CN103011143A - Graphene and fabrication method thereof and super capacitor - Google Patents
Graphene and fabrication method thereof and super capacitor Download PDFInfo
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- CN103011143A CN103011143A CN2012105602516A CN201210560251A CN103011143A CN 103011143 A CN103011143 A CN 103011143A CN 2012105602516 A CN2012105602516 A CN 2012105602516A CN 201210560251 A CN201210560251 A CN 201210560251A CN 103011143 A CN103011143 A CN 103011143A
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Abstract
The invention provides graphene and a fabrication method thereof. The fabrication method comprises the steps of obtaining a nano graphite flake by ball-milling of expanded graphite, obtaining partially oxidized graphene by oxidizing, mixing the partially oxidized graphene with a first activator, obtaining micropore graphene by heating and conducting pore-forming for the first time, mixing the micropore graphene with a second activator, and obtaining the graphene by heating and conducting pore-forming for the second time. Compared with the prior art, the graphene with a central pore structure is obtained by taking the expanded graphite as a raw material through weak oxidation and two pore-forming processes. Firstly, the expanded graphite is taken as the raw material and subjected to the ball-milling to be uniformly dispersed, the nano graphite flake with a thinner lamellar structure is obtained, the expansion pore-forming is conducted on the nano graphite flake, and the graphene with a three-dimensional lamellar structure, the central pore structure and a higher specific surface area is finally obtained; and secondly, the weak oxidization is conducted on the nano graphite flake, and the graphene with a short-rang order and long-range disorder structure and a higher tap density at a macro level is finally fabricated.
Description
Technical field
The invention belongs to the organic semiconductor material technical field, relate in particular to Graphene and preparation method thereof, ultracapacitor.
Background technology
Along with the continuous expansion of informationized society and the appearance of environment and energy dilemma, energy storage is more and more important in the efficiency of conversion problem.In various Energy conversion system, ultracapacitor since 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 or redox capacitors.Double layer capacitor mainly relies on the electrostatic double layer of electrode and electrolyte interface to come stored charge, utilizes the huge specific surface area of electrode materials by the physical process store electrical energy, and its electrode materials is mainly the carbon material of high-specific surface area.The fake capacitance device mainly relies on the quick reversible redox reaction of electrode active material generation to come stored charge, and corresponding electrode materials is mainly metal oxide and conductive polymers.
Ultracapacitor mainly is comprised of parts such as current collection fluid, electrolytic solution, electrode materials and barrier films, and wherein electrode materials plays key effect to the performance of ultracapacitor, is the core component of ultracapacitor.Existing electrode materials has porous carbon materials, metal oxide containing precious metals and conductive polymer polymkeric substance.Wherein gac is a kind of electrode materials that is applied to the earliest ultracapacitor, and it has very large specific surface area and abundant inner hole structure, and the formation that can be electrostatic double layer provides huge surface-area.Especially for the aqueous systems ionogen, the electrolyte ion diameter is less, and 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 can reach the 1-ethyl-3-methylimidazole a tetrafluoro borate (EMIBF of 4V in operating voltage
4) when using in the ionic liquid class ionogen, have following shortcoming: electroconductibility is relatively poor, and most of pore distribution is in the inside of particle, under the 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.Yet the Graphene tap density of dilatometry preparation only has 0.005m
2/ g, low based on the energy density of volume calculation, because Graphene is very easily reunited in preparation and use procedure, the specific surface area utilization ratio is low, therefore is unfavorable for practical application.The Graphene specific surface area of the use thermal reduction methods such as Liu preparation is about 500.6m
2/ g, specific storage 154.1F/g under organism liquid, energy density based on active substance is 85.6Wh/kg(Liu CG, Yasuda S, Yu ZN, et al.Nano Lett.2010,10:4863-4868), 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 Graphene and preparation method thereof, ultracapacitor, and Graphene specific surface area and tap density that the method prepares are higher.
The invention provides a kind of Graphene, have central hole structure, have three-layer laminated structure.
Preferably, the specific surface area of described Graphene is 2000 ~ 2500m
2/ g, the tap density of described Graphene is 0.1 ~ 0.3g/mL.
Preferably, the aperture of described mesopore is 2 ~ 8nm.
Preferably, the thickness of described layer is 0.1 ~ 1 μ m.
The present invention also provides a kind of preparation method of Graphene, may further comprise the steps:
A) expanded graphite is carried out ball milling, obtain nano graphite flakes;
B) described nano graphite flakes is carried out oxidation, obtain the Graphene of partial oxidation; The carbon-to-oxygen ratio of the Graphene of described partial oxidation is 20:1 ~ 3:1;
C) with Graphene and first activator mix of described partial oxidation, heating is carried out the pore-creating first time and is obtained the micropore Graphene;
D) with described micropore Graphene and the second activator mix, heating is carried out the pore-creating second time and is obtained Graphene.
Preferably, the mass ratio of the Graphene of described partial oxidation and the first activator is 1:4 ~ 1:8.
Preferably, the mass ratio of described micropore Graphene and the second activator is 1:1 ~ 1:4.
Preferably, described the first activator and the second activator are selected from a kind of in potassium hydroxide, zinc chloride and the ozone independently of one another.
Preferably, described step C also comprises:
The Graphene of described partial oxidation is flooded in oxalic acid solution first, be heated to 400 ℃ ~ 600 ℃, the 10 ~ 30s that expands is then with the first activator mix.
Preferably, the described pore-creating first time is all carried out in steam-laden inert atmosphere with for the second time pore-creating.
The present invention also provides a kind of ultracapacitor, comprises the described Graphene of claim 1 ~ 4 any one or the prepared Graphene of claim 5 ~ 10 any one.
The invention provides a kind of Graphene and preparation method thereof, the method is carried out ball milling with expanded graphite first, obtains nano graphite flakes; Then carry out oxidation, obtain the Graphene that carbon-to-oxygen ratio is the partial oxidation of 20:1 ~ 3:1; With Graphene and first activator mix of described partial oxidation, heating is carried out the pore-creating first time and is obtained the micropore Graphene again; With the second activator mix, heating is carried out the pore-creating second time and is obtained Graphene at last.Prepare Graphene with prior art by the thermal reduction method and compare, the present invention through weak oxide and twice pore-creating step, obtains having the Graphene of central hole structure take expanded graphite alkene as raw material.At first, the present invention is uniformly dispersed through ball-milling processing take expanded graphite as raw material, obtain having the more nano graphite flakes of laminated layer structure, to its pore-creating of expanding, thereby make the Graphene that finally obtains have three-dimensional laminated structure and central hole structure, make its specific surface area higher; Secondly, the nano graphite flakes that obtains behind the ball milling is carried out weak oxide process, make the Graphene for preparing have short range order, therefore the long-range disordered structure, possesses higher tap density from macroscopic view.
Experimental result shows that the mesopore pore size of the Graphene that the present invention prepares is 2 ~ 8nm, and specific surface area is 2000 ~ 2500m
2/ g, tap density is 0.1 ~ 0.3g/mL.
Description of drawings
Fig. 1 is the stereoscan photograph of the Graphene for preparing in the embodiment of the invention 1;
Fig. 2 is the transmission electron microscope photo of the Graphene for preparing in the embodiment of the invention 1;
Fig. 3 is the X-ray diffractogram of the Graphene for preparing in the embodiment of the invention 1;
Fig. 4 is the graph of pore diameter distribution of the Graphene for preparing in the embodiment of the invention 1;
Fig. 5 is that the button-shaped electrical condenser specific storage for preparing in the embodiment of the invention 1 is with the scanning speed change curve;
Fig. 6 is the energy density graphic representation of the button-shaped electrical condenser for preparing in the embodiment of the invention 1;
Fig. 7 is discharging and recharging than electric capacity figure of the button-shaped electrical condenser for preparing in the embodiment of the invention 1;
Fig. 8 is the cyclic voltammetric performance map of the button-shaped electrical condenser for preparing in the embodiment of the invention 1.
Embodiment
The invention provides a kind of preparation method of Graphene, may further comprise the steps: A) expanded graphite is carried out ball milling, obtain the nano graphite flakes that thickness is 15 ~ 200nm; B) described nano graphite flakes is carried out oxidation, obtain the Graphene of partial oxidation; The carbon-to-oxygen ratio of the Graphene of described partial oxidation is 20:1 ~ 3:1; C) with Graphene and first activator mix of described partial oxidation, heating is carried out the pore-creating first time and is obtained the micropore Graphene; D) with described micropore Graphene and the second activator mix, heating is carried out the pore-creating second time and is obtained Graphene.
Wherein, described expanded graphite is that expanded graphite well known to those skilled in the art gets final product, and there is no special restriction.Expanded graphite described in the present invention is preferably the expanded graphite that is of a size of 50 ~ 300 μ m, more preferably 100 ~ 200 μ m.To obtain having the lamella graphite of nano thickness after the expanded graphite ball-milling processing, produce suitable distance between the lamella of the Graphene that finally obtains, and short range order, also have higher tap density when making the specific surface area of the Graphene that obtains higher.
The method of described ball milling is that method well known to those skilled in the art gets final product, and there is no special restriction, preferably carries out in ball mill among the present invention.The speed of described ball milling is preferably 200 ~ 500r/min, 300 ~ 400r/min more preferably, and the time of described ball milling is preferably 1 ~ 24h, more preferably 5 ~ 20h.
According to the present invention, be preferably 15 ~ 200nm through the thickness of ball milling resulting nano graphite flakes, 50 ~ 100nm more preferably, the easier Graphene that obtains final three-layer laminated structure.
The method for oxidation of described nano graphite flakes is that method well known to those skilled in the art gets final product, can be the Brodie method, in Staudenmaier method and the Hummers method any one, as long as the control method for oxidation make that it obtains for carbon-to-oxygen ratio is the Graphene of the partial oxidation of 20:1 ~ 3:1, there is no special restriction.The carbon-to-oxygen ratio of the Graphene of described partial oxidation is preferably 15:1 ~ 5:1.The degree of oxidation Tai Gaoyi of Graphene makes the Graphene oxygen level that finally obtains higher in the oxidising process, and oxygen-containing functional group can be induced electrolyte decomposition under high working voltage, and degree of oxidation is too low to be unfavorable for activating pore-creating.
The oxidation of nano graphite flakes described in the present invention is preferably carried out according to following steps: concentrated hydrochloric acid, concentrated nitric acid are mixed with nano graphite flakes, then slowly add Potcrate or sodium chlorate, and react under the condition of ice-water bath, obtain the Graphene of partial oxidation.The time of described reaction is preferably 12 ~ 48h, more preferably 20 ~ 35h.Can control the carbon-to-oxygen ratio of the Graphene of partial oxidation by the regulation and control reaction times.
The nano graphite flakes that obtains behind the ball milling is carried out weak oxide process, make the Graphene for preparing have short range order, therefore the long-range disordered structure, possesses higher tap density from macroscopic view.
According to the present invention, described step B preferably also comprise the Graphene water with described partial oxidation clean to the pH value for neutral.Described water is preferably deionized water, to avoid introducing other ionogen.
Described step C preferably also comprises: the Graphene of described partial oxidation is flooded in oxalic acid solution first, be heated to 400 ℃ ~ 600 ℃, be preferably 450 ℃ ~ 550 ℃, the 10 ~ 30s that expands is preferably 15 ~ 25s, then with activator mix.
Wherein, the concentration of described oxalic acid solution is 0.1 ~ 1mol/L, is preferably 0.4 ~ 0.8mol/L.Utilize oxalic acid to infiltrate again low-temperature expansion, can make the Graphene of weak oxide degree when expanding, edge can produce more fold, is beneficial to abundant infiltration and the pore-creating of later stage activator.
Described the first activator and the second activator are selected from a kind of in potassium hydroxide and the zinc chloride independently of one another.There is no impact between the first activator described in the present invention and the second activator, both can be identical material, also can be different compounds, there is no each other impact.
The mass ratio of the Graphene of described partial oxidation and the first activator is 1:4 ~ 1:8, is preferably 1:5 ~ 1:7.
The method of for the first time pore-creating is that pore forming method well known to those skilled in the art gets final product described in the present invention, there is no special restriction, for the first time pore-creating described in the present invention is preferably carried out in steam-laden inert atmosphere, more preferably carries out in steam-laden nitrogen atmosphere.The temperature of the described pore-creating first time is preferably 500 ℃ ~ 900 ℃, and more preferably 600 ℃ ~ 800 ℃, the time of the described pore-creating first time is preferably 5 ~ 24h, more preferably 10 ~ 20h.By the pore-creating first time, can on the Graphene of partial oxidation, etching make micropore, thereby obtain the micropore Graphene.
According to the present invention, reach balance for making for the first time pore-creating reaction, better for the second time pore-creating of control, described step C comprises also preferably micropore Graphene water is cleaned up repeatedly that described water is preferably deionized water, can not introduce other ionogen impurity.
The mass ratio of described micropore Graphene and the second activator is 1: 1 ~ 1:4, is preferably 1:2 ~ 1:3.The method of the described pore-creating second time also is that method well known to those skilled in the art gets final product, and there is no special restriction.Among the present invention, the described pore-creating second time is preferably carried out in steam-laden inert atmosphere, more preferably carries out in steam-laden nitrogen atmosphere.The temperature of the described pore-creating second time is preferably 500 ℃ ~ 900 ℃, and more preferably 600 ℃ ~ 800 ℃, the time of the described pore-creating second time is preferably 5 ~ 24h, more preferably 10 ~ 20h.
The present invention also provides a kind of Graphene, is obtained by above-mentioned preparation method.Described Graphene has central hole structure, has three-layer laminated structure.The aperture of described mesopore is 2 ~ 8nm, is preferably 2 ~ 5nm.The thickness of described layer is 0.1 ~ 1 μ m, is preferably 0.4 ~ 0.8 μ m.
The specific surface area of described Graphene is 2000 ~ 2500m
2/ g is preferably 2200 ~ 2400m
2/ g.The tap density of described Graphene is 0.1 ~ 0.3g/mL, is preferably 0.15 ~ 0.25g/mL.
The present invention also provides a kind of ultracapacitor, comprises the preparation-obtained Graphene of aforesaid method.The electrolytic solution of described ultracapacitor is preferably ionic liquid, more preferably 1-ethyl-3-methylimidazole a tetrafluoro borate (EMIBF
4).
The preparation method of described ultracapacitor is that method well known to those skilled in the art gets final product, and there is no special restriction.Preferably be prepared according to following steps among the present invention: Graphene, binding agent and the N-Methyl pyrrolidone (NMP) of above-mentioned preparation are stirred, obtain slurry; Described slurry is coated on the aluminium foil, oven dry obtains electrode slice, then obtains ultracapacitor with barrier film and electrolytic solution assembling, preferably assembles in glove box, wherein said electrolytic solution is for being preferably ionic liquid, more preferably 1-ethyl-3-methylimidazole a tetrafluoro borate (EMIBF
4).Described binding agent is that binding agent well known to those skilled in the art gets final product, and there is no special restriction.
The thickness that described slurry applies is preferably 150 ~ 250 μ m, more preferably 180 ~ 220 μ m.
Experiment shows, this ultracapacitor is to be 150F/g than electric capacity under the condition of 1mV/s in scanning speed.
In order to further specify the present invention, below in conjunction with embodiment to the invention provides Graphene and preparation method thereof, ultracapacitor is described in detail.
Used reagent is commercially available in following examples.
1.1 5g is of a size of under the condition of 50 μ m expanded graphite 300r/min in ball mill, ball milling 5h obtains the nano graphite flakes that thickness is 100nm.
1.2 mix obtaining nano graphite flakes, 87.5ml concentrated hydrochloric acid and 45ml concentrated nitric acid among the 5g 1.1, then slowly add 45g Potcrate, react 24h under the condition of ice-water bath, obtain the Graphene of partial oxidation, it is cleaned to the pH value repeatedly with deionized water is neutral.
1.3 with the Graphene of the partial oxidation that obtains among the 5g 1.2 in the oxalic acid solution of 0.5mol/L fully behind the dipping, in tube furnace, be heated to 500 ℃ of low-temperature expansion 20s, after Graphene after expanding and potassium hydroxide mixed according to mass ratio 1:6, in the tube furnace of the nitrogen atmosphere that contains water vapour, be heated to 600 ℃ and process 12h, obtain the micropore Graphene.
Mix according to mass ratio 1:2 1.4 the micropore Graphene that obtains in 1.3 is cleaned up rear potassium hydroxide repeatedly with deionized water, in the tube furnace of the nitrogen atmosphere that contains water vapour, be heated to 700 ℃ and process 12h, obtain Graphene.
1.5 with Graphene, binding agent and an amount of NMP that obtains in the 1.4 formation slurry that stirs, the mass ratio of described Graphene and binding agent is 9:1, slurry is coated on the 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, be assembled into 2023 button-shaped electrical condensers with barrier film and electrolytic solution, electrolytic solution is 1-ethyl-3-methylimidazole a tetrafluoro borate (EMIBF
4).
Utilize scanning electron microscope that the Graphene that obtains in 1.4 is analyzed, obtain its stereoscan photograph, as shown in Figure 1.
Utilize transmission electron microscope that the Graphene that obtains in 1.4 is analyzed, obtain its transmission electron microscope photo, as shown in Figure 2.By Fig. 1 and Fig. 2 as can be known, the graphene layer thickness that the present invention prepares is 0.5 μ m, and surface apertures is about 5nm.
Utilize the Graphene that obtains in the Graphene and 1.4 after the expansion that obtains in the Graphene, 1.3 of X-ray diffractometer to the partial oxidation that obtains in 1.2 to analyze, obtain X-ray diffractogram, as shown in Figure 3, wherein a is the Graphene of the partial oxidation that obtains in 1.2, b is the Graphene after the expansion that obtains in 1.3, and c is the Graphene that obtains in 1.4.002 diffraction peak becomes sharply after the Graphene activation pore-creating as shown in Figure 3, and peak width at half height is reduced to 6 degree by 8 degree, and it is large that its particle size becomes, and 002 peak diffracted intensity strengthens simultaneously, illustrates that reunion has to a certain degree occured Graphene in reactivation process.
Utilize the pore size distribution analyser that the Graphene that obtains in 1.4 is analyzed, obtain its graph of pore diameter distribution, as shown in Figure 4, the aperture of Graphene is mainly about 5nm as shown in Figure 4.
By nitrogen absorption test, obtaining its specific surface area is 2500m to the Graphene that obtains in 1.4
2/ g.
The mesopore Graphene of 0.3g is joined in the 25ml graduated cylinder, and through up and down concussion, it is 0.3g/mL that at last range estimation obtains its tap density.
The button-shaped electrical condenser that obtains in 1.5 is carried out electrochemical property test, obtain its specific storage with the scanning speed change curve, as shown in Figure 5, obtain its energy density graphic representation, as shown in Figure 6.By Fig. 5 and Fig. 6 as can be known, sweep under the speed in that 50mV/s is low, the specific storage of button-shaped electrical condenser is 120F/g, and corresponding energy density is 75Wh/kg; Sweep under the speed at the 300mV/s height, the specific storage of button-shaped electrical condenser is 100F/g, and corresponding energy density is 55Wh/kg.
The button-shaped electrical condenser that obtains in 1.5 is carried out the charge-discharge performance test, obtain it and discharge and recharge than electric capacity figure, as shown in Figure 7.As shown in Figure 7, be to circulate 2000 times under the 1A/g condition in current density, capability retention is 80%.
The button-shaped electrical condenser that obtains in 1.5 is utilized cyclic voltammetry analysis, obtain its cyclic voltammetric performance map, as shown in Figure 8, wherein 1 scanning speed is 300mV/s, 2 scanning speeds are 100mV/s, 3 scanning speeds are 50mV/s, as shown in Figure 8, window voltage at 0 ~ 4V, scanning speed is under the condition of 300mV/s, the cyclic voltammetry curve of button-shaped electrical condenser keeps good rectangular configuration, illustrates that the grapheme material that the present invention prepares can keep rock steady structure under the high-voltage cycle charge-discharge, and this material is fit to high current charge-discharge.
2.1 5g is of a size of under the condition of expanded graphite 200r/min in ball mill of 50 μ m, ball milling 24h obtains the nano graphite flakes that thickness is 15nm.
2.2 mix obtaining nano graphite flakes, 87.5ml concentrated hydrochloric acid and 45ml concentrated nitric acid among the 5g 2.1, then slowly add the 45g sodium chlorate, react 48h under the condition of ice-water bath, obtain the Graphene of partial oxidation, it is cleaned to the pH value repeatedly with deionized water is neutral.
2.3 with the Graphene of the partial oxidation that obtains among the 5g 2.2 in the oxalic acid solution of 1mol/L fully behind the dipping, in tube furnace, be heated to 600 ℃ of low-temperature expansion 30s, after Graphene after expanding and potassium hydroxide mixed according to mass ratio 1:8, in the tube furnace of the nitrogen atmosphere that contains water vapour, be heated to 900 ℃ and process 5h, obtain the micropore Graphene.
Mix according to mass ratio 1:1 2.4 the micropore Graphene that obtains in 2.3 is cleaned up rear potassium hydroxide repeatedly with deionized water, in the tube furnace of the nitrogen atmosphere that contains water vapour, be heated to 900 ℃ and process 5h, obtain Graphene.
2.5 with Graphene, binding agent and an amount of NMP that obtains in the 2.4 formation slurry that stirs, the mass ratio of described Graphene and binding agent is 9:1, slurry is coated on the 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, be assembled into 2023 button-shaped electrical condensers with barrier film and electrolytic solution, electrolytic solution is 1-ethyl-3-methylimidazole a tetrafluoro borate (EMIBF
4).
The mesopore Graphene of 0.3g is joined in the 25ml graduated cylinder, and through up and down concussion, it is 0.25g/mL that at last range estimation obtains its tap density.
3.1 5g is of a size of under the condition of expanded graphite 500r/min in ball mill of 100 μ m, ball milling 1h obtains the nano graphite flakes that thickness is 200nm.
3.2 mix obtaining nano graphite flakes, 87.5ml concentrated hydrochloric acid and 45ml concentrated nitric acid among the 5g 3.1, then slowly add 45g Potcrate, react 12h under the condition of ice-water bath, obtain the Graphene of partial oxidation, it is cleaned to the pH value repeatedly with deionized water is neutral.
3.3 with the Graphene of the partial oxidation that obtains among the 5g 3.2 in the oxalic acid solution of 0.1mol/L fully behind the dipping, in tube furnace, be heated to 400 ℃ of low-temperature expansion 10s, after Graphene after expanding and potassium hydroxide mixed according to mass ratio 1:4, in the tube furnace of the nitrogen atmosphere that contains water vapour, be heated to 500 ℃ and process 24h, obtain the micropore Graphene.
Mix according to mass ratio 1:4 3.4 the micropore Graphene that obtains in 3.3 is cleaned up rear potassium hydroxide repeatedly with deionized water, in the tube furnace of the nitrogen atmosphere that contains water vapour, be heated to 500 ℃ and process 24h, obtain Graphene.
3.5 with Graphene, binding agent and an amount of NMP that obtains in the 3.4 formation slurry that stirs, the mass ratio of described Graphene and binding agent is 9:1, slurry is coated on the 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, be assembled into 2023 button-shaped electrical condensers with barrier film and electrolytic solution, electrolytic solution is 1-ethyl-3-methylimidazole a tetrafluoro borate (EMIBF
4).
The mesopore Graphene of 0.3g is joined in the 25ml graduated cylinder, and through up and down concussion, it is 0.1g/mL that at last range estimation obtains its tap density.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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 (11)
1. a Graphene is characterized in that having central hole structure, has three-layer laminated structure.
2. Graphene according to claim 1 is characterized in that, the specific surface area of described Graphene is 2000 ~ 2500m
2/ g, the tap density of described Graphene is 0.1 ~ 0.3g/mL.
3. Graphene according to claim 1 is characterized in that, the aperture of described mesopore is 2 ~ 8nm.
4. Graphene according to claim 1 is characterized in that, the thickness of described layer is 0.1 ~ 1 μ m.
5. the preparation method of a Graphene is characterized in that, may further comprise the steps:
A) expanded graphite is carried out ball milling, obtain nano graphite flakes;
B) described nano graphite flakes is carried out oxidation, obtain the Graphene of partial oxidation; The carbon-to-oxygen ratio of the Graphene of described partial oxidation is 20:1 ~ 3:1;
C) with Graphene and first activator mix of described partial oxidation, heating is carried out the pore-creating first time and is obtained the micropore Graphene;
D) with described micropore Graphene and the second activator mix, heating is carried out the pore-creating second time and is obtained Graphene.
6. preparation method according to claim 5 is characterized in that, the mass ratio of the Graphene of described partial oxidation and the first activator is 1:4 ~ 1:8.
7. preparation method according to claim 5 is characterized in that, the mass ratio of described micropore Graphene and the second activator is 1:1 ~ 1:4.
8. preparation method according to claim 5 is characterized in that, described the first activator and the second activator are selected from a kind of in potassium hydroxide and the zinc chloride independently of one another.
9. preparation method according to claim 5 is characterized in that, described step C also comprises:
The Graphene of described partial oxidation is flooded in oxalic acid solution first, be heated to 400 ℃ ~ 600 ℃, the 10 ~ 30s that expands is then with the first activator mix.
10. preparation method according to claim 5 is characterized in that, the described pore-creating first time is all carried out in steam-laden inert atmosphere with for the second time pore-creating.
11. a ultracapacitor is characterized in that, comprises the described Graphene of claim 1 ~ 4 any one or the prepared Graphene of claim 5 ~ 10 any one.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303913A (en) * | 2013-07-05 | 2013-09-18 | 中国科学院宁波材料技术与工程研究所 | Porous graphene, preparation method thereof, and supercapacitor |
| CN103332689A (en) * | 2013-07-17 | 2013-10-02 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of porous graphene nano band |
| CN103570012A (en) * | 2013-10-29 | 2014-02-12 | 复旦大学 | Preparation method of graphene |
| CN104163417A (en) * | 2013-05-20 | 2014-11-26 | 东丽先端材料研究开发（中国）有限公司 | Method for preparing graphene by peeling off graphite |
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| WO2017190417A1 (en) * | 2016-05-06 | 2017-11-09 | 清华大学深圳研究生院 | Method for preparing thick and dense graphene-based electrode |
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Families Citing this family (1)
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|---|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973542A (en) * | 2010-11-26 | 2011-02-16 | 深圳市今朝时代新能源技术有限公司 | Preparation method of porous carbon material for supercapacitor |
| CN102424382A (en) * | 2011-09-16 | 2012-04-25 | 中国科学院宁波材料技术与工程研究所 | Method for preparing high-specific-surface-area graphene under conditions of normal pressure and low temperature |
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
| CN102543483A (en) * | 2012-01-17 | 2012-07-04 | 电子科技大学 | Preparation method of graphene material of supercapacitor |
| CN102826542A (en) * | 2012-09-14 | 2012-12-19 | 常州第六元素材料科技股份有限公司 | High-specific surface active graphene with mesoporous and preparation method and application thereof |
-
2012
- 2012-12-20 CN CN201210560251.6A patent/CN103011143B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973542A (en) * | 2010-11-26 | 2011-02-16 | 深圳市今朝时代新能源技术有限公司 | Preparation method of porous carbon material for supercapacitor |
| CN102424382A (en) * | 2011-09-16 | 2012-04-25 | 中国科学院宁波材料技术与工程研究所 | Method for preparing high-specific-surface-area graphene under conditions of normal pressure and low temperature |
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
| CN102543483A (en) * | 2012-01-17 | 2012-07-04 | 电子科技大学 | Preparation method of graphene material of supercapacitor |
| CN102826542A (en) * | 2012-09-14 | 2012-12-19 | 常州第六元素材料科技股份有限公司 | High-specific surface active graphene with mesoporous and preparation method and application thereof |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163417B (en) * | 2013-05-20 | 2018-01-12 | 东丽先端材料研究开发（中国）有限公司 | A kind of method for peeling off preparing graphite alkene |
| CN104163417A (en) * | 2013-05-20 | 2014-11-26 | 东丽先端材料研究开发（中国）有限公司 | Method for preparing graphene by peeling off graphite |
| CN103303913A (en) * | 2013-07-05 | 2013-09-18 | 中国科学院宁波材料技术与工程研究所 | Porous graphene, preparation method thereof, and supercapacitor |
| CN103303913B (en) * | 2013-07-05 | 2015-10-07 | 中国科学院宁波材料技术与工程研究所 | A kind of porous graphene and preparation method thereof, ultracapacitor |
| CN103332689B (en) * | 2013-07-17 | 2016-03-30 | 中国科学院宁波材料技术与工程研究所 | A kind of porous graphene nano belt and preparation method thereof and application |
| CN103332689A (en) * | 2013-07-17 | 2013-10-02 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of porous graphene nano band |
| CN103570012B (en) * | 2013-10-29 | 2016-04-27 | 安徽百特新材料科技有限公司 | A kind of preparation method of Graphene |
| CN103570012A (en) * | 2013-10-29 | 2014-02-12 | 复旦大学 | Preparation method of graphene |
| CN104591176A (en) * | 2015-02-04 | 2015-05-06 | 中国科学院宁波材料技术与工程研究所 | Method for preparing graphene |
| CN105271170A (en) * | 2015-11-03 | 2016-01-27 | 山西中兴环能科技有限公司 | Preparation method of nano carbon and composite material of nano carbon |
| CN105271170B (en) * | 2015-11-03 | 2017-04-19 | 山西中兴环能科技有限公司 | Preparation method of nano carbon and composite material of nano carbon |
| WO2017190417A1 (en) * | 2016-05-06 | 2017-11-09 | 清华大学深圳研究生院 | Method for preparing thick and dense graphene-based electrode |
| CN106449129A (en) * | 2016-09-29 | 2017-02-22 | 成都新柯力化工科技有限公司 | Graphene self-assembled electrode material for super-capacitor and preparation method |
| CN106449129B (en) * | 2016-09-29 | 2018-03-27 | 成都新柯力化工科技有限公司 | A kind of ultracapacitor graphene self-assembling electrode material and preparation method |
| CN108155025A (en) * | 2017-12-26 | 2018-06-12 | 北京化工大学 | A kind of high-density graphite alkene material, preparation method and its stored energy application |
| CN108155025B (en) * | 2017-12-26 | 2020-09-04 | 北京化工大学 | High-density graphene material, preparation method and energy storage application thereof |
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