CN103466604A - Preparation method of porous graphene - Google Patents
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Abstract
The invention discloses a preparation method of porous graphene. The method comprises the steps of: (1) stripping graphite oxide in a water/ethanol mixed solution with pH of 9-10, adding a chemical foaming agent and mixing them uniformly, carrying out filtering and drying to obtain a solid mixture; (2) placing the mixture in a reducing atmosphere, and performing heating expansion reduction to obtain expanded graphene; (3) blending the expanded graphene with strong base, and conducting high temperature activation; and (4) washing the product with hydrochloric acid and deionized water, and performing drying so as to obtain porous grapheme. The porous graphene prepared by the method involved in the invention has a specific surface area up to 2075m<2>/g, a pore volume up to 1.8cm<3>/g, and an average pore size of 1-7nm. As a supercapacitor electrode material, the specific capacitance can reach 155F/g under a current density of 1Ag<-1>. As a porous graphene electrode, the specific capacitance can reach 84.4% along with the increase of current density from 0.2Ag<-1> to 20Ag<-1>. The porous graphene has high specific capacitance and cycle stability. The preparation method disclosed in the invention has the advantages of simple process, low cost, and easy scale production.
Description
Technical field
The present invention relates to the grapheme material technical field, specifically, is the preparation method of the porous graphene of the expanded and surface active of a kind of volume.
Background technology
Graphene is as the Two-dimensional Carbon atomic crystal, has high specific surface area, excellent electron conductivity and good mechanical property, is the study hotspot in the fields such as chemistry, material, physics in recent years.But the graphene film interlayer is irreversible agglomeration because van der Waals interaction is prone to, its effective ratio area is reduced greatly, thereby limited its range of application.
In order to enlarge the Application Areas of Graphene, the emphasis of correlative study at present mainly is to adopt surface modification technology and activating technology to improve the effective ratio area of Graphene.Known report has: the people such as Kaner adopt DVD light technology for fast carving on to prepare specific surface area to reach 1520m
2the Graphene of/g [
science, Vol. 335,1326, (2012)].The people such as Murali carry out potassium hydroxide activation and have obtained specific surface area and reach 3100m by microwave being peeled off to graphite oxide
2the porous graphene of/g [
science, Vol. 332,1537, (2011)].Yet above-mentioned method of modifying requires highly to equipment, is not suitable for suitability for industrialized production.
At present, the industrial method for preparing high-ratio surface Activated Graphite alkene is chemical activation method substantially.For example, Chinese patent literature CN102897751A discloses " a kind of method of utilizing Graphene and highly basic to be dry mixed and to be activated after compression moulding ".Chinese patent literature CN102849734A discloses " take transition metal or transistion metal compound prepare the method for porous graphene for activator ".But, the related technology of these methods is not high to the extent of exfoliation of Graphene, the raising of its specific surface area is mainly that the loss by carbon in reactivation process realizes, destruction to the Graphene regularity is larger, do not give full play to the advantage of Graphene two-dimensional nano sheet layer material, affected the overall performance of Graphene.
Summary of the invention
The object of the invention is to solve the above problems, a kind of preparation method of porous graphene is provided, its technique is simple, with low cost, be easy to large-scale production; It is large that the porous graphene prepared with the method has specific surface area, and the characteristics such as pore structure prosperity and chemical property excellence, can show advantage in fields such as electrochemical energy storage, catalysis and absorption.
For achieving the above object, the technical scheme that the present invention takes is.
A kind of preparation method of porous graphene, is characterized in that, comprises the following steps:
(1) prepare the solid mixture of graphene oxide and chemical foaming agent
Graphite oxide is joined in the water/alcohol mixed solution of pH=9～10 (volume ratio of water and ethanol is 2:1), magnetic agitation 48～72 hours, ultrasonic dispersion is 0.5～2 hour again, forms the graphene oxide colloidal dispersion, and the concentration of controlling graphene oxide is 0.5～5mg/mL; Then add chemical foaming agent, stir 2～12 hours, remove by filter unnecessary chemical foaming agent, obtain the solid mixture of graphene oxide and chemical foaming agent after drying;
(2) prepare expanded graphite alkene
The graphene oxide that step (1) is obtained and the solid mixture of chemical foaming agent are placed in tube furnace and carry out expanded reduction at reducing atmosphere: from room temperature, rise to gradually 500 ℃, controlling temperature rise rate is 2～10 ℃/minute, and be incubated 15～30 minutes respectively in the time of 200 ℃, in the time of 500 ℃, insulation is 1～2 hour, obtains expanded graphite alkene;
(3) prepare the activation products of Graphene and highly basic
The expanded graphite alkene that step (2) is obtained is immersed in strong base solution, and the mass ratio of controlling expanded graphite alkene and highly basic is 1: 4～10, fully stirs, and drying obtains the mixture of Graphene and highly basic; Described mixture is placed in to tube furnace, passes into rare gas element protected, be warming up to 700～1000 ℃, constant temperature activates 0.5～3 hour, obtains the activation products of Graphene and highly basic;
(4) prepare porous graphene
The Graphene that step (3) is obtained and the activation products of highly basic are washed till neutrality with hydrochloric acid and the deionized water of 0.5～2mol/L, obtain target product after drying: porous graphene.
Further, the described chemical foaming agent of step (1) is a kind of in Whitfield's ointment, bicarbonate of ammonia or Cellmic C 121.
Further, the mass ratio of the described graphene oxide of step (1) and chemical foaming agent is 1: 0.5～3.
Further, the mixed gas that the described reducing atmosphere of step (2) is hydrogen and rare gas element, wherein the volume ratio of hydrogen and rare gas element is 1: 1～8.
Further, described rare gas element is a kind of of argon gas or nitrogen.
Further, the described highly basic of step (3) is a kind of in potassium hydroxide or sodium hydroxide.
Further, the described rare gas element of step (3) is a kind of of argon gas or nitrogen.
Positively effect of the present invention is:
(1) the thermal reduction technology of chemical foaming and graphene oxide is combined, the small molecules whipping agent enters the graphene oxide sheet interlayer by hydrogen bond or neutralization of acid with base intercalation, improves the extent of exfoliation of graphene oxide lamella; The decomposes that is accompanied by whipping agent during the graphene oxide thermal reduction discharges gas, causes the graphene oxide volumetric expansion to form pore structure, effectively the high temperature reuniting effect of inhibited oxidation Graphene.
(2) the abundant pore structure of expanded graphite alkene is conducive to the dipping of strong base solution, thereby improves activation effect.The Graphene obtained by chemical foaming and high-temperature activation has large specific surface area and flourishing nano-pore structure, is conducive to the diffusion of electrolytic solution and the transmission of electric charge, thereby gives the chemical property of porous graphene excellence.
(3) method technique of the present invention is simple, cost is lower, be easy to large-scale production.
(4) porous graphene prepared by method of the present invention has a large amount of nanometer micropore (1～7nm), there is higher specific surface area, more be applicable to the migration of electrolyte ion, as the super capacitance electrode material application, can present higher ratio electric capacity and multiplying power property.
The accompanying drawing explanation
The preparation method's that Fig. 1 is a kind of porous graphene of the present invention process flow diagram.
The field emission scanning electron microscope photo that Fig. 2 is comparative example 1.
Fig. 3 is that comparative example 1 is at 1Ag
-1charging and discharging curve under current density.
The ratio electric capacity that Fig. 4 is comparative example 1-current density curve.
The field emission scanning electron microscope photo that Fig. 5 is comparative example 2.
Fig. 6 is that comparative example 2 is at 1Ag
-1charging and discharging curve under current density.
The ratio electric capacity that Fig. 7 is comparative example 2-current density curve.
The transmission electron microscope photo that Fig. 8 is embodiment 1.
The graph of pore diameter distribution that Fig. 9 is embodiment 1.
Figure 10 is that embodiment 1 is at 1Ag
-1charging and discharging curve under current density.
The ratio electric capacity that Figure 11 is embodiment 1-current density curve.
Embodiment
Provide the preparation method's of a kind of porous graphene of invention embodiment below in conjunction with accompanying drawing, 4 embodiment and 2 comparative examples are provided.But it should be pointed out that enforcement of the present invention is not limited to following embodiment.
comparative example 1(for the comparison with embodiment 1)
The preparation method of porous graphene comprises the following steps:
(1) the 0.5g graphite oxide is joined in the water/alcohol mixed solution of 125mLpH=9～10 (volume ratio of water and ethanol is 2:1), magnetic agitation 72 hours, more ultrasonic dispersion 40 minutes, form the graphene oxide colloidal dispersion; Obtain the graphene oxide solids after drying;
(2) in the reducing atmosphere of hydrogen/argon gas (volume ratio is 1: 4), the graphene oxide solids that step (1) is obtained is placed in tube furnace and carries out expanded reduction: from room temperature, rise to gradually 500 ℃, controlling temperature rise rate is 5 ℃/minute, and be incubated respectively 15 minutes and 1 hour when 200 ℃ and 500 ℃, obtain Graphene;
(3) Graphene step (2) obtained is immersed in potassium hydroxide solution, and the mass ratio of controlling Graphene and potassium hydroxide is 1: 6, fully stirs, and drying obtains the mixture of Graphene and potassium hydroxide; The mixture of described Graphene and potassium hydroxide is placed in to tube furnace, passes into argon gas protected, be warming up to 800 ℃, constant temperature activates 1 hour, obtains the activation products of Graphene and potassium hydroxide;
(4) activation products that step (3) obtained are washed till neutrality with hydrochloric acid and the deionized water of the 1mol/L boiled, obtain the porous graphite ene product after drying.
the product analysis of comparative example 1:
Field emission scanning electron microscope (FESEM) photo shows (referring to Fig. 2), and the Graphene of comparative example 1 preparation presents a kind of form of comparatively assembling, and does not fully peel off between layers.Its specific surface area reaches 1372m
2/ g, pore volume is 1.3cm
3/ g.
Charging and discharging curve (referring to Fig. 3) shows, the porous graphene prepared by the method for comparative example 1 as electrode material for super capacitor at 1Ag
-1under current density, than electric capacity, reach 129F/g.Than electric capacity-current density curve (referring to Fig. 4), show, the porous graphene electrode prepared by the method for comparative example 1 along with current density from 0.2Ag
-1increase to 20Ag
-1than electric capacity conservation rate, be 80.6 %.
comparative example 2(continuing on for the comparison with embodiment 1)
The preparation method of porous graphene comprises the following steps:
(1) the 0.5g graphite oxide is joined in the water/alcohol mixed solution of 125mLpH=9～10 (volume ratio of water and ethanol is 2:1), magnetic agitation 72 hours, more ultrasonic dispersion 40 minutes, form the graphene oxide colloidal dispersion; Then add the 0.5g Whitfield's ointment, stir 6 hours, remove by filter unnecessary Whitfield's ointment, obtain graphene oxide and salicylic solid mixture after drying;
(2) in the reducing atmosphere of hydrogen/argon gas (volume ratio is 1: 4), the graphene oxide that step (1) is obtained and salicylic solid mixture are placed in tube furnace and carry out expanded reduction: from room temperature, rise to gradually 500 ℃, controlling temperature rise rate is 5 ℃/minute, and be incubated respectively 15 minutes and 1 hour when 200 ℃ and 500 ℃, obtain expanded graphite alkene.
the product analysis of comparative example 2:
Field emission scanning electron microscope (FESEM) photo shows (referring to Fig. 5), and the Graphene of comparative example 2 preparations presents a kind of fluffy structure, has between layers larger space.Its specific surface area reaches 1023m
2/ g, pore volume is 0.89cm
3/ g.
Charging and discharging curve (referring to Fig. 6) shows, the expanded graphite alkene prepared by the method for comparative example 2 as electrode material for super capacitor at 1Ag
-1under current density, than electric capacity, reach 91F/g.Than electric capacity-current density curve (referring to Fig. 7), show, the expanded graphite alkene electrode prepared by the method for comparative example 2 along with current density from 0.2Ag
-1increase to 20Ag
-1than electric capacity conservation rate, be 79.4%.
A kind of preparation method of porous graphene comprises the following steps:
(1) the 0.5g graphite oxide is joined in the water/alcohol mixed solution of 125mLpH=9～10 (volume ratio of water and ethanol is 2:1), magnetic agitation 72 hours, more ultrasonic dispersion 40 minutes, form the graphene oxide colloidal dispersion; Then add the 0.5g Whitfield's ointment, stir 6 hours, remove by filter unnecessary Whitfield's ointment, obtain graphene oxide and salicylic solid mixture after drying;
(2) in the reducing atmosphere of hydrogen/argon gas (volume ratio is 1: 4), the graphene oxide that step (1) is obtained and salicylic solid mixture are placed in tube furnace and carry out expanded reduction: from room temperature, rise to gradually 500 ℃, controlling temperature rise rate is 5 ℃/minute, and be incubated 15 minutes respectively in the time of 200 ℃, in the time of 500 ℃, insulation is 1 hour, obtains expanded graphite alkene;
(3) expanded graphite alkene step (2) obtained is immersed in potassium hydroxide solution, and the mass ratio of controlling expanded graphite alkene and potassium hydroxide is 1: 6, fully stirs, and drying obtains the mixture of Graphene and potassium hydroxide; Described mixture is placed in to tube furnace, passes into argon gas protected, be warming up to 800 ℃, constant temperature activates 1 hour, obtains the activation products of Graphene and potassium hydroxide;
(4) Graphene step (3) obtained and the activation products of potassium hydroxide are washed till neutrality with hydrochloric acid and the deionized water of the 1mol/L boiled, obtain target product after drying: porous graphene.
the product analysis of embodiment 1:
Transmission electron microscope (HRTEM) photo shows (referring to Fig. 8), and the Graphene of embodiment 1 preparation presents a kind of vesicular structure, and its specific surface area reaches 2075m
2/ g, pore volume is 1.8cm
3/ g, mean pore size at 1～7nm(referring to Fig. 9).Such nano-pore structure is conducive to the diffusion of electrolytic solution, and the electrical property that improves Graphene is had to active effect.
Charging and discharging curve (referring to Figure 10) shows, with the porous graphene of embodiment 1 preparation as electrode material for super capacitor at 1Ag
-1under current density, than electric capacity, reach 155F/g, apparently higher than the ratio electric capacity of comparative example 1 and comparative example 2.Than electric capacity-current density curve (referring to Figure 11), show, with the porous graphene electrode of embodiment 1 preparation along with current density from 0.2Ag
-1increase to 20Ag
-1still reach 84.4 % than electric capacity conservation rate, obviously be better than the multiplying power property of comparative example 1 and comparative example 2 under equal conditions.
embodiment 2
A kind of preparation method of porous graphene comprises the following steps:
(1) the 0.1g graphite oxide is joined in the water/alcohol mixed solution of 200mLpH=9～10 (volume ratio of water and ethanol is 2:1), magnetic agitation 48 hours, more ultrasonic dispersion 1 hour, form the graphene oxide colloidal dispersion; Then add 0.3g bicarbonate of ammonia, stir 2 hours, remove by filter unnecessary bicarbonate of ammonia, obtain the solid mixture of graphene oxide and bicarbonate of ammonia after drying;
(2) in the reducing atmosphere of hydrogen/argon gas (volume ratio is 1: 8), the graphene oxide that step (1) is obtained and the solid mixture of bicarbonate of ammonia are placed in tube furnace and carry out expanded reduction: from room temperature, rise to gradually 500 ℃, controlling temperature rise rate is 10 ℃/minute, and be incubated 20 minutes respectively in the time of 200 ℃, in the time of 500 ℃, insulation is 2 hours, obtains expanded graphite alkene;
(3) expanded graphite alkene step (2) obtained is immersed in potassium hydroxide solution, and the mass ratio of controlling expanded graphite alkene and potassium hydroxide is 1: 10, fully stirs, and drying obtains the mixture of Graphene and potassium hydroxide; Described mixture is placed in to tube furnace, passes into argon gas protected, be warming up to 1000 ℃, constant temperature activates 1 hour, obtains the activation products of Graphene and potassium hydroxide;
(4) Graphene step (3) obtained and the activation products of potassium hydroxide are washed till neutrality with hydrochloric acid and the deionized water of 2mol/L, obtain target product after drying: porous graphene.
the product analysis of embodiment 2:
The porous graphene specific surface area that embodiment 2 obtains reaches 2297m
2/ g, pore volume is 2.0cm
3/ g.The porous graphene prepared by the method for embodiment 2 as electrode material for super capacitor at 1Ag
-1under current density, than electric capacity, reach 169F/g, current density is from 0.2Ag
-1increase to 20Ag
-1than electric capacity conservation rate, be 76.7%.
embodiment 3
A kind of preparation method of porous graphene comprises the following steps:
(1) the 0.5g graphite oxide is joined in the water/alcohol mixed solution of 100mLpH=9～10 (volume ratio of water and ethanol is 2:1), magnetic agitation 60 hours, more ultrasonic dispersion 2 hours, form the graphene oxide colloidal dispersion; Then add the 0.15g Cellmic C 121, stir 12 hours, remove by filter unnecessary Cellmic C 121, obtain the solid mixture of graphene oxide and Cellmic C 121 after drying;
(2) in the reducing atmosphere of hydrogen/nitrogen (volume ratio is 1: 1), the graphene oxide that step (1) is obtained and Cellmic C 121 solid mixture are placed in tube furnace and carry out expanded reduction: from room temperature, rise to gradually 500 ℃, controlling temperature rise rate is 2 ℃/minute, and be incubated 30 minutes respectively in the time of 200 ℃, in the time of 500 ℃, insulation is 1 hour, obtains expanded graphite alkene;
(3) expanded graphite alkene step (2) obtained is immersed in potassium hydroxide solution, and the mass ratio of controlling expanded graphite alkene and potassium hydroxide is 1: 4, fully stirs, and drying obtains the mixture of Graphene and potassium hydroxide; Described mixture is placed in to tube furnace, passes into argon gas protected, be warming up to 700 ℃, constant temperature activates 3 hours, obtains the activation products of Graphene and potassium hydroxide;
(4) Graphene step (3) obtained and the activation products of potassium hydroxide are washed till neutrality with hydrochloric acid and the deionized water of 0.5mol/L, obtain target product after drying: porous graphene.
the product analysis of embodiment 3:
The porous graphene specific surface area that embodiment 3 obtains reaches 1596m
2/ g, pore volume is 1.5cm
3/ g.The porous graphene prepared by the method for embodiment 3 as electrode material for super capacitor at 1Ag
-1under current density, than electric capacity, reach 128F/g, current density is from 0.2Ag
-1increase to 20Ag
-1than electric capacity conservation rate, be 82.8%.
embodiment 4
A kind of preparation method of porous graphene comprises the following steps:
(1) the 0.5g graphite oxide is joined in the water/alcohol mixed solution of 125mL pH=9～10 (volume ratio of water and ethanol is 2:1), magnetic agitation 48 hours, more ultrasonic dispersion 0.5 hour, form the graphene oxide colloidal dispersion; Then add the 1g Whitfield's ointment, stir 6 hours, remove by filter unnecessary Whitfield's ointment, obtain graphene oxide and salicylic solid mixture after drying;
(2) in the reducing atmosphere of hydrogen/argon gas (volume ratio is 1: 4), the graphene oxide that step (1) is obtained and salicylic solid mixture are placed in tube furnace and carry out expanded reduction: from room temperature, rise to gradually 500 ℃, controlling temperature rise rate is 5 ℃/minute, and be incubated 15 minutes respectively in the time of 200 ℃, in the time of 500 ℃, insulation is 2 hours, obtains expanded graphite alkene;
(3) expanded graphite alkene step (2) obtained is immersed in sodium hydroxide solution, and the mass ratio of controlling expanded graphite alkene and sodium hydroxide is 1: 6, fully stirs, and drying obtains the mixture of Graphene and sodium hydroxide; Described mixture is placed in to tube furnace, passes into nitrogen protected, be warming up to 900 ℃, constant temperature activates 0.5 hour, obtains the activation products of Graphene and sodium hydroxide;
(4) Graphene step (3) obtained and the activation products of sodium hydroxide are washed till neutrality with hydrochloric acid and the deionized water of 1mol/L, obtain target product after drying: porous graphene.
the product analysis of embodiment 4:
The porous graphene specific surface area that embodiment 4 obtains reaches 1882m
2/ g, pore volume is 1.7cm
3/ g.The porous graphene prepared by the method for embodiment 4 as electrode material for super capacitor at 1Ag
-1under current density, than electric capacity, reach 142F/g, current density is from 0.2Ag
-1increase to 20Ag
-1than electric capacity conservation rate, be 79.9%.
Claims (7)
1. the preparation method of a porous graphene, is characterized in that, comprises the following steps:
(1) prepare the solid mixture of graphene oxide and chemical foaming agent
Graphite oxide is joined in the water/alcohol mixed solution of pH=9～10, the volume ratio of water and ethanol is 2:1; Magnetic agitation 48～72 hours, more ultrasonic dispersion 0.5～2 hour, form the graphene oxide colloidal dispersion, and the concentration of controlling graphene oxide is 0.5～5mg/mL; Then add chemical foaming agent, stir 2～12 hours, remove by filter unnecessary chemical foaming agent, obtain the solid mixture of graphene oxide and chemical foaming agent after drying;
(2) prepare expanded graphite alkene
The graphene oxide that step (1) is obtained and the solid mixture of chemical foaming agent are placed in tube furnace and carry out expanded reduction at reducing atmosphere: from room temperature, rise to gradually 500 ℃, controlling temperature rise rate is 2～10 ℃/minute, and be incubated 15～30 minutes respectively in the time of 200 ℃, in the time of 500 ℃, insulation is 1～2 hour, obtains expanded graphite alkene;
(3) prepare the activation products of Graphene and highly basic
The expanded graphite alkene that step (2) is obtained is immersed in strong base solution, and the mass ratio of controlling expanded graphite alkene and highly basic is 1: 4～10, fully stirs, and drying obtains the mixture of Graphene and highly basic; Described mixture is placed in to tube furnace, passes into rare gas element protected, be warming up to 700～1000 ℃, constant temperature activates 0.5～3 hour, obtains the activation products of Graphene and highly basic;
(4) prepare porous graphene
The Graphene that step (3) is obtained and the activation products of highly basic are washed till neutrality with hydrochloric acid and the deionized water of 0.5～2mol/L, obtain target product after drying: porous graphene.
2. the preparation method of a kind of porous graphene according to claim 1, is characterized in that, the described chemical foaming agent of step (1) is a kind of in Whitfield's ointment, bicarbonate of ammonia or Cellmic C 121.
3. the preparation method of a kind of porous graphene according to claim 1 and 2, is characterized in that, the mass ratio of the described graphene oxide of step (1) and chemical foaming agent is 1: 0.5～3.
4. the preparation method of a kind of porous graphene according to claim 1, is characterized in that, the mixed gas that the described reducing atmosphere of step (2) is hydrogen and rare gas element, and wherein the volume ratio of hydrogen and rare gas element is 1: 1～8.
5. the preparation method of a kind of porous graphene according to claim 4, is characterized in that, described rare gas element is a kind of of argon gas or nitrogen.
6. the preparation method of a kind of porous graphene according to claim 1, is characterized in that, the described highly basic of step (3) is a kind of in potassium hydroxide or sodium hydroxide.
7. the preparation method of a kind of porous graphene according to claim 1, is characterized in that, the described rare gas element of step (3) is a kind of of argon gas or nitrogen.
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