite material.
The second embodiment is as follows: the difference between the first embodiment and the second embodiment is that the concentration of the graphene oxide dispersion liquid I in the first step is 1.25-1.75 mg mL-1(ii) a The rest is the same as the first embodiment.
The third concrete implementation mode: the difference between the embodiment and the first or second embodiment is that 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); the other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the embodiment is different from the first to the third embodiment in that the mass percentage concentration of the high-purity argon in the second step is more than or equal to 99.999 percent; the others are the same as in one of the first to third embodiments.
The beneficial effects of the present invention were verified by the following tests:
test 1: three-dimensional spherical conductive graphene/Co of the test1-xThe preparation method of the S composite material comprises the following steps:
firstly, graphite flakes purchased from Alfa-Elisa (China) chemical Co., Ltd are used as raw materials, and the preparation concentration is 1.5mg mL by the Hummer method-1The graphene oxide dispersion liquid I;
secondly, 0.36g of ZrO2Charging grinding balls and 40ml of graphene oxide dispersion liquid I prepared in the first step into a mixture with ZrO2Adding 1.2ml of hydrazine hydrate solution with the mass percentage concentration of 4% 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 a graphene oxide dispersion liquid II;
thirdly, adding 0.33 g of CoCl into 40mL of graphene oxide dispersion liquid II2·6H2O, ultrasonic dispersing for 10min, then 10mol L-1Regulating the p H value of the mixed dispersion liquid II to be 13.65 by using the NaOH solution to obtain a mixed dispersion liquid III;
fourthly, 0.66 g of Na is added into the mixed dispersion liquid III2S·9H2O, performing ultrasonic dispersion for 30min to obtain a mixed dispersion liquid IV;
fifthly, adding the mixed dispersion liquid IV into a hydrothermal kettle, and keeping the temperature in an oven at 180 ℃ for 12 hours to obtain the three-dimensional spherical conductive graphene/Co1-xS composite material, the three-dimensional spherical conductive graphene/Co1-xThe S composite is a hydrogel.
FIG. 1 shows three-dimensional spherical conductive graphene/Co prepared in experiment 11-xS composite material photograph, as can be seen from figure 1, the composite material is a spherical solid sphere structure, the diameter of the composite material is 14mm, and the sphericity is good.
FIG. 2 shows three-dimensional spherical conductive graphene/Co prepared in experiment 11-xAs can be seen from FIG. 2, the material has a spongy internal structure, and nano Co with uniform size is loaded on a graphene sheet1- xAnd (4) S particles.
FIG. 3 shows three-dimensional spherical conductive graphene/Co prepared in experiment 11-xAn XRD spectrum of the S composite material; as can be seen from FIG. 3, the composite material is composed of graphene and Co1-xAnd S.
The three-dimensional spherical conductive graphene/Co prepared in the experiment 11-xThe S composite material and the hydrogel material are freeze-dried for 48 hours to prepare a hydrogen storage electrode and form a battery, and an electrochemical performance test is carried out to obtain a cycle performance curve as shown in figure 4. As can be seen from FIG. 4, the three-dimensional spherical conductive graphene/Co1-xThe maximum hydrogen storage capacity of the S composite material is 2.14 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 76%. FIG. 5 shows three-dimensional spherical conductive graphene/Co prepared in experiment 11-xAs can be seen from FIG. 5, the discharge capacity of the S composite material is still maintained above 64% under the condition of a discharge current density of 1000 mA/g.
Test 2: three-dimensional spherical conductive graphene/Co of the test1-xThe preparation method of the S composite material comprises the following steps:
a,Graphite flakes purchased from Alfa-Elisa (China) chemical Co., Ltd are used as raw materials, and the preparation concentration is 1.7mg mL by the Hummer method-1The graphene oxide dispersion liquid I;
secondly, 0.41 g of ZrO is added2Charging grinding balls and 40ml of graphene oxide dispersion liquid I prepared in the first step into a mixture with 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 into a ball mill, carrying out ball milling for 50 hours under the condition that the rotating speed of the ball mill is 1100rpm, 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 0.44g of CoCl into 40mL of graphene oxide dispersion liquid II2·6H2O, ultrasonic dispersing for 10min, and then 10mol L-1Regulating the p H value of the mixed dispersion liquid II to be 13.85 by using the NaOH solution to obtain a mixed dispersion liquid III;
fourthly, 0.73g of Na is added into the mixed dispersion liquid III2S·9H2O, performing ultrasonic dispersion for 30min to obtain a mixed dispersion liquid IV;
fifthly, adding the mixed dispersion liquid IV into a hydrothermal kettle, and keeping the temperature in an oven at 180 ℃ for 12 hours to obtain the three-dimensional spherical conductive graphene/Co1-xS composite material, the three-dimensional spherical conductive graphene/Co1-xThe S composite is a hydrogel.
FIG. 6 shows three-dimensional spherical conductive graphene/Co prepared in experiment 21-xS composite material photograph, from figure 6 can see, this composite material is the structure of spherical solid sphere, its diameter is 13mm, the sphericity is good.
FIG. 7 shows three-dimensional spherical conductive graphene/Co prepared in experiment 21-xAs can be seen from FIG. 7, the S composite material has a spongy internal structure, and nano Co with uniform size is loaded on a graphene sheet1- xAnd (4) S particles.
FIG. 8 shows three-dimensional spherical conductive graphene/Co prepared in experiment 21-xAn XRD spectrum of the S composite material; as can be seen from FIG. 8, the composite material is composed of graphene and Co1-xAnd S.
The three-dimensional spherical conductive graphene/Co prepared in the experiment 21-xThe S composite hydrogel material is freeze-dried for 48 hours to prepare a hydrogen storage electrode to form a battery, and the obtained cycle performance curve is shown in figure 9. As can be seen from FIG. 9, the three-dimensional spherical conductive graphene/Co1-xThe maximum hydrogen storage capacity of the S composite material is 2.20 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 76%. The obtained rate performance curve is shown in FIG. 10, and it can be seen from FIG. 10 that the discharge capability is maintained at 64% or more under the discharge current density condition of 1000 mA/g.
Claims (3)
1. Three-dimensional spherical conductive graphene/Co1-xThe preparation method of the S composite material is characterized by comprising the following steps of:
firstly, graphite flakes are used as raw materials, and the preparation method is adopted to prepare the graphite flakes with the concentration of 1.25-1.75 mg mL by the Hummer method-1A graphene oxide dispersion liquid I;
di, according to ZrO2The mass ratio of the grinding balls to the graphene oxide is (5-8): 1, and ZrO is added2ZrO is filled with grinding balls and graphene oxide dispersion liquid I2Adding a hydrazine hydrate solution into the ball milling tank with the lining, filling high-purity argon, fixing the ball milling tank in a ball mill, performing ball milling for 48-60 hours under the condition that the rotating speed of the ball mill is 1050-1100 rpm, and cooling the ball milling tank to room temperature to obtain a graphene oxide dispersion liquid II; the mass percentage concentration of the high-purity argon is more than or equal to 99.999 percent;
thirdly, adding CoCl into the graphene oxide dispersion liquid II2·6H2O, wherein the graphene oxide and CoCl in the graphene oxide dispersion liquid II2·6H2The mass ratio of O is 1: (3.5-9.5), ultrasonically dispersing for 5-10 min, and adjusting the p H value to 13.55-13.85 by using NaOH to obtain a mixed dispersion liquid III;
fourthly, adding Na into the mixed dispersion liquid III2S·9H2O, wherein Na2S·9H2O and CoCl2·6H2The molar ratio of O is 1: (0.5 to 0.7) ultrasonic separationDispersing for 20-30 min to obtain a mixed dispersion liquid IV;
fifthly, adding the mixed dispersion liquid IV 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/Co1-xAnd (3) an S composite material.
2. The three-dimensional spherical conductive graphene/Co of claim 11-xThe preparation method of the S composite material is characterized in that the concentration of the graphene oxide dispersion liquid I in the step one is 1.45-1.55 mg mL-1。
3. The three-dimensional spherical conductive graphene/Co according to claim 1 or 21-xThe preparation method of the S composite material is characterized in that the mass percentage concentration of the hydrazine hydrate solution in the step two is 2-4%; the volume ratio of the hydrazine hydrate solution to the graphene oxide dispersion liquid I is 1: (30-50).
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