CN109928383B - Preparation method for preparing graphene/porous carbon material by ionic liquid-based Pickering emulsion method - Google Patents
Preparation method for preparing graphene/porous carbon material by ionic liquid-based Pickering emulsion method Download PDFInfo
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- CN109928383B CN109928383B CN201910331151.8A CN201910331151A CN109928383B CN 109928383 B CN109928383 B CN 109928383B CN 201910331151 A CN201910331151 A CN 201910331151A CN 109928383 B CN109928383 B CN 109928383B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparation method for preparing a graphene/porous carbon material by an ionic liquid-based Pickering emulsion method. The method comprises the following steps: mixing a certain amount of water and a certain amount of ionic liquid to prepare water/ionic liquid microemulsion; adding graphene oxide into the ionic liquid microemulsion to form a Pickering emulsion; adding a carbon source into the pickering emulsion; and preparing the graphene/porous carbon material from the Pickering emulsion through a hydrothermal process. According to the method provided by the invention, graphene oxide is used as a surfactant, and the formation of Pickering emulsion is promoted by utilizing the electrostatic action between the graphene oxide and the ionic liquid. After the graphene oxide layer is stabilized by the ionic liquid, the carbon material is polymerized on the other side of the graphene oxide nanosheet layer. The aggregation of graphene is inhibited by the stabilizing effect of the ionic liquid, and a two-dimensional nanosheet structure is obtained. The finally prepared composite material can be used as an electrode of an energy storage device and shows excellent electrochemical performance.
Description
Technical Field
The invention relates to a preparation method for preparing a graphene/porous carbon material by an ionic liquid-based Pickering emulsion method.
Background
Since the 2004, graphene is obtained from highly oriented pyrolytic graphite by a micro mechanical stripping method, the graphene has attracted much attention due to its advantages of good conductivity, high chemical stability, large specific surface area, and the like. The graphene-based nanocomposite combines the inherent excellent characteristics of graphene, and is widely researched to solve the key problems in the fields of energy storage, optical and electronic devices, catalysis and the like. However, the strong van der waals interactions existing between graphene layers may cause severe agglomeration of graphene. In order to solve this problem, researchers have formed a structure that can limit graphene stacking to some extent mainly by compositing two-dimensional graphene with a carbon material. However, the preparation process has the problems of complicated steps, long time consumption, very limited sulfur carrying space when the obtained nano composite material is used for the sulfur positive electrode of the lithium-sulfur battery, and the like.
The method for inhibiting the agglomeration of the graphene by utilizing the special environment of the ionic liquid microemulsion is a simple and effective method. The ionic liquid is an organic salt completely composed of anions and cations, and due to excellent performances of good thermal stability, high conductivity, extremely low vapor pressure, nonflammability, proper polarity, wide electrochemical window and the like, the ionic liquid receives extensive attention, and more researchers use the ionic liquid as a green solvent to replace volatile organic solvents in chemical reactions and material synthesis. In addition, the ionic liquid microemulsion formed by adding the ionic liquid into the microemulsion has the advantages of both the ionic liquid and the microemulsion: excellent chemical stability, good thermal stability, wider polarity and designable ionic liquid structure. In the preparation process of the ionic liquid microemulsion, the surfactant can stabilize the dispersion system, so that the selection of the proper surfactant has important significance for the formation of the ionic liquid microemulsion.
The added graphene oxide can be used as a surfactant of the ionic liquid microemulsion to improve the stability of a dispersion system, and a new unique environment, namely Pickering emulsion, can be constructed to create favorable conditions for the subsequent preparation of graphene/porous carbon. Pickering emulsions refer to emulsions stabilized by solid particles, and pickering emulsions also have several types of conventional emulsions, such as oil-in-water (O/W) emulsions, water-in-oil (W/O) emulsions, and double layer emulsions. Compared with the traditional emulsion, the pickering emulsion has unique advantages: the emulsion can form stable emulsion without (or with a small amount of) emulsifier, is nontoxic and environment-friendly, has advantages in the fields of food, medicine and the like, and has stronger stability because the adsorption of solid particles on an oil-water interface is almost irreversible. In recent years, pickering emulsions have received increasing attention due to their low cost, environmental friendliness, high stability, and the like.
Disclosure of Invention
Aiming at the problem of graphene agglomeration of the graphene-based nanocomposite material, the invention aims to provide an ionic liquid-based Pickering emulsion method capable of simply preparing the graphene/porous carbon composite material.
The technical scheme of the invention is as follows:
the preparation method for preparing the graphene/porous carbon material by the ionic liquid based Pickering emulsion method comprises the following steps:
(1) at room temperature, according to the volume ratio of 2: 1-8: 1, ultrasonically mixing water and ionic liquid to prepare water/ionic liquid microemulsion;
(2) adding graphene oxide into the water/ionic liquid microemulsion to form Pickering emulsion by ultrasonic treatment, wherein the concentration of the graphene oxide in the Pickering emulsion is 2 mg/mL-8 mg/mL;
(3) dispersing a carbon source in the Pickering emulsion, wherein the mass ratio of the carbon source to the graphene oxide is 4: 1-10: 1;
(4) carrying out hydrothermal reaction on the Pickering emulsion obtained in the step (3) for 12-24 hours at the temperature of 160-200 ℃ to obtain a composite material precursor; and (3) sequentially carrying out freeze drying overnight, high-temperature carbonization, acid washing and drying overnight at 80 ℃ on the composite material precursor to obtain the graphene/porous carbon material.
And the high-temperature carbonization is carried out for 2 to 5 hours at the high temperature of between 800 and 1000 ℃ in the inert atmosphere of argon or helium.
The ionic liquid is 1-butyl-3-methylimidazolium hexafluorophosphate ([ BMIm)]PF6) 1-hexyl-3-methylimidazolium hexafluorophosphate ([ HMim ]]PF6) 1-octyl-3-butylimidazolium hexafluorophosphate ([ OMIm)]PF6) 1-butyl-3-methylimidazolium ferric chloride ([ BMIm)][FeCl4]) 1-butyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt ([ BMIm)][Tf2N]) 1-hexyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt ([ HMim ]][Tf2N]) 1-octyl-3-butylimidazole bistrifluoromethanesulfonylimide salt ([ OMIm)][Tf2N]) 1-acetoxy-3-methylimidazolium hexafluorophosphate ([ EAMIm]PF6) 1-allyl-3-methylimidazolium hexafluorophosphate ([ AMIm]PF6) One or more than two of the components are mixed.
The carbon material is one or more of glucose, fructose, galactose, lactose, sucrose, maltose, starch, chitosan and cyclodextrin.
The graphene oxide is a suspension of 10 mg/mL-20 mg/mL.
The acid washing is one of 1mol/L hydrochloric acid, nitric acid and sulfuric acid.
The graphene/porous carbon material may be used in an energy storage device, wherein the energy storage device is a capacitor, a supercapacitor, or a rechargeable battery.
The invention has the beneficial effects that: the graphene/porous carbon nano composite material is prepared by taking graphene oxide as a surfactant and adopting an ionic liquid-based Pickering emulsion method. The electrostatic interaction between the negative charges on the surface of the graphene oxide and the cations in the ionic liquid promotes the formation of the pickering emulsion. After the graphene oxide layer is stabilized by the ionic liquid, the dissolved carbon material is polymerized on the other side of the graphene oxide nanosheet layer. The stability of the ionic liquid inhibits the agglomeration of the graphene oxide, and a two-dimensional nanosheet structure is obtained. The prepared composite material is used as an electrode of an energy storage device.
Drawings
Fig. 1 is a scanning electron microscope image of the graphene/porous carbon material in example 1 of the present invention;
fig. 2 is a constant current charge and discharge curve of the graphene/porous carbon material in example 1 of the present invention.
Detailed Description
Specific examples of the production method of the present invention are given below. These examples are only intended to illustrate the preparation process of the present invention in detail and do not limit the scope of protection of the claims of the present application.
Example 1
(1) And preparing the graphene oxide by adopting an improved Hummers method.
(2) To 2.5mL of deionized water was added 1.0mL of ionic liquid [ BMIm ]][FeCl4]And carrying out ultrasonic treatment for 2h to form the ionic liquid microemulsion.
(3) 35mg of graphene oxide was dissolved in 2.5mL of deionized water and dispersed to form a 14.0mg/mL graphene oxide suspension.
(4) And adding 2.5mL of graphene oxide suspension into the ionic liquid microemulsion, and carrying out ultrasonic treatment for 3h to form a Pickering emulsion.
(5) 1.0g of sucrose was dispersed in the pickering emulsion and sonicated for 1h at room temperature.
(6) The mixture was charged into a 25ml TFE lined autoclave and reacted at 180 ℃ for 20 hours.
(7) After the hydrothermal reaction, the resulting composite material precursor was washed with ethanol and deionized water and freeze-dried overnight.
(8) Mixing the obtained powder with solid KOH according to the mass ratio of 3:1, and then treating for 4 hours in a tubular furnace at the temperature of 800 ℃ and Ar gas, wherein the heating rate is 5 ℃/min.
(9) The composite material synthesized was ultrasonically mixed with 1M aqueous HCl for 1h, followed by filtration of the black powder suspension, rinsing with ultra pure water until the pH of the solution reached 7, and finally drying at 80 ℃ overnight.
Example 2
(1) And preparing the graphene oxide by adopting an improved Hummers method.
(2) Adding 1.5mL of ionic liquid into 4mL of deionized waterBody [ BMIm]PF6And carrying out ultrasonic treatment for 2h to form the ionic liquid microemulsion.
(3) 70mg of graphene oxide is dissolved in 4mL of deionized water and dispersed into 17.5mg/mL of graphene oxide suspension.
(4) And adding 2.5mL of graphene oxide suspension into the ionic liquid microemulsion, and carrying out ultrasonic treatment for 3h to form a Pickering emulsion.
(5) 1.5g of glucose was dispersed in the pickering emulsion and sonicated for 1h at room temperature.
(6) The mixture was charged to a 25ml TFE lined autoclave and reacted at 160 ℃ for 16 hours.
(7) After the hydrothermal reaction, the resulting composite material precursor was washed with ethanol and deionized water and freeze-dried overnight.
(8) Mixing the obtained powder with solid KOH according to the mass ratio of 3:1, and then treating for 3h in a tubular furnace at 850 ℃ and Ar gas, wherein the heating rate is 5 ℃/min.
(9) The composite material synthesized was ultrasonically mixed with 1M aqueous HCl for 1h, followed by filtration of the black powder suspension, rinsing with ultra pure water until the pH of the solution reached 7, and finally drying at 80 ℃ overnight.
Example 3
(1) And preparing the graphene oxide by adopting an improved Hummers method.
(2) To 6mL of deionized water was added 2.0mL of ionic liquid [ HMIm][Tf2N]And carrying out ultrasonic treatment for 2h to form the ionic liquid microemulsion.
(3) 70mg of graphene oxide is dissolved in 7mL of deionized water and dispersed into a 10mg/mL graphene oxide suspension.
(4) And adding 2.5mL of graphene oxide suspension into the ionic liquid microemulsion, and carrying out ultrasonic treatment for 3h to form a Pickering emulsion.
(5) 1.0g galactose was dispersed in the pickering emulsion described above and sonicated for 1h at room temperature.
(6) The mixture was charged to a 25ml TFE lined autoclave and reacted at 190 ℃ for 22 hours.
(7) After the hydrothermal reaction, the resulting composite material precursor was washed with ethanol and deionized water and freeze-dried overnight.
(8) Mixing the obtained powder with solid KOH according to the mass ratio of 3:1, and then treating for 2 hours in a tubular furnace at 900 ℃ and Ar gas, wherein the heating rate is 5 ℃/min.
(9) The composite material synthesized was ultrasonically mixed with 1M aqueous HCl for 1h, followed by filtration of the black powder suspension, rinsing with ultra pure water until the pH of the solution reached 7, and finally drying at 80 ℃ overnight.
Claims (6)
1. A preparation method for preparing graphene/porous carbon material by an ionic liquid-based Pickering emulsion method is characterized by comprising the following steps:
(1) at room temperature, according to the volume ratio of 2: 1-8: 1, ultrasonically mixing water and ionic liquid to prepare water/ionic liquid microemulsion;
the ionic liquid is one or the mixture of more than two of 1-butyl-3-methylimidazole hexafluorophosphate, 1-hexyl-3-methylimidazole hexafluorophosphate, 1-octyl-3-butylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole ferric chloride, 1-butyl-3-methylimidazole bistrifluoromethane sulfimide salt, 1-hexyl-3-methylimidazole bistrifluoromethane sulfimide salt, 1-octyl-3-butylimidazole bistrifluoromethane sulfimide salt, 1-ethyl acetate-3-methylimidazole hexafluorophosphate and 1-allyl-3-methylimidazole hexafluorophosphate;
(2) adding graphene oxide into the water/ionic liquid microemulsion to form a Pickering emulsion by ultrasonic treatment, wherein the concentration of the graphene oxide in the Pickering emulsion is 2 mg/mL-8 mg/mL;
(3) dispersing a carbon source in the Pickering emulsion, wherein the mass ratio of the carbon source to the graphene oxide is 4: 1-10: 1;
(4) carrying out hydrothermal reaction on the Pickering emulsion obtained in the step (3) for 12-24 hours at the temperature of 160-200 ℃ to obtain a composite material precursor; and (3) sequentially carrying out freeze drying overnight, high-temperature carbonization, acid washing and drying overnight at 80 ℃ on the composite material precursor to obtain the graphene/porous carbon material.
2. The preparation method of claim 1, wherein the high-temperature carbonization in the step (4) is performed at 800-1000 ℃ for 2-5 h under an inert atmosphere of argon or helium; the acid washing is 1mol/L hydrochloric acid, nitric acid or sulfuric acid.
3. The method according to claim 1 or 2, wherein the carbon source is one or more selected from glucose, fructose, galactose, lactose, sucrose, maltose, starch, chitosan, and cyclodextrin.
4. The method according to claim 1 or 2, wherein the graphene oxide added in step (2) is a suspension of 10mg/mL to 20 mg/mL.
5. The method according to claim 3, wherein the graphene oxide added in the step (2) is a suspension of 10mg/mL to 20 mg/mL.
6. Use of the graphene/porous carbon material prepared by the preparation method according to any one of claims 1 to 5 in an energy storage device, wherein the energy storage device is a capacitor or a rechargeable battery.
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