CN105368045A - Graphene-polypyrrole composite aerogel and preparation method and application thereof - Google Patents
Graphene-polypyrrole composite aerogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses graphene-polypyrrole composite aerogel and a preparation method and application thereof. The aerogel is mainly formed by compositing graphene and polypyrrole and has the advantages of being appropriate in pore diameter, large in porosity, high in specific surface area, low in density, good in electric conductivity of 0.1-100 S/m, high in energy storage modulus and the like. The preparation method of the aerogel comprises the steps that oxidized graphene and pyrrole monomers are taken as raw materials, the oxidized graphene is dispersed into uniform and stable dispersion liquid in an acidic or neutral environment, the oxidized graphene and the pyrrole are mixed evenly through mechanical stirring and ultrasound, standing is performed on gel at room temperature, and then drying is performed to obtain the graphene-polypyrrole composite aerogel. The aerogel obtained through the method is excellent in comprehensive performance, can serve as an electrode material of a supercapacitor, an adsorbing agent for aromatic organic dye and the like and is simple in preparation technology, low in energy consumption, green, environmentally friendly and suitable for mass production.
Description
Technical field
The present invention is specifically related to a kind of graphene-polypyrrole composite aerogel and preparation method thereof and application, belongs to nano-porous materials technical field.
Background technology
Graphene is with Sp
2the cellular crystalline structure of the carbon atom close-packed arrays that hydridization connects, its thickness is only the thickness (0.34nm) of a carbon atomic layer, is the thinnest material found at present.Graphene can be envisioned as the atom grid formed by carbon atom and its covalent linkage.The preparation method of Graphene expands to other various methods gradually by initial tear tape method/slight rubbing manipulation, and as silicon carbide epitaxy, metallic surface grows, colloidal chemistry synthesis etc.The structure of Graphene is highly stable, and carbon-carbon bond is only
connection between the carbon atom of Graphene inside is very pliable and tough, and when applying external force in Graphene, the meeting flexural deformation of carbon atom face, make carbon atom need not rearrange to adapt to external force, thus holding structure is stablized.In addition, when the electronics in Graphene moves in track, or foreign atom can not be introduced and scattering occurs because of lattice imperfection.Because interatomic force is very strong, at normal temperatures, even if around carbon atom telescopes, the interference that Graphene internal electron is subject to is also very little.The characteristic of its many excellence given by the special geometric of Graphene and electronic structure, comprises excellent electric property, optical property, mechanical property, thermal property and high carrier mobility.Each carbon atom on Graphene is that strong п-п bond is closed, and contributes residue P orbital electron to form the large п key of conjugation, and the п electronics of delocalization is welcome freely movable, gives the electroconductibility of Graphene excellence.In Graphene, the movement velocity of electronics reaches 1/300 of the light velocity, considerably beyond the movement velocity of electronics in general conductor.Graphene is the thinnest in the world is also the hardest nano material, and its breaking tenacity 125GPa, namely area is 1m
2graphene sheet layer can bear the power of 4Kg, the ultimate strength of its strength ratio ordinary steel is high 100 times.The Young's modulus of Graphene is about 1.1TPa, has higher snappiness, easy pleat easy to break.Due to the electronic structure of Graphene uniqueness, it is almost completely transparent, and single-layer graphene is to the absorption 2.3% of visible ray, and namely transmitance is 97.7%.Graphene has the thermal property of quite stable.The thermal conductivity of Graphene controls by being conducted by trajectory under diffusion conduction and low temperature by under phonon transmission and high temperature.At room temperature, the thermal conductivity of single-layer graphene up to 5300W/ (mK), higher than carbon nanotube and diamond.The theoretical specific surface area of Graphene can reach 2630m
2/ g, the sensor prepared with Graphene can respond to single atom or molecule.Ultra-thin according to Graphene, the characteristic of intensity super large, Graphene can be widely used in each field, such as ultralight flak jackets, ultra-thin and ultra-light type aircraft materials etc.According to the electroconductibility of its excellence, it is made also to have huge application potential at microelectronic.Graphene likely can become the substitute of silicon, manufactures superminiature transistor, is used for producing following supercomputer, and the electronic mobility that carbon is higher can make following computer obtain higher speed.Grapheme material or a kind of excellent properties-correcting agent, at new energy field as in ultracapacitor, lithium ion battery, due to its highly conc, high-specific surface area, be applicable to the auxiliary agent as electrode materials in addition.
On the other hand, aerogel is the highly porous nano material with extremely-low density and high-specific surface area.Its preparation adopts special technique usually, as lyophilize or supercritical drying, the liquid displacement in wet gel is become gas and does not change the original network structure of gel and obtain.Graphene aerogel is born in 2009 the earliest, by the people such as MarkW.Ellsworth of the U.S. by the aqueous solution lyophilize of graphene oxide being obtained.Graphene aerogel has high porosity, high-specific surface area, and the feature such as low density and high connductivity is widely used in the field such as stored energy and conversion, gas phase catalysis, clean environment, sensing.At present, the method preparing graphene aerogel mainly contains the methods such as hydro-thermal, chemical reduction, chemically crosslinked.Utilize these methods to prepare in the process of graphene aerogel to be difficult to avoid using High Temperature High Pressure, poisonous and hazardous pharmaceutical chemicals etc., complicated operation, cost are high, do not meet the theory of energy-conserving and environment-protective, secondly, the graphene aerogel obtained shows poor mechanical property usually, be unfavorable for graphene aerogel application in practice, finally, Graphene is in an assembling process because Π-Π stronger between lamella interacts, cause stacking phenomenon serious between graphene sheet layer, this advantage that inhibit the high-specific surface area of Graphene own serious again.
In view of the problem run in conventional graphite alkene aerogel preparation process, technician in the urgent need to this ambit proposes a kind of less energy-consumption, environmental protection and a kind of method that can give full play to the advantage of graphene sheet layer own to prepare graphene aerogel, pushes graphene aerogel to greenization, industrialization gradually.
Summary of the invention
Main purpose of the present invention is to provide a kind of graphene-polypyrrole composite aerogel and preparation method thereof, to overcome deficiency of the prior art.
Another object of the present invention is the purposes providing foregoing graphites alkene-polypyrrole composite aerogel.
For realizing aforementioned invention object, the technical solution used in the present invention comprises:
A kind of graphene-polypyrrole composite aerogel, be compounded to form primarily of Graphene and polypyrrole, and the aperture of described graphene-polypyrrole aerogel is 1nm ~ 4 μm, porosity 75.0-99.5%, density is 0.02-0.5g/cm
3, specific surface area is 100-900m
2/ g, specific conductivity is 0.1 ~ 100S/m, and storage modulus is 2-25MPa.
A preparation method for graphene-polypyrrole composite aerogel, comprises the steps:
(1) be scattered in by graphene oxide in acidity or neutral aqueous solution, being formed can the stable existence graphene oxide dispersion of more than 1 day;
(2) described graphene oxide solution is placed in room temperature environment, and adds pyrrole monomer, after Homogeneous phase mixing, more than ultrasonic disperse 0.5min, then room temperature leaves standstill more than 1 day, obtains graphene-polypyrrole composite aquogel;
(3) obtained graphene-polypyrrole composite aquogel is carried out lyophilize or supercritical drying, obtain described graphene-polypyrrole composite aerogel.
As one of comparatively preferred scheme, this preparation method comprises following concrete steps:
(1) be scattered in by graphene oxide in acidity or neutral aqueous solution, being formed at least can the graphene oxide dispersion of stable existence 1-300 days;
(2) described graphene oxide solution is placed in room temperature environment, and adds pyrrole monomer, stir 1min ~ 900min, ultrasonic disperse 0.5 ~ 200min, then leave standstill 1 ~ 28 day in 5 ~ 80 DEG C, obtain graphene-polypyrrole composite aquogel;
(3) obtained graphene-polypyrrole composite aquogel is carried out lyophilize or supercritical drying, obtain described graphene-polypyrrole composite aerogel.
Further, described acidic aqueous solution can preferably from concentration be 10
-4the hydrochloric acid of ~ 1.0mol/L, phosphoric acid or sulphuric acid soln etc., but be not limited thereto.
Further, the concentration of described graphene oxide dispersion preferably at 0.4mg/mL ~ 15mg/mL, but is not limited thereto.
Preferably, the pyrrole monomer adopted in step (2) is purified through underpressure distillation, and the condition of underpressure distillation comprises: vacuum tightness 50 ~ 100Pa, temperature 60 ~ 90 DEG C.
Preferably, the graphene oxide adopted in step (2) and the mass ratio of pyrroles are 40:1 ~ 1:40.
Preferably, the stirring velocity adopted in step (2) is 10 ~ 10000 revs/min.
Preferably, the ultrasonic disperse power adopted in step (2) is 50 ~ 1000W, frequency is 50 ~ 100KHz.
Preferably, described in step (3), cryodesiccated condition comprises: freezing temp is-20 DEG C ~-170 DEG C, and drying temperature is 0 DEG C ~ 80 DEG C, and vacuum tightness is 100 ~ 60000Pa, and time of drying is 2 ~ 48 hours.
Preferably, described in step (3), supercritical drying comprises:
Small molecular alcohol or small molecules ketone is adopted to replace the aqueous solvent existed in graphene-polypyrrole composite aquogel and soluble reaction thing, reaction product, obtain graphene-polypyrrole compound alcogel or graphene-polypyrrole compound ketone gel, described small molecular alcohol comprises ethanol, and described small molecules ketone comprises acetone;
Adopt Supercritical Ethanol or supercritical co to carry out drying to described graphene-polypyrrole compound alcogel or graphene-polypyrrole compound ketone gel, obtain described graphene-polypyrrole composite aerogel.
Any one graphene-polypyrrole composite aerogel aforementioned is preparing the application in electrode materials or sorbent material.
A kind of electrode material for electric double layer capacitor, comprise any one graphene-polypyrrole composite aerogel aforesaid, and the ratio capacitance of described electrode materials is 100 ~ 500F/g, internal resistance is 2 ~ 40 ohm.
Compared with prior art, advantage of the present invention comprises:
(1) the present invention obtain aerogel not only there is good mechanical property, and the polypyrrole in aerogel can also suppress the stack-up issue of graphene sheet layer in self assembling process well, give full play to the advantage that graphene sheet layer itself is special, it is when being applied as electrode material for super capacitor, demonstrate high ratio capacitance performance, and be applied as sorbent material, such as, during fragrant organic dye adsorbent namely, show higher adsorptive power.
(2) aerogel preparation technology of the present invention simple, less energy-consumption, environmental protection, scale operation is suitable for.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, the accompanying drawing that the following describes is only some embodiments recorded in the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 a is the electron scanning micrograph of graphene-polypyrrole composite aerogel in embodiment 2;
Fig. 1 b is the transmission electron microscope photo of graphene-polypyrrole composite aerogel in embodiment 2;
Fig. 2 a is the nitrogen adsorption/desorption curve schematic diagram of embodiment 2 China and Mexico alkene-polypyrrole composite aerogel;
Fig. 2 b is the pore size distribution curve schematic diagram of embodiment 2 China and Mexico alkene-polypyrrole composite aerogel;
Fig. 3 is the X-ray diffraction curve synoptic diagram of graphene-polypyrrole composite aerogel in embodiment 2;
Fig. 4 is the nano impress curve synoptic diagram of graphene-polypyrrole composite aerogel in embodiment 2;
Fig. 5 a is the cyclic voltammetry curve schematic diagram of graphene-polypyrrole composite aerogel electrode in embodiment 2;
Fig. 5 b is the charging and discharging curve schematic diagram of graphene-polypyrrole composite aerogel electrode in embodiment 2.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be described in detail the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite not making creative work, all belongs to the scope of protection of the invention.
One aspect of the present invention provides a kind of preparation method of graphene-polypyrrole composite aerogel, its with graphene oxide and pyrrole monomer for initial reactant, by stirring, ultrasonic disperse, room temperature leaves standstill the key step such as gel and supercritical drying and obtains three-dimensional grapheme-polypyrrole composite aerogel.
Another aspect of the present invention provides a kind of graphene-polypyrrole composite aerogel, it is compounded to form primarily of Graphene and polypyrrole, and the aperture of described graphene-polypyrrole aerogel is 1nm ~ 4um, porosity 75.0-99.5%, density is 0.02-0.5g/cm
3, specific surface area is 100-900m
2/ g, specific conductivity is 0.1 ~ 100S/m, and storage modulus is up to 2-25MPa.
As one of exemplary embodiments, a kind of preparation method of graphene-polypyrrole composite aerogel can comprise the following steps:
(1) in acidic aqueous solution, add graphene oxide, carry out mechanical stirring and ultrasonic disperse until form uniform graphene oxide solution; Described graphene oxide solution is stable existence 1-300 days at least;
(2) described graphene oxide water solution is placed in room temperature environment, add pyrrole monomer, machinery (or magnetic force) stirs 1 ~ 900 minute, ultrasonic 0.5 ~ 200 minute, then room temperature leaves standstill 1 ~ 28 day, obtains graphene-polypyrrole composite aquogel;
(3) by carrying out lyophilize or supercritical drying to described graphene-polypyrrole hydrogel, graphene-polypyrrole composite aerogel is obtained.
Wherein, graphene oxide can be prepared by Hummers chemical method.
Graphene-polypyrrole composite aerogel of the present invention can as electrode materials, the such as application such as electrode material for super capacitor or organic-fuel sorbent material.
Such as, when applying as electrode material for electric double layer capacitor, its ratio capacitance can be 100 ~ 500F/g, and internal resistance can be 2 ~ 40 ohm.
Aerogel structure of the present invention is novel, has good mechanical, electric property etc., and preparation technology is simple, less energy-consumption, environmental protection, can be mass-produced, and can avoid adopting High Temperature High Pressure needed in the art, hazardous chemical reductive agent etc.
Also technical scheme of the present invention is further described by reference to the accompanying drawings below by way of some embodiments.But selected embodiment only for illustration of the present invention, and does not limit and scope of the present invention.
Embodiment 1: solution graphene oxide dispersion being configured to 8mg/mL, stirs 20 minutes, ultrasonic 30 minutes, obtains the graphene oxide solution that dispersion is homogeneous; Get this solution 10mL, add the pyrrole monomer of 16.5 μ L wherein, stir 30 minutes, more ultrasonic 15 minutes; By the dispersion liquid of the graphene oxide mixed that obtains and pyrroles, room temperature leaves standstill 7 days, obtains graphene-polypyrrole composite aquogel.The hydrogel obtained is obtained graphene-polypyrrole compound alcogel through dissolve with ethanol displacement, afterwards that graphene-polypyrrole compound alcogel is dry through supercritical co, obtain graphene-polypyrrole composite aerogel.The ratio of this aerogel starting raw material graphene oxide and pyrrole monomer is 5:1, is denoted by GP5.
The structure of graphene-polypyrrole composite aerogel (GP5) obtained in this embodiment and performance perameter are in table 1.
Embodiment 2: solution graphene oxide dispersion being configured to 8mg/mL, stirs 20 minutes, ultrasonic 30 minutes, obtains the graphene oxide solution that dispersion is homogeneous; Get this solution 10mL, add the pyrrole monomer of 27.5 μ L wherein, stir 20 minutes, more ultrasonic 20 minutes; By the dispersion liquid of the graphene oxide mixed that obtains and pyrroles, room temperature leaves standstill 7 days, obtains graphene-polypyrrole composite aquogel.The hydrogel obtained is obtained graphene-polypyrrole compound alcogel through dissolve with ethanol displacement, afterwards that graphene-polypyrrole compound alcogel is dry through supercritical co, obtain graphene-polypyrrole composite aerogel.The ratio of this aerogel starting raw material graphene oxide and pyrrole monomer is 3:1, is denoted by GP3.Fig. 1 a is the electron scanning micrograph of graphene-polypyrrole composite aerogel obtained in this embodiment; Fig. 1 b is the transmission electron microscope photo of graphene-polypyrrole composite aerogel obtained in this embodiment; Fig. 2 a is the nitrogen adsorption/desorption curve schematic diagram of graphene-polypyrrole composite aerogel obtained in this embodiment; Fig. 2 b is the pore size distribution curve schematic diagram of graphene-polypyrrole composite aerogel obtained in this embodiment; Fig. 3 is the X-ray diffraction curve synoptic diagram of graphene-polypyrrole composite aerogel obtained in this embodiment; Fig. 4 should be obtained in embodiment the nano impress curve synoptic diagram of graphene-polypyrrole composite aerogel; Fig. 5 a is the cyclic voltammetry curve schematic diagram of graphene-polypyrrole composite aerogel obtained in this embodiment; Fig. 5 b is the constant current charge-discharge curve synoptic diagram of graphene-polypyrrole composite aerogel obtained in this embodiment.
Other performance perameters of graphene-polypyrrole composite aerogel obtained in this embodiment are in table 1.
Embodiment 3: solution graphene oxide dispersion being configured to 8mg/mL, stirs 20 minutes, ultrasonic 30 minutes, obtains the graphene oxide solution that dispersion is homogeneous; Get this solution 10mL, add the pyrrole monomer of 82.6 μ L wherein, stir 20 minutes, more ultrasonic 20 minutes; By the dispersion liquid of the graphene oxide mixed that obtains and pyrroles, room temperature leaves standstill 5 days, obtains graphene-polypyrrole composite aquogel.The hydrogel obtained is obtained graphene-polypyrrole compound alcogel through dissolve with ethanol displacement, afterwards that graphene-polypyrrole compound alcogel is dry through supercritical co, obtain graphene-polypyrrole composite aerogel.The ratio of this aerogel starting raw material graphene oxide and pyrrole monomer is 1:1, is denoted by GP1.
The structure of graphene-polypyrrole composite aerogel (GP1) obtained in this embodiment and performance perameter are in table 1.
Embodiment 4: solution graphene oxide dispersion being configured to 8mg/mL, stirs 20 minutes, ultrasonic 30 minutes, obtains the graphene oxide solution that dispersion is homogeneous; Get this solution 10mL, add the pyrrole monomer of 247.7uL wherein, stir 20 minutes, more ultrasonic 20 minutes; By the dispersion liquid of the graphene oxide mixed that obtains and pyrroles, room temperature leaves standstill 5 days, obtains graphene-polypyrrole composite aquogel.The hydrogel obtained is obtained graphene-polypyrrole compound alcogel through dissolve with ethanol displacement, afterwards that graphene-polypyrrole compound alcogel is dry through supercritical co, obtain graphene-polypyrrole composite aerogel.The ratio of this aerogel starting raw material graphene oxide and pyrrole monomer is 1:3, is denoted by PG3.
The structure of graphene-polypyrrole composite aerogel (PG3) obtained in this embodiment and performance perameter are in table 1.
Embodiment 5: solution graphene oxide dispersion being configured to 8mg/mL, stirs 20 minutes, ultrasonic 30 minutes, obtains the graphene oxide solution that dispersion is homogeneous; Get this solution 10mL, add the pyrrole monomer of 412.8 μ L wherein, stir 20 minutes, more ultrasonic 20 minutes; By the dispersion liquid of the graphene oxide mixed that obtains and pyrroles, room temperature leaves standstill 5 days, obtains graphene-polypyrrole composite aquogel.The hydrogel obtained is obtained graphene-polypyrrole compound alcogel through dissolve with ethanol displacement, afterwards that graphene-polypyrrole compound alcogel is dry through supercritical co, obtain graphene-polypyrrole composite aerogel.The ratio of this aerogel starting raw material graphene oxide and pyrrole monomer is 1:5, is denoted by PG5.
The structure of graphene-polypyrrole composite aerogel (PG5) obtained in this embodiment and performance perameter are in table 1.
Graphene-polypyrrole composite aerogel structure and performance parameters in table 1. embodiment 1-5
It should be noted that, in this article, the such as relational terms of first and second grades and so on is only used for an entity or operation to separate with another entity or operational zone, and not necessarily requires or imply the relation that there is any this reality between these entities or operation or sequentially.And, term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability, thus make to comprise the process of a series of key element, method, article or equipment and not only comprise those key elements, but also comprise other key elements clearly do not listed, or also comprise by the intrinsic key element of this process, method, article or equipment.When not more restrictions, the key element limited by statement " comprising ... ", and be not precluded within process, method, article or the equipment comprising described key element and also there is other identical element.
The above is only the specific 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 (12)
1. a graphene-polypyrrole composite aerogel, is characterized in that it is compounded to form primarily of Graphene and polypyrrole, and the aperture of described graphene-polypyrrole aerogel is 1nm ~ 4 μm, porosity 75.0-99.5%, and density is 0.02-0.5g/cm
3, specific surface area is 100-900m
2/ g, specific conductivity is 0.1 ~ 100S/m, and storage modulus is 2-25MPa.
2. the preparation method of graphene-polypyrrole composite aerogel as claimed in claim 1, is characterized in that comprising the steps:
(1) be scattered in by graphene oxide in acidity or neutral aqueous solution, being formed can the stable existence graphene oxide dispersion of more than 1 day;
(2) described graphene oxide solution is placed in room temperature environment, and adds pyrrole monomer, after Homogeneous phase mixing, more than ultrasonic disperse 0.5min, then room temperature leaves standstill more than 1 day, obtains graphene-polypyrrole composite aquogel;
(3) obtained graphene-polypyrrole composite aquogel is carried out lyophilize or supercritical drying, obtain described graphene-polypyrrole composite aerogel.
3. the preparation method of graphene-polypyrrole composite aerogel as claimed in claim 2, is characterized in that comprising following concrete steps:
(1) be scattered in by graphene oxide in acidity or neutral aqueous solution, being formed at least can the graphene oxide dispersion of stable existence 1-300 days;
(2) described graphene oxide solution is placed in room temperature environment, and adds pyrrole monomer, stir 1min ~ 900min, ultrasonic disperse 0.5 ~ 200min, then leave standstill 1 ~ 28 day in 5 ~ 80 DEG C, obtain graphene-polypyrrole composite aquogel;
(3) obtained graphene-polypyrrole composite aquogel is carried out lyophilize or supercritical drying, obtain described graphene-polypyrrole composite aerogel.
4. the preparation method of graphene-polypyrrole composite aerogel as claimed in claim 2 or claim 3, it is characterized in that described acidic aqueous solution comprises concentration is 10
-4the hydrochloric acid of ~ 1.0mol/L, phosphoric acid or sulphuric acid soln.
5. graphene-polypyrrole composite aerogel preparation method as claimed in claim 2 or claim 3, is characterized in that the concentration of described graphene oxide dispersion is at 0.4mg/mL ~ 15mg/mL.
6. the preparation method of graphene-polypyrrole composite aerogel as claimed in claim 2 or claim 3, it is characterized in that, the pyrrole monomer adopted in step (2) is purified through underpressure distillation, and the condition of underpressure distillation comprises: vacuum tightness 50 ~ 100Pa, temperature 60 ~ 90 DEG C.
7. the preparation method of graphene-polypyrrole composite aerogel as claimed in claim 2 or claim 3, it is characterized in that, the graphene oxide adopted in step (2) and the mass ratio of pyrroles are 40:1 ~ 1:40.
8. the preparation method of graphene-polypyrrole composite aerogel as claimed in claim 2 or claim 3, is characterized in that, the stirring velocity adopted in step (2) is 10 ~ 10000 revs/min, and the ultrasonic power of ultrasonic disperse is 50 ~ 1000W, frequency is 50 ~ 100KHz.
9. the preparation method of graphene-polypyrrole composite aerogel as claimed in claim 2 or claim 3, it is characterized in that, described in step (3), cryodesiccated condition comprises: freezing temp is-20 DEG C ~-170 DEG C, drying temperature is 0 DEG C ~ 80 DEG C, vacuum tightness is 100 ~ 60000Pa, and time of drying is 2 ~ 48 hours.
10. the preparation method of graphene-polypyrrole composite aerogel as claimed in claim 2 or claim 3, it is characterized in that, described in step (3), supercritical drying comprises:
Small molecular alcohol or small molecules ketone is adopted to replace the aqueous solvent existed in graphene-polypyrrole composite aquogel and soluble reaction thing, reaction product, obtain graphene-polypyrrole compound alcogel or graphene-polypyrrole compound ketone gel, described small molecular alcohol comprises ethanol, and described small molecules ketone comprises acetone;
Adopt Supercritical Ethanol or supercritical co to carry out drying to described graphene-polypyrrole compound alcogel or graphene-polypyrrole compound ketone gel, obtain described graphene-polypyrrole composite aerogel.
Graphene-polypyrrole composite aerogel according to any one of 11. claim 1-10 is preparing the application in electrode materials or sorbent material.
12. 1 kinds of electrode material for electric double layer capacitor, is characterized in that the graphene-polypyrrole composite aerogel comprised according to any one of claim 1-10, and the ratio capacitance of described electrode materials is 100 ~ 500F/g, and internal resistance is 2 ~ 40 ohm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874796A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof |
| CN103601913A (en) * | 2013-11-15 | 2014-02-26 | 复旦大学 | Graphene/polypyrrole hybrid aerogel and preparation method thereof |
-
2014
- 2014-08-27 CN CN201410425289.1A patent/CN105368045B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874796A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof |
| CN103601913A (en) * | 2013-11-15 | 2014-02-26 | 复旦大学 | Graphene/polypyrrole hybrid aerogel and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| FAN YANG ET AL: ""Self-assembled hierarchical graphene/polyaniline hybrid aerogels for forelectrochemical capacitive energy storage"", 《ELECTROCHIMICA ACTA》 * |
| SHIBING YE，JIACHUN FENG: "Self-Assembled Three-Dimensional Hierarchical Graphene/Polypyrrole Nanotube Hybrid Aerogel and Its Application for Supercapacitors", 《ACS APPLIED MATERIALS INTERFACES》 * |
| 孙瑞，张学同: "自发组装合成石墨烯/聚吡咯气凝胶", 《中国化学会第29届学术年会摘要集——第33分会：纳米材料合成与组装》 * |
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