CN103523771A - Graphene, activation method of graphene and supercapcitor using graphene - Google Patents
Graphene, activation method of graphene and supercapcitor using graphene Download PDFInfo
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Abstract
The invention provides an activation method of graphene. The activation method of graphene comprises the following steps: treating graphite oxide for 1-12 hours at the temperature of 800-1200 DEG C in a protective gas atmosphere, so as to obtain graphene; heating the graphene to 700-900 DEG C in an inert gas atmosphere, and then reacting for 0.5-2 hours in a carbon dioxide atmosphere, thus obtaining activated graphene. According to the activation method, carbon dioxide and grapheme react, carbon dioxide molecules are diffused into graphene and react with a part of carbon with higher activity on the graphene to generate gas, and the gas is diffused inside graphene, so that the original clearances are increased; meanwhile, pores are communicated by virtue of ablation of pore walls of graphene, so that new gas pores are formed and specific surface area of graphene is relatively large. The invention also provides graphene obtained by using the activation method and a supercapacitor using the graphene.
Description
Technical field
The electrode materials preparation field that the present invention relates to energy storage device, particularly relates to a kind of Graphene and activation method thereof and ultracapacitor.
Background technology
Ultracapacitor (Supercapacitors), claim again electrochemical capacitor (Electrochemical Capacitors) or double layer capacitor (Electric Double Layer Capacitors), it is a kind of novel energy-storing element between traditional capacitor and battery, compare with traditional capacitor and there is more high-specific capacitance super and energy density, compare with battery and there is higher power density; Because ultracapacitor has that the speed of discharging and recharging is fast, environmentally safe and the advantage such as have extended cycle life, promise to be novel green energy resource in this century.Electrode materials is the important component part of ultracapacitor, be affect ultracapacitor capacitive character can and the key factor of production cost, so research and develop high-performance, electrode materials is the important content of ultracapacitor research work cheaply.The electrode materials of the ultracapacitor of research mainly contains Carbon Materials, metal oxide and hydrate electrode materials thereof and conductive polymer electrodes material at present.
At present the electrode materials of double electric layers supercapacitor is mainly carbon material, has good heat conduction and conductivity, higher specific surface area, is widely used in electrochemical field and makes electrode materials, and carbon material is the most successfully one of electrode materials of current industrialization.At present, the research of carbon-based electrode material mainly concentrates on the research that research and development have the aspects such as porous carbon materials that high-specific surface area, internal resistance are less.Graphene has high specific surface area, fabulous electroconductibility, good thermal conductivity, and the cost performance of the Graphene obtaining by graphite oxide reduction method is higher, and good stability, is the ideal electrode material of ultracapacitor.The ultracapacitor that use Graphene produces will be all higher than the energy storage density of at present all ultracapacitors.But actual obtain Graphene electrodes material owing to reuniting etc. former thereby having reduced the specific surface area of Graphene, make capacity on the low side, in water system, capacity is 135F/g, organic system capacity 99F/g, Distance Theory capacity (550F/g) differs far away.
Summary of the invention
Based on this, be necessary to provide a kind of activation method of Graphene, to obtain the Graphene that specific surface area is higher, and provide a kind of ultracapacitor that uses the Graphene that this activation method obtains.
An activation method for Graphene, comprises the steps:
Graphite oxide is processed and within 1 ~ 12 hour, obtained Graphene in shielding gas atmosphere at 800 ~ 1200 ℃; And
Described Graphene is warming up to 700 ~ 900 ℃ in atmosphere of inert gases, then in carbonic acid gas atmosphere, reacts 0.5 ~ 2 hour the Graphene after being activated.
Therein in an embodiment, the step that described Graphene is reacted in carbonic acid gas atmosphere comprises: described Graphene is packed in uncovered silica tube, then described silica tube is put into boiler tube, and pass into rare gas element and described boiler tube is warming up to 700 ~ 900 ℃ to described boiler tube, then to described silica tube, pass into carbonic acid gas and react with described Graphene, silica tube described in reaction process rotates around the axis of silica tube.
In an embodiment, the velocity of rotation of described silica tube is 10 ~ 25 turn/min therein.
In an embodiment, the flow of described carbonic acid gas is 1000 ~ 2000mL/min therein.
Therein in an embodiment, described rare gas element is selected from a kind of in argon gas, nitrogen, helium and neon.
Therein in an embodiment, described shielding gas is selected from a kind of in hydrogen, argon gas or nitrogen.
In an embodiment, described graphite oxide is adopted preparation with the following method therein:
Graphite is added in the mixing acid being comprised of the vitriol oil and concentrated nitric acid and forms mixed solution, the temperature of described mixed solution is remained on to-2 ~ 2 ℃ and stir 10 ~ 30 minutes;
To described mixed solution, add potassium permanganate, the mixture of described mixed solution and potassium permanganate is remained on to-2 ~ 2 ℃ and stir 1 hour, then described mixture is heated to 80 ~ 90 ℃, and keeps 0.5 ~ 2 hour;
To described mixture, add deionized water, then at 80 ~ 90 ℃, keep 0.5 ~ 2 hour, then add hydrogen peroxide, stirring, suction filtration, washing, obtain graphite oxide after dry;
Wherein, described graphite, the vitriol oil are 1g:80 ~ 110ml:15 ~ 35ml with the ratio of concentrated nitric acid, the mass ratio of described graphite and potassium permanganate is 1:1 ~ 10, and described graphite is 1g:46 ~ 92ml with the ratio of deionized water, and described potassium permanganate is 1g:1 ~ 3ml with the ratio of superoxol.
The Graphene that above-mentioned activation method obtains.
, comprising positive plate, described positive plate comprises collector and be coated in the anode sizing agent layer on described collector, the material of described anode sizing agent layer comprises binding agent, conductive agent and above-mentioned Graphene.
In an embodiment, described binding agent is polyvinylidene difluoride (PVDF) therein, and described conductive agent is acetylene black, and the mass ratio of described Graphene, binding agent and conductive agent is 88:10:2; Described ultracapacitor also comprises housing, barrier film, negative plate and electrolytic solution, after described positive plate, barrier film and negative plate stack gradually, be contained in described housing, described electrolytic solution is filling in described housing, and described electrolytic solution is ionic liquid, the positively charged ion of described ionic liquid is quaternary ammonium salt, pyridinium salt or pyrroles's salt positive ion, and the negatively charged ion of described ionic liquid is PF
6 -or BF
4 -.
The activation method of above-mentioned Graphene reduces graphite oxide to obtain Graphene under high temperature; then under protection of inert gas, under high temperature, adopt carbonic acid gas to react that with Graphene Graphene is activated; carbon dioxide molecule is by diffusing into Graphene inside; and with last minute active higher carbon of the Graphene generation gas that reacts; the diffusion of gas in Graphene inside increases original space; ablation due to Graphene hole wall simultaneously communicates Kong Yukong; form new gas duct, make the specific surface area of the Graphene that obtains of activation larger.
Accompanying drawing explanation
Fig. 1 is the schema of activation method of the Graphene of an embodiment;
Fig. 2 is the structural representation of reaction unit of activation method of the Graphene of an embodiment.
Embodiment
Below by embodiment and accompanying drawing to the activation method of above-mentioned Graphene, the Graphene being obtained by this activation method and use the ultracapacitor of this Graphene further to set forth.
Refer to Fig. 1, the activation method of an embodiment Graphene, comprises the steps:
Step S110: prepare graphite oxide.
Graphite is provided.The graphite that preferably purity is 99.%.
Graphite is added in the mixing acid being comprised of the vitriol oil and concentrated nitric acid and forms mixed solution, the temperature of mixed solution is remained on to-2 ~ 2 ℃ and stir 10 ~ 30 minutes.The vitriol oil adopts the sulfuric acid that massfraction is 98%, and concentrated nitric acid adopts the nitric acid that massfraction is 65%.Graphite, the vitriol oil are 1g:80 ~ 110ml:15 ~ 35ml with the ratio of concentrated nitric acid.
Then to mixed solution, add potassium permanganate, the mixture of mixed solution and potassium permanganate is remained on to-2 ~ 2 ℃ and stir 1 hour, then mixture is heated to 80 ~ 90 ℃, and keeps 0.5 ~ 2 hour.The mass ratio of graphite and potassium permanganate is 1:1 ~ 10.
To mixture, add deionized water, then at 80 ~ 90 ℃, keep 0.5 ~ 2 hour, then add hydrogen peroxide to remove potassium permanganate, fully stirring, suction filtration, washing, obtain graphite oxide after dry.Graphite is 1g:46 ~ 92ml with the ratio of deionized water.The massfraction of hydrogen peroxide is 30%, and potassium permanganate is 1g:1 ~ 3ml with the ratio of superoxol.
Washing is carried out suction filtration after adopting dilute hydrochloric acid and deionized water repetitive scrubbing, and then the solid matter obtaining by the vacuum-drying 24 hours at 120 ℃ of this solid matter, obtains dehydration graphite oxide.
Step S120: graphite oxide is processed and obtained Graphene for 1 ~ 12 hour in shielding gas atmosphere at 800 ~ 1200 ℃.
The graphite oxide that will dewater is processed and within 1 ~ 12 hour, is carried out the oxygen-containing functional group that graphite oxide interlayer is removed in pyrolysis in shielding gas atmosphere at 800 ~ 1200 ℃, and graphite oxide reduction obtains Graphene.
At 800 ~ 1200 ℃, process and within 1 ~ 12 hour, carry out high temperature reduction, not only make graphite oxide reduction obtain after Graphene, other oxy radical cracking that are more conducive to Graphene are removed, thereby have reduced the oxygen level of Graphene, improve the conductivity of Graphene.
Shielding gas is selected from a kind of in hydrogen, argon gas or nitrogen.
Step S130: Graphene is warming up in atmosphere of inert gases to 700 ~ 900 ℃, then reacts 0.5 ~ 2 hour the Graphene after being activated in carbonic acid gas atmosphere.
Step S120 is prepared after Graphene, in order to improve the specific surface area of Graphene, further Graphene is carried out to activation treatment.
Please refer to Fig. 2, activation treatment is carried out in boiler tube 100.Graphene is packed in silica tube 200, then silica tube 200 is positioned over to boiler tube 100 central authorities, the central axis of boiler tube 100 is parallel with the axis of silica tube 200.Silica tube 200 is uncovered cylindrical tube, and boiler tube 100 communicates with silica tube 200.Boiler tube 100 two ends are clogged and are coated with seal gum by plug with holes 110.Plug with holes 110 by boiler tube 100 one end passes into air-flow 300 to boiler tube 100, and air-flow 300 from the plug with holes 110 of boiler tube 100 the other ends out.Air-flow 300 is rare gas element.Because boiler tube 100 communicates with silica tube 200, in the protection atmosphere of the Graphene of silica tube 200 inside in rare gas element.In the protection atmosphere of rare gas element, boiler tube 100 is warming up to 700 ~ 900 ℃, then changes air-flow 300 into carbonic acid gas, carbonic acid gas enters silica tube 200 inside and reacts with Graphene 0.5 ~ 2 hour.In reaction process, silica tube 200 rotates around its central axis.Silica tube 200 rotates so that the graphene powder of silica tube 200 inside fully contacts with carbon dioxide gas stream thereupon overturning, to improve treatment effect.
The flow of carbonic acid gas is preferably 1000 ~ 2000mL/min, the rotating speed of silica tube is preferably 10 ~ 25 turn/min, so that the upset degree of Graphene matches and makes Graphene can contact more abundant with carbonic acid gas with the flow of carbonic acid gas, avoid occurring dead angle, improve treatment effect and processing efficiency simultaneously.
Be appreciated that in other embodiments, also can in other devices, pass into carbonic acid gas Graphene is processed, guarantee that carbonic acid gas fully contacts with Graphene.
In activation treatment process, carbon dioxide gas stream fully contacts with Graphene, carbon dioxide molecule by diffuse into Graphene inner and with last minute active higher carbon of the Graphene generation gas that reacts, reaction formula is: C+CO
2→ 2CO.The diffusion of the gas generating in Graphene inside increases the original space of graphene molecules, simultaneously under high temperature action, because the ablation of Graphene hole wall communicates Kong Yukong, form new gas duct, thereby the specific surface area of the Graphene after activation is increased.
The increase of Graphene specific surface area, has improved the capacity of Graphene, and has reduced the equivalent series resistance of Graphene, has effectively improved the chemical property of Graphene.
The activation method of above-mentioned Graphene reduces graphite oxide to obtain Graphene under high temperature, then under protection of inert gas, under high temperature, adopts carbonic acid gas to react with Graphene to activate and obtains the Graphene that specific surface area is high.It is raw material that this activation method adopts the graphite oxide of dehydration, finally obtains the graphene powder that specific surface area is higher, and without filtering, washing and drying and other steps, technique is simple, easily realizes extensive preparation.
And carbonic acid gas is easy to get, preparation cost is low.Than add other materials in order to prevent Graphene from reuniting, as carbon nanotube, metal oxide etc., preparing graphene-carbon nano tube composite material or Graphene-metal oxide composite compares to improve the method for the specific surface area of Graphene, the raw materials cost of the activation method of above-mentioned Graphene reduces greatly, is conducive to reduce the cost of Graphene.
Further, improve a kind of Graphene being obtained by above-mentioned activation method.The specific surface area of this Graphene is larger, has good chemical property, is good electrode materials.
Further, also provide a kind of ultracapacitor that uses this Graphene.This ultracapacitor comprises positive plate.Positive plate comprises collector and is coated in the anode sizing agent layer on collector.The material of anode sizing agent layer comprises binding agent, conductive agent and above-mentioned Graphene.Collector can be flat for aluminium foil, copper foil etc.
Binding agent is polyvinylidene difluoride (PVDF), and conductive agent is acetylene black, and the mass ratio of Graphene, binding agent and conductive agent is 88:10:2.
This ultracapacitor also comprises housing, barrier film, negative plate and electrolytic solution.
Positive plate, barrier film and negative plate stack gradually and are assembled into battery core, and battery core is contained in housing.
Electrolytic solution is filling in housing.Electrolytic solution is ionic liquid.The positively charged ion of ionic liquid is quaternary ammonium salt, pyridinium salt or pyrroles's salt positive ion, is preferably carbonatoms and is greater than quaternary ammonium salt, pyridinium salt or the pyrroles's salt positive ion that 6 small molecules alkane replaces.The negatively charged ion of ionic liquid is PF
6 -or BF
4 -.
Above-mentioned Graphene has advantages of that specific surface area is high, can effectively improve the capacity of this ultracapacitor, is conducive to provide the performance of ultracapacitor.
The preparation method of this ultracapacitor is as follows:
1, prepare ultracapacitor positive plate
First, select Graphene prepared by aforesaid method as positive electrode active materials;
Secondly, the ratio that is 88:10:2 according to mass ratio, Graphene, polyvinylidene difluoride (PVDF) binding agent and conductive agent acetylene black are mixed, obtain anode sizing agent;
Finally, anode sizing agent is coated on aluminium foil, drying, roll film, trimming is processed, and makes the positive plate of ultracapacitor.
2, the assembling of ultracapacitor
Order stack of laminations according to positive plate, barrier film, negative plate is dressed up battery core, then uses housing seal battery core, injects electrolytic solution subsequently by the spout being opened on housing in battery container, and sealing spout, obtains ultracapacitor.
Electrolytic solution adopts ionic liquid, and the positively charged ion of ionic liquid can be following three kinds: quaternary ammonium salt, pyridinium salt, pyrroles's salt positive ion etc., negatively charged ion is PF
6 -, BF
4 -deng.
It is below specific embodiment.
Embodiment 1
The preparation of Graphene
(1) prepare graphite oxide: take 30g purity and be 99.5% the graphite vitriol oil that to add by 240mL massfraction be 98% and 45mL massfraction and be in the mixing acid that 65% concentrated nitric acid forms and form mixed solution, mixeding liquid temperature being remained on to-2 ~ 2 ℃ stirs 10 minutes, in mixed solution, add 3g potassium permanganate at leisure again, stir 1 hour, then the mixture of mixed solution and potassium permanganate is heated to 80 ℃ and keep 2 hours, add afterwards 138mL deionized water to continue at 80 ℃, to keep 2 hours, the superoxol that finally adds 3mL massfraction 30%, after fully stirring, carry out suction filtration, with 300mL dilute hydrochloric acid and 450mL deionized water, solids is washed respectively successively again, wash altogether three times, the vacuum-drying 24 hours at 120 ℃ of last solid matter, graphite oxide must dewater,
(2) prepare Graphene: graphite oxide is put into retort furnace, under hydrogen atmosphere, under 1200 ℃ of high temperature, reduce and within 1 hour, obtain Graphene;
(3) activation of Graphene: 20g Graphene is packed in silica tube; then silica tube is put into the central authorities of boiler tube; boiler tube two ends are clogged and are coated with seal gum by plug with holes, and boiler tube is warming up to 700 ℃ under the condition of argon shield, change logical carbonic acid gas so that Graphene is activated.The flow of carbonic acid gas is 1000mL/min.In reactivation process, silica tube rotates with the speed of 10 turn/min, make graphene powder equably with carbon dioxide reaction, activate the Graphene that obtains high-specific surface area for 2 hours.
Embodiment 2
The preparation of Graphene
(1) prepare graphite oxide: take 40g purity and be 99.5% the graphite vitriol oil that to add by 440mL massfraction be 98% and 140mL massfraction and be in the mixing acid that 65% concentrated nitric acid forms and form mixed solution, mixeding liquid temperature being remained on to-2 ~ 2 ℃ stirs 30 minutes, in mixed solution, add 40g potassium permanganate at leisure again, stir 1 hour, then the mixture of mixed solution and potassium permanganate is heated to 90 ℃ and keep 0.5 hour, add afterwards 368mL deionized water to continue at 90 ℃, to keep 0.5 hour, the superoxol that finally adds 120mL massfraction 30%, after fully stirring, carry out suction filtration, with 400mL dilute hydrochloric acid and 600mL deionized water, solids is washed respectively successively again, wash altogether three times, the vacuum-drying 24 hours at 120 ℃ of last solid matter, graphite oxide must dewater,
(2) prepare Graphene: graphite oxide is put into retort furnace, under argon gas atmosphere, under 800 ℃ of high temperature, reduce and within 12 hours, obtain Graphene;
(3) activation of Graphene: 20g Graphene is put into silica tube; then silica tube is put into the central authorities of boiler tube; boiler tube two ends are clogged and are coated with seal gum by plug with holes, and boiler tube is warming up to 750 ℃ under the condition of nitrogen protection, change logical carbonic acid gas so that Graphene is activated.The flow of carbonic acid gas is 2000mL/min.In reactivation process, silica tube rotates with the speed of 25 turn/min, make graphene powder equably with carbon dioxide reaction, activate the Graphene that obtains high-specific surface area for 0.5 hour.
Embodiment 3
The preparation of Graphene
(1) prepare graphite oxide: take 50g purity and be 99.5% the graphite vitriol oil that to add by 500mL massfraction be 98% and 125mL massfraction and be in the mixing acid that 65% concentrated nitric acid forms and form mixed solution, mixeding liquid temperature being remained on to-2 ~ 2 ℃ stirs 20 minutes, in mixed solution, add 50g potassium permanganate at leisure again, stir 1 hour, then the mixture of mixed solution and potassium permanganate is heated to 85 ℃ and keep 1 hour, add afterwards 400mL deionized water to continue at 85 ℃, to keep 1 hour, the superoxol that finally adds 40mL massfraction 30%, after fully stirring, carry out suction filtration, with 500mL dilute hydrochloric acid and 750mL deionized water, solids is washed respectively successively again, wash altogether three times, the vacuum-drying 24 hours at 120 ℃ of last solid matter, graphite oxide must dewater,
(2) prepare Graphene: graphite oxide is put into retort furnace, under nitrogen atmosphere, under 1000 ℃ of high temperature, reduce and within 5 hours, obtain Graphene;
(3) activation of Graphene: 20g Graphene is put into silica tube; then silica tube is put into the central authorities of boiler tube; boiler tube two ends are clogged and are coated with seal gum by plug with holes, and boiler tube is warming up to 850 ℃ under the condition of helium protection, change logical carbonic acid gas so that Graphene is activated.The flow of carbonic acid gas is 1500mL/min.In reactivation process, silica tube rotates with the speed of 15 turn/min, make graphene powder equably with carbon dioxide reaction, activate the Graphene that obtains high-specific surface area for 1.5 hours.
Embodiment 4
The preparation of Graphene
(1) prepare graphite oxide: take 60g purity and be 99.5% the graphite vitriol oil that to add by 570mL massfraction be 98% and 120mL massfraction and be in the mixing acid that 65% concentrated nitric acid forms and form mixed solution, mixeding liquid temperature being remained on to-2 ~ 2 ℃ stirs 25 minutes, in mixed solution, add 36g potassium permanganate at leisure again, stir 1 hour, then the mixture of mixed solution and potassium permanganate is heated to 88 ℃ and keep 1.5 hours, add afterwards 510mL deionized water to continue at 88 ℃, to keep 1.5 hours, the superoxol that finally adds 108mL massfraction 30%, after fully stirring, carry out suction filtration, with 600mL dilute hydrochloric acid and 900mL deionized water, solids is washed respectively successively again, wash altogether three times, the vacuum-drying 24 hours at 120 ℃ of last solid matter, graphite oxide must dewater,
(2) prepare Graphene: the graphite oxide obtaining is put into retort furnace, under argon gas atmosphere, under 900 ℃ of high temperature, reduce and within 8 hours, obtain Graphene;
(3) activation of Graphene: 20g Graphene is put into silica tube; then silica tube is put into the central authorities of boiler tube; boiler tube two ends are clogged and are coated with seal gum by plug with holes, and boiler tube is warming up to 900 ℃ under the condition of neon protection, change logical carbonic acid gas so that Graphene is activated.The flow of carbonic acid gas is 1800mL/min.In reactivation process, silica tube rotates with the speed of 20 turn/min, make graphene powder equably with carbon dioxide reaction, activate the Graphene that obtains high-specific surface area for 1 hour.
Embodiment 5
The preparation of the ultracapacitor of the Graphene of use embodiment 1 preparation
(1) prepare ultracapacitor positive plate
First, select the Graphene of embodiment 1 preparation as positive electrode active materials;
Secondly, the ratio that is 88:10:2 according to mass ratio, Graphene, polyvinylidene difluoride (PVDF) binding agent and conductive agent acetylene black are mixed, obtain anode sizing agent;
Finally, anode sizing agent is coated on aluminium foil, drying, roll film, trimming is processed, and makes the positive plate of ultracapacitor.
2, the assembling of ultracapacitor
Order stack of laminations according to positive plate, barrier film, negative plate is dressed up battery core, then uses housing seal battery core, injects tetraethyl ammonium Tetrafluoroboric acid salt electrolyte subsequently by the spout being opened on housing in housing, and sealing spout, obtains ultracapacitor.
Embodiment 6
The preparation of the ultracapacitor of the Graphene of use embodiment 2 preparations
1, prepare ultracapacitor positive plate
First, select the Graphene of embodiment 2 preparations as positive electrode active materials;
Secondly, the ratio that is 88:10:2 according to mass ratio, Graphene, polyvinylidene difluoride (PVDF) binding agent and conductive agent acetylene black are mixed, obtain anode sizing agent;
Finally, anode sizing agent is coated on aluminium foil, drying, roll film, trimming is processed, and makes the positive plate of ultracapacitor.
2, the assembling of ultracapacitor
Order stack of laminations according to positive plate, barrier film, negative plate is dressed up battery core, then uses housing seal battery core, injects tetraethyl ammonium Tetrafluoroboric acid salt electrolyte subsequently by the spout being opened on housing in housing, and sealing spout, obtains ultracapacitor.
Embodiment 7
The preparation of the ultracapacitor of the Graphene of use embodiment 3 preparations
1, prepare ultracapacitor positive plate
First, select the Graphene of embodiment 3 preparations as positive electrode active materials;
Secondly, the ratio that is 88:10:2 according to mass ratio, Graphene, polyvinylidene difluoride (PVDF) binding agent and conductive agent acetylene black are mixed, obtain anode sizing agent;
Finally, anode sizing agent is coated on aluminium foil, drying, roll film, trimming is processed, and makes the positive plate of ultracapacitor.
2, the assembling of ultracapacitor
Order stack of laminations according to positive plate, barrier film, negative plate is dressed up battery core, then uses housing seal battery core, injects TBuA Tetrafluoroboric acid salt electrolyte subsequently by the spout being opened on housing in housing, and sealing spout, obtains ultracapacitor.
Embodiment 8
The preparation of the ultracapacitor of the Graphene of use embodiment 4 preparations
1, prepare ultracapacitor positive plate
First, select the Graphene of embodiment 4 preparations as positive electrode active materials;
Secondly, the ratio that is 88:10:2 according to mass ratio, Graphene, polyvinylidene difluoride (PVDF) binding agent and conductive agent acetylene black are mixed, obtain anode sizing agent;
Finally, anode sizing agent is coated on aluminium foil, drying, roll film, trimming is processed, and makes the positive plate of ultracapacitor.
2, the assembling of ultracapacitor
Order stack of laminations according to positive plate, barrier film, negative plate is dressed up battery core, then uses housing seal battery core, injects tetrapropyl ammonium Tetrafluoroboric acid salt electrolyte subsequently by the spout being opened on housing in housing, and sealing spout, obtains ultracapacitor.
Comparative example 1
The preparation of Graphene
(1) prepare graphite oxide: take 1g purity and be 99.5% the graphite vitriol oil that to add by 80mL massfraction be 98% and 15mL massfraction and be in the mixing acid that 65% concentrated nitric acid forms and form mixed solution, mixeding liquid temperature being remained on to-2 ~ 2 ℃ stirs 10 minutes, in mixed solution, add 1g potassium permanganate at leisure again, stir 1 hour, then the mixture of mixed solution and potassium permanganate is heated to 80 ℃ and keep 2 hours, add afterwards 46mL deionized water to continue at 80 ℃, to keep 2 hours, the superoxol that finally adds 1mL massfraction 30%, after fully stirring, carry out suction filtration, with 100mL dilute hydrochloric acid and 150mL deionized water, solids is washed respectively successively again, wash altogether three times, the vacuum-drying 24 hours at 120 ℃ of last solid matter, graphite oxide must dewater,
(2) prepare Graphene: graphite oxide is put into retort furnace, under the atmosphere such as hydrogen, under 1200 ℃ of high temperature, reduce and within 1 hour, obtain Graphene.
Comparative example 2
The preparation of the ultracapacitor of the Graphene of use comparative example 1
(1) prepare super capacitor electrode slice
First, select the Graphene of comparative example 1 preparation as positive electrode active materials;
Secondly, the ratio that is 88:10:2 according to mass ratio, Graphene, polyvinylidene difluoride (PVDF) binding agent and conductive agent acetylene black are mixed, obtain anode sizing agent;
Finally, anode sizing agent is coated on aluminium foil, drying, roll film, trimming is processed, and makes the positive plate of ultracapacitor.
(2) assembling of ultracapacitor
Order stack of laminations according to positive plate, barrier film, negative plate is dressed up battery core, then uses housing seal battery core, injects tetraethyl ammonium Tetrafluoroboric acid salt electrolyte subsequently by the spout being opened on housing in housing, and sealing spout, obtains ultracapacitor.
Table 1 is the specific surface area of the Graphene of embodiment 1 ~ 4 and comparative example 1 preparation
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Specific surface area m 2/g | 892 | 921 | 806 | 869 | 652 |
Embodiment 1 is identical with comparative example 1 raw material, proportioning, technique etc., just carries out a step activation treatment more, and after overactivation, the specific surface area of the Graphene after activation has obtained effective raising as can be seen from Table 1.
Table 2 is embodiment 5 ~ 8 and comparative example 2 charge-discharge test results
| Embodiment | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 2 |
| Specific storage F/g | 115 | 117 | 103 | 111 | 74 |
Embodiment 5 adopts identical technique to be prepared into ultracapacitor with comparative example 2, is the difference of positive electrode active materials, and the capacity of the ultracapacitor that not activated Graphene is prepared into (comparative example 2) is starkly lower than (embodiment 5) after activation.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an activation method for Graphene, is characterized in that, comprises the steps:
Graphite oxide is processed and within 1 ~ 12 hour, obtained Graphene in shielding gas atmosphere at 800 ~ 1200 ℃; And
Described Graphene is warming up to 700 ~ 900 ℃ in atmosphere of inert gases, then in carbonic acid gas atmosphere, reacts 0.5 ~ 2 hour the Graphene after being activated.
2. the activation method of Graphene according to claim 1, it is characterized in that, the step that described Graphene is reacted in carbonic acid gas atmosphere comprises: described Graphene is packed in uncovered silica tube, then described silica tube is put into boiler tube, and pass into rare gas element and described boiler tube is warming up to 700 ~ 900 ℃ to described boiler tube, then to described silica tube, pass into carbonic acid gas and react with described Graphene, silica tube described in reaction process rotates around the axis of silica tube.
3. the activation method of Graphene according to claim 2, is characterized in that, the velocity of rotation of described silica tube is 10 ~ 25 turn/min.
4. the activation method of Graphene according to claim 1, is characterized in that, the flow of described carbonic acid gas is 1000 ~ 2000mL/min.
5. the activation method of Graphene according to claim 1, is characterized in that, described rare gas element is selected from a kind of in argon gas, nitrogen, helium and neon.
6. the activation method of Graphene according to claim 1, is characterized in that, described shielding gas is selected from a kind of in hydrogen, argon gas or nitrogen.
7. the activation method of Graphene according to claim 1, is characterized in that, described graphite oxide is adopted preparation with the following method:
Graphite is added in the mixing acid being comprised of the vitriol oil and concentrated nitric acid and forms mixed solution, the temperature of described mixed solution is remained on to-2 ~ 2 ℃ and stir 10 ~ 30 minutes;
To described mixed solution, add potassium permanganate, the mixture of described mixed solution and potassium permanganate is remained on to-2 ~ 2 ℃ and stir 1 hour, then described mixture is heated to 80 ~ 90 ℃, and keeps 0.5 ~ 2 hour;
To described mixture, add deionized water, then at 80 ~ 90 ℃, keep 0.5 ~ 2 hour, then add hydrogen peroxide, stirring, suction filtration, washing, obtain graphite oxide after dry;
Wherein, described graphite, the vitriol oil are 1g:80 ~ 110ml:15 ~ 35ml with the ratio of concentrated nitric acid, the mass ratio of described graphite and potassium permanganate is 1:1 ~ 10, and described graphite is 1g:46 ~ 92ml with the ratio of deionized water, and described potassium permanganate is 1g:1 ~ 3ml with the ratio of superoxol.
8. the Graphene obtaining according to the activation method described in claim 1 ~ 7 any one.
9. a ultracapacitor, comprises positive plate, it is characterized in that, described positive plate comprises collector and be coated in the anode sizing agent layer on described collector, and the material of described anode sizing agent layer comprises binding agent, conductive agent and Graphene according to claim 8.
10. ultracapacitor according to claim 9, is characterized in that, described binding agent is polyvinylidene difluoride (PVDF), and described conductive agent is acetylene black, and the mass ratio of described Graphene, binding agent and conductive agent is 88:10:2; Described ultracapacitor also comprises housing, barrier film, negative plate and electrolytic solution, after described positive plate, barrier film and negative plate stack gradually, be contained in described housing, described electrolytic solution is filling in described housing, and described electrolytic solution is ionic liquid, the positively charged ion of described ionic liquid is quaternary ammonium salt, pyridinium salt or pyrroles's salt positive ion, and the negatively charged ion of described ionic liquid is PF6-or BF4-.
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