CN108946707A - Graphene aerogel and its preparation method and application - Google Patents
Graphene aerogel and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to material engineering fields, disclose a kind of preparation method of graphene aerogel, which is characterized in that this method includes that the combustible solvent in the graphene liquid phase gel containing combustible solvent is made to burn, and obtains graphene aerogel.Method of the invention is simple, quick, efficient, and graphene aerogel space net structure obtained is complete, porosity is high and large specific surface area.
Description
Technical field
The present invention relates to material engineering fields, are related to a kind of preparation method of graphene aerogel, and in particular to Yi Zhongtong
Cross the method that burning solvent prepares graphene aerogel.
Background technique
Graphene aerogel is three-dimensional porous structure material made of being connected with each other as graphene sheet layer, have light weight,
Many advantages, such as good conductivity, elastic superpower, large specific surface area, oleophylic fire prevention, porosity superelevation, in water process, electrochemistry, energy
Many fields such as source, catalyst, sensor, super capacitor, absorption, thermal control have a wide range of applications with excellent performance, but
The too high factor of preparation cost limits its real industrial application.
Solvent medium in graphene liquid phase gel is usually replaced as what gas medium obtained by graphene aerogel, and
One step solvent heat or hydro-thermal method are to prepare one of most common method of graphene liquid phase gel, have and are simple and efficient, sample purity
High feature.The graphene liquid phase gel of preparation is since there are surface tension for the solvent inside gel skeleton, in common drying
Under the conditions of will cause the collapse of skeleton, so the drying process for being able to maintain gel porous network structure is always graphene airsetting
One of the emphasis of difficult point and related scientific research worker research in glue preparation.
During preparing graphene aerogel, researcher mostly uses greatly freeze-drying or supercritical drying at present, with
Just completely retain the microcellular structure of aeroge as far as possible.Freeze-drying is to be chilled to water-containing materials below freezing, changes water
For ice, ice is then changed into steam under high vacuum and the drying means that removes.Supercritical drying is to develop in recent years
The new technology come, replacement that is mild using supercritical solvent, quickly realizing solvent in gel, supercritical solvent exists later
When reaching the critical point of its own, become a kind of uniform fluid between gas and liquid, gas-liquid interface disappears, hair
Thin event resolves would not cause the contraction and structural damage of gelinite, to obtain nanometer when fluid being discharged from gel
The complete gel rubber material of network structure.But both drying means require expensive equipment and low temperature, high vacuum or height
The harsh experiment condition such as pressure, for example CN104163423 discloses a kind of method of freeze-drying preparation spongy graphene,
Freeze-drying is stated described in claim are as follows: -60 DEG C or less, lower than under conditions of 12Pa, vacuum freeze drying 12-24h, experiment
Period is relatively long, yield is lower, higher cost, seriously limits the industrialized production of graphene aerogel.
Therefore, the graphene liquid phase gel drying side for finding a kind of simple process, capable of completely retaining gel pore structure
Can method be that have problem to be overcome, and be directly related to graphene aerogel and produce and apply on a large scale.
Summary of the invention
The purpose of the invention is to overcome the problems, such as it is of the existing technology it is complicated for operation, time-consuming, at high cost, provide
A kind of preparation method of simple, quick, efficient graphene aerogel, this method is easy to operate, quick, and graphite obtained
Alkene aeroge space net structure is complete, porosity is high and large specific surface area.
It was found by the inventors of the present invention that can by making the combustible solvent in the graphene liquid phase gel containing combustible solvent burn
Simplicity quickly prepares graphene aerogel, and obtained graphene aerogel space net structure is complete, porosity is high simultaneously
And large specific surface area.More it is especially surprising that being obtained by graphene aerogel obtained by the above method than freeze-drying
Aeroge have bigger specific surface area, absorption and in terms of have great application prospect；And it is dry with freezing
It is dry to compare, expensive instrument and equipment was not only needed, but also shorten the period of preparation, and had been very beneficial for large-scale industrial production.
To achieve the goals above, one aspect of the present invention provides a kind of preparation method of graphene aerogel, this method packet
Including makes the combustible solvent in the liquid phase gel of the graphene containing combustible solvent burn, and obtains graphene aerogel.
Preferably, the content that combustible solvent accounts for all solvents in the graphene liquid phase gel containing combustible solvent is 60 weights
Measure % or more.
Preferably, the graphene liquid phase gel containing combustible solvent contains surfactant.It is highly preferred that the surface
Activating agent is selected from one of lignosulfonates, dodecyl benzene sulfonate and lauryl sulfate or a variety of.
Preferably, the graphene liquid phase gel containing combustible solvent is graphene liquid phase gel made from solvent-thermal method.
Preferably, the graphene liquid phase gel containing combustible solvent be will be in graphene hydrogel made from hydro-thermal method
Water is replaced as graphene liquid phase gel obtained from combustible solvent.
Second aspect of the present invention provides graphene aerogel obtained by the above method.
Third aspect present invention provides above-mentioned graphene aerogel in electrode material, hydrogen storage material, catalyst material, heat-insulated
Application in material and sorbent material.
Through the above technical solutions, preparation method of the invention is easy to operate, reproducible, it is not necessarily to special equipment, technique
Simply, short preparation period, and cost is extremely low, substantially increases production efficiency, is very beneficial for industrial graphene aerogel
Batch production.Also, this method avoid the uses and prolonged drying process of expensive drying instrument, in routine experimentation
It can be rapidly completed under the conditions of room.
Detailed description of the invention
Fig. 1 is pair of the graphene aerogel that the embodiment of the present invention 1 obtains and the graphene aerogel that comparative example 1 obtains
Than figure；
Fig. 2 is the adsorption desorption isothermal curve figure for the graphene aerogel that the embodiment of the present invention 1 obtains；
Fig. 3 is the graph of pore diameter distribution for the graphene aerogel that the embodiment of the present invention 1 obtains；
Fig. 4 is the graph of pore diameter distribution for the graphene aerogel that comparative example 2 of the present invention obtains；
Fig. 5 is the electron scanning micrograph for the graphene aerogel that the embodiment of the present invention 1 obtains；
Fig. 6 is the transmission electron microscope photo for the graphene aerogel that the embodiment of the present invention 1 obtains；
Fig. 7 is the electron scanning micrograph for the graphene aerogel that 1-4 of the embodiment of the present invention is obtained；
The XRD spectrum for the graphene aerogel that Fig. 8 is 1-3 of the embodiment of the present invention and comparative example 1 obtains.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The preparation method of graphene aerogel of the invention include make in the graphene liquid phase gel containing combustible solvent can
Solvent burning is fired, graphene aerogel is obtained.
According to the present invention, the purpose for making combustible solvent burn is to make to remove the solvent in graphene liquid phase gel, simultaneously
Make graphene liquid phase gel drying, obtains graphene aerogel, and by way of making combustible solvent burn, it is ensured that
The chemical property for the aeroge that burning front and back gel volume is basically unchanged or varies less, and do not influence.
In the present invention, there is no particular limitation for the mode for making combustible solvent burn, and can ignite selected from open fire, heat radiation
It ignites or one of arc ignition or a variety of.There is no particular limitation for the condition that combustible solvent burning carries out, and completes flammable molten
Agent full combustion.For example, burning environment temperature can be room temperature or high temperature (such as 5 DEG C or more), oxygen concentration be greater than or
Equal to minimum oxygen concentration needed for combustible solvent burning.
In the present invention, as long as the combustible solvent can be removed by burning, can be used in be existing
Solvent-thermal method prepares the organic solvent of graphene liquid phase gel, or can be used in replacing graphene hydrogel made from hydro-thermal method
In water organic solvent.The combustible solvent can be for selected from one of alcohols, ketone, ethers, aldehydes and acids or more
Kind.Preferably, the alcohols is lower aliphatic alcohols, more preferably fatty alcohol of the carbon atom number less than 6, such as methanol, ethyl alcohol, third
Alcohol, isopropanol, butanol, amylalcohol, hexanol etc.；The ketone is lower aliphatic ketone, more preferably fat of the carbon atom number less than 6
Ketone, such as acetone, butanone, 2 pentanone, propione, hexanone etc.；The ethers is lower aliphatic ether, and more preferably carbon atom number is small
In 6 aliphatic ether, such as methyl ether, ether, ethyl methyl ether etc.；The aldehydes is lower aliphatic aldehyde, and more preferably carbon atom number is less than 6
Fatty aldehyde, such as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral etc.；The acids is lower fatty acid, more preferably carbon atom number
Fatty acid less than 6, such as acetic acid, propionic acid etc..From the point of view of easily obtaining, the combustible solvent can for selected from methanol,
One of ethyl alcohol, propyl alcohol, isopropanol, acetone, ether, formaldehyde and acetic acid are a variety of.
A preferred embodiment according to the present invention, in order to guarantee that burning can sufficiently remove graphene liquid phase gel
In solvent, in the graphene liquid phase gel containing combustible solvent combustible solvent account for the content of all solvents be 60 weight % with
On, more preferably 70 weight % or more, further preferably 80 weight % or more, further preferably 90 weight % or more, into
One step is preferably 95 weight % or more, further preferably 98 weight % or more, further preferably 99 weight % or more, into one
Step is preferably 99.5 weight % or more.It is all molten by accounting for combustible solvent in the graphene liquid phase gel containing combustible solvent
The content of agent is controlled in above range, so that it may pass through the solvent in the sufficiently removal graphene liquid phase gel that burns.
Present inventor has further discovered that by making the graphene liquid phase gel containing combustible solvent contain surface-active
Agent can be further improved the physical property of graphene aerogel that burning obtains, such as specific surface area and aperture etc., more added with
Conducive to the application of graphene aerogel.Its principle speculates are as follows: surfactant can be with during burning removes combustible solvent
Play the role of skeletal support, reduces pore structure caused by reducing as solvent and collapse, so as to obtain with Gao Bibiao
The graphene aerogel of area.In addition, can burn simultaneously by combustion process and remove the surfactant, finally obtain not
Graphene aerogel containing surfactant.
There is no particular limitation for the type of the surfactant, can be with as long as not influencing the burning of combustible solvent
For cationic surfactant, anionic surfactant and nonionic surfactant.From the angle for reducing introducing foreign ion
Degree considers that the surfactant is preferably anionic surfactant.It is highly preferred that the anionic surfactant is choosing
It is particularly preferably wooden from one of lignosulfonates, dodecyl benzene sulfonate and lauryl sulfate or a variety of
Plain sulfonate.Above-mentioned anionic surfactant can be its sodium salt, sylvite, lithium salts etc..
In the present invention, consider from the mechanical strength of the graphene aerogel further increased, before preferably making burning
Graphene liquid phase gel have good mechanical strength.
A preferred embodiment according to the present invention, the graphene liquid phase gel containing combustible solvent are solvent heat
Graphene liquid phase gel made from method.For the ease of carrying out the burning of solvent, it is preferable that the graphene liquid containing combustible solvent
Combustible solvent in phase gel is solvent used in the solvent-thermal method.By using combustible solvent as in solvent-thermal method
Solvent, after solvent-thermal method heat treatment obtained graphene liquid phase gel can directly through the invention in method fired
Burning processing, obtains graphene aerogel.And solvent used in solvent-thermal method be not easy to burning when, can also be by graphite obtained
Solvent in alkene liquid phase gel is replaced as combustible solvent, and method of replacing and the water phase for replacing following graphene hydrogels are same.
Preferred embodiment according to another preferred, the graphene liquid phase gel containing combustible solvent is will
Water in graphene hydrogel made from hydro-thermal method is replaced as graphene liquid phase gel obtained from combustible solvent.By the way that water is set
The displacement process for changing organic solvent into, prepare graphene hydrogel made from hydro-thermal reaction can also by means of the present invention
Graphene aerogel.
There is no particular limitation for the displaced mode, the water in graphene hydrogel can be replaced with combustible solvent,
Obtain the graphene liquid phase gel containing combustible solvent.From the point of view of the sufficiently progress that makes to burn, it is preferable that the displacement
The higher the better for the degree of progress.The displaced mode may include immersion treatment and/or flushing processing.
As immersion treatment, graphene hydrogel can be impregnated in combustible solvent, immersion treatment can carry out 1
More than secondary, preferably 1-3 times.In order to improve the speed of displacement, the temperature of immersion treatment is 0-250 DEG C, preferably 80-180 DEG C.
In order to carry out displacement reaction at a higher temperature, can be carried out by way of heating in a kettle.In order to guarantee to replace
Effect, time of immersion treatment is 10min or more, preferably 0.5-3h.The combustible solvent used when as immersion treatment
Volume, relative to 1 volume graphene hydrogel, preferably 4-20 volume, more preferably 8-10 volume.
It handles, graphene hydrogel can be rinsed with combustible solvent as flushing.Rinsing number of processing can be 2 times
More than, preferably 3-4 times.As rinsing the volume of combustible solvent used when processing, relative to 1 volume graphene hydrogel,
Preferably 4-30 volume, more preferably 10-12 volume.
In the present invention, the solvent-thermal method can be the existing solvent heat that can be used in preparing graphene liquid phase gel
Method.The solvent-thermal method includes: to be heat-treated the organic solvent solution of graphene oxide.
It can be 50-250 DEG C as the temperature being heat-treated in solvent-thermal method, preferably 120-180 DEG C, the time can be
6-48h, preferably 12-24h.
It can be 0.2-10mg/mL as the concentration of graphene oxide in the organic solvent solution of graphene oxide.In order to
The mechanical strength of graphene hydrogel is improved, the concentration of above-mentioned graphene oxide is preferably 1-5mg/mL, more preferably 2-
3.5mg/mL。
In the present invention, the hydro-thermal method can be the existing hydro-thermal side that can be used in preparing graphene liquid phase gel
Method.The hydro-thermal method includes: to be heat-treated the aqueous solution of graphene oxide.
It can be 50-250 DEG C as the temperature being heat-treated in hydro-thermal method, preferably 120-180 DEG C, the time can be
0.5-48h, preferably 12-24h.
It can be 0.2-10mg/mL as the concentration of graphene oxide in the aqueous solution of graphene oxide.In order to improve stone
The mechanical strength of black alkene hydrogel, the concentration of above-mentioned graphene oxide are preferably 1-5mg/mL, more preferably 2-3.5mg/mL.
There is no particular limitation by the pH of aqueous solution as graphene oxide, and graphene hydrogel can be made, excellent
It is selected as 2-6 perhaps 8-11 more preferably 4-5 or 8-10, particularly preferably 9-10.
Present inventor has further discovered that before being heat-treated, in the organic solvent solution or water of graphene oxide
Surfactant is added in solution (hereinafter referred to as graphene oxide solution), and the effect of burning processing not only can be improved, may be used also
To improve the mechanical strength of graphene aerogel obtained.Therefore, in the graphene liquid phase gel containing surfactant, preferably
The surfactant is added before heat treatment carries out.Surfactant can promote the dispersion of graphene oxide solution, make
The graphene liquid phase gel that must be heat-treated has bigger volume, so that biggish specific surface area and gap structure are obtained,
It can play the role of skeletal support when burning removes combustible solvent simultaneously, further increase the ratio table of graphene liquid phase gel
Area.There is no particular limitation for the surfactant, can be to prepare the common surfactant of graphene liquid phase gel, only
Otherwise influence the burning of combustible solvent.From the point of view of reducing introducing foreign ion, the surfactant is preferably
Anionic surfactant.It is highly preferred that the anionic surfactant is selected from lignosulfonates, detergent alkylate sulphur
One of hydrochlorate and lauryl sulfate are a variety of, particularly preferably lignosulfonates.Above-mentioned anion surface active
Agent can be its sodium salt, sylvite, lithium salts etc..
By adding surfactant, can be easier that graphene liquid phase gel is prepared, and it is mechanical strong to improve it
Degree.Surfactant can according to need addition appropriate, it is preferable that relative to the graphene oxide of 1 parts by weight, the surface
The additional amount of activating agent is 0.5-3 parts by weight, preferably 0.5-2 parts by weight, more preferably 1-1.5 parts by weight.
In order to guarantee going on smoothly for heat treatment, before being heat-treated, as needed in graphene oxide solution
Add one of reducing agent, catalyst, load raw material of substance or a variety of.By the way that reducing agent and/or catalyst is added, can make
Graphene liquid phase gel can be also made when carrying out at a lower temperature in heat treatment.Raw material of substance is loaded by being added, can be made
Modified graphene liquid phase gel or the compound liquid phase gel of graphene.
It, can be molten by the organic solvent of graphene oxide before being heat-treated in order to guarantee to be heat-treated abundant progress
Liquid or aqueous solution are mixed, such as are carried out by stirring and/or being ultrasonically treated, and the time can be 10min or more, preferably
0.5-2h。
Method of the invention can be widely applied to the preparation of various graphene aerogels.That is, the graphene
There is no particular limitation for aeroge, and the graphene aerogel can also be redox graphene aeroge, the graphene
The graphene composite aerogel that aeroge can also be combined for graphene with other materials.The graphene composite aerogel
It can be redox graphene/oxide composite aerogel, redox graphene/hydroxide composite aerogel, reduction
Graphene oxide/nitride composite aerogel, redox graphene/sulfide composite aerogel, redox graphene/selenium
Compound composite aerogel, redox graphene/cyanide composite aerogel, the compound airsetting of redox graphene/fluoride
One of glue, redox graphene/chloride composite aerogel, redox graphene/metal composite aeroge is more
Kind.
In the present invention, the graphene can be for without modified graphene, or modified graphene,
Such as the graphene doped with N, B, P etc..
The second aspect of the invention is additionally provided according to graphene aerogel obtained by the above method.
The third aspect of the invention additionally provides above-mentioned graphene aerogel in electrode material, hydrogen storage material, catalyst
Application in material, heat-barrier material and sorbent material.Graphene aerogel prepared by the method for the present invention also has simultaneously
There are a good electrical properties, specific capacity is big, high rate performance and cyclical stability are good, is particularly suitable for application as supercapacitor
Electrode material.
The present invention will be described in detail by way of examples below.In following embodiment, scanning electron microscope is purchased from
Jeol Ltd., model JSM-6390；Transmission electron microscope is purchased from Japan Electronics Corporation, model JEOL-2100；It inhales
Desorption isotherm and the instrument of pore-size distribution test are purchased from Beijing Bei Shide instrument Science and Technology Ltd., model 3H-2000PSI；X
X ray diffractometer x is purchased from Rigaku Co., Ltd., model D/MAX-Ultima；Agents useful for same is commercially available analytical reagents.
Preparation example 1
This preparation example is for illustrating the method that one step hydro thermal method prepares graphene hydrogel.
1) it with a certain amount of deionized water dissolving graphene oxide, stirs evenly, after being ultrasonically treated 2h, stirs evenly, obtain
To graphene oxide solution.The mode for using drying to weigh demarcates the concentration of wherein graphene oxide as 2mg/mL.
2) to prepare a certain concentration, the graphene oxide of certain pH value with the graphene oxide solution configured in step 1) molten
Surfactant is added as needed in liquid, stirs 0.5h, is transferred in water heating kettle, carries out hydro-thermal reaction, and temperature is controlled 180
DEG C, time 12h.
3) hydrogel is taken out after the completion of hydro-thermal reaction, be washed with deionized 2-3 times.
Embodiment 1
The present embodiment is used to illustrate the preparation method of graphene aerogel of the invention.
1) according to the method for preparation example 1, (pH 10 contains sulfomethylated lignin to the graphene oxide solution for being 2mg/mL with concentration
Sour sodium 2mg/mL) graphene hydrogel is prepared.
2) with isopropanol immersion treatment graphene hydrogel 24 hours of 5 times of volumes of graphene hydrogel, solvent is completed
Displacement.
3) the graphene hydrogel after completing displacement is directly lighted in draught cupboard, after isopropanol burning completely,
Obtain graphene aerogel G1.
Embodiment 2
The present embodiment is used to illustrate the preparation method of graphene aerogel of the invention.
It is carried out according to the method for embodiment 1, difference is only that, sodium lignin sulfonate is replaced with to the dodecane of identical weight
Graphene aerogel G2 is made in base benzene sulfonic acid sodium salt.
Embodiment 3
The present embodiment is used to illustrate the preparation method of graphene aerogel of the invention.
It is carried out according to the method for embodiment 1, difference is only that, sodium lignin sulfonate is replaced with to the dodecane of identical weight
Graphene aerogel G3 is made in base sodium sulphate.
Embodiment 4
The present embodiment is used to illustrate the preparation method of graphene aerogel of the invention.
It is carried out according to the method for embodiment 1, difference is only that, does not use sodium lignin sulfonate, and graphene aerogel is made
G4。
Comparative example 1
This comparative example is for illustrating that normal pressure drying seasoning prepares graphene aerogel.
It step 1) and 2) carries out according to the method for embodiment 1, difference is, is added without surfactant.
Step 3) is that the graphene hydrogel after completing displacement is put into direct 50 DEG C of 5 hours of drying process in baking oven
To constant weight, graphene aerogel D1 is obtained.
Comparative example 2
This comparative example is for illustrating that freeze-drying prepares graphene aerogel.
Graphene hydrogel is made according to the method for step 1) in embodiment 1, difference is, is added without surfactant.
It after the graphene hydrogel is carried out precooling processing, is placed in freeze drier, sample cools down simultaneously with drying box, after stablizing
It is maintained at -50 DEG C, under conditions of 8Pa, vacuum freeze drying to constant weight, obtains graphene aerogel D2 for 24 hours.
Test case 1
The method that this test case is used to illustrate to test the specific surface area of graphene aerogel.
Graphene aerogel obtained in above-described embodiment 1-4 and comparative example 1-2 is de-gassed at 200 DEG C
90min tests its BET adsorption isotherm, and the maximum specific surface area of graphene aerogel is calculated.
The comparison diagram for the graphene aerogel that the graphene aerogel and comparative example 1 that the embodiment of the present invention 1 obtains obtain
As shown in Figure 1；The adsorption desorption isothermal curve figure for the graphene aerogel that embodiment 1 obtains is as shown in Figure 2；Embodiment 1-4 and right
The relevant parameter of graphene aerogel obtained is as shown in table 1 in ratio 1-2.
Table 1
| Surfactant | Specific surface area (m2/g) | Aperture (nm) | |
| Comparative example 1 | - | 6.78 | 4.42 |
| Comparative example 2 | - | 261.59 | 3.34 |
| Embodiment 1 | Sodium lignin sulfonate | 731.77 | 6.88 |
| Embodiment 2 | Neopelex | 610.4 | 8.33 |
| Embodiment 3 | Lauryl sodium sulfate | 553.52 | 8.47 |
| Embodiment 4 | - | 405.18 | 6.16 |
Test case 2
The method that this test case is used to illustrate to test the pore-size distribution of graphene aerogel.
The pore-size distribution of graphene aerogel G1 and D2, as a result distinguish made from BJH testing example 1 and comparative example 2
As shown in Figure 3 and Figure 4；
As shown in figure 3, it is very sharp using peak in the pore size distribution curve figure of the graphene aerogel of the method for the present invention preparation,
Illustrate even aperture distribution, being measured its aperture size is about 6.88nm.And as shown in figure 4, the graphene of freeze-drying preparation
The aperture size of aeroge is about 3.34nm, much smaller than the aperture of the graphene aerogel of the method for the present invention preparation.
Test case 3
This test case is used to illustrate the microcellular structure of graphene aerogel of the invention.
Using the microstructure of scanning electron microscopic observation graphene aerogel G1, as a result as shown in Figure 5.
From fig. 5, it can be seen that graphene aerogel G1 has good microcellular structure, aperture is evenly distributed, explanation
Solvent burning of the invention does not damage graphene aerogel microstructure, still remains the microcosmic stratiform knot of graphene
Structure has biggish specific surface area.
Test case 4
This test case is used to illustrate the microcellular structure of graphene aerogel of the invention.
Graphene aerogel G1 microstructure is observed using projection electron microscope, as a result as shown in Figure 6.
From fig. 6, it can be seen that Fig. 6 A shows reunion and overlapping only a small amount of between the lamella of graphene aerogel G1,
And it can be seen that the spatial network for reflecting the graphene hydrogel of hydro-thermal method preparation there are about 3-4 layers from enlarged photograph Fig. 6 B
Structure is obtaining good holding after solvent burning is dry.
Test case 5
Utilize graphene aerogel G1-4 obtained in scanning electron microscope observation embodiment 1-4, result such as Fig. 7 institute
Show.
It can be seen from figure 7 that the graphene aerogel of embodiment 1-4 all has relatively uniform distribution of pores, and
There is biggish pore structure, lamella accumulates lesser extent, this has graphene aerogel compared with Large ratio surface between lamella
Long-pending and specific capacity.
Test case 6
This test case is used to illustrate the lattice structure of graphene aerogel of the invention.
With the XRD spectrum of the obtained graphene aerogel of X-ray diffractometer measurement embodiment 1-3 and comparative example 1, such as Fig. 8
It is shown.
As can be seen from Figure 8 the graphene aerogel G1-G3 that embodiment 1-3 is obtained, there is apparent stone at 25.26 °
Black alkene characteristic peak, and this feature peak is more sharp than the graphene characteristic peak for the graphene aerogel D1 that comparative example 1 obtains, explanation
Burning drying process of the invention makes the knot of graphene aerogel not only without destroying the lattice structure of graphene aerogel
Brilliant degree further increases, and keeps lattice more complete.
Can be seen that the drying of the normal pressure in comparative example 1 by the comparison of embodiment 1 and comparative example 1-2 needs sample drying
Continuous processing 3 hours or more in case, the aperture for the graphene aerogel that this method obtains collapses, and surface area is very small, only
6.78m2/g；Freeze-drying in comparative example 2 is true under conditions of needing sample in freeze dryer with -50 DEG C or less, lower than 12Pa
Vacuum freecing-dry 12-24h, this method needs large-scale instrument and the period is long；And the method in embodiment 1 only need to directly light graphite
Organic solvent in alkene gel, obtained aeroge large specific surface area are not necessarily to special equipment, simple process, manufacturing cycle
It is short, and cost is extremely low, substantially increases production efficiency, is very beneficial for the industrial batch production of graphene aerogel.
It can be seen that the graphene aerogel prepared using method of the invention with very big by above-mentioned test result
Specific surface area.Specifically, compared by embodiment 1 and comparative example 1 as can be seen that as shown in Figure 1,1 combustion method of embodiment obtains
Graphene aerogel macroscopical volume it is larger, and the graphene aerogel macroscopic view volume that room temperature oven drying method obtains in comparative example 1
It is smaller.It can reach by the specific surface area that the result of table 1 can be seen that the graphene aerogel that the method for the present invention obtains
731.7m2/ g, and the specific surface area for the graphene aerogel that freeze-drying obtains is only 261.59m2/g。
Further as seen in Figure 3, the pore-size distribution of 1 obtained graphene aerogel is equal through the embodiment of the present invention
Even, size is about 6.88nm；And as seen in Figure 4, the hole for the graphene aerogel that freeze-drying obtains in comparative example 2
Diameter size is only 3.34nm.
The above results show graphene aerogel prepared by the present invention than oven drying under traditional freeze-drying and normal pressure
Obtained graphene has higher specific surface area, it may have bigger utility value.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (11)
1. a kind of preparation method of graphene aerogel, which is characterized in that this method includes making the graphene liquid containing combustible solvent
Combustible solvent burning in phase gel, obtains graphene aerogel.
2. according to the method described in claim 1, wherein, combustible solvent accounts in the graphene liquid phase gel containing combustible solvent
The content of all solvents is 60 weight % or more.
3. according to the method described in claim 1, wherein, the graphene liquid phase gel containing combustible solvent contains surface-active
Agent；
Preferably, the surfactant is in lignosulfonates, dodecyl benzene sulfonate and lauryl sulfate
It is one or more.
4. method described in any one of -3 according to claim 1, wherein the graphene liquid phase gel containing combustible solvent
For graphene liquid phase gel made from solvent-thermal method.
5. according to the method described in claim 4, wherein, the combustible solvent in the graphene liquid phase gel containing combustible solvent
For solvent used in the solvent-thermal method；
Preferably, the combustible solvent is selected from one of alcohols, ketone, ethers, aldehydes or acids or a variety of；
Preferably, the alcohols is lower aliphatic alcohols, and the ketone is lower aliphatic ketone, and the ethers is lower aliphatic ether, institute
Stating aldehydes is lower aliphatic aldehyde, and the acids is lower fatty acid；
Preferably, the alcohols is methanol, ethyl alcohol, propyl alcohol, isopropanol, and the ketone is acetone, butanone, and the ethers is second
Ether, the aldehydes are formaldehyde, acetaldehyde, propionic aldehyde, and the acids is acetic acid.
6. method described in any one of -3 according to claim 1, wherein the graphene liquid phase gel containing combustible solvent
For the water in graphene hydrogel made from hydro-thermal method is replaced as graphene liquid phase gel obtained from combustible solvent；
Preferably, the displaced mode includes immersion treatment and/or flushing processing；
Preferably, the temperature of the immersion treatment is 0-250 DEG C, and the time is 10min or more, the temperature of the more preferable immersion treatment
Degree is 80-180 DEG C, time 0.5-3h；
Preferably, the combustible solvent is selected from one of alcohols, ketone, ethers, aldehydes or acids or a variety of；
Preferably, the alcohols is lower aliphatic alcohols, and the ketone is lower aliphatic ketone, and the ethers is lower aliphatic ether, institute
Stating aldehydes is lower aliphatic aldehyde, and the acids is lower fatty acid；
Preferably, the alcohols is methanol, ethyl alcohol, propyl alcohol, isopropanol, and the ketone is acetone, butanone, and the ethers is second
Ether, the aldehydes are formaldehyde, acetaldehyde, propionic aldehyde, and the acids is acetic acid.
7. according to the method described in claim 6, wherein, the hydro-thermal method includes: that the aqueous solution of graphene oxide is carried out heat
Processing；
Preferably, in the aqueous solution of the graphene oxide, the concentration of graphene oxide is 0.2-10mg/mL, more preferably 1-
5mg/mL；
Preferably, the pH of the aqueous solution of the graphene oxide is 2-11, preferably 2-6 or 8-11；
Preferably, before being heat-treated, surfactant, the surface-active are added in the aqueous solution of graphene oxide
Agent is selected from one of lignosulfonates, dodecyl benzene sulfonate and lauryl sulfate or a variety of；
Preferably, the graphene oxide relative to 1 parts by weight, the additional amount of the surfactant are 0.5-3 parts by weight.
8. method according to any one of claims 1-7, wherein the mode for making combustible solvent burn is drawn selected from open fire
Combustion, heat radiation are ignited or one of arc ignition or a variety of.
9. according to the method described in claim 1, wherein, the graphene aerogel further includes graphene complex aeroge；
Preferably, the graphene complex aeroge is redox graphene/oxide composite aerogel, oxygen reduction fossil
Black alkene/hydroxide composite aerogel, redox graphene/nitride composite aerogel, redox graphene/sulfide
Composite aerogel, redox graphene/selenides composite aerogel, redox graphene/cyanide composite aerogel are gone back
Former graphene oxide/fluoride composite aerogel, redox graphene/chloride composite aerogel, redox graphene/
One of metal composite aeroge is a variety of.
10. the graphene aerogel that method described in -9 obtains according to claim 1.
11. graphene aerogel described in any one of claim 10 electrode material, hydrogen storage material, catalyst material, heat-barrier material and
Application in sorbent material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103551091A (en) * | 2013-11-25 | 2014-02-05 | 北京化工大学 | Method for drying aerogel |
| US8663593B2 (en) * | 2010-11-19 | 2014-03-04 | Research and Business Foundation Sungyunkwan University | Method for fabricating three dimensional graphene structures using catalyst templates |
| CN103922351A (en) * | 2013-01-14 | 2014-07-16 | 成都首能新能源开发有限公司 | Preparation method of silica aerogel thermal insulation coating layer |
| KR101427033B1 (en) * | 2012-01-30 | 2014-08-06 | 연세대학교 산학협력단 | Three Dimensional Graphene Structure and Preparation Method of the Same |
| CN106032274A (en) * | 2015-03-19 | 2016-10-19 | 中国科学院上海应用物理研究所 | Graphene hydrogel, graphene aerogel as well as preparation method and application thereof |
| CN106517160A (en) * | 2016-11-22 | 2017-03-22 | 青岛科技大学 | Method for preparing isotropic superelastic graphene aerogel |
-
2017
- 2017-05-19 CN CN201710357127.2A patent/CN108946707B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8663593B2 (en) * | 2010-11-19 | 2014-03-04 | Research and Business Foundation Sungyunkwan University | Method for fabricating three dimensional graphene structures using catalyst templates |
| KR101427033B1 (en) * | 2012-01-30 | 2014-08-06 | 연세대학교 산학협력단 | Three Dimensional Graphene Structure and Preparation Method of the Same |
| CN103922351A (en) * | 2013-01-14 | 2014-07-16 | 成都首能新能源开发有限公司 | Preparation method of silica aerogel thermal insulation coating layer |
| CN103551091A (en) * | 2013-11-25 | 2014-02-05 | 北京化工大学 | Method for drying aerogel |
| CN106032274A (en) * | 2015-03-19 | 2016-10-19 | 中国科学院上海应用物理研究所 | Graphene hydrogel, graphene aerogel as well as preparation method and application thereof |
| CN106517160A (en) * | 2016-11-22 | 2017-03-22 | 青岛科技大学 | Method for preparing isotropic superelastic graphene aerogel |
Non-Patent Citations (1)
| Title |
|---|
| 巩金瑞: "三维石墨烯复合材料的制备与应用研究", 《热加工工艺》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111874892A (en) * | 2020-07-28 | 2020-11-03 | 广东石油化工学院 | Graphene aerogel and preparation method and application thereof |
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