CN105645381B - The method that potent microwave method prepares graphene carbon nanometer tube composite materials - Google Patents
The method that potent microwave method prepares graphene carbon nanometer tube composite materials Download PDFInfo
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- CN105645381B CN105645381B CN201610018438.1A CN201610018438A CN105645381B CN 105645381 B CN105645381 B CN 105645381B CN 201610018438 A CN201610018438 A CN 201610018438A CN 105645381 B CN105645381 B CN 105645381B
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention relates to a kind of method that potent microwave method prepares graphene carbon nanometer tube composite materials, based on microwave irradiation method, graphite oxide is put into micro-wave oven and carries out microwave irradiation, 2~5min is the graphite oxide that can be reduced and peeled off, it is mixed with ferrocene and carries out secondary microwave under the same conditions, Graphene/carbon nanotube composite material is finally made.The Graphene/carbon nanotube composite material technique that is prepared using the above method is simple, cost is low, and the Gr/CNTs composites produced have good electric conductivity and magnetic.
Description
Technical field
The present invention relates to a kind of nano carbon composite material, more particularly to a kind of potent microwave method prepares graphene carbon nanometer
The method of pipe composite.
Background technology
Electrochemical capacitor is as a kind of new type of energy storage device, because its charge-discharge velocity is fast, power density is high, the circulation longevity
The advantages of ordering long, is the energy storage device after another great application potential and Development volue after lithium ion battery.But energy density
Relatively low is a key factor for restricting ultracapacitor development and application, explores the energy density for how improving ultracapacitor
It is the emphasis of the current area research.Energy density is improved according to the calculation formula of energy density mainly in terms of two to start with, one
Aspect improves the voltage window of electrochemical capacitor；Still further aspect is to improve the specific capacity of electrode material, and these two aspects is carried
Gao Douhui brings the raising of energy density.
Graphene, as a kind of two-dimentional monolayer material, is one with higher specific surface area and higher electrical conductivity
The preferable electrochemical capacitor electrode material of kind, but the method complex process of tradition preparation graphene carbon nanometer tube composite materials,
Cost is higher and reduced graphene is using toxic reagents such as hydrazine hydrates, therefore for a long time, graphene carbon nanotube composite
The production of material is always a urgent problem to be solved.
The content of the invention
Subject matter to be solved by this invention is：To produce a kind of low cost, production method simple and fast, safe nothing
The graphene carbon nanometer tube composite materials of murder by poisoning, have invented a kind of potent microwave method production graphene carbon nanometer tube composite materials
Method.This method simple and fast, whole preparation process will not use any reagent raw material toxic to human body, safety non-toxic
Evil.
The present invention is implemented by following technical solution：
The method that potent microwave method prepares graphene carbon nanometer tube composite materials, comprises the following steps：
1) 2~4g graphite is added in the beaker equipped with 100~120mL concentrated sulfuric acids at ambient temperature, then in ice bath
Under the conditions of be slowly added to after 15~20g potassium permanganate, by reaction solution be transferred to 28~33 DEG C stirred in water bath reaction 20~
50min, reaction adds 300~450mL frozen water after terminating is diluted, and H is added dropwise2O2Solution is until bubble-free generation, is taken out
Filter and rinse obtained golden yellow filter cake with a large amount of clear water, obtained powder is dried overnight in vacuum drying chamber；
2) the graphite oxide powder that step 1 is prepared is put into vial, be placed in micro-wave oven, 1000W microwaves 20
~50s, obtains MRGO；
3) take 13~18mgMRGO and 20~35mg ferrocene to be put into jointly in agate mortar and grind 15min, be well mixed
Afterwards, well mixed black powder is transferred in vial, 20~50s of 1000W microwaves, you can obtain pattern uniform
Gr/CNTs composites.
Specifically, the step 1) the middle H being added dropwise2O2The mass fraction of solution is 13~18%.
Specifically, the step 1) in using vacuum drying chamber graphite oxide powder is dried temperature be set as 30~
45℃。
Beneficial effects of the present invention：(1) preparation process will not use the toxic reagent such as hydrazine hydrate, and safe production process can
By pollution-free；(2) whole preparation process is that can reach requirement only with microwave twice, is not required to the extreme environments such as HTHP real
Test, therefore extremely suitable industrialization large-scale production.
Embodiment：
The following is the specific embodiment of the present invention, technical scheme is described further, but the present invention
Protection domain is not limited to these embodiments.Every change or equivalent substitute without departing substantially from present inventive concept is included in the present invention
Protection domain within.
Embodiment 1
1) 2.2 graphite are added in the beaker equipped with the 105mL concentrated sulfuric acids at ambient temperature, then delayed under condition of ice bath
Slow to add after 16g potassium permanganate, the stirred in water bath that reaction solution is transferred into 29 DEG C reacts 23min, and reaction is added after terminating
After 430mL frozen water is diluted, dropwise addition mass fraction is 14%H2O2Solution is until bubble-free is produced.Carry out suction filtration and incite somebody to action
The golden yellow filter cake arrived is rinsed with a large amount of clear water, and obtained powder is dried overnight in 32 DEG C of vacuum drying chamber；
2) the graphite oxide powder that step 1 is prepared is put into vial, be placed in micro-wave oven, 1000W microwaves
30s, obtains MRGO；
3) take 16mg MRGO and 33mg ferrocene to be put into jointly in agate mortar and grind 15min, will be mixed after being well mixed
Close uniform black powder to be transferred in vial, 1000W microwave 44s, obtain the uniform Gr/CNTs composite woods of black pattern
Material.
Embodiment 2
1) 3.6g graphite is added in the beaker equipped with the 112mL concentrated sulfuric acids at ambient temperature, then under condition of ice bath
It is slowly added to after 18g potassium permanganate, the stirred in water bath that reaction solution is transferred into 30 DEG C reacts 44min, reaction is added after terminating
After 390mL frozen water is diluted, dropwise addition mass fraction is 16%H2O2Solution is until bubble-free is produced.Carry out suction filtration and incite somebody to action
The golden yellow filter cake arrived is rinsed with a large amount of clear water, and obtained powder is dried overnight in 42 DEG C of vacuum drying chamber；
2) the graphite oxide powder that step 1 is prepared is put into vial, be placed in micro-wave oven, 1000W microwaves
35s, obtains MRGO；
3) take 16mg MRGO and 25mg ferrocene to be put into jointly in agate mortar and grind 15min, will be mixed after being well mixed
Close uniform black powder to be transferred in vial, 1000W microwaves 29s, you can obtain the uniform Gr/CNTs composite woods of pattern
Material.
Embodiment 3
1) 3.2g graphite is added in the beaker equipped with the 114mL concentrated sulfuric acids at ambient temperature, then under condition of ice bath
It is slowly added to after 16g potassium permanganate, the stirred in water bath that reaction solution is transferred into 31 DEG C reacts 42min, reaction is added after terminating
After 340mL frozen water is diluted, dropwise addition mass fraction is 17.3%H2O2Solution is until bubble-free is produced.Progress suction filtration simultaneously will
Obtained golden yellow filter cake is rinsed with a large amount of clear water, and obtained powder is dried overnight in 42 DEG C of vacuum drying chamber；
2) the graphite oxide powder that step 1 is prepared is put into vial, be placed in micro-wave oven, 1000W microwaves
38s, obtains MRGO；
3) take 15mg MRGO and 26mg ferrocene to be put into jointly in agate mortar and grind 15min, will be mixed after being well mixed
Close uniform black powder to be transferred in vial, 1000W microwaves 39s, you can obtain the uniform Gr/CNTs composite woods of pattern
Material.
Embodiment 4
1) 2g graphite is added in the beaker equipped with the 100mL concentrated sulfuric acids at ambient temperature, then delayed under condition of ice bath
Slow to add after 15g potassium permanganate, the stirred in water bath that reaction solution is transferred into 33 DEG C reacts 50min, and reaction is added after terminating
After 300mL frozen water is diluted, dropwise addition mass fraction is 13%H2O2Solution is until bubble-free is produced.Carry out suction filtration and incite somebody to action
The golden yellow filter cake arrived is rinsed with a large amount of clear water, and obtained powder is dried overnight in 45 DEG C of vacuum drying chamber；
2) the graphite oxide powder that step 1 is prepared is put into vial, be placed in micro-wave oven, 1000W microwaves
50s, obtains MRGO；
3) take 13mg MRGO and 20mg ferrocene to be put into jointly in agate mortar and grind 15min, will be mixed after being well mixed
Close uniform black powder to be transferred in vial, 1000W microwaves 20s, you can obtain the uniform Gr/CNTs composite woods of pattern
Material.
Embodiment 5
1) 4g graphite is added in the beaker equipped with the 120mL concentrated sulfuric acids at ambient temperature, then delayed under condition of ice bath
Slow to add after 20g potassium permanganate, the stirred in water bath that reaction solution is transferred into 28 DEG C reacts 20min, and reaction is added after terminating
After 450mL frozen water is diluted, dropwise addition mass fraction is 18%H2O2Solution is until bubble-free is produced.Carry out suction filtration and incite somebody to action
The golden yellow filter cake arrived is rinsed with a large amount of clear water, and obtained powder is dried overnight in 30 DEG C of vacuum drying chamber；
2) the graphite oxide powder that step 1 is prepared is put into vial, be placed in micro-wave oven, 1000W microwaves
20s, obtains MRGO；
3) take 18mg MRGO and 35mg ferrocene to be put into jointly in agate mortar and grind 15min, will be mixed after being well mixed
Close uniform black powder to be transferred in vial, 1000W microwaves 50s, you can obtain the uniform Gr/CNTs composite woods of pattern
Material.
Claims (2)
1. the method that potent microwave method prepares graphene carbon nanometer tube composite materials, it is characterised in that comprise the following steps：
1) 2~4g graphite is added in the beaker equipped with 100~120mL concentrated sulfuric acids at ambient temperature, then in condition of ice bath
Under be slowly added to after 15~20g potassium permanganate, by reaction solution be transferred to 28~33 DEG C stirred in water bath react 20~50min,
Reaction adds 300~450mL frozen water after terminating is diluted, and H is added dropwise2O2Solution is until bubble-free is produced, and progress suction filtration simultaneously will
Obtained golden yellow filter cake is rinsed with a large amount of clear water, and obtained powder is dried overnight in vacuum drying chamber；The H of the dropwise addition2O2
The mass fraction of solution is 13~18%；
2) the graphite oxide powder that step 1 is prepared is put into vial, be placed in micro-wave oven, 1000W microwaves 20~
50s, obtains MRGO；
3) take 13~18mg MRGO and 20~35mg ferrocene to be put into jointly in agate mortar and grind 15min, after being well mixed,
Well mixed black powder is transferred in vial, 20~50s of 1000W microwaves, you can obtain the uniform Gr/ of pattern
CNTs composites.
2. the method that potent microwave method according to claim 1 prepares graphene carbon nanometer tube composite materials, its feature exists
In the step 1) in temperature be dried to graphite oxide powder be set as 30~45 DEG C using vacuum drying chamber.
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| CN106882798B (en) * | 2017-02-09 | 2020-06-05 | 广东派勒智能纳米科技股份有限公司 | Preparation process of graphene and carbon nanotube composite material |
| CN108039499B (en) * | 2017-10-23 | 2023-10-03 | 广东工业大学 | Preparation method of nitrogen-doped exfoliated carbon nanotube loaded cobaltosic oxide material |
| CN107895653B (en) * | 2017-10-27 | 2019-10-25 | 西安理工大学 | Microwave prepares cigarette filter/graphene composite material method and application thereof |
| CN108726515A (en) * | 2018-05-31 | 2018-11-02 | 西北师范大学 | Preparation method with three-dimensional structure redox graphene-ferrocene composite material |
| CN108511760A (en) * | 2018-06-13 | 2018-09-07 | 天合光能股份有限公司 | A kind of lithium battery conductive agent and preparation method thereof |
| CN109231190A (en) * | 2018-11-02 | 2019-01-18 | 重庆大学 | Prepare redox graphene method and its redox graphene obtained |
| CN111302328A (en) * | 2020-02-24 | 2020-06-19 | 西北工业大学 | Carbon nanotube/graphene hybrid material and preparation method and application thereof |
| CN116535124B (en) * | 2023-05-09 | 2024-04-12 | 青岛理工大学 | CNTs@microbead core-shell filler, cement-based composite material, preparation method and application |
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