CN103545115A - Graphene-carbon nano tube composite material, preparation method thereof and super capacitor - Google Patents
Graphene-carbon nano tube composite material, preparation method thereof and super capacitor Download PDFInfo
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Abstract
Disclosed is a preparation method of a graphene-carbon nano tube composite material. The method includes adding graphite oxide and carbon nano tubes into water according to a mass ratio of 1.66-165:1, and performing ultrasonic treatment for 1-5h to obtain dispersion liquid; adding a potassium hydroxide solution into the dispersion liquid, and stirring until coagulation appears to obtain suspension liquid, wherein a ratio of the total mass of the graphite oxide and the carbon nano tubes to the weight of potassium hydroxide is 1:1-30; filtering and drying the suspension liquid to obtain solid powder, allowing the solid powder to react for 1-5h at 800-1200 DEG C, washing, filtering and drying. By the preparation method, the carbon nano tubes can effectively prevent graphite coagulation, and activation effect and high-temperature effect of potassium hydroxide are combined, so that specific surface area of graphene and the carbon nano tubes is greatly increased, and the specific surface area of the graphene-carbon nano tube composite material is enabled to be high.
Description
Technical field
The electrode material preparation field that the present invention relates to energy storage device, particularly relates to a kind of graphene-carbon nano tube composite material and preparation method thereof and ultracapacitor.
Background technology
Ultracapacitor (Supercapacitors) claims again electrochemical capacitor (Electrochemical Capacitors) or double electric 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 material 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 material is the important content of ultracapacitor research work cheaply.The electrode material of the ultracapacitor of research mainly contains Carbon Materials, metal oxide and hydrate electrode material thereof and conductive polymer electrodes material at present.
At present the electrode material of double electric layers supercapacitor is mainly material with carbon element, has good heat conduction and electric conductivity, higher specific area, is widely used in electrochemical field and makes electrode material, and material with carbon element is the most successfully one of electrode material 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 area, fabulous conductivity, good thermal conductivity, and the cost performance of the Graphene obtaining by graphite oxide reducing process 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 the actual Graphene electrodes material preparing, due to reasons such as reunions, make its specific area not high enough, thereby capacity is on the low side, in water system, capacity is 135F/g, organic system capacity 99F/g, Distance Theory capacity (550F/g) differs far away, is difficult to bring into play the advantage of Graphene.
Summary of the invention
Based on this, be necessary to provide a kind of preparation method of graphene-carbon nano tube composite material, to prepare the graphene-carbon nano tube composite material that specific area is higher, and use the ultracapacitor of this graphene-carbon nano tube composite material.
A preparation method for graphene-carbon nano tube composite material, comprises the steps:
1.66 ~ 165:1 is added to the water graphite oxide and carbon nano-tube in mass ratio, and carries out ultrasonic processing 1 ~ 5 hour, obtains dispersion liquid;
Potassium hydroxide solution is added in described dispersion liquid, stir until appearance cohesion obtains suspension, wherein, the gross mass of described graphite oxide and carbon nano-tube and the mass ratio of described potassium hydroxide are 1:1 ~ 30; And
By described suspension filtered, after dry, obtain pressed powder, described pressed powder reacted 1 ~ 5 hour at 800 ~ 1200 ℃, washing, filter, the dry graphene-carbon nano tube composite material that obtains.
In an embodiment, the concentration of described potassium hydroxide solution is 0.1 ~ 10mol/L therein.
In an embodiment, the concentration of described graphite oxide in dispersion liquid is 8.3 ~ 16.5g/L therein, and the concentration of described carbon nano-tube in dispersion liquid is 0.1 ~ 5g/L.
In an embodiment, the power of described ultrasonic processing is 600 ~ 800W therein.
In an embodiment, by after described suspension filtered, at 60 ~ 80 ℃, be dried and within 24 ~ 48 hours, obtain pressed powder therein.
In an embodiment, described washing step is that water washs therein.
The graphene-carbon nano tube composite material that above-mentioned preparation method prepares.
A kind of ultracapacitor, comprise housing, be arranged at battery core and filling electrolyte in described housing in described housing, described battery core comprises positive plate, barrier film and the negative plate stacking gradually, described positive plate comprises aluminium foil and is coated in the anode sizing agent layer on described aluminium foil, the material of described anode sizing agent layer comprise binding agent and, the graphene-carbon nano tube composite material for preparing of conductive agent and above-mentioned preparation method.
In an embodiment, described binding agent is Kynoar therein, and described conductive agent is acetylene black, and the mass ratio of described graphene-carbon nano tube composite material, binding agent and conductive agent is 88:10:2.
In an embodiment, described electrolyte is ionic liquid therein, and the cation of described ionic liquid is quaternary ammonium salt, pyridiniujm or pyrroles's salt cation, and the anion of described ionic liquid is PF
6 -or BF
4 -.
The preparation method of above-mentioned graphene-carbon nano tube composite material carries out by graphite oxide and carbon nano-tube graphene oxide-carbon nano-tube aqueous dispersions that ultrasonic processing obtains mixing, by potassium hydroxide active oxidation Graphene and carbon nano-tube, then after high-temperature process, generate graphene-carbon nano tube composite material again.Carbon nano-tube can effectively prevent Graphene cohesion, and the activation of combining hydrogen oxidation potassium and high temperature action have improved the specific area of Graphene and carbon nano-tube greatly, make the specific area of graphene-carbon nano tube composite material higher.
Accompanying drawing explanation
Fig. 1 is preparation method's the process chart of the graphene-carbon nano tube composite material of an execution mode.
Embodiment
By embodiment and accompanying drawing, the preparation method of above-mentioned graphene-carbon nano tube composite material is further set forth below.
Refer to Fig. 1, the preparation method of the graphene-carbon nano tube composite material of an execution mode, comprises the steps:
Step S110: 1.66 ~ 165:1 is added to the water graphite oxide and carbon nano-tube in mass ratio, and carry out ultrasonic processing 1 ~ 5 hour, obtain dispersion liquid.
Graphite oxide is added to the water and carries out ultrasonic processing, so that graphite oxide is peeled off, form individual layer or the lower graphene oxide of the number of plies.The concentration of graphite oxide in dispersion liquid is preferably 8.3 ~ 16.5g/L, so that it is better to peel off effect, improves the conversion ratio that graphite oxide is converted to graphene oxide.
Carrying out adding carbon nano-tube before ultrasonic processing, so that in ultrasonic processing procedure, carbon nano-tube can effectively prevent graphene oxide reunion.The concentration of carbon nano-tube in dispersion liquid is preferably 0.1 ~ 5g/L.Carbon nano-tube can be Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
Compare with carbon nano-tube, Graphene has higher conductivity and thermal conductivity, high carrier mobility, electronics mobile space, high strength and rigidity freely.In order to guarantee that in graphene-carbon nano tube composite material, the mass percent of Graphene is greater than 50%, to give full play to the advantage of Graphene and to give full play to the effect that Graphene is reunited that prevents of carbon nano-tube, the mass ratio of graphite oxide and carbon nano-tube is preferably 1.66 ~ 165:1.When the mass ratio of graphite oxide and carbon nano-tube is lower than 1.66:1, be difficult to guarantee that the mass percent of Graphene in the follow-up graphene-carbon nano tube composite material of preparing gained is greater than 50%; When the mass ratio of graphite oxide and carbon nano-tube is higher than 165:1, can not effectively prevent that Graphene from reuniting and not reaching the effect that improves Graphene specific area.
Ultrasonic processing is after 1 ~ 5 hour, and graphite oxide is peeled off formation graphene oxide, and graphene oxide and carbon nano-tube are compounded to form graphene oxide-carbon nano-tube aqueous dispersions.Graphene oxide and carbon nano-tube are compound under ultrasonication, make both mixing more even, and carbon nano-tube is well-dispersed in Graphene.
The power of ultrasonic processing is preferably 600 ~ 800w, to guarantee to prevent under the prerequisite for the treatment of effeciency that graphite oxide from peeling off the graphene oxide of formation and sustain damage and affect its electric conductivity.
Step S120: potassium hydroxide solution is added in dispersion liquid, stir until appearance cohesion obtains suspension.
Compound concentration is potassium hydroxide (KOH) solution of 0.1 ~ 10mol/L, then this potassium hydroxide solution is added in the dispersion liquid of step 110 gained.Potassium hydroxide is used for activating Graphene and carbon nano-tube, increases the porosity on Graphene surface, to increase the specific area of Graphene.And, due to the activation of potassium hydroxide, the tack between Graphene and carbon nano-tube is improved, both are better compound.
Be stirred to and occur obtaining suspension by gel.Preferably, the gross mass of graphite oxide and carbon nano-tube and the mass ratio of potassium hydroxide are 1:1 ~ 30.
The concentration of potassium hydroxide is according to the mass ratio choose reasonable of the gross mass of graphite oxide and carbon nano-tube and potassium hydroxide.When the ratio of the gross mass of graphite oxide and carbon nano-tube and the mass ratio of potassium hydroxide hour, be that the amount of potassium hydroxide is when larger, the larger value of the corresponding selection of concentration of potassium hydroxide, volume with guarantee system is unlikely to excessive, with in extensive preparation, reduce the requirement of equipment and power of agitator.
Step S130: by suspension filtered, after dry, obtain pressed powder, pressed powder reacted 1 ~ 5 hour at 800 ~ 1200 ℃, washing, filter, the dry graphene-carbon nano tube composite material that obtains.
The suspension of step S120 gained is filtered, then the dry pressed powder that obtains for 24 ~ 48 hours at 60 ~ 80 ℃.
This pressed powder is graphene oxide-carbon nano tube compound material.In order to obtain graphene-carbon nano tube composite material, this pressed powder is reacted 1 ~ 5 hour at 800 ~ 1200 ℃, make the oxygen-containing functional group degraded of graphene oxide generate CO
2and H
2the little molecule escaping such as O, graphene oxide reduces to obtain single-layer graphene and forms graphene-carbon nano tube composite material.
Under the high temperature of 800 ~ 1200 ℃, process graphene oxide-carbon nano tube compound material, not only can generate graphene-carbon nano tube composite material, and under high temperature action, can further reduce the oxygen content of Graphene, be conducive to improve the conductivity of graphene-carbon nano tube composite material.
Pressed powder is reacted at 800 ~ 1200 ℃ and after 1 ~ 5 hour, wash to remove impurity and obtain the graphene-carbon nano tube composite material that purity is higher.K is removed in washing
+, OH
-plasma.Preferably adopt water to wash, comparatively environmental protection.Washing can be carried out repeatedly, with abundant purifying graphene-carbon nano tube compound material.
After washing, filter, be dried, obtain graphene-carbon nano tube composite material.In the graphene-carbon nano tube composite material of gained, the mass fraction of Graphene accounts for 50 ~ 99%.
In potassium hydroxide for step S120 (KOH) activation Graphene process, potassium hydroxide (KOH) occurs to react as follows with Graphene:
4KOH+CH
2→K
2CO
3+K
2O+3H
2
8KOH+2CH→2K
2CO
3+2K
2O+5H
2
K
2CO
3+2C→2K+3CO
Potassium hydroxide (KOH) is in the process of activation Graphene, on the one hand by generating potash (K
2cO
3) consume the carbon in Graphene and carbon nano-tube, make the Pore development in Graphene and carbon nano-tube, on the other hand potash (K
2cO
3) react generation metallic potassium with the carbon in Graphene and carbon nano-tube.Further, in step S130, under high temperature (800 ~ 1200 ℃) effect of boiling point that surpasses metallic potassium, potassium vapor can be diffused into the different carbon-coating of Graphene, form new pore structure, between the synusia of gaseous state potassium crystallite, walk, strut fragrant synusia and it is distorted or is out of shape, create the micropore making new advances.
Therefore, Graphene and carbon nano-tube are passed through high-temperature process after the activation of potassium hydroxide (KOH) again, make the original Pore development of Graphene and carbon nano-tube, and increased the number cells of Graphene, greatly increased the specific area of graphene-carbon nano tube composite material.
The preparation method of above-mentioned graphene-carbon nano tube composite material carries out by graphite oxide and carbon nano-tube graphene oxide-carbon nano-tube aqueous dispersions that ultrasonic processing obtains mixing, by potassium hydroxide active oxidation Graphene and carbon nano-tube, then after high-temperature process, generate graphene-carbon nano tube composite material again.Carbon nano-tube can effectively prevent Graphene cohesion, and the activation of potassium hydroxide and high temperature action have improved the specific area of Graphene and carbon nano-tube greatly, make the specific area of graphene-carbon nano tube composite material higher.
Adopt graphene-carbon nano tube composite material prepared by the preparation method of above-mentioned graphene-carbon nano tube composite material can give full play to the advantages such as Graphene high-specific surface area, high conductivity, this graphene-carbon nano tube composite material is applied to the energy storage devices such as ultracapacitor, can significantly improves the capacity of the energy storage devices such as ultracapacitor.
Equipment, technique that the preparation method of above-mentioned graphene-carbon nano tube composite material requires are simple, are easy to realize large-scale production.
Further, provide a kind of graphene-carbon nano tube composite material being prepared by the preparation method of above-mentioned graphene-carbon nano tube composite material.
Adopting graphene-carbon nano tube composite material prepared by the preparation method of above-mentioned graphene-carbon nano tube composite material is the electrode material of good memory device.
Further, also provide a kind of ultracapacitor that uses above-mentioned graphene-carbon nano tube composite material.This ultracapacitor comprises housing, is arranged at battery core and filling electrolyte in housing in housing.Battery core comprises positive plate, barrier film and the negative plate stacking gradually.Positive plate comprises aluminium foil and be coated in the anode sizing agent layer on aluminium foil, and the material of anode sizing agent layer comprises above-mentioned graphene-carbon nano tube composite material, binding agent and conductive agent.
Binding agent is Kynoar, and conductive agent is acetylene black, and the mass ratio of graphene-carbon nano tube composite material, binding agent and conductive agent is 88:10:2.
Electrolyte is ionic liquid.The cation of this ionic liquid is quaternary ammonium salt, pyridiniujm or pyrroles's salt cation, and anion is PF
6 -or BF
4 -.Quaternary ammonium salt, pyridiniujm or pyrroles's salt cation can be respectively carbon number and be greater than quaternary ammonium salt, pyridiniujm or the pyrroles's salt cation that six little molecule alkane replaces.
Above-mentioned graphene-carbon nano tube composite material has advantages of that specific area is high, can effectively improve the capacity of this ultracapacitor, is conducive to improve the performance of ultracapacitor.
The preparation method of this ultracapacitor is as follows:
1, prepare ultracapacitor positive plate
First, select graphene-carbon nano tube composite material prepared by said method as positive electrode active materials;
Secondly, the ratio that is 88:10:2 according to mass ratio, graphene-carbon nano tube composite material, Kynoar 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 electrolyte subsequently by the liquid injection port being opened on housing in housing, and sealing liquid injection port, obtains ultracapacitor.
It is following three all that electrolyte adopts ionic liquid, the cation of ionic liquid can be: quaternary ammonium salt, pyridiniujm, pyrroles's salt cation etc., anion is PF6-, BF4-etc.
It is below specific embodiment.
Embodiment 1
Prepare graphene-carbon nano tube composite material
(1) 8.3g graphite oxide and 5g carbon nano-tube are added in 1000mL water, under power 600W ultrasonic 1 hour, obtain dispersion liquid;
(2) the KOH solution that configuration concentration is 0.1mol/L, joins KOH solution in above-mentioned dispersion liquid, stirs until appearance cohesion obtains suspension, and wherein the gross mass of graphite oxide and carbon nano-tube and the mass ratio of KOH are 1: 1;
(3) above-mentioned suspension is filtered, 60 ℃ dry 48 hours, obtain pressed powder, then pressed powder put into Muffle furnace, 800 ℃ of reactions 5 hours, cooling after, washing, filter, the dry graphene-carbon nano tube composite material that obtains high-specific surface area.
Embodiment 2
Prepare graphene-carbon nano tube composite material
(1) by 16.5g graphite oxide and 0.1g carbon nano-tube by adding in 1000mL water, under power 700W ultrasonic 5 hours, obtain dispersion liquid;
(2) the KOH solution that configuration concentration is 10mol/L, joins KOH solution in above-mentioned dispersion liquid, stirs until appearance cohesion obtains suspension, and wherein the gross mass of graphite oxide and carbon nano-tube and the mass ratio of KOH are 1:30;
(3) above-mentioned suspension is filtered, 80 ℃ are dried 24 hours, obtain pressed powder, then pressed powder is put into Muffle furnace, 1200 ℃ of reactions 1 hour, cooling after, washing, filter, the dry graphene-carbon nano tube composite material that obtains high-specific surface area.
Embodiment 3
Prepare graphene-carbon nano tube composite material
(1) 13.3g graphite oxide and 2g carbon nano-tube are added to 1000mL water, under power 800W ultrasonic 2 hours, obtain dispersion liquid;
(2) the KOH solution that configuration concentration is 2mol/L, joins KOH solution in above-mentioned dispersion liquid, stirs until appearance cohesion obtains suspension, and wherein the gross mass of graphite oxide and carbon nano-tube and the mass ratio of KOH are 1:7;
(3) above-mentioned suspension is filtered, 70 ℃ are dried 36 hours, obtain pressed powder, then pressed powder is put into Muffle furnace, 1000 ℃ of reactions 3 hours, cooling after, washing, filter, the dry graphene-carbon nano tube composite material that obtains high-specific surface area.
Embodiment 4
Prepare graphene-carbon nano tube composite material
(1) 11.6g graphite oxide and 3g carbon nano-tube are added in 1000mL water, under power 600W ultrasonic 4 hours, obtain dispersion liquid;
(2) the KOH solution that configuration concentration is 7mol/L, joins KOH solution in above-mentioned dispersion liquid, stirs until appearance cohesion obtains suspension, and wherein the gross mass of graphite oxide and carbon nano-tube and the mass ratio of KOH are 1:15;
(3) suspension is filtered, 65 ℃ dry 40 hours, obtain pressed powder, then pressed powder put into Muffle furnace, 900 ℃ of reactions 4 hours, cooling after, washing, filter, the dry graphene-carbon nano tube composite material that obtains high-specific surface area.
Embodiment 5
The preparation of the ultracapacitor of the graphene-carbon nano tube composite material of embodiment 1 preparation of using
(1) prepare ultracapacitor positive plate
First, select the graphene-carbon nano tube composite material of embodiment 1 preparation as positive electrode active materials;
Secondly, the ratio that is 88:10:2 according to mass ratio, graphene-carbon nano tube composite material, Kynoar 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, use again battery housing seal battery core, by the liquid injection port being opened on housing, in housing, inject N-methyl-N-N-ethyl pyrrole N-hexafluorophosphoric acid salt electrolyte subsequently, sealing liquid injection port, obtains ultracapacitor.
Embodiment 6
The preparation of the ultracapacitor of the graphene-carbon nano tube composite material of embodiment 2 preparations of using
(1) prepare ultracapacitor positive plate
First, select the graphene-carbon nano tube composite material of embodiment 2 preparations as positive electrode active materials;
Secondly, the ratio that is 88:10:2 according to mass ratio, graphene-carbon nano tube composite material, Kynoar 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 battery housing seal battery core, injects tetraethyl ammonium hexafluorophosphoric acid salt electrolyte subsequently by the liquid injection port being opened on housing in housing, and sealing liquid injection port, obtains ultracapacitor.
Embodiment 7
The preparation of the ultracapacitor of the graphene-carbon nano tube composite material of embodiment 3 preparations of using
(1) prepare ultracapacitor positive plate
First, select the graphene-carbon nano tube composite material of embodiment 3 preparations as positive electrode active materials;
Secondly, the ratio that is 88:10:2 according to mass ratio, graphene-carbon nano tube composite material, Kynoar 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, use again battery housing seal battery core, by the liquid injection port being opened on housing, in housing, inject N-normal-butyl pyridinium tetrafluoroborate salt electrolyte subsequently, sealing liquid injection port, obtains ultracapacitor.
Embodiment 8
The preparation of the ultracapacitor of the graphene-carbon nano tube composite material of embodiment 4 preparations of using
(1) prepare ultracapacitor positive plate
First, select the graphene-carbon nano tube composite material of embodiment 4 preparations as positive electrode active materials;
Secondly, the ratio that is 88:10:2 according to mass ratio, graphene-carbon nano tube composite material, Kynoar 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, use again battery housing seal battery core, by the liquid injection port being opened on housing, in housing, inject N-methyl-N-N-ethyl pyrrole N-tetrafluoro boric acid salt electrolyte subsequently, sealing liquid injection port, obtains ultracapacitor.
Table 1 is Graphene mass fraction in the graphene-carbon nano tube composite material of embodiment 1 ~ 4 preparation
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| The mass fraction of Graphene | 52% | 99% | 82% | 71% |
Table 2 is the charge-discharge test result of the ultracapacitor of embodiment 5 ~ 8 preparations
| Embodiment | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Specific capacity F/g | 158 | 162 | 172 | 165 |
The capacity of Graphene in ionic liquid is generally less than 100F/g at present, and the specific capacity of the ultracapacitor that the graphene-carbon nano tube composite material that application is obtained by above-mentioned preparation method obtains improves a lot.
The above embodiment has only expressed several execution mode 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 range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for graphene-carbon nano tube composite material, is characterized in that, comprises the steps:
1.66 ~ 165:1 is added to the water graphite oxide and carbon nano-tube in mass ratio, and carries out ultrasonic processing 1 ~ 5 hour, obtains dispersion liquid;
Potassium hydroxide solution is added in described dispersion liquid, stir until appearance cohesion obtains suspension, wherein, the gross mass of described graphite oxide and carbon nano-tube and the mass ratio of described potassium hydroxide are 1:1 ~ 30; And
By described suspension filtered, after dry, obtain pressed powder, described pressed powder reacted 1 ~ 5 hour at 800 ~ 1200 ℃, washing, filter, the dry graphene-carbon nano tube composite material that obtains.
2. the preparation method of graphene-carbon nano tube composite material according to claim 1, is characterized in that, the concentration of described potassium hydroxide solution is 0.1 ~ 10mol/L.
3. the preparation method of graphene-carbon nano tube composite material according to claim 1, is characterized in that, the concentration of described graphite oxide in dispersion liquid is 8.3 ~ 16.5g/L, and the concentration of described carbon nano-tube in dispersion liquid is 0.1 ~ 5g/L.
4. the preparation method of graphene-carbon nano tube composite material according to claim 1, is characterized in that, the power of described ultrasonic processing is 600 ~ 800w.
5. the preparation method of graphene-carbon nano tube composite material according to claim 1, is characterized in that, by after described suspension filtered, and the dry pressed powder that obtains for 24 ~ 48 hours at 60 ~ 80 ℃.
6. the preparation method of graphene-carbon nano tube composite material according to claim 1, is characterized in that, described washing step is that water washs.
7. the graphene-carbon nano tube composite material preparing according to the preparation method described in claim 1 ~ 6 any one.
8. a ultracapacitor, comprise housing, be arranged at battery core and filling electrolyte in described housing in described housing, described battery core comprises positive plate, barrier film and the negative plate stacking gradually, it is characterized in that, described positive plate comprises aluminium foil and be coated in the anode sizing agent layer on described aluminium foil, and the material of described anode sizing agent layer comprises binding agent, conductive agent and graphene-carbon nano tube composite material according to claim 7.
9. ultracapacitor according to claim 8, is characterized in that, described binding agent is Kynoar, and described conductive agent is acetylene black, and the mass ratio of described graphene-carbon nano tube composite material, binding agent and conductive agent is 88:10:2.
10. ultracapacitor according to claim 8, is characterized in that, described electrolyte is ionic liquid, and the cation of described ionic liquid is quaternary ammonium salt, pyridiniujm or pyrroles's salt cation, and the anion of described ionic liquid is PF
6 -or BF
4 -.
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| CN106298277A (en) * | 2016-07-26 | 2017-01-04 | 上海师范大学 | A kind of Graphene/carbon nanotube composite material of microwave liquid phase fast low temperature fabricated in situ and its preparation method and application |
| CN106298277B (en) * | 2016-07-26 | 2018-06-19 | 上海师范大学 | A kind of Graphene/carbon nanotube composite material of microwave liquid phase fast low temperature fabricated in situ and its preparation method and application |
| CN107170985A (en) * | 2017-05-12 | 2017-09-15 | 安徽大学 | Preparation method of activated three-dimensional graphene/foamed nickel for lithium ion battery |
| CN110828881A (en) * | 2019-08-28 | 2020-02-21 | 深圳先进技术研究院 | Dual-ion battery and preparation method thereof |
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