CN103395779A - Porous graphene and preparation method thereof - Google Patents
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Abstract
The invention provides a porous graphene and a preparation method thereof. The preparation method comprises the following steps: under the action of an oxidant, heating a graphite substance and sulfur in a solvent to react, thereby obtaining the porous graphene, wherein the graphite substance is one or more of graphene oxide, graphene and graphite microsheets. The porous graphene provided by the invention has a mesopore structure, and thus, has higher specific area. When the porous graphene provided by the invention is used in a supercapacitor electrode material, the supercapacitor has favorable high-power charging/discharging property.
Description
Technical field
The invention belongs to the carbon material technical field, relate in particular to a kind of porous graphene and preparation method thereof.
Background technology
Along with the continuous expansion of informationized society and the appearance of environment and energy dilemma, energy storage and efficiency of conversion problem are more and more important.In various Energy conversion systems, ultracapacitor due to have the speed of discharging and recharging fast, have extended cycle life, comparatively safe, use temperature is wide, environmental friendliness and the good characteristic such as non-maintaining and be applied to standby power supply, start the fields such as power supply, the pulse power, grid balance.According to the difference of energy storage mechanism, ultracapacitor can be divided into double layer capacitor and fake capacitance device.Double layer capacitor mainly relies on the electrostatic double layer of electrode and electrolyte interface to carry out stored charge, utilize the specific surface area that electrode materials is huge to pass through the physical process store electrical energy, by ionogen, can be divided into aqueous super capacitor and the double-deck ultracapacitor of organic system, its electrode materials is mainly the carbon material of high-specific surface area.
Gac has very large specific surface area and abundant inner hole structure, the formation that can be electrostatic double layer provides huge surface-area, therefore be a kind of electrode materials that is applied to the earliest ultracapacitor, it is especially for the aqueous systems ionogen, the electrolyte ion diameter is less, diffusion mass transfer is easier to carry out in micropore, activated carbon surface is also more easily infiltrated, thereby material surface area can be fully used.
But the gac energy density is lower, can only be applied in the aqueous systems ionogen, and in operating voltage, can reach the 1-ethyl-3-methylimidazole a tetrafluoro borate (EMIBF of 4V
4) while applying in ionic liquid class ionogen, have following shortcoming: electroconductibility is poor, and most of pore distribution is in the inside of particle, under high current charge-discharge, ion is obstructed at the gac pore diffusion of complications, and specific storage descends rapidly.Activated carbon surface has the part oxygen-containing functional group simultaneously, and oxygen-containing functional group can be induced the decomposition of electrolytic solution under high working voltage.At present the commercial organic system super capacitor energy density based on mesopore activated carbon only has 5～6Wh/kg, compares with the energy density (being about 150Wh/kg) of lithium ion battery that still there is a big difference.
Research is found, Graphene not only has huge theoretical specific surface area, and physicochemical property are stable, can under high working voltage and large electric current fast charging and discharging, keep good structural stability, also has simultaneously excellent electroconductibility, can reduce internal resistance, improve the cyclical stability of ultracapacitor.
The preparation method of graphite alkene is disclosed in prior art, Liu(Liu CG wherein, Yasuda S, Yu ZN, et al.Nano Lett.2010,10:4863-4868) etc. a kind of method of using hot reducing method to prepare Graphene is disclosed, its prepared Graphene specific surface area is about 500.6m
2/ g, the specific storage 154.1F/g in organic system electrolytic solution, be 85.6Wh/kg based on the energy density of active substance, and its specific surface area still has very large gap apart from theoretical specific surface area, and therefore the modification for Graphene still has very large space.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of porous graphene and preparation method thereof, this porous graphene has central hole structure and higher specific surface area, during for electrode material for super capacitor, makes ultracapacitor have high rate charge-discharge performance preferably.
The invention provides a kind of preparation method of porous graphene, comprise the following steps:
A) under the effect of oxygenant, graphite-like material and sulphur heat and react in solvent, obtain porous graphene;
Described graphite-like material is one or more in graphene oxide, Graphene and graphite nanosheets.
Preferably, described steps A) be specially:
A1) sulphur is mixed with organic solvent, obtain the first mixed solution;
A2) the graphite-like material is immersed in to above-mentioned steps A1) in the first mixed solution of obtaining, after oven dry, obtain the first mixture;
A3) by above-mentioned the first mixture with after oxidizing agent solution mixes, heating reacts, and obtains porous graphene.
Preferably, the temperature of described heating is 500～800 ℃.
Preferably, described organic solvent is dithiocarbonic anhydride.
Preferably, described oxygenant is saltpetre, SODIUMNITRATE, ammonium nitrate, ammonium chlorate, Potcrate or sodium chlorate.
Preferably, the mass ratio of described graphite-like material, sulphur and oxygenant is 1:(0.05～10): (0.1～10).
The invention provides a kind of porous graphene, it is characterized in that, have central hole structure, the aperture of described mesopore is 10～20nm; The specific surface area of described porous graphene is 1900～2600m
2/ g.
The invention provides a kind of porous graphene and preparation method thereof, the present invention, under the effect of oxygenant, heats graphite-like material and sulphur to react in solvent, obtain porous graphene.The prepared porous graphene of the present invention has central hole structure, and has higher specific surface area.With existing porous graphene, compare, the porous graphene of preparation has central hole structure according to the method described in the present invention, and has higher specific surface area.During for electrode material for super capacitor, has high rate charge-discharge performance preferably.Experimental result shows, the prepared porous graphene aperture of the present invention is 10～20nm, and specific surface area is about 1900～2600m
2/ g.Use the button-shaped electrical condenser of the prepared porous graphene assembling of the present invention, under the window voltage of 4V, after 5000 circulations, the conservation rate of specific storage is 94.5%～96%.
The accompanying drawing explanation
Fig. 1 is the transmission electron microscope figure of the porous graphene for preparing of the embodiment of the present invention 1;
Fig. 2 is the isothermal adsorption desorption graphic representation of the porous graphene for preparing of the embodiment of the present invention 1;
Fig. 3 for the specific storage of the button-shaped electrical condenser of the porous graphene assembling of using the embodiment of the present invention 1 preparation with the scanning speed change curve;
5000 recycle ratio capability retention change curves of button-shaped electrical condenser that Fig. 4 assembles for the porous graphene that uses the embodiment of the present invention 1 preparation.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just in order to further illustrate the features and advantages of the present invention, rather than to the restriction of invention claim.
The invention provides a kind of preparation method of porous graphene, comprise the following steps: under the effect of oxygenant, graphite-like material and sulphur heat and react in solvent, obtain porous graphene, described graphite-like material is one or more in graphene oxide, Graphene and graphite nanosheets.
Porous graphene prepared by method of the present invention has central hole structure, and has higher specific surface area.
All raw materials of the present invention, be not particularly limited its source, and that on market, buys gets final product.
There is no particular restriction to the source of described graphene oxide in the present invention, preferably adopts improved Hummers method preparation:
1.5g graphite, 1.5g saltpetre and the 90mL vitriol oil are mixed to rear and 9g potassium permanganate reaction, and reaction adds 100mL deionized water and 2mL hydrogen peroxide after finishing, and obtains the 2g graphene oxide.The present invention is not particularly limited for described hybrid mode, and hybrid mode well known to those skilled in the art gets final product; Described reaction is preferably under the condition that stirs reacts; Described temperature of reaction is preferably room temperature; The described reaction times is preferably 1～10h; Described add after deionized water and hydrogen peroxide preferably also comprise centrifugal rear cleaning supernatant liquor to pH for neutral.The present invention is for described centrifugation unrestricted, and centrifugation well known to those skilled in the art gets final product.
There is no particular restriction to the source of described Graphene in the present invention, preferably adopts the method for thermal reduction graphene oxide to obtain; There is no particular restriction to the source of described graphite nanosheets in the present invention, and preferred the employing obtains the method for expanded graphite ultrasonic dispersion in the aqueous solution.
The present invention reacts graphite-like material, oxygenant, sulphur and solvent post-heating, obtains porous graphene; The mass ratio of described graphite-like material, sulphur and oxygenant is preferably 1:(0.05～10): (0.1～10), more preferably 1:(0.1～8): (0.2～8).
The preparation method of porous graphene of the present invention, detailed process preferably carry out according to the following steps:
A1) sulphur is mixed with organic solvent, obtain the first mixed solution;
A2) the graphite-like material is immersed in to above-mentioned steps A1) in the first mixed solution of obtaining, after oven dry, obtain the first mixture;
A3) by above-mentioned the first mixture with after oxidizing agent solution mixes, heating reacts, and obtains porous graphene.
At first the present invention is mixed to dissolving fully by sulphur and organic solvent, obtains the first mixed solution; Described organic solvent is preferably dithiocarbonic anhydride; The present invention is not particularly limited the condition of described mixing, with mixing condition well known to those skilled in the art, gets final product; The present invention is not particularly limited the equipment of described mixing, with mixing equipment well known to those skilled in the art, gets final product.
The present invention is immersed in the graphite-like material in the first mixed solution that above-mentioned steps obtains, and after oven dry, obtains the first mixture.Described graphite-like material is preferably one or more in graphene oxide, Graphene and graphite nanosheets, more preferably graphene oxide; The present invention is not particularly limited the mode of described dipping, is preferably complete submergence; The present invention is not particularly limited the condition of described dipping, with immersion condition well known to those skilled in the art, gets final product; The present invention is not particularly limited described oven dry, is preferably the evaporation of the liquid phase on the graphite-like material is got final product fully; The present invention is not particularly limited the temperature and time of described oven dry, with the temperature and time of oven dry well known to those skilled in the art, gets final product; The present invention is not particularly limited the equipment of described oven dry, with drying plant well known to those skilled in the art, gets final product.
The first mixture that the present invention obtains above-mentioned steps is with after oxidizing agent solution mixes, heating reacts, obtain porous graphene, detailed process is preferably according to following steps carries out, first oxygenant is mixed with to oxidizing agent solution, then mixes with the first mixture, after oven dry, obtain the second mixture, the the second mixture heating that again above-mentioned steps is obtained reacts, and finally obtains porous graphene.
At first the present invention is mixed with oxidizing agent solution by oxygenant, then mixes with the first mixture, after oven dry, obtains the second mixture; Described oxygenant is preferably saltpetre, SODIUMNITRATE, ammonium nitrate, ammonium chlorate, Potcrate or sodium chlorate, more preferably SODIUMNITRATE or ammonium chlorate; The present invention is not particularly limited the solvent in described oxidizing agent solution, is preferably deionized water; The present invention is not particularly limited the concentration of described oxidizing agent solution, with oxygenant, can fully dissolve and get final product; The present invention is not particularly limited the mode of described mixing, is preferably even mixing; The present invention is not particularly limited the condition of described mixing, with mixing condition well known to those skilled in the art, gets final product; The present invention is not particularly limited described oven dry, is preferably the evaporation of the liquid phase on the graphite-like material is got final product fully; The present invention is not particularly limited the temperature and time of described oven dry, with the temperature and time of oven dry well known to those skilled in the art, gets final product; The present invention is not particularly limited the equipment of described oven dry, with drying plant well known to those skilled in the art, gets final product.
The present invention reacts above-mentioned the second mixture heating, obtains porous graphene.The temperature of described heating is preferably 500～800 ℃, more preferably 600～700 ℃; The present invention is not particularly limited the mode of described heating, in conventional heating mode well known to those skilled in the art, gets final product, and the time of described heating is preferably 20～40 seconds, more preferably 25～35 seconds; The mode of heating of the present invention can also be microwave heating, and the power of described microwave heating is preferably 800～1200KW, more preferably 900～1100KW; The time of described microwave heating is preferably 120～240 seconds, more preferably 150～200 seconds.
The present invention, after the heating of above-mentioned the second mixture and oxidizing agent solution reacts, preferably passes through aftertreatment, finally obtains porous graphene.The present invention is not particularly limited described aftertreatment, is preferably first and removes foreign ion through washing, then dry the removal liquid phase substance.The present invention is not particularly limited described washing, is preferably with deionized water and washs; The present invention is not particularly limited the condition of washing, with wash conditions well known to those skilled in the art, gets final product; The present invention is not particularly limited the mode of washing, with mode of washing well known to those skilled in the art, gets final product; The present invention is not particularly limited the temperature and time of described oven dry, with the temperature and time of oven dry well known to those skilled in the art, gets final product; The present invention is not particularly limited the equipment of described oven dry, with drying plant well known to those skilled in the art, gets final product.
The preparation method of porous graphene of the present invention, detailed process can be also:
B1) the graphite-like material is immersed in oxidizing agent solution, after oven dry, obtains the first mixture;
B2) sulphur is mixed with organic solvent, obtain the first mixed solution;
B3) by above-mentioned the first mixture with after the first mixed solution mixes, heating reacts, and obtains porous graphene.
In above-mentioned steps, described raw material, reaction conditions and conversion unit all with preferred detailed process in identical, therefore, repeat no longer one by one.
The invention provides a kind of porous graphene, it has central hole structure, and the aperture of described mesopore is preferably 10～20nm, more preferably 12～18nm; The specific surface area of described porous graphene is preferably 1900～2600m
2/ g, more preferably 2000～2500m
2/ g.
The preparation-obtained porous graphene of the present invention has central hole structure and higher specific surface area, and during therefore for the preparation of electrode of super capacitor, the ultracapacitor that makes has high rate charge-discharge performance preferably.The present invention is not particularly limited the concrete grammar of described porous graphene for ultracapacitor, preferably according to following steps, carries out, and above-mentioned porous graphene, carbon black are mixed with binding agent, after filming, obtains the electrode slice of ultracapacitor.The mass ratio of described porous graphene, carbon black and binding agent is (6～9): 1:1, more preferably (6～8): 1:1; The present invention is not particularly limited described carbon black, thinks that carbon black well known to those skilled in the art gets final product; The present invention is not particularly limited described binding agent, thinks that binding agent well known to those skilled in the art gets final product.
Porous graphene provided by the invention and preparation method thereof, this porous graphene has central hole structure, and has higher specific surface area.Experimental result shows, the prepared porous graphene aperture of the present invention is 10nm, and specific surface area is about 2600m
2/ g.Use the button-shaped electrical condenser of the prepared porous graphene assembling of the present invention, under the window voltage of 4V, after 5000 circulations, the conservation rate of specific storage is 94.5～96%.
In order to further illustrate the present invention, below in conjunction with embodiment, porous graphene provided by the invention and preparation method thereof is described in detail.
Embodiment 1
At first 1.5g graphite, 1.5g saltpetre and the 90mL vitriol oil are mixed to rear and 9g potassium permanganate reaction, reaction adds 100mL deionized water and 2mL hydrogen peroxide after finishing, and obtains the 2g graphene oxide.
Then 0.6g sulphur is dissolved in 10ml dithiocarbonic anhydride, obtains the dithiocarbonic anhydride solution of sulphur, the 0.3g graphene oxide is immersed in the dithiocarbonic anhydride solution of above-mentioned sulphur, then will after the graphene oxide oven dry of having flooded, obtain the first mixture.
10g saltpetre is dissolved in the 50ml deionized water and obtains Alkitrate, then by above-mentioned the first mixture with after Alkitrate mixes, dry and obtain the second mixture.
Finally above-mentioned the second mixture is carried out to microwave treatment, power is 1 kilowatt, and the treatment time is 3 minutes, and the rear taking-up that is disposed washes away ion wherein with deionized water, and oven dry obtains the 0.1g porous graphene.
Porous graphene prepared by aforesaid method carries out the transmission electron microscope detection, result as shown in Figure 1, Fig. 1 is the scanning electron microscope diagram of the porous graphene for preparing of the embodiment of the present invention 1, as shown in Figure 1, the present invention has obtained having the porous graphene of central hole structure, and aperture is about 5～20nm.
Porous graphene prepared by aforesaid method carries out nitrogen absorption test, result as shown in Figure 2, Fig. 2 is the isothermal adsorption desorption graphic representation of the porous graphene for preparing of the embodiment of the present invention 1, and as shown in Figure 2, the specific surface area of porous graphene prepared by aforesaid method is about 2500m
2/ g.
The ratio that porous graphene prepared by aforesaid method and carbon black, binding agent are 8:1:1 according to mass ratio is dispersed in N-Methyl pyrrolidone (NMP) the formation slurry that stirs, slurry is coated on aluminium foil, thickness is 200 μ m, under 120 ℃ of conditions, dry, then be cut into the electrode slice that diameter is 13mm, in glove box, electrode slice and barrier film and electrolytic solution are assembled into to 2023 button-shaped electrical condensers, electrolytic solution is 1-ethyl-3-methylimidazole a tetrafluoro borate (EMIBF
4).
This button-shaped electrical condenser is carried out to electrochemical property test, obtain the graphic representation that specific storage changes with scanning speed, as shown in Figure 3, Fig. 3 for the specific storage of the button-shaped electrical condenser of the porous graphene assembling of using the embodiment of the present invention 1 preparation with the scanning speed change curve, as shown in Figure 3, at 50mV/s, hang down and sweep under speed, the specific storage of button-shaped electrical condenser is 130F/g, sweep under speed 300mV/s is high, the specific storage of button-shaped electrical condenser is 95F/g.
By above-mentioned button-shaped electrical condenser under the window voltage of 4V, carry out 5000 recycle ratio volume tests, obtain specific storage conservation rate change curve, as shown in Figure 4, Fig. 4 is 5000 recycle ratio capability retention change curves of button-shaped electrical condenser of the porous graphene assembling of the use embodiment of the present invention 1 preparation.As shown in Figure 4, under the window voltage of 4V, after 5000 circulations, the specific storage conservation rate is 95.2%.
Embodiment 2
6g sulphur is dissolved in 50ml dithiocarbonic anhydride, obtains the dithiocarbonic anhydride solution of sulphur, the 3g graphite nanosheets is immersed in the dithiocarbonic anhydride solution of above-mentioned sulphur, then will after the graphite nanosheets oven dry of having flooded, obtain the first mixture.
10g saltpetre is dissolved in the 50ml deionized water and obtains Alkitrate, then by above-mentioned the first mixture with after Alkitrate mixes, dry and obtain the second mixture.
Finally above-mentioned the second mixture was heated 30 seconds in retort furnace, temperature is 500 ℃, and the rear taking-up that is disposed washes away ion wherein with deionized water, and oven dry obtains the 2g porous graphene.
Through transmission electron microscope, detect, the porous graphene aperture that the present invention obtains is about 5～45nm.The porous graphene that obtains is adsorbed to test by nitrogen, obtain its specific surface area for being about 2600m
2/ g.
The ratio that porous graphene prepared by aforesaid method and carbon black, binding agent are 8:1:1 according to mass ratio is dispersed in N-Methyl pyrrolidone (NMP) the formation slurry that stirs, slurry is coated on aluminium foil, thickness is 200 μ m, under 120 ℃ of conditions, dry, then be cut into the electrode slice that diameter is 13mm, in glove box, electrode slice and barrier film and electrolytic solution are assembled into to 2023 button-shaped electrical condensers, electrolytic solution is 1-ethyl-3-methylimidazole a tetrafluoro borate (EMIBF
4).
This button-shaped electrical condenser is carried out to electrochemical property test, and under the window voltage of 4V, after 5000 circulations, the specific storage conservation rate of this button-shaped electrical condenser is 94.8%.
Embodiment 3
5g sulphur is dissolved in 30ml dithiocarbonic anhydride, obtains the dithiocarbonic anhydride solution of sulphur, the 1g Graphene is immersed in the dithiocarbonic anhydride solution of above-mentioned sulphur, then will after the graphene oxide oven dry of having flooded, obtain the first mixture.
The 10g SODIUMNITRATE is dissolved in the 50ml deionized water and obtains sodium nitrate aqueous solution, then by above-mentioned the first mixture with after sodium nitrate aqueous solution mixes, dry and obtain the second mixture.
Finally above-mentioned the second mixture was heated 30 seconds in retort furnace, temperature is 800 ℃, and the rear taking-up that is disposed washes away ion wherein with deionized water, and oven dry obtains the 0.6g porous graphene.
Through transmission electron microscope, detect, the porous graphene aperture that the present invention obtains is about 20～45nm.The porous graphene that obtains is adsorbed to test by nitrogen, obtain its specific surface area for being about 2000m
2/ g.
The ratio that porous graphene prepared by aforesaid method and carbon black, binding agent are 8:1:1 according to mass ratio is dispersed in N-Methyl pyrrolidone (NMP) the formation slurry that stirs, slurry is coated on aluminium foil, thickness is 200 μ m, under 120 ℃ of conditions, dry, then be cut into the electrode slice that diameter is 13mm, in glove box, electrode slice and barrier film and electrolytic solution are assembled into to 2023 button-shaped electrical condensers, electrolytic solution is 1-ethyl-3-methylimidazole a tetrafluoro borate (EMIBF
4).
This button-shaped electrical condenser is carried out to electrochemical property test, and under the window voltage of 4V, after 5000 circulations, the specific storage conservation rate of this button-shaped electrical condenser is 96%.
Embodiment 4
At first 1.5g graphite, 1.5g saltpetre and the 90mL vitriol oil are mixed to rear and 9g potassium permanganate reaction, reaction adds 100mL deionized water and 2mL hydrogen peroxide after finishing, and obtains the 2g graphene oxide.
Then 1.0g sulphur is dissolved in 30ml dithiocarbonic anhydride, obtains the dithiocarbonic anhydride solution of sulphur, the 1.0g graphene oxide is immersed in the dithiocarbonic anhydride solution of above-mentioned sulphur, then will after the graphene oxide oven dry of having flooded, obtain the first mixture.
10g ammonium nitrate is dissolved in the 50ml deionized water and obtains aqueous ammonium nitrate solution, then by above-mentioned the first mixture with after aqueous ammonium nitrate solution mixes, dry and obtain the second mixture.
Finally above-mentioned the second mixture was heated 30 seconds in retort furnace, temperature is 600 ℃, and the rear taking-up that is disposed washes away ion wherein with deionized water, and oven dry obtains the 0.4g porous graphene.
Through transmission electron microscope, detect, the porous graphene aperture that the present invention obtains is about 5～15nm.The porous graphene that obtains is adsorbed to test by nitrogen, obtain its specific surface area for being about 1900m
2/ g.
The ratio that porous graphene prepared by aforesaid method and carbon black, binding agent are 8:1:1 according to mass ratio is dispersed in N-Methyl pyrrolidone (NMP) the formation slurry that stirs, slurry is coated on aluminium foil, thickness is 200 μ m, under 120 ℃ of conditions, dry, then be cut into the electrode slice that diameter is 13mm, in glove box, electrode slice and barrier film and electrolytic solution are assembled into to 2023 button-shaped electrical condensers, electrolytic solution is 1-ethyl-3-methylimidazole a tetrafluoro borate (EMIBF
4).
This button-shaped electrical condenser is carried out to electrochemical property test, and under the window voltage of 4V, after 5000 circulations, the specific storage conservation rate of this button-shaped electrical condenser is 95.6%.
Embodiment 5
At first 1.5g graphite, 1.5g saltpetre and the 90mL vitriol oil are mixed to rear and 9g potassium permanganate reaction, reaction adds 100mL deionized water and 2mL hydrogen peroxide after finishing, and obtains the 2g graphene oxide.
Then 2g sulphur is dissolved in 30ml dithiocarbonic anhydride, obtains the dithiocarbonic anhydride solution of sulphur, the 0.5g graphene oxide is immersed in the dithiocarbonic anhydride solution of above-mentioned sulphur, then will after the graphene oxide oven dry of having flooded, obtain the first mixture.
The 10g ammonium chlorate is dissolved in the 50ml deionized water and obtains the ammonium chlorate aqueous solution, then by above-mentioned the first mixture and ammonium chlorate aqueous solution evenly after, dry and obtain the second mixture.
Finally above-mentioned the second mixture was heated 30 seconds in retort furnace, temperature is 700 ℃, and the rear taking-up that is disposed washes away ion wherein with deionized water, and oven dry obtains the 0.25g porous graphene.
Through transmission electron microscope, detect, the porous graphene aperture that the present invention obtains is about 10～45nm.The porous graphene that obtains is adsorbed to test by nitrogen, obtain its specific surface area for being about 2000m
2/ g.
The ratio that porous graphene prepared by aforesaid method and carbon black, binding agent are 8:1:1 according to mass ratio is dispersed in N-Methyl pyrrolidone (NMP) the formation slurry that stirs, slurry is coated on aluminium foil, thickness is 200 μ m, under 120 ℃ of conditions, dry, then be cut into the electrode slice that diameter is 13mm, in glove box, electrode slice and barrier film and electrolytic solution are assembled into to 2023 button-shaped electrical condensers, electrolytic solution is 1-ethyl-3-methylimidazole a tetrafluoro borate (EMIBF
4).
This button-shaped electrical condenser is carried out to electrochemical property test, and under the window voltage of 4V, after 5000 circulations, the specific storage conservation rate of this button-shaped electrical condenser is 94.5%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. the preparation method of a porous graphene comprises the following steps:
A) under the effect of oxygenant, graphite-like material and sulphur heat and react in solvent, obtain porous graphene;
Described graphite-like material is one or more in graphene oxide, Graphene and graphite nanosheets.
2. preparation method according to claim 1, is characterized in that, described steps A) be specially:
A1) sulphur is mixed with organic solvent, obtain the first mixed solution;
A2) the graphite-like material is immersed in to above-mentioned steps A1) in the first mixed solution of obtaining, after oven dry, obtain the first mixture;
A3) by above-mentioned the first mixture with after oxidizing agent solution mixes, heating reacts, and obtains porous graphene.
3. preparation method according to claim 1, is characterized in that, the temperature of described heating is 500～800 ℃.
4. preparation method according to claim 1, is characterized in that, described organic solvent is dithiocarbonic anhydride.
5. preparation method according to claim 1, is characterized in that, described oxygenant is saltpetre, SODIUMNITRATE, ammonium nitrate, ammonium chlorate, Potcrate or sodium chlorate.
6. preparation method according to claim 1, is characterized in that, the mass ratio of described graphite-like material, sulphur and oxygenant is 1:(0.05～10): (0.1～10).
7. a porous graphene, is characterized in that having central hole structure, and the aperture of described mesopore is 10～20nm; The specific surface area of described porous graphene is 1900～2600m
2/ g.
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Cited By (3)
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| CN107311155A (en) * | 2017-08-07 | 2017-11-03 | 中国科学院合肥物质科学研究院 | The preparation method of porous graphene |
| CN110550621A (en) * | 2018-05-30 | 2019-12-10 | 中国石油化工股份有限公司 | Graphene and preparation method thereof |
| CN110550620A (en) * | 2018-05-30 | 2019-12-10 | 中国石油化工股份有限公司 | Graphene and preparation method thereof |
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| CN102115069A (en) * | 2010-12-20 | 2011-07-06 | 中国石油大学(北京) | Graphene with porous structure and preparation method of graphene |
| TW201326027A (en) * | 2011-12-28 | 2013-07-01 | Hon Hai Prec Ind Co Ltd | Method for making sulfur-graphene composite material |
| CN102718183A (en) * | 2012-07-13 | 2012-10-10 | 常州大学 | High-hydrogen-storage-capacity lithium borohydride/graphene (LiBH4/RGO) composite hydrogen storage material and preparation method thereof |
| CN102910581A (en) * | 2012-10-22 | 2013-02-06 | 常州大学 | Me-RGO (Reduced Graphene Oxide)/LiBH4 hydrogen storage material with high hydrogen storage capacity and preparation methods of Me-RGO/LiBH4 hydrogen storage material |
| CN103112849A (en) * | 2013-03-13 | 2013-05-22 | 上海第二工业大学 | Sulfur-bond-containing porous graphene nanomaterial and preparation method thereof |
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| CN107311155A (en) * | 2017-08-07 | 2017-11-03 | 中国科学院合肥物质科学研究院 | The preparation method of porous graphene |
| CN110550621A (en) * | 2018-05-30 | 2019-12-10 | 中国石油化工股份有限公司 | Graphene and preparation method thereof |
| CN110550620A (en) * | 2018-05-30 | 2019-12-10 | 中国石油化工股份有限公司 | Graphene and preparation method thereof |
| CN110550620B (en) * | 2018-05-30 | 2021-06-11 | 中国石油化工股份有限公司 | Graphene and preparation method thereof |
| CN110550621B (en) * | 2018-05-30 | 2021-07-09 | 中国石油化工股份有限公司 | Graphene and preparation method thereof |
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