CN103011143B - Graphene and fabrication method thereof and super capacitor - Google Patents
Graphene and fabrication method thereof and super capacitor Download PDFInfo
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- CN103011143B CN103011143B CN201210560251.6A CN201210560251A CN103011143B CN 103011143 B CN103011143 B CN 103011143B CN 201210560251 A CN201210560251 A CN 201210560251A CN 103011143 B CN103011143 B CN 103011143B
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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 organic semiconducting materials technical field, particularly relate to Graphene and preparation method thereof, ultracapacitor.
Background technology
Along with the continuous expansion of informationized society and the appearance of environment and energy crisis, energy storage is more and more important in conversion efficiency problem.In various energy conversion system, ultracapacitor due to have charge/discharge rates fast, have extended cycle life, comparatively safe, serviceability temperature is wide, environmental friendliness and the good characteristic such as non-maintaining and be applied to stand-by power supply, start the fields such as power supply, the pulse power, grid balance.According to the difference of energy storage mechnism, ultracapacitor can be divided into double electric layer capacitor and pseudocapacitors or redox capacitors.Double electric layer capacitor mainly relies on the electric double layer of electrode and electrolyte interface to carry out stored charge, and the specific area utilizing electrode material huge is by physical process store electrical energy, and its electrode material is mainly the material with carbon element of high-specific surface area.Pseudocapacitors mainly relies on the redox reaction of electrode active material generation Rapid reversible to carry out stored charge, and corresponding electrode material is mainly metal oxide and conducting polymer.
Ultracapacitor is primarily of parts compositions such as current collection fluid, electrolyte, electrode material and barrier films, and wherein the performance of electrode material to ultracapacitor plays key effect, is the core component of ultracapacitor.Existing electrode material has porous carbon materials, metal oxide containing precious metals and conductive polymer polymer.Wherein active carbon is a kind of electrode material being applied to ultracapacitor the earliest, and it has very large specific area and abundant inner hole structure, and the formation that can be electric double layer provides huge surface area.Especially for aqueous systems electrolyte, electrolyte ion diameter is less, and in micropore, diffusion mass transfer is easier to carry out, and also more easily infiltrates activated carbon surface, thus material surface area can be fully used.
But active carbon energy density is lower, can only be applied in aqueous systems electrolyte, and the 1-ethyl-3-methylimidazole tetrafluoroborate (EMIBF of 4V can be reached in operating voltage
4) when applying in ionic liquid class electrolyte, have following shortcoming: conductivity is poor, and most of pore size distribution is in the inside of particle, under high current charge-discharge, ion is obstructed at the active carbon pore diffusion of complications, and specific capacity declines rapidly.Activated carbon surface has part oxygen-containing functional group simultaneously, and under high working voltage, oxygen-containing functional group can induce the decomposition of electrolyte.Commercial organic system super capacitor energy density at present based on mesopore activated carbon only has 5 ~ 6Wh/kg, and still there is a big difference compared with the energy density (being about 150Wh/kg) of lithium ion battery.
Research finds, Graphene not only has huge theoretical specific surface area, and physicochemical properties are stablized, good structural stability can be kept under high working voltage and big current fast charging and discharging, also there is excellent conductivity simultaneously, can internal resistance be reduced, improve the cyclical stability of ultracapacitor.But Graphene tap density prepared by dilatometry only has 0.005m
2/ g, the energy density based on volume computing is low, and because Graphene is very easily reunited in preparation and use procedure, specific area utilance is low, is therefore unfavorable for practical application.The Graphene specific area that Liu etc. use thermal reduction method to prepare is about 500.6m
2/ g, specific capacity 154.1F/g under organism liquid, energy density based on active material is 85.6Wh/kg(Liu CG, Yasuda S, Yu ZN, et al.Nano Lett.2010,10:4863-4868), its specific area still has very large gap apart from theoretical specific surface area, and the modification therefore 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, the Graphene specific area that the method prepares and tap density higher.
The invention provides a kind of Graphene, there is central hole structure, there is three-layer laminated structure.
Preferably, the specific 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 μm.
Present invention also offers a kind of preparation method of Graphene, comprise the following steps:
A) expanded graphite is carried out ball milling, obtain nano graphite flakes;
B) described nano graphite flakes is oxidized, obtains the Graphene of partial oxidation; The carbon-to-oxygen ratio of the Graphene of described partial oxidation is 20:1 ~ 3:1;
C) by the Graphene of described partial oxidation and the first activator mix, heating is carried out first time pore-creating and is obtained micropore Graphene;
D) by described micropore Graphene and the second activator mix, heating is carried out second time pore-creating and is obtained Graphene.
Preferably, the Graphene of described partial oxidation and the mass ratio of the first activator are 1:4 ~ 1:8.
Preferably, the mass ratio of described micropore Graphene and the second activator is 1:1 ~ 1:4.
Preferably, described first activator and the second activator are selected from the one in potassium hydroxide, zinc chloride and ozone independently of one another.
Preferably, described step C also comprises:
First flooded in oxalic acid solution by the Graphene of described partial oxidation, be heated to 400 DEG C ~ 600 DEG C, expand 10 ~ 30s, then with the first activator mix.
Preferably, described first time pore-creating is all carried out with second time pore-creating in steam-laden inert atmosphere.
Present invention also offers a kind of ultracapacitor, comprise the Graphene described in claim 1 ~ 4 any one or the Graphene prepared by claim 5 ~ 10 any one.
The invention provides a kind of Graphene and preparation method thereof, expanded graphite is first carried out ball milling by the method, obtains nano graphite flakes; Then be oxidized, obtain the Graphene that carbon-to-oxygen ratio is the partial oxidation of 20:1 ~ 3:1; Again by the Graphene of described partial oxidation and the first activator mix, heating is carried out first time pore-creating and is obtained micropore Graphene; Finally with the second activator mix, heating is carried out second time pore-creating and is obtained Graphene.Prepare compared with Graphene with prior art by thermal reduction method, the present invention for raw material, through weak oxide and twice pore-creating step, obtains the Graphene with central hole structure with expanded graphite alkene.First, the present invention is raw material with expanded graphite, is uniformly dispersed through ball-milling treatment, obtain having the nano graphite flakes of more lamella structure, expansion pore-creating is carried out to it, thus makes the Graphene finally obtained have three-dimensional plate Rotating fields and central hole structure, make its specific area higher; Secondly, weak oxide process is carried out to the nano graphite flakes obtained after ball milling, makes the Graphene prepared have shortrange order, longrange disorder structure, therefore, from macroscopically possessing higher tap density.
Experimental result shows, the mesopore pore size size of the Graphene that the present invention prepares is 2 ~ 8nm, and specific area is 2000 ~ 2500m
2/ g, tap density is 0.1 ~ 0.3g/mL.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the Graphene prepared in the embodiment of the present invention 1;
Fig. 2 is the transmission electron microscope photo of the Graphene prepared in the embodiment of the present invention 1;
Fig. 3 is the X-ray diffractogram of the Graphene prepared in the embodiment of the present invention 1;
Fig. 4 is the graph of pore diameter distribution of the Graphene prepared in the embodiment of the present invention 1;
Fig. 5 is that the button-shaped capacitor specific capacity for preparing in the embodiment of the present invention 1 is with sweep speed change curve;
Fig. 6 is the energy density profile figure of the button-shaped capacitor prepared in the embodiment of the present invention 1;
Fig. 7 is the discharge and recharge ratio capacitance figure of the button-shaped capacitor prepared in the embodiment of the present invention 1;
Fig. 8 is the cyclic voltammetric performance map of the button-shaped capacitor prepared in the embodiment of the present invention 1.
Embodiment
The invention provides a kind of preparation method of Graphene, comprise the following 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 oxidized, obtains the Graphene of partial oxidation; The carbon-to-oxygen ratio of the Graphene of described partial oxidation is 20:1 ~ 3:1; C) by the Graphene of described partial oxidation and the first activator mix, heating is carried out first time pore-creating and is obtained micropore Graphene; D) by described micropore Graphene and the second activator mix, heating is carried out second time pore-creating and is obtained Graphene.
Wherein, described expanded graphite is expanded graphite well known to those skilled in the art, there is no special restriction.Expanded graphite described in the present invention is preferably of a size of the expanded graphite of 50 ~ 300 μm, is more preferably 100 ~ 200 μm.Obtain the Sheet Graphite with nano thickness by after expanded graphite ball-milling treatment, between the lamella of the Graphene finally obtained, produce suitable distance, and shortrange order, while making the specific area of the Graphene obtained higher, also there is higher tap density.
The method of described ball milling is method well known to those skilled in the art, there is no special restriction, preferably carries out in ball mill in the present invention.The speed of described ball milling is preferably 200 ~ 500r/min, is more preferably 300 ~ 400r/min, and the time of described ball milling is preferably 1 ~ 24h, is more preferably 5 ~ 20h.
According to the present invention, the thickness of the nano graphite flakes obtained through ball milling is preferably 15 ~ 200nm, is more preferably 50 ~ 100nm, more easily obtains the Graphene of final three-layer laminated structure.
The method for oxidation of described nano graphite flakes is method well known to those skilled in the art, can be Brodie method, any one in Staudenmaier method and Hummers method, as long as the Graphene of what controlled oxidization method made it obtain for carbon-to-oxygen ratio the is 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.In oxidizing process, the degree of oxidation Tai Gaoyi of Graphene makes the Graphene oxygen content that finally obtains higher, and under high working voltage, oxygen-containing functional group can induce electrolyte decomposition, and degree of oxidation too low being unfavorable for carries out activation pore-creating.
The oxidation of nano graphite flakes described in the present invention is preferably carried out according to following steps: concentrated hydrochloric acid, red fuming nitric acid (RFNA) are mixed with nano graphite flakes, then slowly adds potassium chlorate or sodium chlorate, and reacts under the condition of ice-water bath, obtains the Graphene of partial oxidation.The time of described reaction is preferably 12 ~ 48h, is more preferably 20 ~ 35h.Control by the regulation and control carbon-to-oxygen ratio of reaction time to the Graphene of partial oxidation.
Weak oxide process is carried out to the nano graphite flakes obtained after ball milling, makes the Graphene prepared have shortrange order, longrange disorder structure, therefore, from macroscopically possessing higher tap density.
According to the present invention, it is neutral that described step B preferably also comprises the Graphene water of described partial oxidation cleaning to pH value.Described water is preferably deionized water, to avoid the electrolyte introducing other.
Described step C preferably also comprises: first flooded in oxalic acid solution by the Graphene of described partial oxidation, be heated to 400 DEG C ~ 600 DEG C, is preferably 450 DEG C ~ 550 DEG C, and expand 10 ~ 30s, 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 carry out infiltrating low-temperature expansion again, the Graphene of weak oxide degree can be made when expanding, and edge can produce more fold, is beneficial to abundant infiltration and the pore-creating of later stage activator.
Described first activator and the second activator are selected from the one in potassium hydroxide and zinc chloride independently of one another.There is no impact between first activator and the second activator described in the present invention, both can be identical material, also can be different compounds, there is no impact each other.
The Graphene of described partial oxidation and the mass ratio of the first activator are 1:4 ~ 1:8, are preferably 1:5 ~ 1:7.
Described in the present invention, the method for first time pore-creating is pore forming method well known to those skilled in the art, there is no special restriction, first time pore-creating described in the present invention is preferably carried out in steam-laden inert atmosphere, is more preferably and carries out in steam-laden nitrogen atmosphere.The temperature of described first time pore-creating is preferably 500 DEG C ~ 900 DEG C, is more preferably 600 DEG C ~ 800 DEG C, and the time of described first time pore-creating is preferably 5 ~ 24h, is more preferably 10 ~ 20h.By first time pore-creating, can etch on the Graphene of partial oxidation and manufacture micropore, thus obtain micropore Graphene.
According to the present invention, for making first time pore-creating reaction reach balance, control second time pore-creating better, described step C preferably also comprises and repeatedly being cleaned up by micropore Graphene water, and described water is preferably deionized water, can not introduce other electrolyte 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 described second time pore-creating is also method well known to those skilled in the art, there is no special restriction.In the present invention, described second time pore-creating is preferably carried out in steam-laden inert atmosphere, is more preferably and carries out in steam-laden nitrogen atmosphere.The temperature of described second time pore-creating is preferably 500 DEG C ~ 900 DEG C, is more preferably 600 DEG C ~ 800 DEG C, and the time of described second time pore-creating is preferably 5 ~ 24h, is more preferably 10 ~ 20h.
Present invention also offers a kind of Graphene, 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 μm, is preferably 0.4 ~ 0.8 μm.
The specific 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.
Present invention also offers a kind of ultracapacitor, comprise the preparation-obtained Graphene of said method.The electrolyte of described ultracapacitor is preferably ionic liquid, is more preferably 1-ethyl-3-methylimidazole tetrafluoroborate (EMIBF
4).
The preparation method of described ultracapacitor is method well known to those skilled in the art, there is no special restriction.Preferably be prepared according to following steps in the present invention: the Graphene of above-mentioned preparation, binding agent and 1-METHYLPYRROLIDONE (NMP) are stirred, obtains slurry; Described slurry is coated on aluminium foil, oven dry obtains electrode slice, then assembles with barrier film and electrolyte and obtains ultracapacitor, preferably assemble in glove box, wherein said electrolyte, for being preferably ionic liquid, is more preferably 1-ethyl-3-methylimidazole tetrafluoroborate (EMIBF
4).Described binding agent is binding agent well known to those skilled in the art, there is no special restriction.
The thickness of described slurry coating is preferably 150 ~ 250 μm, is more preferably 180 ~ 220 μm.
Experiment shows, this ultracapacitor ratio capacitance under sweep speed is the condition of 1mV/s is 150F/g.
In order to further illustrate the present invention, below in conjunction with embodiment to the invention provides Graphene and preparation method thereof, ultracapacitor is described in detail.
Reagent used in following examples is commercially available.
Embodiment 1
1.1 5g is of a size of the condition of 50 μm of expanded graphite 300r/min in ball mill under, ball milling 5h, obtains the nano graphite flakes that thickness is 100nm.
1.2 by obtaining nano graphite flakes in 5g 1.1,87.5ml concentrated hydrochloric acid mixes with 45ml red fuming nitric acid (RFNA), then 45g potassium chlorate is slowly added, under the condition of ice-water bath, react 24h, obtain the Graphene of partial oxidation, it is neutral for it repeatedly being cleaned to pH value with deionized water.
1.3 by the Graphene of partial oxidation that obtains in 5g 1.2 in the oxalic acid solution of 0.5mol/L fully after dipping, 500 DEG C of low-temperature expansion 20s are heated in tube furnace, after Graphene after expansion is mixed according to mass ratio 1:6 with potassium hydroxide, in the tube furnace of the nitrogen atmosphere containing steam, be heated to 600 DEG C of process 12h, obtain micropore Graphene.
The micropore Graphene deionized water obtained in 1.3 is cleaned up rear potassium hydroxide by 1.4 repeatedly to be mixed according to mass ratio 1:2, is heated to 700 DEG C of process 12h, obtains Graphene in the tube furnace of the nitrogen atmosphere containing steam.
The Graphene obtained in 1.4, binding agent and appropriate NMP to stir formation slurry by 1.5, the mass ratio of described Graphene and binding agent is 9:1, slurry is coated on aluminium foil, thickness is 200 μm, dry under 120 DEG C of conditions, be then cut into the electrode slice that diameter is 13mm, in glove box, be assembled into 2023 button-shaped capacitors with barrier film and electrolyte, electrolyte is 1-ethyl-3-methylimidazole tetrafluoroborate (EMIBF
4).
Utilize ESEM to analyze the Graphene obtained in 1.4, obtain its stereoscan photograph, as shown in Figure 1.
Utilize transmission electron microscope to analyze the Graphene obtained in 1.4, obtain its transmission electron microscope photo, as shown in Figure 2.From Fig. 1 and Fig. 2, the graphene layer thickness that the present invention prepares is 0.5 μm, and surface apertures is about 5nm.
X-ray diffractometer is utilized to analyze the Graphene obtained in the Graphene and 1.4 after the expansion obtained in the Graphene, 1.3 of the partial oxidation obtained in 1.2, obtain X-ray diffractogram, as shown in Figure 3, wherein a is the Graphene of the partial oxidation obtained in 1.2, b is the Graphene after the expansion obtained in 1.3, and c is the Graphene obtained in 1.4.After Graphene activation pore-creating, 002 diffraction maximum becomes sharp-pointed as shown in Figure 3, and half-peak breadth is reduced to 6 degree by 8 degree, and its particle size becomes large, and 002 peak diffracted intensity strengthens simultaneously, illustrates that Graphene there occurs reunion to a certain degree in activation process.
Utilize pore-size distribution analyzer to analyze the Graphene obtained in 1.4, obtain its graph of pore diameter distribution, as shown in Figure 4, the aperture of Graphene is mainly at about 5nm as shown in Figure 4.
Tested by N2 adsorption the Graphene obtained in 1.4, obtaining its specific area is 2500m
2/ g.
Join in 25ml graduated cylinder by the mesopore Graphene of 0.3g, through shaking up and down, finally range estimation obtains its tap density is 0.3g/mL.
Electrochemical property test is carried out to the button-shaped capacitor obtained in 1.5, obtains its specific capacity with sweep speed change curve, as shown in Figure 5, obtain its energy density profile figure, as shown in Figure 6.From Fig. 5 and Fig. 6,50mV/s is low sweep speed under, the specific capacity of button-shaped capacitor is 120F/g, and corresponding energy density is 75Wh/kg; 300mV/s is high sweep speed under, the specific capacity of button-shaped capacitor is 100F/g, and corresponding energy density is 55Wh/kg.
Charge-discharge performance test is carried out to the button-shaped capacitor obtained in 1.5, obtains its discharge and recharge ratio capacitance figure, as shown in Figure 7.As shown in Figure 7, circulate 2000 times under current density is 1A/g condition, capability retention is 80%.
Cyclic voltammetry analysis is utilized to the button-shaped capacitor obtained in 1.5, obtain its cyclic voltammetric performance map, as shown in Figure 8, wherein 1 sweep speed is 300mV/s, 2 sweep speeds are 100mV/s, 3 sweep speeds are 50mV/s, as shown in Figure 8, in the window voltage of 0 ~ 4V, sweep speed is under the condition of 300mV/s, the cyclic voltammetry curve of button-shaped capacitor keeps good rectangular configuration, and illustrate that the grapheme material that the present invention prepares can keep rock-steady structure under high voltage cycle charge-discharge, this material is applicable to high current charge-discharge.
Embodiment 2
2.1 5g is of a size of the condition of expanded graphite 200r/min in ball mill of 50 μm under, ball milling 24h, obtains the nano graphite flakes that thickness is 15nm.
2.2 by obtaining nano graphite flakes in 5g 2.1,87.5ml concentrated hydrochloric acid mixes with 45ml red fuming nitric acid (RFNA), then 45g sodium chlorate is slowly added, under the condition of ice-water bath, react 48h, obtain the Graphene of partial oxidation, it is neutral for it repeatedly being cleaned to pH value with deionized water.
2.3 by the Graphene of partial oxidation that obtains in 5g 2.2 in the oxalic acid solution of 1mol/L fully after dipping, 600 DEG C of low-temperature expansion 30s are heated in tube furnace, after Graphene after expansion is mixed according to mass ratio 1:8 with potassium hydroxide, in the tube furnace of the nitrogen atmosphere containing steam, be heated to 900 DEG C of process 5h, obtain micropore Graphene.
The micropore Graphene deionized water obtained in 2.3 is cleaned up rear potassium hydroxide by 2.4 repeatedly to be mixed according to mass ratio 1:1, is heated to 900 DEG C of process 5h, obtains Graphene in the tube furnace of the nitrogen atmosphere containing steam.
The Graphene obtained in 2.4, binding agent and appropriate NMP to stir formation slurry by 2.5, the mass ratio of described Graphene and binding agent is 9:1, slurry is coated on aluminium foil, thickness is 200 μm, dry under 120 DEG C of conditions, be then cut into the electrode slice that diameter is 13mm, in glove box, be assembled into 2023 button-shaped capacitors with barrier film and electrolyte, electrolyte is 1-ethyl-3-methylimidazole tetrafluoroborate (EMIBF
4).
Join in 25ml graduated cylinder by the mesopore Graphene of 0.3g, through shaking up and down, finally range estimation obtains its tap density is 0.25g/mL.
Embodiment 3
3.1 5g is of a size of the condition of expanded graphite 500r/min in ball mill of 100 μm under, ball milling 1h, obtains the nano graphite flakes that thickness is 200nm.
3.2 by obtaining nano graphite flakes in 5g 3.1,87.5ml concentrated hydrochloric acid mixes with 45ml red fuming nitric acid (RFNA), then 45g potassium chlorate is slowly added, under the condition of ice-water bath, react 12h, obtain the Graphene of partial oxidation, it is neutral for it repeatedly being cleaned to pH value with deionized water.
3.3 by the Graphene of partial oxidation that obtains in 5g 3.2 in the oxalic acid solution of 0.1mol/L fully after dipping, 400 DEG C of low-temperature expansion 10s are heated in tube furnace, after Graphene after expansion is mixed according to mass ratio 1:4 with potassium hydroxide, in the tube furnace of the nitrogen atmosphere containing steam, be heated to 500 DEG C of process 24h, obtain micropore Graphene.
The micropore Graphene deionized water obtained in 3.3 is cleaned up rear potassium hydroxide by 3.4 repeatedly to be mixed according to mass ratio 1:4, is heated to 500 DEG C of process 24h, obtains Graphene in the tube furnace of the nitrogen atmosphere containing steam.
The Graphene obtained in 3.4, binding agent and appropriate NMP to stir formation slurry by 3.5, the mass ratio of described Graphene and binding agent is 9:1, slurry is coated on aluminium foil, thickness is 200 μm, dry under 120 DEG C of conditions, be then cut into the electrode slice that diameter is 13mm, in glove box, be assembled into 2023 button-shaped capacitors with barrier film and electrolyte, electrolyte is 1-ethyl-3-methylimidazole tetrafluoroborate (EMIBF
4).
Join in 25ml graduated cylinder by the mesopore Graphene of 0.3g, through shaking up and down, finally range estimation obtains its tap density is 0.1g/mL.
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 (10)
1. a Graphene, is characterized in that, has central hole structure, has three-layer laminated structure; The specific area of described Graphene is 2000 ~ 2500m
2/ g, the tap density of described Graphene is 0.1 ~ 0.3g/mL.
2. Graphene according to claim 1, is characterized in that, the aperture of described mesopore is 2 ~ 8nm.
3. Graphene according to claim 1, is characterized in that, the thickness of described layer is 0.1 ~ 1 μm.
4. a preparation method for Graphene, is characterized in that, comprises the following steps:
A) expanded graphite is carried out ball milling, obtain nano graphite flakes;
B) described nano graphite flakes is oxidized, obtains the Graphene of partial oxidation; The carbon-to-oxygen ratio of the Graphene of described partial oxidation is 20:1 ~ 3:1;
C) by the Graphene of described partial oxidation and the first activator mix, heating is carried out first time pore-creating and is obtained micropore Graphene;
D) by described micropore Graphene and the second activator mix, heating is carried out second time pore-creating and is obtained Graphene.
5. preparation method according to claim 4, is characterized in that, the Graphene of described partial oxidation and the mass ratio of the first activator are 1:4 ~ 1:8.
6. preparation method according to claim 4, is characterized in that, the mass ratio of described micropore Graphene and the second activator is 1:1 ~ 1:4.
7. preparation method according to claim 4, is characterized in that, described first activator and the second activator are selected from the one in potassium hydroxide and zinc chloride independently of one another.
8. preparation method according to claim 4, is characterized in that, described step C also comprises:
First flooded in oxalic acid solution by the Graphene of described partial oxidation, be heated to 400 DEG C ~ 600 DEG C, expand 10 ~ 30s, then with the first activator mix.
9. preparation method according to claim 4, is characterized in that, described first time pore-creating is all carried out with second time pore-creating in steam-laden inert atmosphere.
10. a ultracapacitor, is characterized in that, comprises the Graphene described in claims 1 to 3 any one or the Graphene prepared by claim 4 ~ 9 any one.
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