CN107651675A - A kind of three-dimensional drape redox graphene and preparation method thereof - Google Patents
A kind of three-dimensional drape redox graphene and preparation method thereof Download PDFInfo
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- CN107651675A CN107651675A CN201711104334.3A CN201711104334A CN107651675A CN 107651675 A CN107651675 A CN 107651675A CN 201711104334 A CN201711104334 A CN 201711104334A CN 107651675 A CN107651675 A CN 107651675A
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Abstract
The present invention provides a kind of preparation method of three-dimensional drape redox graphene, is specially：A three-dimensional porous tubular graphene alkene) is prepared using sponge template, the three-dimensional porous tubular graphene alkene is reduced, obtains three-dimensional porous tubulose redox graphene；The sponge of the sponge template is melamine sponge；B the three-dimensional porous tubulose redox graphene) is subjected to hydro-thermal process in supercritical water environment, then is freeze-dried, obtains three-dimensional drape redox graphene.Present invention firstly provides the work that method progress graphene three dimension scale crimp design is collapsed using template, using the special analog thermoplastic collapse process of thermosetting melamine sponge under hydrothermal conditions, the synthesis of three dimension scale pleated structure is successfully realized.Three-dimensional drape grapheme material prepared by the present invention possesses sensing sensitivity height in sensor research field practical value, can test scope it is wide the features such as, also there is high directiveness to act on macroscopical self-assembling method of nanometer primitive.
Description
Technical field
The present invention relates to nano material macroscopic view assembling field, more particularly to a kind of three-dimensional drape redox graphene and its
Preparation method.
Background technology
Fold, bending corrugation and the bending flexion of nano wire and the ripples of 1-dimention nano ball surface comprising two-dimensional nano piece
Ripples shape structure.This pleated structure can not only improve the specific surface area of nano material, moreover it is possible to have to the mechanical property of nano material
Significantly improvement result.
In recent years, the research of fold pattern is increasingly fiery in fields such as energy storage, sensing, stretchable device and self-assembled materials
Heat.For example, the U.S.《Science》Magazine (Science, 2010,329:1637.) one kind is reported in metal nanoparticle surface shape
Piece is received into graphene, it can significantly improve the stored energy capacitance of double layer capacitor, and because its special curved structure can not only
Lower device step, moreover it is possible to beneficial to ionic conduction, and then lower its filter effect.Britain《Self-heating nanometer technology》(Nature
nanotechnology,2011,6:788.) it is prepared for using one-dimensional CNT a kind of saturating with pressure and stress correspondence
Bright bionics skin, the pre-stretching twin shaft contraction process based on flexible substrates, there is the spring shape CNT to be formed excellent
Tensility.Britain《Nature material》(Nature materials,2013,12(4):321.) dimethyl silicone polymer is utilized
(PDMS) pre-stretching template, the graphene nanometer sheet with two-dimensional drape structure, and the side of structure one of fold are smoothly synthesized
Face improves its draftability, and on the other hand its hydrophilic and hydrophobic is also had a significant impact.But these reports are all based on low latitudes
The synthesis of fold pattern is realized, because low latitudes forms stress template and is relatively simple to realize.There has been no on three at present
The report of fold pattern is tieed up, this is relatively complicated mainly due to three dimension scale formation stress contraction process, it is difficult to realizes.
The assemble method report about graphene pleated structure is many at present, and zero-dimension nano ball is carried out based on grapheme material
The assemble method of particle mainly has spray drying process and the soft ball shrinkage method of nucleocapsid, and this method operation is relatively easy, but is applicable model
Enclose relatively limited.For example, the U.S.《Nanometer bulletin》(Nano letters,2011,12(1):486-489.) report a kind of oxygen
The spray-drying process of graphite aqueous solution, and smoothly synthesize the fold balls of 150nm to 400nm not etc.；The U.S.《Physics is commented
By bulletin》(Physical review letters,2011,106(23):234301.) simulated using the drying contraction of pea
The contraction process of this bulb surface crust.The assemble method for carrying out sweep based on monodimension nanometer material mainly has pre-stretching to receive
Contracting method and stencil methods, this method is applied widely, but relatively low to the controllability of package assembly.For example, the U.S.《Advanced material
Material》(Advanced Materials,2015,27(18):2866-2875.) report a kind of pre-stretching Ecoflex
The process of silicone rubber substrate over-assemble nano silver wires, having synthesized has highly stretchable fexible film.
The above-mentioned work about three-dimensional drape only produces folding line in the two-dimensional direction, and is only in another dimension
Thickness is superimposed, and is not three-dimensional drape material on stricti jurise, such material can not embody the advantage of fold pattern completely.
Method that the preparation method of the pattern of this " three-dimensional drape " mainly has an ice template method and poor solvent is collapsed.For example, Britain《Naturally it is logical
News》It is exactly to utilize that (Nature communications, 2016,7,12920.), which reports a kind of three-dimensional arch graphene-structured,
Prepared by ice template method, due to introducing orderly bow-shaped structural in a three-dimensional structure, material is possessed excellent sensing characteristicses.
The U.S.《ACS nanometers》(ACS nano,2017,11(8):8092) a kind of graphene pleated structure is reported, is to dissolve first
Graphene is transferred in poor solvent in good solvent, and then the graphene for making to unfold is shunk, by top-down
Method layer assembly forms " three-dimensional drape graphene ".However, there has been no on being upwardly formed fold pattern in three dimensionality side
Report, main cause is that there has been no the suitable driving force that contraction can be produced in three dimensions.
The content of the invention
Present invention solves the technical problem that it is to provide a kind of preparation method of three-dimensional drape redox graphene, this Shen
The preparation method that please be provided can prepare the redox graphene of three-dimensional drape yardstick.
In view of this, this application provides a kind of preparation method of three-dimensional drape redox graphene, including following step
Suddenly：
A), three-dimensional porous tubular graphene alkene is prepared using sponge template, the three-dimensional porous tubular graphene alkene is carried out
Reduction, obtains three-dimensional porous tubulose redox graphene；The sponge of the sponge template is melamine sponge；
B), the three-dimensional porous tubulose redox graphene is subjected to hydro-thermal process in supercritical water environment, then entered
Row freeze-drying, obtains three-dimensional drape redox graphene.
Preferably, also include after freeze：
Obtained three-dimensional drape redox graphene progress high-temperature heat treatment will be freeze-dried.
Preferably, step B) described in hydro-thermal process temperature be 60~180 DEG C, the time is 60~180min.
Preferably, the process of the freeze-drying is specially：
Graphene after hydro-thermal process is first frozen using Liquid nitrogen precooler, is then dried again.
Preferably, the preparation process of the three-dimensional porous tubular graphene alkene is specially：
Three-dimensional porous tubular graphene alkene is obtained by melamine sponge impregnating in graphene solution, after application of vacuum.
Preferably, the reducing agent of the reduction is hydroiodic acid.
Preferably, the temperature of the high-temperature heat treatment is 200~250 DEG C, and the time is 1~2h.
Present invention also provides a kind of three-dimensional drape redox graphene, redox graphene radial direction with it is tangential
Shrink same ratio in direction.
Preferably, the contraction yardstick of the three-dimensional drape redox graphene is 0~70%.
Preferably, the fold yardstick of the three-dimensional drape redox graphene is 0.2~5 μm.
This application provides a kind of preparation method of three-dimensional drape redox graphene, it is first with sponge template
Three-dimensional porous tubular graphene alkene is prepared for, then is reduced, obtains three-dimensional porous tubulose redox graphene, then will
Three-dimensional porous tubulose redox graphene carries out hydro-thermal process in supercritical water environment, and three-dimensional pleat is obtained after freeze-drying
Wrinkle redox graphene.During three-dimensional drape redox graphene is prepared, the application using melamine sponge as template,
Macroscopical assembling is carried out using sponge template is dilute to graphite, has synthesized the graphene nano pipe skeleton structure with loose structure,
Reduced again to improve graphene conductive, recycle hydro-thermal process to collapse sponge template afterwards, wrap up top layer
Graphene carry out stress contraction, due to the special equal proportion contraction of sponge template, possess three-dimensional porous graphene
Microcosmic orderly multistage pleated structure；The freeze-drying finally carried out maintains the pleated structure of graphene.
Brief description of the drawings
Fig. 1 is the composition principle figure of three-dimensional porous fold graphene tubular structure prepared by the embodiment of the present invention；
Fig. 2 is the pictorial diagram and SEM figures of sponge；
Fig. 3 is the pictorial diagram and SEM figures of the sponge of graphene oxide parcel；
Fig. 4 is the pictorial diagram and SEM figures of the sponge of redox graphene parcel；
Fig. 5 is the pictorial diagram and SEM figures of three-dimensional porous fold graphene tubular structure；
The shrinkage factor for the sponge that Fig. 6 wraps up for the redox graphene after hydro-thermal process and processing time graph of a relation；
Fig. 7 is sponge, graphene oxide, the Raman figure of redox graphene and fold graphene before and after hydro-thermal process；
Fig. 8 is the pictorial diagram of the three-dimensional porous fold graphene tubular structure of different shrinkage factors；
Fig. 9 is the SEM figures of the three-dimensional porous fold graphene tubular structure of different shrinkage factors；
Figure 10 is the fibre length and draw ratio variation diagram of melamine sponge contraction process；
Figure 11 is that the thermal infrared of melamine sponge hydrothermal decomposition product absorbs figure；
Figure 12 is the dry strength and wet strength comparison diagram of melamine sponge；
Figure 13 be hydro-thermal process after melamine sponge thermogravimetric analysis figure；
Figure 14 be hydro-thermal process after melamine sponge BET pore analysis figures；
Figure 15 be different hydro-thermal time-triggered protocols after different shrinkage factors melamine sponge pictorial diagram；
Figure 16 schemes for the melamine sponge SEM of the different shrinkage factors after different hydro-thermal time-triggered protocols.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
In view of fold has the effective tensility for improving nano material, but at present there has been no suitable template for three
Pleated structure is tieed up, and fold technology at this stage is only limitted to two-dimentional yardstick, has the invention provides one kind on three-dimensional and has
There is the grapheme material of three-dimensional drape structure.Specifically, this application provides one kind can occur stress on three dimension scale
The melamine sponge template of contraction, this template have a negative poisson's ratio characteristic, and available for synthesis with three-dimensional with pleat
The material for structure of wrinkling.As shown in figure 1, Fig. 1 is the schematic diagram that the present invention prepares three-dimensional porous wrinkle reduction graphene oxide.Specifically
, the invention provides a kind of preparation method of three-dimensional drape redox graphene, comprise the following steps：
A), three-dimensional porous tubular graphene alkene is prepared using sponge template, the three-dimensional porous tubular graphene alkene is carried out
Reduction, obtains three-dimensional porous tubulose redox graphene；The sponge of the sponge template is melamine sponge；
B), the three-dimensional porous tubulose redox graphene is subjected to hydro-thermal process in supercritical water environment, then entered
Row freeze-drying, obtains three-dimensional drape redox graphene.
During three-dimensional drape redox graphene is prepared, the dilute nanometer sheet of graphite is entered first with sponge template
Row macroscopic view assembling, graphene nano pipe skeleton structure of the synthesis with loose structure, specifically using melamine sponge as template, with graphite
Alkene is shrink-down material, and using sponge Template synthesis, three-dimensional porous tubular graphene alkene is graphene oxide parcel melamine sponge.
Specifically, the preparation process of the three-dimensional porous tubular graphene alkene is：
By melamine sponge impregnating in graphene solution, using the gas inside application of vacuum removing sponge, make parcel
Graphene thickness is more uniform, and the unnecessary graphene of absorption is removed by centrifuging.
In above process, graphene concentration is different, then can synthesize the three-dimensional porous graphene tubular structure of different-thickness.
Above-mentioned graphene and source the application of melamine sponge have no particular limits, and are obtained according to mode well known to those skilled in the art
.
Melamine sponge is a kind of heat cured resin, does not possess thermoplastic shrinkage character under usual conditions；And in hydro-thermal
In environment, because melamine sponge is there occurs reversible hydrolysis process, strand reconstructs under the effect of cohesion power, and then generates
Heat shrinkability characteristic.Said process is different from the thermal contraction process of general thermoplastic again, due to moieties in thermal and hydric environment
Dissolved after chain hydrolysis, the Mass lost of material, overall volume is reduced, thus can be shunk on three-dimensional, is formd
Shrinkage character with negative poisson's ratio.Thus, by the use of the melamine sponge with three-dimensional porous structure as template, in hydrothermal condition
Under, utilize its special analog thermoplastic negative poisson's ratio contraction process, it is possible to achieve truly realize three-dimensional multistage fold
It is prepared by the template of pattern.
After three-dimensional porous tubular graphene alkene is obtained, then reduced, to improve the electric conductivity of graphene.It is above-mentioned
The reagent of reduction is hydroiodic acid.The process of the reduction is specially：
By hydroiodic acid and water with 1:1 volume ratio is added in beaker, and oil bath heating is to 90 DEG C, by three-dimensional porous tubular graphene
Alkene is impregnated in 5~10s in above-mentioned mixed liquor, and the sample after reduction is cleaned using ethanol solution, obtains three-dimensional porous tubulose also
Former graphene oxide.
Then the application is carried out the three-dimensional porous tubulose redox graphene at hydro-thermal in supercritical water environment
Reason, sponge collapses contraction in water environment in the process, and its contraction process shrinks identical for radially and tangentially direction
Ratio, the graphene tubular structure on its top layer is stressed to drive in sponge template collapse process to be shunk, and forms fold
Pattern.Result of the test shows, the macroshrinkage yardstick of the application sponge template is 0~70%, graphene fold yardstick is 0.2~
5μm.In above-mentioned hydrothermal treatment process, the temperature of the hydro-thermal process is 60~180 DEG C, and the time is 60~180min；Having
In body embodiment, the temperature of the hydro-thermal process is 120~180 DEG C.
According to the present invention, finally the product after hydro-thermal process is freeze-dried, so as to not broken during product drying
The pleated structure of bad graphene.The process of herein described freeze-drying is specially：
After the product cleaning after hydro-thermal process, first frozen using Liquid nitrogen precooler, adopt and be dried using Freeze Drying Technique.
Above-mentioned freeze-drying is carried out at -45 DEG C.
In order to further improve the performance of three-dimensional drape redox graphene, the three-dimensional that the application finally will preferably obtain
Wrinkle reduction graphene oxide has carried out high-temperature heat treatment, can both avoid sponge framework deformation, also can reductive water to greatest extent
The fold graphene obtained after heat treatment.The temperature of the high-temperature heat treatment is 200~250 DEG C, and the time is 1~2h.
Thus the application additionally provides a kind of three-dimensional drape redox graphene, its radial direction in redox graphene
Same ratio is shunk with tangential direction.
Test result indicates that the contraction yardstick of herein described three-dimensional drape redox graphene is 0~70%, fold
Yardstick is 0.2~5 μm.
Method synthesis, which is collapsed, the invention provides a kind of template has the three-dimensional grapheme pleated structure of Microscopic order；This method
It is under specific condition, nanometer is realized using the collapsing for three-dimensional porous material melamine sponge with negative poisson's ratio shrinkage character
The self assembling process of material graphene three-dimensional multistage fold pattern.Specifically, first, using sponge template to graphene nano
Piece carries out macroscopical assembling, and synthesis has loose structure graphene nano pipe skeleton structure；Recycle hydroiodic acid thermal reduction oxidation stone
Black alkene, improve graphene conductive；The process for recycling hydro-thermal sponge template to collapse afterwards, carry out the graphene that top layer is wrapped up
Stress shrinks, and due to the special equal proportion contraction of sponge template, makes three-dimensional porous graphene be provided simultaneously with microcosmic having
The multistage pleated structure of sequence.The pleated structure of graphene is finally kept using Freeze Drying Technique, and is entered using high-temperature heat treatment
One step reduced graphene, improve its functionalization intensity.
The innovative point of the present invention is to propose first to collapse the work that method carries out three dimension scale crimp design using template, by
In the special analog thermoplastic collapse process of thermosetting melamine sponge under hydrothermal conditions, and then it is successfully realized three dimension scale fold
The synthesis of structure.Three-dimensional drape grapheme material prepared by the present invention possesses biography in sensor research field practical value, material
Feel high sensitivity, can test scope it is wide the features such as, the present invention also there is high directiveness to make the assemble method of nanometer primitive
With.
For a further understanding of the present invention, the oxygen reduction fossil with reference to embodiment to three-dimensional drape provided by the invention
The preparation method of black alkene is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Weigh 10g graphite flakes and 7.5g sodium nitrate to be well mixed in 2L beakers, be slowly added to the 300mL concentrated sulfuric acid, then
Be slowly added to 40g potassium permanganate, stir to sticky state, it is static peel off 5 days after, be slowly added to 1L deionized water and 60mL
H2O2, 8000r/min centrifugation, 10min being centrifuged every time, takes thick yellow intermediate layer, centrifugation product is filled in bag filter and dialyses 7
It obtains graphene to remove the wherein impurity such as manganese；
By clean melamine sponge impregnating in 3mg/mL graphene solution, inside application of vacuum removing sponge
Gas, make the graphene thickness of parcel evenly, and the unnecessary graphene of absorption is removed with 3500r/min centrifugation rates, obtain
Graphene wraps up melamine sponge, and its structure is macroscopically shown as yellow, covering amount about 0.1mg/cm3.Utilize sponge template bag
Two-dimensional graphene material is wrapped up in, according to the difference of graphene concentration, the three-dimensional porous graphene tubular structure of different-thickness can be synthesized.
Fig. 2 is the pictorial diagram and SEM figures of sponge；Fig. 3 is the pictorial diagram and SEM figures of the sponge of graphene oxide parcel；
By hydroiodic acid and deionized water with 1:1 volume ratio is added in sesame seed cake, and oil bath heating is to 90 DEG C, by graphene bag
Wrap up in melamine sponge impregnating such as hydroiodic acid hot solution and reduce 5 to 10 seconds, the sample after taking-up reduction, which is put into ethanol solution, to be impregnated
Cleaning, removing iodine residual, redox graphene parcel melamine sponge is obtained, it is macroscopically being shown as black；Fig. 4 is reduction
The pictorial diagram and SEM figures of the sponge of graphene oxide parcel；
The sponge that hydro-thermal process redox graphene wraps up in supercritical water environment, makes sponge occur in water environment
Collapse contraction, its contraction process shrinks same ratio for radially and tangentially direction, macroshrinkage yardstick 0%~70% it
Between, the graphene tubular structure on its top layer receives stress in sponge template collapse process to be driven and shrinks, and forms fold shape
Looks, the yardstick of fold is between 0.2~5 μm, and the temperature of hydro-thermal process is 160 DEG C, and the time is 60~180min；The sample that will be obtained
After product are beforehand through liquid nitrogen freezing, it is subzero 45 DEG C of freeze-dryings；High-temperature heat treatment is finally carried out, temperature is 200 DEG C, processing
Time 2h, it can both avoid sponge skeleton from being denatured, and can also reduce the fold graphene obtained after hydro-thermal process to greatest extent, obtain
Three-dimensional drape redox graphene.Fig. 5 is the pictorial diagram and SEM figures of three-dimensional porous fold graphene tubular structure.
Embodiment 2
7 pieces of the melamine sponge of redox graphene parcel prepared by Example 1, stripping and slicing is 6*2*2cm sizes, is put into
In 50mL reactor, add 40mL deionized waters, reactor is placed in 160 DEG C of baking ovens, respectively hydro-thermal process 60,80,
100th, 120,140,160 and 180min, reaction are naturally cooling to room temperature, about 5h after terminating, will obtain sample from reactor transfer
Move to impregnate in deionized water and clean；Dried, obtained not with Freeze Drying Technique after obtained sample is frozen with Liquid nitrogen precooler
With the three-dimensional drape redox graphene of shrinkage factor.
Macro-size measurement, scanning electronic microscope observation and Raman table are carried out to the sample of the different shrinkage factors of acquisition
Sign, infrared spectrum analysis is carried out to the catabolite of hydro-thermal melamine sponge, as shown in Figure 6 and Figure 7, Fig. 6 is after hydro-thermal process
The shrinkage factor and processing time graph of a relation of the sponge of redox graphene parcel；Fig. 7 is sponge before and after hydro-thermal process, aoxidizes stone
The Raman figure of black alkene, redox graphene and fold graphene.
Embodiment 3
It is 120~180 DEG C to change the hydrothermal temperature in embodiment 2, controls the hydro-thermal time can be with 40~200min respectively
Reach the purpose collapsed in various degree to the melamine sponge of redox graphene parcel.As shown in Figure 8 and Figure 9, Fig. 8 is
The pictorial diagram of the three-dimensional porous fold graphene tubular structure of different shrinkage factors；Fig. 9 is the three-dimensional porous fold of different shrinkage factors
The SEM figures of graphene tubular structure.
Comparative example 1
Take 7 pieces of clean melamine sponge, stripping and slicing is 6*2*2cm sizes, is put into 50mL reactor, add 40mL go from
Sub- water, respectively in 120~180 degrees Celsius of baking ovens are placed on, 60~180min of hydro-thermal process, reaction is naturally cooling to room after terminating
Temperature, about 5h, sample is transferred to impregnate in deionized water from reactor and cleaned；With freezing after sample is frozen with Liquid nitrogen precooler
Dry technology is dried.
Melamine sponge before and after hydro-thermal is carried out macro-size sign, scanning electronic microscope observation, stretching strength measurement,
Thermogravimetric analysis and BET geographical approach process analysis, GAP analysises, infrared spectrum analysis is carried out to the catabolite of hydro-thermal melamine sponge, such as Figure 10~Figure 14
It is shown；Figure 10 is the fibre length and draw ratio variation diagram of melamine sponge contraction process；Figure 11 produces for melamine sponge hydrothermal decomposition
The thermal infrared of thing absorbs figure；Figure 12 is the dry strength and wet strength comparison diagram of melamine sponge；Figure 13 is the melamine after hydro-thermal process
The thermogravimetric analysis figure of sponge；Figure 14 be hydro-thermal process after melamine sponge BET pore analysis figures.
Comparative example 2
It is 120~180 degrees Celsius to change the hydrothermal temperature in embodiment 1, controls the hydro-thermal time respectively in 40~200min
The purpose collapsed in various degree to melamine sponge can be reached.As shown in Figure 15 and Figure 16, Figure 15 is the different hydro-thermal times
The melamine sponge pictorial diagram of different shrinkage factors after processing；Figure 16 be different hydro-thermal time-triggered protocols after different shrinkage factors melamine
Sponge SEM schemes.
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, professional and technical personnel in the field are enable to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (10)
1. a kind of preparation method of three-dimensional drape redox graphene, comprises the following steps：
A), three-dimensional porous tubular graphene alkene is prepared using sponge template, the three-dimensional porous tubular graphene alkene is reduced,
Obtain three-dimensional porous tubulose redox graphene；The sponge of the sponge template is melamine sponge；
B), the three-dimensional porous tubulose redox graphene is subjected to hydro-thermal process in supercritical water environment, then carried out cold
It is lyophilized dry, obtain three-dimensional drape redox graphene.
2. preparation method according to claim 1, it is characterised in that also include after freeze：
Obtained three-dimensional drape redox graphene progress high-temperature heat treatment will be freeze-dried.
3. preparation method according to claim 1 or 2, it is characterised in that step B) described in the temperature of hydro-thermal process be
60~180 DEG C, the time is 60~180min.
4. preparation method according to claim 1 or 2, it is characterised in that the process of the freeze-drying is specially：
Graphene after hydro-thermal process is first frozen using Liquid nitrogen precooler, is then dried again.
5. preparation method according to claim 1 or 2, it is characterised in that the preparation of the three-dimensional porous tubular graphene alkene
Process is specially：
Three-dimensional porous tubular graphene alkene is obtained by melamine sponge impregnating in graphene solution, after application of vacuum.
6. preparation method according to claim 1 or 2, it is characterised in that the reducing agent of the reduction is hydroiodic acid.
7. preparation method according to claim 2, it is characterised in that the temperature of the high-temperature heat treatment is 200~250
DEG C, the time is 1~2h.
8. a kind of three-dimensional drape redox graphene, shunk mutually on year-on-year basis with tangential direction in the radial direction of redox graphene
Example.
9. three-dimensional drape redox graphene according to claim 8, it is characterised in that the three-dimensional drape oxygen reduction
The contraction yardstick of graphite alkene is 0~70%.
10. three-dimensional drape redox graphene according to claim 8, it is characterised in that the three-dimensional drape reduction
The fold yardstick of graphene oxide is 0.2~5 μm.
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| CN111682796A (en) * | 2020-05-20 | 2020-09-18 | 武汉汉烯科技有限公司 | Flexible piezoelectric energy collector based on negative Poisson ratio macroscopic graphene film |
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| WENLU LIU ETC.: "Conductive Graphene-Melamine Sponge Prepared via Microwave Irradiation", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| YOUHUA XIAO ETC.: "Sheet Collapsing Approach for Rubber-like Graphene Papers", 《ACS NANO》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110124629A (en) * | 2019-04-08 | 2019-08-16 | 华南师范大学 | A kind of melamine sponge-graphene oxide adsorbent material and its preparation method and application |
| CN111682796A (en) * | 2020-05-20 | 2020-09-18 | 武汉汉烯科技有限公司 | Flexible piezoelectric energy collector based on negative Poisson ratio macroscopic graphene film |
| CN111682796B (en) * | 2020-05-20 | 2024-04-19 | 武汉汉烯科技有限公司 | Flexible piezoelectric energy collector based on negative poisson ratio macroscopic graphene film |
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