CN112980184B - Preparation method of ionic liquid modified graphene composite polyaniline hollow microspheres - Google Patents
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Abstract
The invention discloses a preparation method of ionic liquid modified graphene composite polyaniline hollow microspheres, which comprises the following steps: (1) preparing reduced graphene oxide modified by ionic liquid; (2) preparing an oil-in-water Pickering emulsion; (3) preparing hollow microspheres; the preparation method disclosed by the invention is characterized in that a Pickering emulsion soft template method is utilized, reduced graphene oxide modified by ionic liquid is used as a particle emulsifier, aniline polymerization in an oil phase is initiated, and then the oil phase is removed to prepare the graphene/polyaniline composite hollow microspheres modified by the ionic liquid. The method has simple process and mild process.
Description
Technical Field
The invention relates to the technical field of graphene composite materials, in particular to a preparation method of ionic liquid modified graphene composite polyaniline hollow microspheres.
Background
Graphene, as a two-dimensional network structure formed by a single layer of carbon atoms, has unique physicochemical properties such as large specific surface area, stable mechanical properties, excellent electrochemical properties and the like, and has attracted extensive attention of researchers in various fields such as supercapacitors, sensing, catalysis, electromagnetic shielding and the like. However, due to the interlayer pi-pi effect, stacking and agglomeration are easily caused between graphene sheets, so that the specific surface area of the graphene sheets is greatly reduced, and the actual performance of the graphene material in application is influenced to a great extent. The polyaniline is a conductive high polymer material with unique doping/de-doping characteristics, has lower cost, good environmental stability, unique electrochemical activity and extremely high theoretical specific capacitance, and has wide application in the fields of electricity, optics, sensing, corrosion prevention and the like. The graphene and the polyaniline are compounded, so that the defects of single materials such as low specific capacitance of the graphene, low conductivity of the polyaniline, poor mechanical property and the like can be overcome, and the energy density of the super capacitor can be improved without sacrificing high power density and circulation stability by using the graphene/polyaniline composite material as the electrode material of the super capacitor and simultaneously utilizing two energy storage mechanisms of double electric layer capacitance and pseudo capacitance.
Although the graphene composite material has the excellent performances of graphene to a certain extent, a certain gap still exists between the graphene composite material and theoretical data in practical application, and therefore the three-dimensional hollow graphene material enters the sight of researchers. As a special three-dimensional hollow structure, the three-dimensional hollow microsphere has a small density and an exceptionally large specific surface area, and thus has received much attention from researchers. The preparation method of the graphene hollow microspheres is various, such as a self-assembly method, a layer-by-layer self-assembly method, a chemical vapor deposition technology, a hydrothermal method, a microfluid method, a Pickering emulsion method, a spray drying method and the like, wherein the Pickering emulsion soft template method has special advantages. The Pickering emulsion is an emulsion stabilized by solid particles instead of a micromolecular surfactant, and the GO nano-sheet has amphiphilicity due to the fact that the GO nano-sheet has a hydrophilic oxygen-containing group and a hydrophobic graphene cluster, so that GO can be directly used as the Pickering emulsifier to stabilize an oil-water interface, and then the graphene hollow microspheres are prepared. The preparation of the graphene hollow microspheres by the Pickering emulsion soft template method is simple and efficient, and has the unique advantages of regular microsphere structure and adjustable size. However, GO has structural drawbacks due to its large number of oxygen-containing groups, and is highly undesirable in conductivity, and rGO is too hydrophobic to stabilize Pickering emulsions well.
Disclosure of Invention
Aiming at the problems in the prior art, the applicant of the present invention provides a preparation method of an ionic liquid modified graphene composite polyaniline hollow microsphere. The preparation method disclosed by the invention is characterized in that a Pickering emulsion soft template method is utilized, reduced graphene oxide modified by ionic liquid is used as a particle emulsifier, aniline polymerization in an oil phase is initiated, and then the oil phase is removed to prepare the graphene/polyaniline composite hollow microspheres modified by the ionic liquid. The method has simple process and mild process.
The technical scheme of the invention is as follows:
a preparation method of ionic liquid modified graphene composite polyaniline hollow microspheres comprises the following steps:
(1) preparation of ionic liquid modified reduced graphene oxide
Dispersing graphene oxide in water to form graphene oxide aqueous dispersion, adding an ionic liquid and a catalyst, and performing modification reaction to obtain ionic liquid modified graphene oxide; then adding a reducing agent, carrying out reduction reaction, and carrying out suction filtration and washing to obtain reduced graphene oxide modified by ionic liquid, namely rGO-IL;
(4) preparation of oil-in-water Pickering emulsion
Dispersing the rGO-IL prepared in the step (1) in water to form an rGO-IL water dispersion liquid serving as a water phase, taking an organic solvent containing aniline monomers as an oil phase, mixing the rGO-IL water dispersion liquid and the oil phase, and emulsifying by using a homogenizer to obtain an oil-in-water Pickering emulsion;
(5) preparation of hollow microspheres
And (3) placing the emulsion prepared in the step (2) in an ice water bath for 20-60min, dropwise adding an ammonium persulfate hydrochloric acid solution which is subjected to ice bath, reacting for 20-28h in the ice water bath, washing and freeze-drying a product after reaction to obtain the hollow microsphere, namely rGO-IL/PANI HS.
In the step (1), the modification reaction conditions are as follows: reacting for 20-28h at 75-85 ℃; the conditions of the reduction reaction are as follows: reacting for 6-10h at 85-95 ℃.
In the step (1), the ionic liquid is one or more of 1- (3-aminopropyl) -3-methylimidazole bromide, 1-aminopropyl-3-methylimidazole chloride, 1-aminoethyl-3-methylimidazole bromide and 1-aminopropyl-3-methylimidazole nitrate; the catalyst is one or more of KOH, NaOH, triethylamine, ethylenediamine, triethanolamine and ethanolamine; the reducing agent is one or more of hydrazine hydrate, sodium borohydride and sodium bisulfite.
In the step (1), the concentration of the graphene oxide aqueous dispersion is 0.3-0.5 mg/mL; the mass ratio of the ionic liquid to the graphene oxide is 1:1-6: 1; the mass ratio of the catalyst to the graphene oxide is 1.5:1-2.5:1, and the mass ratio of the reducing agent to the graphene oxide is 1:1-1: 2.
In the step (2), the concentration of the rGO-IL in the rGO-IL water dispersion liquid is 1-5 mg/mL; the organic solvent is one or more of toluene, benzene, ethyl acetate, anisole acetate, xylene and trimethylbenzene; the aniline content in the oil phase is 2-10 vol%.
In the step (2), the volume ratio of the oil phase to the water phase is 1:1-1:5, the rotation speed of a homogenizer is 8000-30000rpm, and the emulsifying time is 1-3 min.
In the step (3), the concentration of a hydrochloric acid solution in an ammonium persulfate hydrochloric acid solution is 1-3mol/L, and the concentration of ammonium persulfate is 0.2-1 mg/mL; the molar ratio of ammonium persulfate to aniline monomer is 1:1-1: 3.
The beneficial technical effects of the invention are as follows:
the emulsion modified by the ionic liquid and stabilized by the reduced graphene oxide belongs to Pickering emulsion, and has the advantages of high stability, good uniformity, adjustable emulsion droplet size and the like. The ionic liquid has a wider electrochemical window, good ionic conductivity and designability, so that the ionic liquid has research and application values in various fields such as functional materials, energy sources, environment and the like.
The ionic liquid improves the hydrophilicity and hydrophobicity of the reduced graphene oxide, so that an oil-water interface can be better stabilized, the wettability of a hollow microsphere structure to an electrolyte is optimized, and more importantly, the high conductivity of the reduced graphene oxide is not influenced.
The hollow microsphere structure provides a high-conductivity network for electron transmission, and compared with the traditional two-dimensional structure material, the hollow microsphere structure has obviously improved electrochemical performance, so the hollow microsphere structure has obvious application prospect in the fields of super capacitors, electrochemical sensing and the like.
The invention adopts a Pickering emulsion method to prepare rGO-IL/PANI hollow microspheres, the method is simple and efficient, the reaction conditions are mild and safe, the raw material sources are easy to obtain, the cost is low, the finished product structure is regular and the size is controllable, and the electrode material is a super capacitor electrode material with excellent performance.
Drawings
FIG. 1 is a schematic flow chart of the preparation method of the present invention.
FIG. 2 is the GCD curve (a) and specific capacitance (b) of the rGO-IL/PANI HS obtained in example 3 versus the rGO/PANI HS obtained in comparative example 1 at a current density of 1A/g.
Fig. 3 is contact angle, Zeta potential and impedance data for reduced graphene oxide of example 3 and comparative example 1.
FIG. 4 is a photomicrograph and particle size statistics of emulsions stabilized with reduced graphene oxide of example 3 and comparative example 1.
FIG. 5 shows the Raman spectrum and the infrared spectrum of the product obtained in each step of example 3.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1:
a preparation method of ionic liquid modified graphene composite polyaniline hollow microspheres comprises the following steps:
(1) preparation of ionic liquid modified reduced graphene oxide
Dispersing 90mg of graphene oxide in 300mL of water to form 0.3mg/mL of graphene oxide aqueous dispersion, adding 540mg of ionic liquid 1-aminopropyl-3-methylimidazolium chloride and 225/135/180mg of catalyst NaOH, and carrying out modification reaction at 85 ℃ for 20h to obtain ionic liquid modified graphene oxide; then adding 90mg of reducing agent sodium borohydride, reacting for 6 hours at 95 ℃, and performing suction filtration and washing to obtain reduced graphene oxide modified by ionic liquid, namely rGO-IL;
(2) preparation of oil-in-water Pickering emulsion
Dispersing the rGO-IL prepared in the step (1) in water to form 1mg/mL rGO-IL water dispersion serving as a water phase, taking benzene containing 2 vol% of aniline monomer as an oil phase, mixing the rGO-IL water dispersion and the benzene containing 2 vol% of aniline monomer according to the oil-water ratio of 1:1, and emulsifying the mixture for 3min at the rotation speed of 8000rpm by using a homogenizer to obtain an oil-in-water Pickering emulsion;
(3) preparation of hollow microspheres
And (3) placing the emulsion prepared in the step (2) and 0.2mg/mL ammonium persulfate hydrochloric acid solution (the concentration of the hydrochloric acid solution is 2mol/L) in an ice-water bath, after ice-bathing for 20min, dropwise adding the ammonium persulfate hydrochloric acid solution into the emulsion according to the molar ratio of ammonium persulfate to aniline monomer of 1:2, reacting in the ice-water bath for 20h, washing and freeze-drying a product after reaction, and thus obtaining the hollow microsphere, namely rGO-IL/PANI HS.
Example 2:
a preparation method of ionic liquid modified graphene composite polyaniline hollow microspheres comprises the following steps:
(1) preparation of ionic liquid modified reduced graphene oxide
Dispersing 90mg of graphene oxide in 225mL of water to form 0.4mg/mL of graphene oxide aqueous dispersion, adding 90mg of ionic liquid 1-aminoethyl-3-methylimidazolium bromide and 135mg of catalyst triethylamine, and performing modification reaction at 75 ℃ for 28h to obtain ionic liquid modified graphene oxide; then adding 120mg of reducing agent sodium bisulfite, reacting for 10h at 85 ℃, and performing suction filtration and washing to obtain reduced graphene oxide modified by ionic liquid, namely rGO-IL;
(2) preparation of oil-in-water Pickering emulsion
Dispersing the rGO-IL prepared in the step (1) in water to form a 5mg/mL rGO-IL water dispersion liquid as a water phase, taking ethyl acetate containing 10 vol% of aniline monomer as an oil phase, mixing the two according to the oil-water ratio of 1:5, and emulsifying for 1min at the rotating speed of 30000rpm by using a homogenizer to obtain an oil-in-water Pickering emulsion;
(3) preparation of hollow microspheres
And (3) placing the emulsion prepared in the step (2) and 1mg/mL ammonium persulfate hydrochloric acid solution (the concentration of the hydrochloric acid solution is 3mol/L) in an ice-water bath, after ice-bathing for 60min, dropwise adding the ammonium persulfate hydrochloric acid solution into the emulsion according to the molar ratio of ammonium persulfate to aniline monomer of 1:3, reacting in the ice-water bath for 28h, washing and freeze-drying a product after reaction, and thus obtaining the hollow microsphere, namely rGO-IL/PANI HS.
Example 3:
a preparation method of ionic liquid modified graphene composite polyaniline hollow microspheres comprises the following steps:
(1) preparation of ionic liquid modified reduced graphene oxide
Dispersing 90mg of graphene oxide in 180mL of water to form 0.5mg/mL of graphene oxide aqueous dispersion, adding 360mg of ionic liquid 1- (3-aminopropyl) -3-methylimidazolium bromide and 180mg of catalyst KOH, and carrying out modification reaction at 80 ℃ for 24h to obtain ionic liquid modified graphene oxide; then adding 180mg of reducing agent hydrazine hydrate, reacting for 8 hours at 90 ℃, and obtaining reduced graphene oxide modified by ionic liquid, namely rGO-IL, after suction filtration and washing;
(2) preparation of oil-in-water Pickering emulsion
Dispersing the rGO-IL prepared in the step (1) in water to form a 3mg/mL rGO-IL water dispersion liquid as a water phase, taking toluene containing 8 vol% of aniline monomer as an oil phase, mixing the rGO-IL water dispersion liquid and the toluene according to the oil-water ratio of 1:4, and emulsifying for 2min at the rotation speed of 20000rpm by using a homogenizer to obtain an oil-in-water Pickering emulsion;
(3) preparation of hollow microspheres
And (3) placing the emulsion prepared in the step (2) and 0.5mg/mL ammonium persulfate hydrochloric acid solution (the concentration of the hydrochloric acid solution is 1mol/L) in an ice-water bath, after ice-bathing for 30min, dropwise adding the ammonium persulfate hydrochloric acid solution into the emulsion according to the molar ratio of ammonium persulfate to aniline monomer of 1:1, reacting in the ice-water bath for 24h, washing and freeze-drying a product after reaction, and obtaining the hollow microsphere, namely rGO-IL/PANI HS. The Raman spectrum and the infrared spectrum of the obtained material are shown in figure 5, and the figure shows that the rGO-IL/PANI composite material is successfully synthesized.
Comparative example 1
Reduced graphene oxide/polyaniline hollow microspheres (rGO/PANI HS)
(1) Preparing reduced graphene oxide: dispersing 90mg of graphene oxide in 180mL of water to form 0.5mg/mL of graphene oxide aqueous dispersion, adding 180mg of hydrazine hydrate, reacting at 90 ℃ for 8h, and performing suction filtration and washing to obtain reduced graphene oxide (rGO).
(2) Preparation of rGO stable emulsion: dispersing the prepared rGO in water to form 3mg/mL rGO water dispersion serving as a water phase, taking toluene containing 8 vol% of aniline monomer as an oil phase, mixing the water phase and the toluene according to the oil-water ratio of 1:4, and emulsifying for 2min at the rotation speed of 20000rpm by using a homogenizer to obtain an oil-in-water Pickering emulsion;
(3) preparation of rGO/PANI hollow microspheres: placing the emulsion with the stable rGO and 0.5mg/mL ammonium persulfate hydrochloric acid solution (the concentration of the hydrochloric acid solution is 1mol/L) in an ice water bath for 30min, dropwise adding the ammonium persulfate hydrochloric acid solution into the emulsion according to the molar ratio of ammonium persulfate to aniline monomer of 1:1, reacting in the ice water bath for 24h, washing and freeze-drying a product after reaction to obtain the rGO/PANI HS.
Test example:
mixing the microspheres obtained in the example 3 and the comparative example 1 with acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1, and adding a proper amount of N-methyl-2-pyrrolidone serving as a solvent to prepare uniform slurry; and coating a proper amount of slurry on the cleaned and dried carbon cloth, and performing vacuum drying at 120 ℃ for 2 hours to obtain the working electrode. At 1M H2SO4The aqueous solution is used as electrolyte, constant current charge and discharge test is carried out under the current density of 0-0.8V and 1A/g, and the specific capacitance of the material is calculated. The results are shown in FIG. 2; from FIG. 2, it can be seen that the specific capacitance of comparative example 1 (i.e., rGO/PANI HS) is only 278F/g, while the specific capacitance of example 3 (i.e., rGO-IL/PANI HS) reaches 441F/g, which is an improvement of nearly 60% over the comparative example.
Meanwhile, the water contact angle, the Zeta potential and the impedance of the materials prepared in the first step of the embodiment 3 and the comparative example 1 are tested, and the results are shown in figure 3, the modification of the ionic liquid effectively improves the water contact angle (115-44 ℃) of the reduced graphene oxide, reduces the impedance (35.96-19.32 omega), effectively improves the conductivity, and the change of the Zeta potential laterally proves that the rGO-IL is successfully prepared.
The photomicrographs of the emulsions from example 3 and comparative example 1 from the second step are shown in FIG. 4, where the modification of the ionic liquid effectively improved the emulsion properties, and the rGO-IL stabilized emulsions were more uniform and had a narrower particle size distribution than rGO.
Claims (9)
1. A preparation method of ionic liquid modified graphene composite polyaniline hollow microspheres is characterized by comprising the following steps:
(1) preparation of ionic liquid modified reduced graphene oxide
Dispersing graphene oxide in water to form graphene oxide aqueous dispersion, adding an ionic liquid and a catalyst, and performing modification reaction to obtain ionic liquid modified graphene oxide; then adding a reducing agent, carrying out reduction reaction, and carrying out suction filtration and washing to obtain reduced graphene oxide modified by ionic liquid, namely rGO-IL;
the ionic liquid is one or more of 1- (3-aminopropyl) -3-methylimidazole bromide, 1-aminopropyl-3-methylimidazole chloride, 1-aminoethyl-3-methylimidazole bromide and 1-aminopropyl-3-methylimidazole nitrate;
the catalyst is one or more of KOH, NaOH, triethylamine, ethylenediamine, triethanolamine and ethanolamine;
the mass ratio of the ionic liquid to the graphene oxide is 1:1-6: 1; the mass ratio of the catalyst to the graphene oxide is 1.5:1-2.5: 1;
(2) preparation of oil-in-water Pickering emulsion
Dispersing the rGO-IL prepared in the step (1) in water to form an rGO-IL water dispersion liquid serving as a water phase, taking an organic solvent containing aniline monomers as an oil phase, mixing the rGO-IL water dispersion liquid and the oil phase, and emulsifying by using a homogenizer to obtain an oil-in-water Pickering emulsion;
(3) preparation of hollow microspheres
And (3) placing the emulsion prepared in the step (2) in an ice water bath for 20-60min, dropwise adding an ammonium persulfate hydrochloric acid solution which is subjected to ice bath, reacting for 20-28h in the ice water bath, washing and freeze-drying a product after reaction to obtain the hollow microsphere, namely rGO-IL/PANI HS.
2. The method according to claim 1, wherein in the step (1), the modification reaction conditions are: reacting for 20-28h at 75-85 ℃.
3. The production method according to claim 1, wherein in the step (1), the conditions of the reduction reaction are: reacting for 6-10h at 85-95 ℃.
4. The method according to claim 1, wherein in the step (1), the reducing agent is one or more of hydrazine hydrate, sodium borohydride and sodium bisulfite.
5. The preparation method according to claim 1, wherein in the step (1), the concentration of the graphene oxide aqueous dispersion is 0.3-0.5 mg/mL; the mass ratio of the reducing agent to the graphene oxide is 1:1-1: 2.
6. The method of claim 1, wherein in step (2), the concentration of rGO-IL in the aqueous rGO-IL dispersion is 1-5 mg/mL.
7. The preparation method according to claim 1, wherein in the step (2), the organic solvent is one or more of toluene, benzene, ethyl acetate, anisole acetate, xylene, and trimethylbenzene; the aniline content in the oil phase is 2-10 vol%.
8. The preparation method according to claim 1, wherein in the step (2), the volume ratio of the water phase to the oil phase is 1:1-1:5, the rotation speed of the homogenizer is 8000-30000rpm, and the emulsification time is 1-3 min.
9. The preparation method according to claim 1, wherein in the step (3), the concentration of the hydrochloric acid solution in the ammonium persulfate hydrochloric acid solution is 1-3mol/L, and the concentration of the ammonium persulfate is 0.2-1 mg/mL; the molar ratio of ammonium persulfate to aniline monomer is 1:1-1: 3.
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| CN101985354A (en) * | 2010-09-21 | 2011-03-16 | 中国科学院长春应用化学研究所 | Method for preparing ionic liquid functionalized graphene material |
| CN105131596A (en) * | 2015-09-14 | 2015-12-09 | 江南大学 | Preparation method of graphene/polyaniline composite hollow microspheres |
| CN105206430A (en) * | 2015-09-29 | 2015-12-30 | 南京绿索电子科技有限公司 | Polyaniline nanometer tube array/graphene composite material electrode and manufacturing method and application thereof |
| CN105601914A (en) * | 2015-12-29 | 2016-05-25 | 上海第二工业大学 | Preparing method of ionic liquid functionalized graphene/conductive polyaniline nanowire composition material |
| CN106433121A (en) * | 2016-09-09 | 2017-02-22 | 江南大学 | Preparation method of polyaniline-graphene hollow microspheres |
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| CN101985354A (en) * | 2010-09-21 | 2011-03-16 | 中国科学院长春应用化学研究所 | Method for preparing ionic liquid functionalized graphene material |
| CN105131596A (en) * | 2015-09-14 | 2015-12-09 | 江南大学 | Preparation method of graphene/polyaniline composite hollow microspheres |
| CN105206430A (en) * | 2015-09-29 | 2015-12-30 | 南京绿索电子科技有限公司 | Polyaniline nanometer tube array/graphene composite material electrode and manufacturing method and application thereof |
| CN105601914A (en) * | 2015-12-29 | 2016-05-25 | 上海第二工业大学 | Preparing method of ionic liquid functionalized graphene/conductive polyaniline nanowire composition material |
| CN106433121A (en) * | 2016-09-09 | 2017-02-22 | 江南大学 | Preparation method of polyaniline-graphene hollow microspheres |
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