CN104627993A - Preparation method of active porous graphene - Google Patents
Preparation method of active porous graphene Download PDFInfo
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- CN104627993A CN104627993A CN201510022170.4A CN201510022170A CN104627993A CN 104627993 A CN104627993 A CN 104627993A CN 201510022170 A CN201510022170 A CN 201510022170A CN 104627993 A CN104627993 A CN 104627993A
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Abstract
The invention relates to a preparation method of active porous graphene, which is characterized by comprising the following steps: preparing a solid mixture of graphene oxide and a chemical foaming agent; preparing expanded graphene, and preparing an activation product of graphene and strong alkali; preparing active microporous graphene; and finally, carrying out secondary pore forming to obtain the finished product. The finished product has higher tap density, and has properly proportional mesoporous structure and macroporous structure; and the pores provide higher specific area. The carbonization treatment technique is performed to greatly enhance the activity of the porous graphene. When the active porous graphene is used in a capacitor electrode material, the macroporous structure provides quick migration channels for the electrolyte, and the mesoporous structure has equivalent size to ions in the organic electrolyte and is beneficial to quick adsorption and desorption of the ions, so that the capacitor has favorable high-rate charge/discharge performance.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene, particularly relate to a kind of preparation method of active porous Graphene.
Background technology
Graphene is a kind of material of the individual layer sheet structure be made up of carbon atom.Graphene is almost completely transparent, only absorbs the light of 2.3%; Thermal conductivity up to 5300W/mK, higher than carbon nanotube and diamond; Electronic mobility under Graphene normal temperature is more than 15000cm
2/ Vs, exceedes CNT (carbon nano-tube) or silicon crystal; The resistivity of Graphene only has 10
-8Ω m, than copper or silver lower, be the material that world resistivity is minimum.Due to Graphene, to have the transparency good, and the advantages such as resistivity is little, and electron transfer rate is fast, can be used to manufacture transparent touch screen, tabula rasa and solar cell.
Graphene has huge theoretical specific surface area, physicochemical property are stablized, good structural stability can be kept under high working voltage and big current fast charging and discharging, simultaneously, Graphene also has excellent electroconductibility, can internal resistance be reduced, improve the cyclical stability of ultracapacitor, therefore prepare the grapheme material with suitable pore size distribution and be expected to become electrode material for super capacitor of new generation.
At present, the highly basic such as the method preparing high specific surface area porous Graphene adopts KO hour usually, NaO hour etch graphene oxide thus produce abundant pore structure.The preparation method of this Graphene that a kind of method disclosing process for preparing graphenes by chemical vapour deposition as the application number Chinese patent that is 200810113596.0 provides is easy to operate, simple and easy to do, can be used for scale operation; And the Graphene quality that this method prepares is better.But, graphene conductive poor-performing prepared by this technology, and activity is lower, thus limit its commercial applications in energy storage field.
Summary of the invention
Object of the present invention is exactly to solve the above-mentioned problems in the prior art, provides a kind of preparation method of active porous Graphene.
Object of the present invention is achieved through the following technical solutions:
The preparation method of active porous Graphene, wherein: first, prepares the solid mixture of graphene oxide and chemical foaming agent; Afterwards, expanded graphite alkene is prepared; Then, the activation products of Graphene and highly basic are prepared; Subsequently, active micropore Graphene is prepared; Finally, second time pore-creating obtains finished product.
The preparation method of above-mentioned active porous Graphene, wherein: the described solid mixture process preparing graphene oxide and chemical foaming agent is,
Step 1., in water graphite oxide being joined pH=9 to 10 and alcohol mixed solution;
2. step, stirs 1 to 10 hour, then ultrasonic disperse 0.5 to 2 hour, forms graphene oxide colloidal dispersion;
3. step, then adds chemical foaming agent, stirs 2 to 12 hours;
4. step, is crossed and is filtered unnecessary chemical foaming agent, obtain the solid mixture of graphene oxide and chemical foaming agent after drying.
Further, the preparation method of above-mentioned active porous Graphene, wherein: described water and the volume ratio of alcohol mixed solution are 2:1, described alr mode is magnetic agitation, and described chemical foaming agent is bicarbonate of ammonia.
Further, the preparation method of above-mentioned active porous Graphene, wherein: described expanded graphite alkene process of preparing is,
1. the solid mixture of the graphene oxide previously obtained and chemical foaming agent, is carried out expanded reduction at reducing atmosphere by step;
2. step, rises to 500 DEG C gradually from room temperature, and control temperature rise rate is 2 to 10 DEG C/min, and 200 DEG C time, is incubated 15 to 30 minutes respectively, is incubated 1 to 2 hour, obtains expanded graphite alkene 500 DEG C time.
Further, the preparation method of above-mentioned active porous Graphene, wherein: described to be expandedly reduced to, is placed in tube furnace by solid mixture, carries out in the reducing atmosphere of nitrogen.
Further, the preparation method of above-mentioned active porous Graphene, wherein: the described activation products process preparing Graphene and highly basic is, by expanded graphite alkene and the first activator mix, within 0.5 to 4 hour, carry out first time pore-creating 400 DEG C to 800 DEG C heating, obtain micropore Graphene.
Further, the preparation method of above-mentioned active porous Graphene, wherein: the first described activator is sodium hydroxide.
Further; the preparation method of above-mentioned active porous Graphene, wherein: described active micropore Graphene process of preparing is, under the condition of nitrogen protection gas; micropore Graphene is carried out charing process at 600-800 DEG C, obtains active micropore Graphene.
Further, the preparation method of above-mentioned active porous Graphene, wherein: described second time poration process is, carry out using nitration mixture process to micropore Graphene, with the second activator mix, at 600 DEG C to 1000 DEG C temperature, heat 1 to 6 hour, carry out second time pore-creating, obtain active porous Graphene.
Again further, micropore Graphene volume ratio wherein: described nitration mixture is treated to, is that the vitriol oil and the concentrated nitric acid of 3:1 carries out nitration mixture process by the preparation method of above-mentioned active porous Graphene; The second described activator is potassium hydroxide.
The advantage of technical solution of the present invention is mainly reflected in: central hole structure and the macroporous structure also while active porous Graphene of the present invention has higher tap density with proper ratio, this some holes provides higher specific surface area.Further, after charring process process, the activity of porous graphene is substantially increased.When this active porous Graphene is used for capacitor electrode material, macroporous structure is the passage that electrolytic solution provides fast transferring, simultaneously, central hole structure and organic electrolyte intermediate ion sizableness, be beneficial to quick adsorption and the desorption of ion, thus make electrical condenser have good high rate charge-discharge performance.Thus, space has been expanded in the technical progress for this area, and implementation result is good.
Accompanying drawing explanation
Object of the present invention, advantage and disadvantage, by for illustration and explanation for the non-limitative illustration passing through preferred embodiment below.These embodiments are only the prominent examples of application technical solution of the present invention, allly take equivalent replacement or equivalent transformation and the technical scheme that formed, all drop within the scope of protection of present invention.
Fig. 1 is the basic procedure schematic diagram of the preparation method of active porous Graphene.
Embodiment
The preparation method of active porous Graphene as shown in Figure 1, is characterized in that: first, prepares the solid mixture of graphene oxide and chemical foaming agent.Afterwards, expanded graphite alkene is prepared; Then, the activation products of Graphene and highly basic are prepared.Subsequently, active micropore Graphene is prepared; Finally, second time pore-creating obtains finished product.
With regard to the present invention one preferably embodiment, the involved solid mixture process preparing graphene oxide and chemical foaming agent is: in water graphite oxide being joined pH=9 to 10 and alcohol mixed solution, the volume ratio of this water and alcohol mixed solution is 2:1.Afterwards, by magnetic agitation 1 to 10 hour, then ultrasonic disperse 0.5 to 2 hour, form graphene oxide colloidal dispersion.During this period, the concentration of controlled oxidization Graphene is 0.5 to 5mg/mL.Subsequently, add the chemical foaming agent that bicarbonate of ammonia is formed, stir 2 to 12 hours.Finally, cross and filter unnecessary chemical foaming agent, after getting final product drying, obtain the solid mixture of graphene oxide and chemical foaming agent.
Further, the preparation process of the expanded graphite alkene of employing is, the solid mixture of the graphene oxide previously obtained and chemical foaming agent is carried out expanded reduction at reducing atmosphere.Afterwards, rise to 500 DEG C gradually from room temperature and obtain expanded graphite alkene.During this period, control temperature rise rate and be 2 to 10 DEG C/min, and 200 DEG C time, be incubated 15 to 30 minutes respectively, 500 DEG C time, be incubated 1 to 2 hour.Certainly, consider and have preferably expanded reduction, solid mixture can be placed in tube furnace, carry out in the reducing atmosphere of nitrogen.
In order to improve the preparation quality of active porous Graphene, its activation products process preparing Graphene and highly basic is as follows: the first activator mix expanded graphite alkene and sodium hydroxide formed, within 0.5 to 4 hour, carry out first time pore-creating 400 DEG C to 800 DEG C heating, all can obtain micropore Graphene.And then, the preparation of active micropore Graphene can be carried out, both under the condition of nitrogen protection gas, micropore Graphene be carried out charing process at 600-800 DEG C, obtains active micropore Graphene.In the present invention, in order to have preferably output, carbonization time is comparatively applicable with 1-5 hour, especially within 3 hours, is good.
Again further, the second time poration process that the present invention adopts is carry out using nitration mixture process to micropore Graphene.Afterwards, with the second activator mix, at 600 DEG C to 1000 DEG C temperature, heat 1 to 6 hour, carry out second time pore-creating, obtain active porous Graphene.During this period, in order to have preferably reaction effect, nitration mixture is treated to, and is that the vitriol oil and the concentrated nitric acid of 3:1 carries out nitration mixture process by micropore Graphene volume ratio.Further, adopt potassium hydroxide as the second activator, can obtain and prepare effect preferably.
" embodiment one "
In the water that 0.1g graphite oxide is joined 200mL and alcohol mixed solution (volume ratio of water and ethanol is 2:1), during magnetic agitation 2.Afterwards, by ultrasonic disperse 0.5 hour, form graphene oxide colloidal dispersion.Then, add 0.4g bicarbonate of ammonia, stir 2 hours, the bicarbonate of ammonia that removing to be filtered is unnecessary, obtains the solid mixture of graphene oxide and bicarbonate of ammonia after drying.Subsequently, solid mixture is placed in tube furnace and carries out expanded reduction at the reducing atmosphere of hydrogen and nitrogen.
Specifically, between expanded reduction period, rise to 500 DEG C gradually from room temperature, controlling temperature rise rate is 8 DEG C/min, and 200 DEG C time, is incubated 15 minutes respectively, is incubated 1.5 hours afterwards, can obtains expanded graphite alkene 500 DEG C time.
Subsequently, expanded graphite alkene is mixed with sodium hydroxide, within 1 hour, carry out first time pore-creating 450 DEG C of heating and obtain micropore Graphene.
Thus, the present embodiment 1 to micropore Graphene specific surface area reach 1596m
2/ g, pore volume is 1.5cm
3/ g.The porous graphene prepared by embodiment 1 method as electrode material for super capacitor at 1Ag
-1under current density, ratio capacitance reaches 128F/g, and current density is from 0.2Ag
-1increase to 20Ag
-1ratio capacitance conservation rate is 70.8%.
" embodiment two "
In the water that 0.1g graphite oxide is joined 200mL and alcohol mixed solution (volume ratio of water and ethanol is 2:1), magnetic agitation 2 hours, then ultrasonic disperse 0.5 hour, form graphene oxide colloidal dispersion.
Then, add 0.3g bicarbonate of ammonia, stir 2 hours, the bicarbonate of ammonia that removing to be filtered is unnecessary, obtains the solid mixture of graphene oxide and bicarbonate of ammonia after drying.Subsequently, solid mixture is placed in tube furnace and carries out expanded reduction at the reducing atmosphere of hydrogen and nitrogen: both rose to 500 DEG C gradually from room temperature, controlling temperature rise rate is 8 DEG C/min, and 200 DEG C time, is incubated 15 minutes respectively, 500 DEG C time, be incubated 1.5 hours, expanded graphite alkene can be obtained.
Further, expanded graphite alkene is mixed with sodium hydroxide, within 1 hour, carry out first time pore-creating 450 DEG C of heating and obtain micropore Graphene.Next, under the condition of nitrogen, described second intermediate product is carried out charing process at 600-800 DEG C, and obtain active micropore Graphene, carbonization time is 2 hours.
The present embodiment 2 to porous graphene specific surface area reach 1797m
2/ g, pore volume is 1.8cm
3/ g.The porous graphene prepared by embodiment 2 method is as electrode material for super capacitor under 1Ag-1 current density, and ratio capacitance reaches 169F/g, and current density is from 0.2Ag
-1increase to 20Ag
-1ratio capacitance conservation rate is 76.7%.
" embodiment three "
In the water that 0.1g graphite oxide is joined 200mL and alcohol mixed solution (volume ratio of water and ethanol is 2:1), magnetic agitation 2 hours, then ultrasonic disperse 0.5 hour, form graphene oxide colloidal dispersion.Then, add 0.3g bicarbonate of ammonia, stir 2 hours, cross and filter unnecessary bicarbonate of ammonia, after drying, obtain the solid mixture of graphene oxide and bicarbonate of ammonia.Afterwards, solid mixture is placed in tube furnace and carries out expanded reduction at the reducing atmosphere of hydrogen and nitrogen.
Specifically, in order to have preferably expanded reduction effect, between expanded reduction period, temperature is risen to 500 DEG C gradually from room temperature, and controlling temperature rise rate is 8 DEG C/min, and 200 DEG C time, is incubated 15 minutes respectively, 500 DEG C time, be incubated 1.5 hours, expanded graphite alkene can be obtained.Afterwards, expanded graphite alkene is mixed with sodium hydroxide, within 1 hour, carry out first time pore-creating 450 DEG C of heating and obtain micropore Graphene.
Next, under the condition of nitrogen, described second intermediate product is carried out charing process at 600-800 DEG C, obtain active micropore Graphene, and carbonization time is 2 hours.
Be finally after the vitriol oil of 3:1 and the nitration mixture process of concentrated nitric acid by described active micropore Graphene volume ratio, mix with the ratio uniform of potassium hydroxide 8:1 in mass ratio again, under the reducing atmosphere of hydrogen and nitrogen, be heated to 600 DEG C in tube furnace and keep 1.5 hours, so cooling obtains active porous Graphene.
Thus, the present embodiment 3 to porous graphene specific surface area reach 2196m
2/ g, pore volume is 2.0cm
3/ g.The porous graphene prepared by the method for embodiment 3 as electrode material for super capacitor at 1Ag
-1under current density, ratio capacitance reaches 168F/g, and current density is from 0.2Ag
-1increase to 20Ag
-1ratio capacitance conservation rate is 82.8%.
Can be found out by above-mentioned character express, after adopting the present invention, also have central hole structure and the macroporous structure of proper ratio while active porous Graphene of the present invention has higher tap density, this some holes provides higher specific surface area.Further, after charring process process, the activity of porous graphene is substantially increased.When this active porous Graphene is used for capacitor electrode material, macroporous structure is the passage that electrolytic solution provides fast transferring, simultaneously, central hole structure and organic electrolyte intermediate ion sizableness, be beneficial to quick adsorption and the desorption of ion, thus make electrical condenser have good high rate charge-discharge performance.
Claims (10)
1. the preparation method of active porous Graphene, is characterized in that: first, prepares the solid mixture of graphene oxide and chemical foaming agent; Afterwards, expanded graphite alkene is prepared; Then, the activation products of Graphene and highly basic are prepared; Subsequently, active micropore Graphene is prepared; Finally, second time pore-creating obtains finished product.
2. the preparation method of active porous Graphene according to claim 1, is characterized in that: the described solid mixture process preparing graphene oxide and chemical foaming agent is,
Step 1., in water graphite oxide being joined pH=9 to 10 and alcohol mixed solution;
2. step, stirs 1 to 10 hour, then ultrasonic disperse 0.5 to 2 hour, forms graphene oxide colloidal dispersion;
3. step, then adds chemical foaming agent, stirs 2 to 12 hours;
4. step, is crossed and is filtered unnecessary chemical foaming agent, obtain the solid mixture of graphene oxide and chemical foaming agent after drying.
3. the preparation method of active porous Graphene according to claim 2, is characterized in that: described water and the volume ratio of alcohol mixed solution are 2:1, and described alr mode is magnetic agitation, and described chemical foaming agent is bicarbonate of ammonia.
4. the preparation method of active porous Graphene according to claim 1, is characterized in that: described expanded graphite alkene process of preparing is,
1. the solid mixture of the graphene oxide previously obtained and chemical foaming agent, is carried out expanded reduction at reducing atmosphere by step;
2. step, rises to 500 DEG C gradually from room temperature, and control temperature rise rate is 2 to 10 DEG C/min, and 200 DEG C time, is incubated 15 to 30 minutes respectively, is incubated 1 to 2 hour, obtains expanded graphite alkene 500 DEG C time.
5. the preparation method of active porous Graphene according to claim 4, is characterized in that: described to be expandedly reduced to, and solid mixture is placed in tube furnace, carries out in the reducing atmosphere of nitrogen.
6. the preparation method of active porous Graphene according to claim 1, it is characterized in that: the described activation products process preparing Graphene and highly basic is, by expanded graphite alkene and the first activator mix, within 0.5 to 4 hour, carry out first time pore-creating 400 DEG C to 800 DEG C heating, obtain micropore Graphene.
7. the preparation method of active porous Graphene according to claim 6, is characterized in that: the first described activator is sodium hydroxide.
8. the preparation method of active porous Graphene according to claim 1; it is characterized in that: described active micropore Graphene process of preparing is; under the condition of nitrogen protection gas, micropore Graphene is carried out charing process at 600-800 DEG C, obtains active micropore Graphene.
9. the preparation method of active porous Graphene according to claim 1, it is characterized in that: described second time poration process is, carry out using nitration mixture process to micropore Graphene, with the second activator mix, at 600 DEG C to 1000 DEG C temperature, heat 1 to 6 hour, carry out second time pore-creating, obtain active porous Graphene.
10. the preparation method of active porous Graphene according to claim 9, is characterized in that: described nitration mixture is treated to, and is that the vitriol oil and the concentrated nitric acid of 3:1 carries out nitration mixture process by micropore Graphene volume ratio; The second described activator is potassium hydroxide.
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| CN106744882A (en) * | 2016-12-28 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of quick method for preparing Graphene of microwave radiation technology stirring |
| CN110117001A (en) * | 2018-02-06 | 2019-08-13 | 山东欧铂新材料有限公司 | A kind of preparation method and supercapacitor of the porous graphene for supercapacitor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105261486A (en) * | 2015-11-05 | 2016-01-20 | 宁波南车新能源科技有限公司 | Preparation method for core composite carbon electrode material of double-electric-layer capacitor |
| CN106744882A (en) * | 2016-12-28 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of quick method for preparing Graphene of microwave radiation technology stirring |
| CN106744882B (en) * | 2016-12-28 | 2018-11-16 | 成都新柯力化工科技有限公司 | A kind of method that microwave-assisted stirring quickly prepares graphene |
| CN110117001A (en) * | 2018-02-06 | 2019-08-13 | 山东欧铂新材料有限公司 | A kind of preparation method and supercapacitor of the porous graphene for supercapacitor |
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