CN106298277B - A kind of Graphene/carbon nanotube composite material of microwave liquid phase fast low temperature fabricated in situ and its preparation method and application - Google Patents
A kind of Graphene/carbon nanotube composite material of microwave liquid phase fast low temperature fabricated in situ and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 48
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 9
- 239000007791 liquid phase Substances 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 239000011734 sodium Substances 0.000 claims abstract description 43
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 27
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000002604 ultrasonography Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 230000020477 pH reduction Effects 0.000 claims description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 2
- 229940031098 ethanolamine Drugs 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 2
- 239000002071 nanotube Substances 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 abstract 1
- 239000010453 quartz Substances 0.000 description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 36
- 239000002243 precursor Substances 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 238000001914 filtration Methods 0.000 description 12
- 239000003350 kerosene Substances 0.000 description 12
- 239000012982 microporous membrane Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 230000003068 static effect Effects 0.000 description 12
- 229910021642 ultra pure water Inorganic materials 0.000 description 12
- 239000012498 ultrapure water Substances 0.000 description 12
- 239000002699 waste material Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 6
- -1 graphite alkene Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000001652 electrophoretic deposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of new method of a step microwave reaction liquid phase fast low temperature fabricated in situ Graphene/carbon nanotube composite material of simplicity, the preparation method of the composite material includes：（1）Commercially available carbon nanotube is mixed into ultrasound with the common organic molecule reagent of chemical laboratory, it is made to be uniformly dispersed in organic molecule reagent；（2）The above-mentioned organic molecule reagent containing finely dispersed carbon nanotube reacts, and add in a certain amount of alkali metal compound with metallic sodium, obtains microwave reaction presoma；（3）It is reacted in microwave reactor, microwave reaction product is filtered, wash, Graphene/carbon nanotube composite material is obtained after drying.This method has step simplicity, and easy to operate, energy conservation and environmental protection is inexpensive, is expected to realize the advantage of large-scale production etc..In addition, synthesized composite material, which is applied to ultracapacitor energy storage field, has preferable energy storage effect.
Description
Technical field
The invention belongs to field of compound material, relate generally to it is a kind of with microwave liquid phase original position fast low temperature synthesizing graphite alkene/
The method and its synthetic material of carbon nano tube compound material good energy storage effect in terms of as electrode material for super capacitor
Application.
Technical background
Graphene, one kind is by sp2The carbon atom of hydridization interconnects the new carbon formed, has in two dimensional surface
The six-membered carbon ring structure infinitely extended.The graphene stacked in multi-layers of monoatomic layer thickness can form three-dimensional graphite, crimp one week
One-dimensional single-walled carbon nanotube can be formed, seamless coupling can form the fullerene of zero dimension after decomposition.The unique structure group of graphene
Into assigning its many excellent physics and chemical characteristic, the theoretical specific surface area such as with known maximum, excellent carrier moves
Shifting rate, thermal conductivity, translucency and mechanical strength etc..Thus, it is had a wide range of applications in various fields, especially in the energy
Crisis and environmental pollution are increasingly serious instantly, and grapheme material is concerned in energy energy storage and the application of conversion etc..
Ultracapacitor（Also known as electrochemical capacitor）It is a kind of efficient electrochemical energy storage device, there is extensive market
And application prospect.Compared to other energy storage devices, ultracapacitor has power density and energy density height, and the charging time is short,
The advantages that service life is long, and self discharge is slow, safe, and environmental suitability is strong and pollution-free.Performance of the supercapacitor it is good
The bad quality for being decided by its electrode material performance, carbon material is since its is cheap and easy to get, high conductivity, high-specific surface area, high stable
Property etc. become earliest be applied to electrode of super capacitor electrode material.Grapheme material is excellent because of its larger specific surface area
Electric conductivity, mechanical strength etc. becomes the only selection of electrode material for super capacitor, it is however generally that, super capacitor electrode
The number of its energy storage of the size direct relation of pole material specific surface area, therefore, for the height for making full use of grapheme material intrinsic
Specific surface area, the generation for preventing graphene from its effective ratio area being caused to reduce phenomenon due to stacked in multi-layers, graphene/carbon are received
Mitron composite material comes into being, and the intercalation configuration of carbon nanotube and graphene can effectively organize the hair of graphene stacking phenomenon
It is raw, and play the role of electronics conduction between graphene layer.
Currently, the synthetic method of Graphene/carbon nanotube composite material mainly has chemical vapor deposition（CVD）Method（Wherein
Including conventional CVD method and plasma enhanced CVD process）, layer by layer deposition（LBL）Method, electrophoretic deposition, vacuum filtration method coat
Membrane formation process and in-situ chemical reducing process etc..Existing synthetic method is high often with there is equipment requirement, and highly energy-consuming is complicated for operation, production
Measure the deficiency of grade low and of high cost.The present invention is by microwave-assisted synthesis, and using business carbon nanotube as hard template, laboratory is normal
See that the make a living raw material of long graphene of organic molecule reagent is reacted with metallic sodium, liquid phase fast low temperature in situ synthesis from bottom to top
Graphene/carbon nanotube composite material, has easy to operate, saves energy consumption, of low cost and be expected to realize large-scale production etc.
Advantage, in addition, the composite material of synthesis has good application effect in terms of ultracapacitor energy storage.
Invention content
It is an object of the invention to for some are not present on existing Graphene/carbon nanotube composite material synthetic technology
Foot using the advantage of microwave-assisted synthesis, provides a kind of liquid phase, original position, quick, low temperature, inexpensive synthesizing graphite alkene/carbon nanometer
The technical method of pipe composite material, the composite material of preparation have good energy storage effect.
The present invention microwave liquid phase fast low temperature fabricated in situ Graphene/carbon nanotube composite material method, including with
Lower step：
（1）Commercially available carbon nanotube is mixed into ultrasound with the common organic molecule reagent in laboratory, is there is it
It is uniformly dispersed in machine small organic agents；
（2）Dispersion liquid of the above-mentioned carbon nanotube in organic molecule reagent is reacted with metallic sodium, and is added in a kind of certain
The alkali metal compound of amount obtains microwave reaction presoma；
（3）It is reacted in microwave reactor, microwave reaction product is filtered, wash, graphene/carbon nano-tube is obtained after drying
Composite material.
The common organic molecule reagent in laboratory include alcohol reagent, as methanol, ethyl alcohol, ethylene glycol, glycerine,
Isopropanol, the reagent of organic molecule containing hetero atom for example n,N-Dimethylformamide, triethanolamine, diethanol amine, ethanol amine and
Dimethyl sulfoxide.
The type of the commercially available carbon nanotube has：A. carbon length of tube is in 20-40nm；B. carbon length of tube is in 60-
100nm；C. a carbon pipes of acidification；D. the b carbon pipes of acidification, wherein using the b carbon pipe of d. acidifications to be optimal.
The alkali metal compound is NaOH, KOH, Na2CO3Or NaHCO3, preferably Na2CO3。
The commercially available carbon nanotube, the common organic molecule reagent in laboratory, metal Na and alkali metal chemical combination
The amount ratio of object is：5-15mg：0.5-3mL：0.1-1.5g：0.3-1.5g.
The initial temperature of microwave reaction is in the range of 15-40 DEG C；The microwave heating-up time is 7-15min to 170-190 DEG C, micro-
Wave keeps the temperature 0-60min, and cool down 10min after reaction, it is preferable that the microwave heating-up time is 10min to 180 DEG C, keeps the temperature 30min.
It is that a kind of Graphene/carbon nanotube composite material or doped graphene/carbon nanotube are compound made from the above method
Material, the composite material are used for energy storage as electrode material for super capacitor.
The Graphene/carbon nanotube composite material sample of synthesis, acetylene black, Kynoar（PVDF）Three is in mass ratio
8:1:8 mixing after, be ground to mixing sample it is glossy, then add in certain volume 1-Methyl-2-Pyrrolidone（NMP）It is made
The dispersion liquid of about 1mg/10uL.Above-mentioned dispersion liquid is applied in the foam nickel bar of repressed 1cm × 3cm, be dried in vacuo
100 DEG C of dry 12h, obtain electrode of super capacitor in case.By above-mentioned electrode material in 6M KOH solutions, three-electrode system,
The energy storage property of test compound material.
Product prepared by the present invention is synthesized by following instrument and means and characterization test：Using Milestone public affairs
The Ultra WAVE reactors of department's production synthesize product, using Japanese HITACHI S4800 type scanning electron microscope to product
Morphology characterization is carried out, the specific surface area of product is carried out using QuantaChrome Nova 4000e types automatic physical adsorption appearances
Test carries out product using the electrochemical workstation of Wuhan Koster Instrument Ltd. production the test of energy storage characteristic.
The present invention is mixed using commercially available carbon nanotube with common one step of organic molecule reagent of chemical laboratory
For liquid phase feed, a certain amount of alkali metal compound is added in, using metal Na as reducing agent, and special effect is played in microwave reaction
Fruit.Business carbon nanotube is hard template, with liquid phase, fast in the microwave reaction device of current novel synthesis nano-functional material
Speed, low temperature, fabricated in situ Graphene/carbon nanotube composite material or doped graphene/carbon nano tube compound material.This method has
There is step simplicity, easy to operate, energy conservation and environmental protection is inexpensive, is expected to realize the advantage of large-scale production etc..
Description of the drawings
Fig. 1：Methanol is carbon source, and microwave reaction synthesizes the SEM figures of pure Graphene/carbon nanotube composite material；
Fig. 2：Triethanolamine is carbon source, and the SEM of microwave reaction synthesis N doped graphenes/carbon nano tube compound material schemes；
Fig. 3：The N of N doped graphenes/carbon nano tube compound material of different carbon pipe additions2Adsorption desorption isothermal curve；
Fig. 4：Electrochemistry CV test curve of the pure Graphene/carbon nanotube composite material under different scanning rates；
Fig. 5：Electrochemistry constant current charge-discharge test of the pure Graphene/carbon nanotube composite material under different current densities
Curve.
Specific embodiment
With reference to embodiment to the present invention be how to realize do further it is detailed, apparent, completely illustrate, listed reality
Example is applied only to be further described the present invention, it is not thereby limiting the invention：
Embodiment 1
First, methanol reagent 2.5mL is measured in the special quartz test tube of microwave reaction, then, weighing the 60- after acidification
100nm length carbon nanotube 10mg, the ultrasonic disperse 30min in quartz test tube；Secondly, preservation is cut with tweezers, blade, filter paper
Metal Na 1.0g in kerosene carefully slowly put into above-mentioned quartz test tube after chopping, treat that methanol is reacted with metallic sodium
It is static, add in Na into above-mentioned test tube2CO3Powder 1.0g, obtains precursors；Finally, it by above-mentioned precursors, is placed in
In microwave reaction device, microwave operation and reaction, 30 DEG C of initial temperature, heating are carried out according to microwave operating specification and points for attention
Time 10min, 180 DEG C, microwave reaction 30min of microwave reaction temperature, cool down 10min.The product of above-mentioned microwave synthesis is through anhydrous
Ethyl alcohol by unreacted metal sodium waste it is complete after, add ultra-pure water and be adjusted to neutrality, most afterwards through filtering with microporous membrane device, take out
It is dried for standby after filter, washing repeatedly.
Embodiment 2
First, methanol reagent 2.5mL is measured in the special quartz test tube of microwave reaction, then, weighing the 60- after acidification
100nm length carbon nanotube 5mg, the ultrasonic disperse 30min in quartz test tube；Secondly, preservation is cut with tweezers, blade, filter paper
Metal Na 1.0g in kerosene carefully slowly put into above-mentioned quartz test tube after chopping, treat that methanol is reacted with metallic sodium
It is static, add in Na into above-mentioned test tube2CO3Powder 1.0g, obtains precursors；Finally, it by above-mentioned precursors, is placed in
In microwave reaction device, microwave operation and reaction, 30 DEG C of initial temperature, heating are carried out according to microwave operating specification and points for attention
Time 10min, 170 DEG C, microwave reaction 30min of microwave reaction temperature, cool down 10min.The product of above-mentioned microwave synthesis is through anhydrous
Ethyl alcohol by unreacted metal sodium waste it is complete after, add ultra-pure water and be adjusted to neutrality, most afterwards through filtering with microporous membrane device, take out
It is dried for standby after filter, washing repeatedly.
Embodiment 3
First, methanol reagent 2.5mL is measured in the special quartz test tube of microwave reaction, then, weighing the 60- after acidification
100nm length carbon nanotube 15mg, the ultrasonic disperse 30min in quartz test tube；Secondly, preservation is cut with tweezers, blade, filter paper
Metal Na 1.0g in kerosene carefully slowly put into above-mentioned quartz test tube after chopping, treat that methanol is reacted with metallic sodium
It is static, add in Na into above-mentioned test tube2CO3Powder 1.0g, obtains precursors；Finally, it by above-mentioned precursors, is placed in
In microwave reaction device, microwave operation and reaction, 30 DEG C of initial temperature, heating are carried out according to microwave operating specification and points for attention
Time 10min, 170 DEG C, microwave reaction 30min of microwave reaction temperature, cool down 10min.The product of above-mentioned microwave synthesis is through anhydrous
Ethyl alcohol by unreacted metal sodium waste it is complete after, add ultra-pure water and be adjusted to neutrality, most afterwards through filtering with microporous membrane device, take out
It is dried for standby after filter, washing repeatedly.
Embodiment 4
First, methanol reagent 2.5mL is measured in the special quartz test tube of microwave reaction, then, weighing the 60- after acidification
100nm length carbon nanotube 10mg, the ultrasonic disperse 30min in quartz test tube；Secondly, preservation is cut with tweezers, blade, filter paper
Metal Na 1.0g in kerosene carefully slowly put into above-mentioned quartz test tube after chopping, treat that methanol is reacted with metallic sodium
It is static, add in Na into above-mentioned test tube2CO3Powder 1.0g, obtains precursors；Finally, it by above-mentioned precursors, is placed in
In microwave reaction device, microwave operation and reaction, 30 DEG C of initial temperature, heating are carried out according to microwave operating specification and points for attention
Time 10min, 170 DEG C, microwave reaction 30min of microwave reaction temperature, cool down 10min.The product of above-mentioned microwave synthesis is through anhydrous
Ethyl alcohol by unreacted metal sodium waste it is complete after, add ultra-pure water and be adjusted to neutrality, most afterwards through filtering with microporous membrane device, take out
It is dried for standby after filter, washing repeatedly.
Embodiment 5
First, methanol reagent 2.5mL is measured in the special quartz test tube of microwave reaction, then, weighing the 60- after acidification
100nm length carbon nanotube 10mg, the ultrasonic disperse 30min in quartz test tube；Secondly, preservation is cut with tweezers, blade, filter paper
Metal Na 1.0g in kerosene carefully slowly put into above-mentioned quartz test tube after chopping, treat that methanol is reacted with metallic sodium
It is static, add in Na into above-mentioned test tube2CO3Powder 1.0g, obtains precursors；Finally, it by above-mentioned precursors, is placed in
In microwave reaction device, microwave operation and reaction, 30 DEG C of initial temperature, heating are carried out according to microwave operating specification and points for attention
Time 10min, 190 DEG C, microwave reaction 30min of microwave reaction temperature, cool down 10min.The product of above-mentioned microwave synthesis is through anhydrous
Ethyl alcohol by unreacted metal sodium waste it is complete after, add ultra-pure water and be adjusted to neutrality, most afterwards through filtering with microporous membrane device, take out
It is dried for standby after filter, washing repeatedly.
Embodiment 6
First, methanol reagent 2.5mL is measured in the special quartz test tube of microwave reaction, then, weighing the 60- after acidification
100nm length carbon nanotube 10mg, the ultrasonic disperse 30min in quartz test tube；Secondly, preservation is cut with tweezers, blade, filter paper
Metal Na 1.0g in kerosene carefully slowly put into above-mentioned quartz test tube after chopping, treat that methanol is reacted with metallic sodium
It is static, add in Na into above-mentioned test tube2CO3Powder 1.0g, obtains precursors；Finally, it by above-mentioned precursors, is placed in
In microwave reaction device, microwave operation and reaction, 30 DEG C of initial temperature, heating are carried out according to microwave operating specification and points for attention
Time 10min, 180 DEG C, microwave reaction 60min of microwave reaction temperature, cool down 10min.The product of above-mentioned microwave synthesis is through anhydrous
Ethyl alcohol by unreacted metal sodium waste it is complete after, add ultra-pure water and be adjusted to neutrality, most afterwards through filtering with microporous membrane device, take out
It is dried for standby after filter, washing repeatedly.
Embodiment 7
First, triethanolamine reagent 1.0mL is measured in the special quartz test tube of microwave reaction, then, weighing after being acidified
60-100nm length carbon nanotube 10mg, the ultrasonic disperse 30min in quartz test tube；Secondly, it is cut with tweezers, blade, filter paper
The metal Na 0.7g being stored in kerosene carefully slowly put into above-mentioned quartz test tube after chopping, wait to react static, to
Na is added in above-mentioned test tube2CO3Powder 0.5g, obtains precursors；Finally, by above-mentioned precursors, it is anti-to be placed in microwave
It answers in device, microwave operation and reaction, 35 DEG C of initial temperature, heating-up time is carried out according to microwave operating specification and points for attention
10min, 180 DEG C, microwave reaction 30min of microwave reaction temperature, cool down 10min.The product of above-mentioned microwave synthesis is through absolute ethyl alcohol
By unreacted metal sodium waste it is complete after, add ultra-pure water and be adjusted to neutrality, most filter, wash through filtering with microporous membrane device afterwards
It is dried for standby after washing repeatedly.
Embodiment 8
First, triethanolamine reagent 1.0mL is measured in the special quartz test tube of microwave reaction, then, weighing after being acidified
60-100nm length carbon nanotube 10mg, the ultrasonic disperse 30min in quartz test tube；Secondly, it is cut with tweezers, blade, filter paper
The metal Na 0.7g being stored in kerosene carefully slowly put into above-mentioned quartz test tube after chopping, wait to react static, to
Na is added in above-mentioned test tube2CO3Powder 0.5g, obtains precursors；Finally, by above-mentioned precursors, it is anti-to be placed in microwave
It answers in device, microwave operation and reaction, 35 DEG C of initial temperature, heating-up time is carried out according to microwave operating specification and points for attention
10min, 170 DEG C, microwave reaction 30min of microwave reaction temperature, cool down 10min.The product of above-mentioned microwave synthesis is through absolute ethyl alcohol
By unreacted metal sodium waste it is complete after, add ultra-pure water and be adjusted to neutrality, most filter, wash through filtering with microporous membrane device afterwards
It is dried for standby after washing repeatedly.
Embodiment 8
First, triethanolamine reagent 1.0mL is measured in the special quartz test tube of microwave reaction, then, weighing after being acidified
60-100nm length carbon nanotube 10mg, the ultrasonic disperse 30min in quartz test tube；Secondly, it is cut with tweezers, blade, filter paper
The metal Na 0.7g being stored in kerosene carefully slowly put into above-mentioned quartz test tube after chopping, wait to react static, to
Na is added in above-mentioned test tube2CO3Powder 0.5g, obtains precursors；Finally, by above-mentioned precursors, it is anti-to be placed in microwave
It answers in device, microwave operation and reaction, 35 DEG C of initial temperature, heating-up time is carried out according to microwave operating specification and points for attention
10min, 190 DEG C, microwave reaction 30min of microwave reaction temperature, cool down 10min.The product of above-mentioned microwave synthesis is through absolute ethyl alcohol
By unreacted metal sodium waste it is complete after, add ultra-pure water and be adjusted to neutrality, most filter, wash through filtering with microporous membrane device afterwards
It is dried for standby after washing repeatedly.
Embodiment 9
First, triethanolamine reagent 1.0mL is measured in the special quartz test tube of microwave reaction, then, weighing after being acidified
60-100nm length carbon nanotube 10mg, the ultrasonic disperse 30min in quartz test tube；Secondly, it is cut with tweezers, blade, filter paper
The metal Na 0.7g being stored in kerosene carefully slowly put into above-mentioned quartz test tube after chopping, wait to react static, to
Na is added in above-mentioned test tube2CO3Powder 0.5g, obtains precursors；Finally, by above-mentioned precursors, it is anti-to be placed in microwave
It answers in device, microwave operation and reaction, 35 DEG C of initial temperature, heating-up time is carried out according to microwave operating specification and points for attention
10min, 180 DEG C, microwave reaction 60min of microwave reaction temperature, cool down 10min.The product of above-mentioned microwave synthesis is through absolute ethyl alcohol
By unreacted metal sodium waste it is complete after, add ultra-pure water and be adjusted to neutrality, most filter, wash through filtering with microporous membrane device afterwards
It is dried for standby after washing repeatedly.
Embodiment 10
First, triethanolamine reagent 1.0mL is measured in the special quartz test tube of microwave reaction, then, weighing after being acidified
60-100nm length carbon nanotube 5mg, the ultrasonic disperse 30min in quartz test tube；Secondly, guarantor is cut with tweezers, blade, filter paper
The metal Na 0.7g being stored in kerosene carefully slowly put into above-mentioned quartz test tube after chopping, wait to react static, upwards
It states and Na is added in test tube2CO3Powder 0.5g, obtains precursors；Finally, by above-mentioned precursors, it is placed in microwave reaction
In device, microwave operation and reaction, 35 DEG C of initial temperature, heating-up time are carried out according to microwave operating specification and points for attention
10min, 180 DEG C, microwave reaction 30min of microwave reaction temperature, cool down 10min.The product of above-mentioned microwave synthesis is through absolute ethyl alcohol
By unreacted metal sodium waste it is complete after, add ultra-pure water and be adjusted to neutrality, most filter, wash through filtering with microporous membrane device afterwards
It is dried for standby after washing repeatedly.
Embodiment 11
First, triethanolamine reagent 1.0mL is measured in the special quartz test tube of microwave reaction, then, weighing after being acidified
60-100nm length carbon nanotube 15mg, the ultrasonic disperse 30min in quartz test tube；Secondly, it is cut with tweezers, blade, filter paper
The metal Na 0.7g being stored in kerosene carefully slowly put into above-mentioned quartz test tube after chopping, wait to react static, to
Na is added in above-mentioned test tube2CO3Powder 0.5g, obtains precursors；Finally, by above-mentioned precursors, it is anti-to be placed in microwave
It answers in device, microwave operation and reaction, 35 DEG C of initial temperature, heating-up time is carried out according to microwave operating specification and points for attention
10min, 180 DEG C, microwave reaction 30min of microwave reaction temperature, cool down 10min.The product of above-mentioned microwave synthesis is through absolute ethyl alcohol
By unreacted metal sodium waste it is complete after, add ultra-pure water and be adjusted to neutrality, most filter, wash through filtering with microporous membrane device afterwards
It is dried for standby after washing repeatedly.
Claims (2)
- A kind of 1. method of microwave liquid phase fast low temperature fabricated in situ Graphene/carbon nanotube composite material, which is characterized in that packet Include following steps：(1) commercially available carbon nanotube is mixed into ultrasound with the common organic molecule reagent in laboratory, makes it organic small It is uniformly dispersed in molecular agents；The common organic molecule reagent in laboratory be selected from methanol, ethyl alcohol, ethylene glycol, glycerine, Isopropanol, N,N-dimethylformamide, triethanolamine, diethanol amine, ethanol amine and dimethyl sulfoxide；The commercially available carbon The type of nanotube has：A. carbon length of tube is in 20-40nm；B. carbon length of tube is in 60-100nm；C. a carbon pipes of acidification；d. The b carbon pipes of acidification；(2) dispersion liquid of the above-mentioned carbon nanotube in organic molecule reagent is reacted with metallic sodium, and is added in a kind of a certain amount of Alkali metal compound obtains microwave reaction presoma；The alkali metal compound is NaOH, KOH, Na2CO3Or NaHCO3；Business is purchased The amount ratio of carbon nanotube, the common organic molecule reagent in laboratory, metal Na and alkali metal compound bought is：5- 15mg：0.5-3mL：0.1-1.5g：0.3-1.5g；(3) it is reacted in microwave reactor, it is compound by graphene/carbon nano-tube is obtained after microwave reaction product suction filtration, washing, drying Material；The initial temperature of microwave reaction is in the range of 15-40 DEG C；The microwave heating-up time is 7-15min to 170-190 DEG C, heat preservation 0-60min, microwave cooling 10min.
- 2. the side of microwave liquid phase fast low temperature fabricated in situ Graphene/carbon nanotube composite material according to claim 1 Method, which is characterized in that the microwave heating-up time is 10min to 180 DEG C, keeps the temperature 30min, microwave cooling 10min.
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| CN103011147A (en) * | 2012-12-27 | 2013-04-03 | 中南大学 | Method for preparing graphene through thermal reduction |
| CN103545115A (en) * | 2012-07-09 | 2014-01-29 | 海洋王照明科技股份有限公司 | Graphene-carbon nano tube composite material, preparation method thereof and super capacitor |
| CN103779097A (en) * | 2012-10-23 | 2014-05-07 | 海洋王照明科技股份有限公司 | Graphene-carbon nanotube composite material, and preparation method and application thereof |
| CN103964425A (en) * | 2014-05-15 | 2014-08-06 | 河南大学 | Method for quickly preparing graphene through ultrasonic radiation |
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| CN103545115A (en) * | 2012-07-09 | 2014-01-29 | 海洋王照明科技股份有限公司 | Graphene-carbon nano tube composite material, preparation method thereof and super capacitor |
| CN103779097A (en) * | 2012-10-23 | 2014-05-07 | 海洋王照明科技股份有限公司 | Graphene-carbon nanotube composite material, and preparation method and application thereof |
| CN103011147A (en) * | 2012-12-27 | 2013-04-03 | 中南大学 | Method for preparing graphene through thermal reduction |
| CN103964425A (en) * | 2014-05-15 | 2014-08-06 | 河南大学 | Method for quickly preparing graphene through ultrasonic radiation |
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