CN107814379A - A kind of method that low defect graphene ribbon sponge is prepared using CNT sponge - Google Patents
A kind of method that low defect graphene ribbon sponge is prepared using CNT sponge Download PDFInfo
- Publication number
- CN107814379A CN107814379A CN201711174212.1A CN201711174212A CN107814379A CN 107814379 A CN107814379 A CN 107814379A CN 201711174212 A CN201711174212 A CN 201711174212A CN 107814379 A CN107814379 A CN 107814379A
- Authority
- CN
- China
- Prior art keywords
- sponge
- graphene ribbon
- cnt
- graphene
- ribbon sponge
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The present invention discloses a kind of method that low defect graphene ribbon sponge is prepared using CNT sponge, belongs to materials science field.It mainly solves the graphene sponge of existing method preparation the problems of in terms of interface with scattered aspect and mechanical property.The present invention realizes as steps described below：First, the preparation of CNT sponge；2nd, strong oxidizing solution is configured；3rd, the preparation of graphene ribbon sponge；4th, the washing of graphene ribbon sponge；5th, the drying of graphene ribbon sponge；6th, the reduction of graphene ribbon sponge.Prepare the low defect graphene ribbon sponge for having synthesized this special edge effect, good compression performance and high specific surface area.
Description
Technical field
The invention belongs to materials science field, and in particular to one kind prepares low defect graphene ribbon using CNT sponge
The method of sponge.
Background technology
Sponge is considered as the most low aquatic multicellular animals of most original, and it possesses all basic animal characters.
Various cutin, calcium carbonate, silicon stone matter constitute the bone of spongia, and its internal fiber interlocks complicated such as net, and special is porous
Physiological structure, it is set to possess excellent elasticity and absorption property.Natural sponge is just made extensively as advanced bath articles from ancient times
With its mesh is thin, resilient beam, good water absorption, is good cleaning material.Artificial sponge is rapidly developed in recent years, sea
Continuous superior performance, the diversification of product make its widely used, and being related to industry wide includes：Clothes, family property, electronics, printing consumption
The numerous areas such as material, aviation, automobile, beautifying medical, packaging, sports goods, daily necessities, which present, higher and higher applies valency
Value.
Inspired by sponge structure, the extremely excellent CNT of performance and graphene are carried out group by scholars in recent years
Dress, prepares CNT sponge and graphene sponge, this kind of material realizes nano material micro-property to Macro-Functions
Great-leap-forward development, nano material is set no longer to stop in the lab, under microscope.However, the graphene sponge obtained at present by
In factors such as the nonpolar structure of material surface, the sizes of nanometer, its interface still suffers from some problems, Er Qieqi with dispersive property
Mechanical property is also unsatisfactory.Therefore graphene sponge want to turn into excellent performance at this stage application material still need it is deep
Scientific research.
In summary, at interface and scattered aspect there is problem in the product of existing graphene sponge or CNT sponge,
And its mechanical property is unsatisfactory.
The content of the invention
The present invention solves existing graphene sponge or CNT sponge interface and the dispersive property of existing method preparation
Undesirable, the problem of mechanical property is poor, there is provided a kind of to prepare low defect graphene ribbon sponge using CNT sponge
Method.
The method provided by the invention that low defect graphene ribbon sponge is prepared using CNT sponge, according to following steps
Carry out：
First, the preparation of CNT sponge：The preparation of CNT sponge is carried out using the method for chemical vapor deposition：Will
Catalyst ferrocene is dissolved in liquid carbon source 1, and catalyst/carbon source solution is obtained in 2- dichloro-benzenes, and catalyst/carbon source solution is noted
Enter and vaporized in tube furnace preheating zone, H2/ Ar carrier gas is brought carbon source into tube furnace reaction zone with catalyst and reacted, and forms carbon and receives
Mitron sponge；
2nd, strong oxidizing solution is configured：Potassium permanganate is added in sulfuric acid and phosphoric acid mixing acid, ultrasonic disperse is configured to by force
Oxidizing solution；
3rd, the preparation of graphene ribbon sponge：By the CNT sponge that step 1 obtains be immersed in step 2 obtain it is strong
In oxidisability mixed solution, being stood under normal temperature, vacuumize removing air afterwards, the CNT sponge that will be filled with solution is taken out,
Stand, obtain graphene ribbon sponge；
4th, the washing of graphene ribbon sponge：Take hydrogen peroxide to instill in frozen water, the step of will be cooled to room temperature three obtained stones
Black alkene band sponge is put into wherein, until bubble-free generates；Afterwards graphene ribbon sponge is put into soak in hydrochloric acid solution and removed
Impurity；Then using deionized water displacement hydrochloric acid, until pH value range is 5-8；Deionized water is replaced using absolute ethyl alcohol；
5th, the drying of graphene ribbon sponge：Using CO2The graphene ribbon sea that supercritical drying drying steps four obtain
It is continuous；
6th, the reduction of graphene ribbon sponge：The graphene ribbon sponge that step 5 obtains is put into reaction vessel with hydrazine hydrate
In, reaction obtains the low defect graphene ribbon sponge after electronation.
Above-mentioned steps are specially：
First, the preparation of CNT sponge：The preparation of CNT sponge is carried out using the method for chemical vapor deposition：Will
Catalyst ferrocene ultrasonic dissolution obtains catalyst/carbon source solution in liquid carbon source 1,2- dichloro-benzenes, and configuration proportion is per 10-
500ml 1,2- dichloro-benzenes dissolving 0.1-40g ferrocene powder.Using precise injection pump by catalyst/carbon source solution injection tube
Rapid vaporization in formula stove preheating zone, H2/ Ar carrier gas is brought carbon source into tube furnace reaction zone with catalyst and cracked, and cracks out
Carbon atom and Carbon Cluster are grown to serve as CNT under the iron catalyst effect that ferrocene cracks out.CNT exists
Reaction zone is piled up to form CNT sponge due to Action of Gravity Field.
Wherein described preheating zone temperature is 150 DEG C -450 DEG C, and high temperature reaction zone temperature is 700 DEG C -1000 DEG C.
2nd, strong oxidizing solution is configured：Potassium permanganate is weighed, low whipping speed is 100r/min-900r/min condition
Under, potassium permanganate is added portionwise in sulfuric acid and phosphoric acid mixing acid mixture A is made, mixture A is stirred into 10min-90min
Afterwards, the ultrasonic disperse 1h-24h in the case where frequency is 10KHz-100KHz.It is configured to strong oxidizing solution.
The quality of described potassium permanganate and the volume ratio of sulfuric acid and phosphoric acid mixing acid are (0.2g-60g):1L, sulfuric acid and phosphorus
The volume ratio of acid is (2-10):1.
3rd, the preparation of graphene ribbon sponge；The CNT sponge that step 1 obtains (can be cut to cube as needed
Etc. shape) it is immersed in potassium permanganate/concentrated sulfuric acid/phosphoric acid strong oxidizing property mixed solution that step 2 obtains, stand 1h- under normal temperature
24h, removing air is vacuumized afterwards.The CNT sponge that will be filled with solution is taken out, and 1- is stood under the conditions of 30 DEG C -90 DEG C
24h。
Described vacuumize is carried out in vacuum drying oven, and vacuum is -0.1--0.5Mpa.
4th, the washing of graphene ribbon sponge；Every 1ml-30ml hydrogen peroxide is taken to instill in 100ml-400ml frozen water, by step
Three obtained graphene ribbon sponges are put into wherein after being cooled to room temperature, until bubble-free generates.Graphene ribbon sponge is put afterwards
Enter and soak 1-24h into the hydrochloric acid that concentration is 1%wt-30wt%, to remove the impurity of residual.Then replaced using deionized water
Hydrochloric acid, until pH value range is 5-8 (during which operation changes the deionized water of immersion repeatedly to be soaked with deionized water).Adopt
With absolute ethyl alcohol displacement deionized water 1h-32h, (operation is during which to change the anhydrous second of immersion with soaked in absolute ethyl alcohol repeatedly
Alcohol).
The hydrogen peroxide concentration is 30wt%.
5th, the drying of graphene ribbon sponge:Using CO2Supercritical drying obtains graphene ribbon sponge.
6th, the reduction of graphene ribbon sponge:The graphene ribbon sponge that every 0.02g-10g step 5 is obtained and 5ml-40ml
Hydrazine hydrate is put into reaction vessel, and reaction vessel is sealed and placed in into 50 DEG C of -150 DEG C of generation reduction reaction 3h-50h, changed
Learn the low defect graphene ribbon sponge after reduction.
Preferably, the preheating zone temperature described in step 1 be 200 DEG C -400 DEG C, high temperature reaction zone temperature be 800 DEG C -
1000℃；The H2/ Ar carrier gas, H2/ Ar volume ratios are 1:1-1:4, flow rate of carrier gas 400-2000mL/min.
Preferably, the nitration mixture in strong oxidizing solution described in step 2, by mass fraction 10%-98% sulfuric acid and quality
Fraction 10%-85% phosphoric acid is according to volume ratio (5-10):1 composition.
Preferably, the concentration of potassium permanganate is 5g/L-50g/L in the mixture A described in step 2.
Preferably, the vacuum vacuumized described in step 3 is -0.1Mpa--0.2Mpa.
Preferably, the carrying out washing treatment described in step 4 is carried out according to the following steps：
Take every 1ml-20ml hydrogen peroxide to instill in 100ml-300ml frozen water, put after graphene ribbon sponge is cooled into room temperature
Enter wherein, until bubble-free generates；Graphene ribbon sponge is put into the hydrochloric acid that concentration is 1%wt-20%wt afterwards and soaked
1-20h；Then using deionized water displacement hydrochloric acid, until pH value range is 7-8；Using absolute ethyl alcohol displacement deionized water 1h-
24h。
Preferably, the drying mode of the graphene ribbon sponge described in step 5 is freeze-drying.
Preferably, the reduction temperature of graphene ribbon sponge described in step 6 is 70 DEG C -100 DEG C, reaction time 5h-24h.
Beneficial effect
The CNT sponge that the present invention is prepared chemical vapour deposition technique using CNT oxidation cutting technique is in situ
It is changed into graphene ribbon sponge, SEM the and TEM results of graphene ribbon sponge also demonstrate CNT and have been converted to graphene
Band.Substantial amounts of graphene ribbon is mutually overlapped, winds, supported, and is assembled into tridimensional network, is formed between graphene ribbon a large amount of
Through hole hole, existing graphene sponge or CNT the sponge interface for solving existing method preparation are paid no attention to dispersive property
Think, the problem of mechanical property is poor, so as to get low defect graphene ribbon sponge density be only 7-15mg/cm3, due to stone itself
The special edge effect of black alkene nanobelt, therefore the graphene ribbon sponge being prepared into similarly has special edge effect,
And good compression performance is shown, under conditions of compression ratio is 80%, it still is able to restore to the original state completely；This embodiment party simultaneously
Graphene ribbon sponge prepared by formula has higher specific surface area, and sponge specific surface area is 85m after oxidized cutting2/g-115m2/
g；Graphene ribbon sponge specific capacitance rises most 90F/g-110.6F/g simultaneously, is more excellent energy storage material.
By brand-new preparation concept, using CNT sponge as presoma, aoxidized and cut using in-situ carbon nanotube wall
Technology, CNT in CNT sponge is changed into graphene ribbon, while not only lifting the specific surface area of reinforcement, changed
The surface physicses form and chemical property of kind reinforcement and polymer, and significantly lift the performance of composite
Brief description of the drawings
Fig. 1 is the shape appearance figure of gained graphene ribbon sponge in the step 6 of embodiment two；
Fig. 2 is that gained graphene ribbon sponge prepares schematic diagram in the step 3 of embodiment two；
Fig. 3 is the TEM photos of gained graphene ribbon sponge in the step 6 of embodiment two；
Fig. 4 is the SEM photograph of gained graphene ribbon sponge in the step 6 of embodiment two.
Embodiment
Technical solution of the present invention is not limited to act embodiment set forth below, in addition between each embodiment
Any combination.
Embodiment one：Present embodiment can be used for CNT sponge to prepare low defect graphene ribbon sponge, press
Following steps are realized：
First, the preparation of CNT sponge：The preparation of CNT sponge is carried out using the method for chemical vapor deposition.Will
In liquid carbon source 1,2- dichloro-benzenes, 1, the 2- dichloro-benzenes that configuration proportion is 10-500ml dissolves catalyst ferrocene ultrasonic dissolution
0.1-40g ferrocene powder.Catalyst/carbon source solution is injected by rapid vaporization in preheating zone, H using precise injection pump2/ Ar is carried
Gas is brought carbon source into reaction zone with catalyst and cracked, what the carbon atom and Carbon Cluster cracked out cracked out in ferrocene
Under iron catalyst effect, CNT is grown to serve as.CNT is piled up due to Action of Gravity Field in reaction zone and to be formed carbon
Nanotube sponge.
Wherein described preheating zone temperature is 150 DEG C -450 DEG C, and high temperature reaction zone temperature is 700 DEG C -1000 DEG C.
2nd, strong oxidizing solution is configured：0.1g-30g potassium permanganate, low whipping speed 100r/min- are weighed respectively
Under conditions of 900r/min, potassium permanganate is added portionwise in sulfuric acid and phosphoric acid mixing acid mixture A is made, mixture A is stirred
After mixing 10min-90min, the ultrasonic disperse 1h-24h in the case where frequency is 10KHz-100KHz.It is configured to strong oxidizing solution.
The quality of described potassium permanganate and the volume ratio of sulfuric acid and phosphoric acid mixing acid are (0.2g-60g):1L, sulfuric acid and phosphorus
The volume ratio of acid is (2-10):1.
3rd, the preparation of graphene ribbon sponge；CNT sponge is cut to cube, be immersed in potassium permanganate/concentrated sulfuric acid/
In phosphoric acid strong oxidizing property mixed solution, 1h-24h is stood under normal temperature, vacuumizes removing air afterwards.It will be filled with the carbon nanometer of solution
Pipe sponge is taken out, and 1-24h is stood under the conditions of 30 DEG C -90 DEG C.
The vacuum of the vacuum drying oven is -0.1--0.5Mpa.
4th, the washing of graphene ribbon sponge；1ml-30ml hydrogen peroxide is taken to instill in 100ml-400ml frozen water, by graphene
Band block is put into wherein after being cooled to room temperature, until bubble-free generates.Graphene ribbon block is put into concentration as 1% afterwards
1-24h is soaked in wt-30wt% hydrochloric acid, to remove the impurity of residual.Then using deionized water displacement hydrochloric acid, until pH value
Scope is 5-8.Using absolute ethyl alcohol displacement deionized water 1h-32h.
The hydrogen peroxide concentration is 30wt%.
5th, the drying of graphene ribbon sponge:Using CO2Supercritical drying obtains graphene ribbon sponge.
6th, the reduction of graphene ribbon sponge:Graphene ribbon sponge and 5ml-40ml hydrazine hydrates are put into reaction vessel, will
Reaction vessel is sealed and placed in 50 DEG C of -150 DEG C of reaction 3h-50h, obtains the low defect graphene ribbon sponge after electronation.
The beneficial effect of present embodiment is：First, present embodiment utilizes the special edge effect of graphene ribbon, preparation
Graphene ribbon sponge possesses controllable property more more flexible than graphene sponge and bigger application value；2nd, present embodiment system
It possesses high Young's modulus, tensile strength, good heat conductivility to standby graphene ribbon sponge, and it has more than CNT
High specific surface area, this all makes graphene ribbon sponge turn into preferable polymer matrix composite reinforcement；3rd, present embodiment
Pass through adjustment control carbon source solution feed rate, H2The preparation parameter such as the flow of/Ar carrier gas and reaction temperature can be had
The CNT sponge of different performance index, it further can obtain the graphene ribbon sponge material of different performance.
Embodiment two：Present embodiment and the preheating zone unlike embodiment one described in step 1
Temperature is 200 DEG C -400 DEG C, and high temperature reaction zone temperature is 800 DEG C -1000 DEG C.Other specification is identical with embodiment one.
Embodiment three：Present embodiment is strong described in step 2 unlike embodiment one or two
Oxidizing solution is by mass fraction 10%-98% sulfuric acid and mass fraction 10%-85% phosphoric acid according to volume ratio (5-10):
1 composition.Other specification is identical with embodiment one or two.
Embodiment four：Unlike one of present embodiment and embodiment one to three described in step 2
Mixture A in the mass concentration of potassium permanganate be 5g/L-50g/L.One of other specification and embodiment one to three phase
Together.
Embodiment five：Unlike one of present embodiment and embodiment one to four described in step 3
The vacuum of vacuum drying oven be -0.1--0.2Mpa.Other specification is identical with one of embodiment one to four.
Embodiment six：Unlike one of present embodiment and embodiment one to five described in step 4
Carrying out washing treatment carry out according to the following steps：
Take 1ml-20ml hydrogen peroxide to instill in 100ml-300ml frozen water, be put into after graphene ribbon block is cooled into room temperature
Wherein, until bubble-free generates.Graphene ribbon block is put into the hydrochloric acid that concentration is 1%wt-20%wt afterwards and soaks 1-
20h, to remove the impurity of residual.Then using deionized water displacement hydrochloric acid, until pH value range is 7-8.Using absolute ethyl alcohol
Replace deionized water 1h-24h.Other specification is identical with one of embodiment one to five.
Embodiment seven：Unlike one of present embodiment and embodiment one to six described in step 5
The drying mode of graphene ribbon sponge be freeze-drying.Other specification is identical with one of embodiment one to six.
Embodiment eight：Unlike one of present embodiment and embodiment one to seven described in step 6
Graphene ribbon sponge reduction temperature is 70 DEG C -100 DEG C and reacts 5h-24h.One of other specification and embodiment one to seven phase
Together.
Beneficial effects of the present invention are verified using following examples：
Embodiment one
The method that low defect graphene ribbon sponge is prepared using CNT sponge, is realized according to the following steps：
First, the preparation of CNT sponge：The preparation of CNT sponge is carried out using the method for chemical vapor deposition.Will
Catalyst ferrocene 20g ultrasonic dissolutions are in 300ml liquid carbon source 1,2- dichloro-benzenes.Using precise injection pump by catalyst/carbon
Rapid vaporization in the solution injection preheating zone of source, H2/ Ar carrier gas is brought carbon source into reaction zone with catalyst and cracked, and cracks out
Carbon atom and Carbon Cluster are grown to serve as CNT under the iron catalyst effect that ferrocene cracks out.CNT exists
Reaction zone is piled up to form CNT sponge due to Action of Gravity Field.
Wherein described preheating zone temperature is 400 DEG C, and high temperature reaction zone temperature is 950 DEG C.
2nd, strong oxidizing solution is configured：20g potassium permanganate is weighed respectively, under conditions of low whipping speed is 700r/min,
Potassium permanganate is added portionwise in sulfuric acid and phosphoric acid mixing acid mixture A is made, after mixture A is stirred into 20min, be in frequency
Ultrasonic disperse 9h under 90KHz.It is configured to strong oxidizing solution.
Described sulfuric acid and the volume of phosphoric acid mixing acid are 1.5L, and the volume ratio of sulfuric acid and phosphoric acid is 6:1.
3rd, the preparation of graphene ribbon sponge；CNT sponge is cut to cube, be immersed in potassium permanganate/concentrated sulfuric acid/
In phosphoric acid strong oxidizing property mixed solution, 5h is stood under normal temperature, vacuumizes removing air afterwards.It will be filled with the CNT sea of solution
Silk floss is taken out, and 5h is stood under the conditions of 60 DEG C.
The vacuum of the vacuum drying oven is -0.3Mpa.
4th, the washing of graphene ribbon sponge；Take 5ml hydrogen peroxide to instill in 200ml frozen water, graphene ribbon block is cooled to
It is put into after room temperature wherein, until bubble-free generates.Graphene ribbon block is put into the hydrochloric acid that concentration is 6%wt afterwards and soaked
5h, to remove the impurity of residual.Then using deionized water displacement hydrochloric acid, until pH value range is 5.Replaced using absolute ethyl alcohol
Deionized water 5h.
The hydrogen peroxide concentration is 30wt%.
5th, the drying of graphene ribbon sponge:Using CO2Supercritical drying obtains graphene ribbon sponge.
6th, the reduction of graphene ribbon sponge:Graphene ribbon sponge and 15ml hydrazine hydrates are put into reaction vessel, will be reacted
Container is sealed and placed in 70 DEG C of reaction 7h, obtains the low defect graphene ribbon sponge after electronation.
Low defect graphene ribbon sponge density obtained by the present embodiment is 12mg/cm3, have with respect to other sponge materials
More lightweight the characteristics of, this graphene ribbon sponge is 3 D stereo network structure, compression ratio be 80% under conditions of, still be able to
Restore to the original state completely, show good compression performance；The graphene ribbon sponge that simultaneously prepared by present embodiment has higher
Specific surface area, sponge specific surface area rises to 87.8m after oxidized cutting2/ g, larger ratio surface are that graphene ribbon sponge exists
Seawater cleaning etc. needs the application field of Large ratio surface to provide more preferable material；Graphene ribbon sponge specific capacitance is simultaneously
92.6F/g, it is more excellent energy storage material.
Embodiment two
The method that low defect graphene ribbon sponge is prepared using CNT sponge, is realized according to the following steps：
First, the preparation of CNT sponge：The preparation of CNT sponge is carried out using the method for chemical vapor deposition.Will
Catalyst ferrocene 10g ultrasonic dissolutions are in 200ml liquid carbon source 1,2- dichloro-benzenes.Using precise injection pump by catalyst/carbon
Rapid vaporization in the solution injection preheating zone of source, H2/ Ar carrier gas is brought carbon source into reaction zone with catalyst and cracked, and cracks out
Carbon atom and Carbon Cluster are grown to serve as CNT under the iron catalyst effect that ferrocene cracks out.CNT exists
Reaction zone is piled up to form CNT sponge due to Action of Gravity Field.
Wherein described preheating zone temperature is 350 DEG C, and high temperature reaction zone temperature is 800 DEG C.
2nd, strong oxidizing solution is configured：10g potassium permanganate is weighed respectively, under conditions of low whipping speed is 800r/min,
Potassium permanganate is added portionwise in sulfuric acid and phosphoric acid mixing acid mixture A is made, after mixture A is stirred into 30min, be in frequency
Ultrasonic disperse 8h under 80KHz.It is configured to strong oxidizing solution.
Described sulfuric acid and the volume of phosphoric acid mixing acid are 1L, and the volume ratio of sulfuric acid and phosphoric acid is 5:1.
3rd, the preparation of graphene ribbon sponge；CNT sponge is cut to cube, be immersed in potassium permanganate/concentrated sulfuric acid/
In phosphoric acid strong oxidizing property mixed solution, 2h is stood under normal temperature, vacuumizes removing air afterwards.It will be filled with the CNT sea of solution
Silk floss is taken out, and 2h is stood under the conditions of 50 DEG C.
The vacuum of the vacuum drying oven is -0.2Mpa.
4th, the washing of graphene ribbon sponge；Take 3ml hydrogen peroxide to instill in 300ml frozen water, graphene ribbon block is cooled to
It is put into after room temperature wherein, until bubble-free generates.Graphene ribbon block is put into the hydrochloric acid that concentration is 3%wt afterwards and soaked
3h, to remove the impurity of residual.Then using deionized water displacement hydrochloric acid, until pH value range is 6.Replaced using absolute ethyl alcohol
Deionized water 3h.
The hydrogen peroxide concentration is 30wt%.
5th, the drying of graphene ribbon sponge:Using CO2Supercritical drying obtains graphene ribbon sponge.
6th, the reduction of graphene ribbon sponge:Graphene ribbon sponge and 5ml hydrazine hydrates are put into reaction vessel, will be reacted
Container is sealed and placed in 50 DEG C of reaction 5h, obtains the low defect graphene ribbon sponge after electronation.
Fig. 1 is the shape appearance figure of gained graphene ribbon sponge in the step 6 of embodiment two, and as can be seen from the figure graphene is received
Rice band sponge surface is smooth, includes hole；Fig. 3 is the TEM photos of gained graphene ribbon sponge in the step 6 of embodiment two, from figure
In it can be seen that CNT be cut become graphene nanobelt；Fig. 4 is gained graphene ribbon in the step 6 of embodiment two
The SEM photograph of sponge, as can be seen from the figure graphene nanobelt sponge still remain the interlaced of CNT sponge
Microstructure.
Low defect graphene ribbon sponge density obtained by the present embodiment is 7mg/cm3, have with respect to other sponge materials
More lightweight the characteristics of；This graphene ribbon sponge is 3 D stereo network structure, under conditions of compression ratio is 80%, still is able to
Restore to the original state completely, show good compression performance；The graphene ribbon sponge that simultaneously prepared by present embodiment has higher
Specific surface area, sponge specific surface area rises to 115m after oxidized cutting2/g；Larger ratio surface is graphene ribbon sponge in sea
Water warfare etc. needs the application field of Large ratio surface to provide more preferable material；Graphene ribbon sponge specific capacitance is simultaneously
110.6F/g, it is more excellent energy storage material.
Embodiment three
The method that low defect graphene ribbon sponge is prepared using CNT sponge, is realized according to the following steps：
First, the preparation of CNT sponge：The preparation of CNT sponge is carried out using the method for chemical vapor deposition：Will
For catalyst ferrocene ultrasonic dissolution in liquid carbon source 1,2- dichloro-benzenes, configuration proportion is that 1, the 2- dichloro-benzenes per 10ml dissolves
40g ferrocene powder.Using precise injection pump by rapid vaporization, H in the solution injection tube formula stove preheating zone of catalyst/carbon source2/Ar
Carrier gas is brought carbon source into tube furnace reaction zone with catalyst and cracked, and the carbon atom and Carbon Cluster cracked out is in ferrocene
Under the iron catalyst effect cracked out, CNT is grown to serve as.In reaction zone due to Action of Gravity Field heap occurs for CNT
Block forms CNT sponge.
Wherein described preheating zone temperature is 150 DEG C, and high temperature reaction zone temperature is 700 DEG C.
2nd, strong oxidizing solution is configured：Potassium permanganate is weighed, under conditions of low whipping speed is 100r/min, by Gao Meng
Sour potassium, which is added portionwise in sulfuric acid and phosphoric acid mixing acid, is made mixture A, is 10KHz in frequency after mixture A is stirred into 10min
Lower ultrasonic disperse 1h.It is configured to strong oxidizing solution.
The quality of described potassium permanganate and the volume ratio of sulfuric acid and phosphoric acid mixing acid are 0.2g:The body of 1L, sulfuric acid and phosphoric acid
Product is than being 2:1.
3rd, the preparation of graphene ribbon sponge；The CNT sponge that step 1 obtains (can be cut to cube as needed
Etc. shape), it is immersed in potassium permanganate/concentrated sulfuric acid/phosphoric acid strong oxidizing property mixed solution that step 2 obtains, is stood under normal temperature
1h, removing air is vacuumized afterwards.The CNT sponge that will be filled with solution is taken out, and 1h is stood under the conditions of 30 DEG C.
Described vacuumize is carried out in vacuum drying oven, and vacuum is -0.1Mpa.
4th, the washing of graphene ribbon sponge；Every 1ml hydrogen peroxide is taken to instill in 400ml frozen water, the graphite that step 3 is obtained
Alkene band sponge is put into wherein after being cooled to room temperature, until bubble-free generates.Graphene ribbon sponge is put into concentration as 1% afterwards
1h is soaked in wt hydrochloric acid, to remove the impurity of residual.Then using deionized water displacement hydrochloric acid, until pH value is that 5 (operation is
Soaked with deionized water, during which change the deionized water of immersion repeatedly).Using absolute ethyl alcohol displacement deionized water 1h (operations
With soaked in absolute ethyl alcohol, during which to change the absolute ethyl alcohol of immersion repeatedly).
The hydrogen peroxide concentration is 30wt%.
5th, the drying of graphene ribbon sponge:Using CO2Supercritical drying obtains graphene ribbon sponge.
6th, the reduction of graphene ribbon sponge:The graphene ribbon sponge that every 0.02g step 5 obtains and 40ml hydrazine hydrates are put
Enter in reaction vessel, reaction vessel is sealed and placed in 50 DEG C of generation reduction reaction 3h, obtains the low defect stone after electronation
Black alkene band sponge.
The H2/ Ar carrier gas, H2/ Ar volume ratios are 1:4, flow rate of carrier gas 400mL/min.
Nitration mixture in strong oxidizing solution described in step 2, by the sulfuric acid of mass fraction 10% and the phosphorus of mass fraction 10%
Acid.
The drying mode of graphene ribbon sponge described in step 5 is freeze-drying.
Low defect graphene ribbon sponge density obtained by the present embodiment is 8mg/cm3, have with respect to other sponge materials
More lightweight the characteristics of；This graphene ribbon sponge is 3 D stereo network structure, under conditions of compression ratio is 80%, still is able to
Restore to the original state completely, show good compression performance；The graphene ribbon sponge that simultaneously prepared by present embodiment has higher
Specific surface area, sponge specific surface area rises to 105m after oxidized cutting2/g；Larger ratio surface is graphene ribbon sponge in sea
Water warfare etc. needs the application field of Large ratio surface to provide more preferable material.
Example IV
The method that low defect graphene ribbon sponge is prepared using CNT sponge, is realized according to the following steps：
First, the preparation of CNT sponge：The preparation of CNT sponge is carried out using the method for chemical vapor deposition：Will
For catalyst ferrocene ultrasonic dissolution in liquid carbon source 1,2- dichloro-benzenes, configuration proportion is that 1, the 2- dichloro-benzenes per 500ml dissolves
0.1g ferrocene powder.Using precise injection pump by rapid vaporization, H in the solution injection tube formula stove preheating zone of catalyst/carbon source2/
Ar carrier gas is brought carbon source into tube furnace reaction zone with catalyst and cracked, and the carbon atom and Carbon Cluster cracked out is in two cyclopentadienyls
Under the iron catalyst effect that iron cracks out, CNT is grown to serve as.CNT occurs in reaction zone due to Action of Gravity Field
Pile up to form CNT sponge.
Wherein described preheating zone temperature is 450 DEG C, and high temperature reaction zone temperature is 1000 DEG C.
2nd, strong oxidizing solution is configured：Potassium permanganate is weighed, under conditions of low whipping speed is 900r/min, by Gao Meng
Sour potassium, which is added portionwise in sulfuric acid and phosphoric acid mixing acid, is made mixture A, is 100KHz in frequency after mixture A is stirred into 90min
Lower ultrasonic disperse 24h.It is configured to strong oxidizing solution.
The quality of described potassium permanganate and the volume ratio of sulfuric acid and phosphoric acid mixing acid are 60g:The volume of 1L, sulfuric acid and phosphoric acid
Than for 10:1.
3rd, the preparation of graphene ribbon sponge；The CNT sponge that step 1 obtains (can be cut to cube as needed
Etc. shape), it is immersed in potassium permanganate/concentrated sulfuric acid/phosphoric acid strong oxidizing property mixed solution that step 2 obtains, is stood under normal temperature
24h, removing air is vacuumized afterwards.The CNT sponge that will be filled with solution is taken out, and 24h is stood under the conditions of 90 DEG C.
Described vacuumize is carried out in vacuum drying oven, and vacuum is -0.5Mpa.
4th, the washing of graphene ribbon sponge；Every 30ml hydrogen peroxide is taken to instill in 100ml frozen water, the stone that step 3 is obtained
Black alkene band sponge is put into wherein after being cooled to room temperature, until bubble-free generates.Graphene ribbon sponge is put into concentration afterwards is
24h is soaked in 30wt% hydrochloric acid, to remove the impurity of residual.Then using deionized water displacement hydrochloric acid, until pH value is 8
(during which operation changes the deionized water of immersion repeatedly to be soaked with deionized water).Deionized water is replaced using absolute ethyl alcohol
32h (operation is during which to change the absolute ethyl alcohol of immersion with soaked in absolute ethyl alcohol repeatedly).
The hydrogen peroxide concentration is 30wt%.
5th, the drying of graphene ribbon sponge:Using CO2Supercritical drying obtains graphene ribbon sponge.
6th, the reduction of graphene ribbon sponge:The graphene ribbon sponge that every 10g step 5 obtains and 5ml hydrazine hydrates are put into
In reaction vessel, reaction vessel is sealed and placed in 150 DEG C of generation reduction reaction 50h, obtains the low defect stone after electronation
Black alkene band sponge.
The H2/ Ar carrier gas, H2/ Ar volume ratios are 1:1, flow rate of carrier gas 2000mL/min.
Nitration mixture in strong oxidizing solution described in step 2, by the sulfuric acid of mass fraction 98% and the phosphorus of mass fraction 85%
Acid composition.
Preferably, the drying mode of the graphene ribbon sponge described in step 5 is freeze-drying.
Low defect graphene ribbon sponge density obtained by the present embodiment is 9.2mg/cm3, have with respect to other sponge materials
There is the characteristics of more lightweight；This graphene ribbon sponge is 3 D stereo network structure, under conditions of compression ratio is 80%, is remained to
It is enough to restore to the original state completely, show good compression performance；The graphene ribbon sponge that simultaneously prepared by present embodiment has higher
Specific surface area, sponge specific surface area rises to 83.2m after oxidized cutting2/g；Larger ratio surface is graphene ribbon sponge
The application field of Large ratio surface is needed to provide more preferable material in seawater cleaning etc..
Claims (9)
- A kind of 1. method that low defect graphene ribbon sponge is prepared using CNT sponge, it is characterised in that:According to following step It is rapid to carry out：First, the preparation of CNT sponge：The preparation of CNT sponge is carried out using the method for chemical vapor deposition：Will catalysis Agent ferrocene is dissolved in liquid carbon source 1, and catalyst/carbon source solution is obtained in 2- dichloro-benzenes, by catalyst/carbon source solution injection tube Formula stove vaporizes in preheating zone, H2/ Ar carrier gas is brought carbon source into tube furnace reaction zone with catalyst and reacted, and forms CNT Sponge；2nd, strong oxidizing solution is configured：Potassium permanganate is added in sulfuric acid and phosphoric acid mixing acid, ultrasonic disperse is configured to Strong oxdiative Property solution；3rd, the preparation of graphene ribbon sponge：The CNT sponge that step 1 obtains is immersed in the Strong oxdiative that step 2 obtains Property mixed solution in, stood under normal temperature, vacuumize removing air afterwards, will be filled with solution CNT sponge take out, stand, Obtain graphene ribbon sponge；4th, the washing of graphene ribbon sponge：Take hydrogen peroxide to instill in frozen water, the step of will be cooled to room temperature three obtained graphenes Band sponge is put into wherein, until bubble-free generates；Graphene ribbon sponge is put into immersion in hydrochloric acid solution afterwards and removes impurity； Then using deionized water displacement hydrochloric acid, until pH value range is 5-8；Deionized water is replaced using absolute ethyl alcohol；5th, the drying of graphene ribbon sponge：Using CO2The graphene ribbon sponge that supercritical drying drying steps four obtain；6th, the reduction of graphene ribbon sponge：The graphene ribbon sponge that step 5 obtains is put into reaction vessel with hydrazine hydrate, instead The low defect graphene ribbon sponge after electronation should be obtained.
- 2. according to the method for claim 1, it is characterised in that：The step is specially：First, the preparation of CNT sponge：The preparation of CNT sponge is carried out using the method for chemical vapor deposition：Will catalysis Agent ferrocene ultrasonic dissolution obtains catalyst/carbon source solution in liquid carbon source 1,2- dichloro-benzenes, and configuration proportion is per 10- 500ml 1,2- dichloro-benzenes dissolving 0.1-40g ferrocene powder；Using precise injection pump by catalyst/carbon source solution injection tube Rapid vaporization in formula stove preheating zone, H2Carbon source and catalyst are brought into the generation of tube furnace reaction zone, grow and pile up shape by/Ar carrier gas Into CNT sponge；Described preheating zone temperature is 150 DEG C -450 DEG C, and high temperature reaction zone temperature is 700 DEG C -1000 DEG C；2nd, strong oxidizing solution is configured：Potassium permanganate is weighed, will under conditions of low whipping speed is 100r/min-900r/min Potassium permanganate, which is added in sulfuric acid and phosphoric acid mixing acid, is made mixture A, after mixture A is stirred into 10min-90min, is in frequency Ultrasonic disperse 1h-24h under 10KHz-100KHz, is configured to strong oxidizing solution；The quality of described potassium permanganate and sulfuric acid and The cumulative volume ratio of phosphoric acid mixing acid is (0.2g-60g):The volume ratio of 1L, sulfuric acid and phosphoric acid is (2-10):1；3rd, the preparation of graphene ribbon sponge：The CNT sponge that step 1 obtains is immersed in the Strong oxdiative that step 2 obtains In property solution, 1h-24h is stood under normal temperature, vacuumizes removing air afterwards；The CNT sponge that will be filled with solution is taken out, 1-24h is stood under the conditions of 30 DEG C -90 DEG C；Described to vacuumize, vacuum is -0.1Mpa--0.5Mpa；4th, the washing of graphene ribbon sponge：Take every 1ml-30ml hydrogen peroxide to instill in 100ml-400ml frozen water, step 3 is obtained To graphene ribbon sponge be cooled to after room temperature and be put into wherein, until bubble-free generates；Graphene ribbon sponge is put into afterwards Concentration is to soak 1-24h in 1%wt-30wt% hydrochloric acid；Then using deionized water displacement hydrochloric acid, until pH value range is 5- 8；Using absolute ethyl alcohol displacement deionized water 1h-32h；The hydrogen peroxide concentration is 30wt%；5th, the drying of graphene ribbon sponge:Using CO2Supercritical drying obtains graphene ribbon sponge；6th, the reduction of graphene ribbon sponge:The graphene ribbon sponge that every 0.02g-10g step 5 is obtained is hydrated with 5ml-40ml Hydrazine is sealed and placed in 50 DEG C of -150 DEG C of reduction reaction 3h-50h, obtains the low defect graphene ribbon sponge after electronation.
- 3. according to the method for claim 2, it is characterised in that：Preheating zone temperature described in step 1 is 200 DEG C -400 DEG C, high temperature reaction zone temperature is 800 DEG C -1000 DEG C；The H2/ Ar carrier gas, H2/ Ar volume ratios are 1:1-1:4, flow rate of carrier gas 400-2000mL/min。
- 4. according to the method for claim 2, it is characterised in that：Nitration mixture in strong oxidizing solution described in step 2, by matter Fraction 10%-98% sulfuric acid and mass fraction 10%-85% phosphoric acid are measured according to volume ratio (5-10):1 composition.
- 5. according to the method for claim 2, it is characterised in that：Potassium permanganate is dense in mixture A described in step 2 Spend for 5g/L-50g/L.
- 6. according to the method for claim 2, it is characterised in that：The vacuum vacuumized described in step 3 for- 0.1Mpa--0.2Mpa。
- 7. according to the method for claim 2, it is characterised in that：Carrying out washing treatment described in step 4 is to enter according to the following steps Capable：Take every 1ml-20ml hydrogen peroxide to instill in 100ml-300ml frozen water, it is put into after graphene ribbon sponge is cooled into room temperature In, until bubble-free generates；Graphene ribbon sponge is put into the hydrochloric acid that concentration is 1%wt-20%wt afterwards and soaks 1- 20h；Then using deionized water displacement hydrochloric acid, until pH value range is 7-8；Using absolute ethyl alcohol displacement deionized water 1h- 24h。
- 8. according to the method for claim 2, it is characterised in that：The drying mode of graphene ribbon sponge described in step 5 For freeze-drying.
- 9. according to the method for claim 2, it is characterised in that：The reduction temperature of graphene ribbon sponge described in step 6 is 70 DEG C -100 DEG C, reaction time 5h-24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711174212.1A CN107814379A (en) | 2017-11-22 | 2017-11-22 | A kind of method that low defect graphene ribbon sponge is prepared using CNT sponge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711174212.1A CN107814379A (en) | 2017-11-22 | 2017-11-22 | A kind of method that low defect graphene ribbon sponge is prepared using CNT sponge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107814379A true CN107814379A (en) | 2018-03-20 |
Family
ID=61610394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711174212.1A Pending CN107814379A (en) | 2017-11-22 | 2017-11-22 | A kind of method that low defect graphene ribbon sponge is prepared using CNT sponge |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107814379A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109173344A (en) * | 2018-08-31 | 2019-01-11 | 周晓东 | A kind of preparation method of hydrophobicity three-dimensional porous material |
| CN110482528A (en) * | 2019-08-23 | 2019-11-22 | 哈尔滨工业大学 | A kind of carbon nanotube with negative giant magnetoresistance performance/ferroso-ferric oxide composite sponge preparation method |
| CN110723724A (en) * | 2018-07-16 | 2020-01-24 | 天津大学 | Three-dimensional graphene-carbon nanotube network structure and preparation method thereof |
| CN116061510A (en) * | 2022-12-07 | 2023-05-05 | 南通大学 | Multilayer self-adjusting composite non-woven material, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838104A (en) * | 2012-08-10 | 2012-12-26 | 中山大学 | Carbon nanotube macro body with composite structure and preparation method thereof |
| CN103723718A (en) * | 2014-01-23 | 2014-04-16 | 哈尔滨工业大学 | Preparation method of thermal insulating material having ultralow density, ultrahigh elasticity and ultralow thermal conductivity |
| CN103819890A (en) * | 2014-01-23 | 2014-05-28 | 哈尔滨工业大学 | Method for preparing graphene sponge based on traditional sponge serving as template |
| CN103864069A (en) * | 2014-03-26 | 2014-06-18 | 天津师范大学 | Method for preparing graphene by taking carbon nanotubes with discontinuous tube walls as raw materials |
| CN105600767A (en) * | 2015-12-29 | 2016-05-25 | 深圳市纳米港有限公司 | Preparation method and device for carbon nanotube sponge |
-
2017
- 2017-11-22 CN CN201711174212.1A patent/CN107814379A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838104A (en) * | 2012-08-10 | 2012-12-26 | 中山大学 | Carbon nanotube macro body with composite structure and preparation method thereof |
| CN103723718A (en) * | 2014-01-23 | 2014-04-16 | 哈尔滨工业大学 | Preparation method of thermal insulating material having ultralow density, ultrahigh elasticity and ultralow thermal conductivity |
| CN103819890A (en) * | 2014-01-23 | 2014-05-28 | 哈尔滨工业大学 | Method for preparing graphene sponge based on traditional sponge serving as template |
| CN103864069A (en) * | 2014-03-26 | 2014-06-18 | 天津师范大学 | Method for preparing graphene by taking carbon nanotubes with discontinuous tube walls as raw materials |
| CN105600767A (en) * | 2015-12-29 | 2016-05-25 | 深圳市纳米港有限公司 | Preparation method and device for carbon nanotube sponge |
Non-Patent Citations (2)
| Title |
|---|
| QINGYU PENG ETC.: "Graphene Nanoribbon Aerogels Unzipped from Carbon Nanotube Sponges", 《ADVANCED MATERIALS》 * |
| XUCHUN GUI ETC.: "Controllable Synthesis of spongy carbon nanotube blocks with tunable macro-and microstructures", 《NANOTECHNOLOGY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110723724A (en) * | 2018-07-16 | 2020-01-24 | 天津大学 | Three-dimensional graphene-carbon nanotube network structure and preparation method thereof |
| CN109173344A (en) * | 2018-08-31 | 2019-01-11 | 周晓东 | A kind of preparation method of hydrophobicity three-dimensional porous material |
| CN110482528A (en) * | 2019-08-23 | 2019-11-22 | 哈尔滨工业大学 | A kind of carbon nanotube with negative giant magnetoresistance performance/ferroso-ferric oxide composite sponge preparation method |
| CN110482528B (en) * | 2019-08-23 | 2022-02-18 | 哈尔滨工业大学 | Preparation method of carbon nanotube/ferroferric oxide composite sponge with negative giant magnetoresistance performance |
| CN116061510A (en) * | 2022-12-07 | 2023-05-05 | 南通大学 | Multilayer self-adjusting composite non-woven material, preparation method and application thereof |
| CN116061510B (en) * | 2022-12-07 | 2023-12-05 | 南通大学 | Multilayer self-adjusting composite non-woven material, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107814379A (en) | A kind of method that low defect graphene ribbon sponge is prepared using CNT sponge | |
| Long et al. | Renewable and robust biomass carbon aerogel derived from deep eutectic solvents modified cellulose nanofiber under a low carbonization temperature for oil-water separation | |
| CN105499600B (en) | A kind of method for preparing nano silver wire graphene composite aerogel | |
| Wang et al. | Recent progress in template-assisted synthesis of porous carbons for supercapacitors | |
| Wei et al. | Lignin-assisted construction of well-defined 3D graphene aerogel/PEG form-stable phase change composites towards efficient solar thermal energy storage | |
| Qiang et al. | Recent progress in biomass-derived carbonaceous composites for enhanced microwave absorption | |
| CN105217616B (en) | Porous graphene loads carbon nano-onions three-dimensional composite material preparation method | |
| CN105597791B (en) | A kind of selenizing molybdenum/porous carbon nanofiber composite material and preparation method and application | |
| Ming et al. | Steaming multiwalled carbon nanotubes via acid vapour for controllable nanoengineering and the fabrication of carbon nanoflutes | |
| Zhang et al. | Effect of physiochemical properties in biomass-derived materials caused by different synthesis methods and their electrochemical properties in supercapacitors | |
| CN103910356B (en) | A kind of preparation method of three-dimensional grapheme | |
| CN109437157B (en) | Floating catalyst chemical vapor deposition method for single-walled carbon nanotube | |
| JP2010513202A (en) | Airgel based on carbon nanotubes | |
| CN105322146B (en) | A kind of selenizing molybdenum/carbon nano-fiber/graphene composite material and preparation method thereof | |
| CN107746052A (en) | A kind of preparation method of the graphene aerogel of N doping | |
| CN106927458A (en) | A kind of Graphene and the composite aerogels of ZIF 8 and preparation method thereof | |
| CN105251459A (en) | Preparation method of graphene composite material having high oil absorption performance | |
| Yao et al. | Controlled synthesis of core-shell composites with uniform shells of a covalent organic framework | |
| Feng et al. | Biomass derived diverse carbon nanostructure for electrocatalysis, energy conversion and storage | |
| CN106744894A (en) | A kind of preparation method of graphene powder | |
| CN105713017A (en) | High selectivity metal organic skeleton material and preparation method thereof | |
| CN106191804A (en) | A kind of preparation method of magnetic graphene nano belt/graphene composite film | |
| Zhou et al. | 3D Vascular-structured Flame-retardant Cellulose-based photothermal aerogel for Solar-driven interfacial evaporation and wastewater purification | |
| CN107459034A (en) | A kind of preparation method of high-strength flexible grapheme foam body | |
| CN106191805A (en) | A kind of preparation method of magnetic graphene laminated film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180320 |