CN108793128A

CN108793128A - A kind of method that self-propagating high-temperature prepares multi-layer graphene

Info

Publication number: CN108793128A
Application number: CN201810669547.9A
Authority: CN
Inventors: 程军; 杨军; 朱圣宇; 谈辉; 王帅; 刘维民
Original assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Current assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Priority date: 2018-06-26
Filing date: 2018-06-26
Publication date: 2018-11-13

Abstract

The invention discloses a kind of method that self-propagating high-temperature prepares multi-layer graphene, the specific steps are：The magnesium chips of 100~200 mesh of granularity is poured into strip corundum Noah's ark to pave, thickness is maintained between 3~5 mm；The corundum Noah's ark for being loaded with magnesium chips is placed in self-propagating synthesis stove, embedment length and the comparable spiral shape molybdenum filament of corundum Noah's ark, both ends connection electrode in magnesium chips；Self-propagating synthesis stove is sealed, CO is passed through₂Gas fills row to exclude the interference of air, then proceedes to be passed through CO first₂Gas；It is connected to electric current using electric welding machine, lighting magnesium powder makes itself and CO₂Gas reaction is collected target product and is cleaned by ultrasonic using dilute hydrochloric acid after cooling, distilled water is cleaned, filtered, drying obtains the multi-layer graphene of high-purity.The method of the invention have required equipment it is simple, it is simple for process, at low cost, can mass production, material prepared purity it is high, while the CO in air can be efficiently used₂The advantages that greenhouse gases, extensive raw material sources.

Description

A kind of method that self-propagating high-temperature prepares multi-layer graphene

Technical field

The invention belongs to technical field of graphene preparation, are related to a kind of method that self-propagating high-temperature prepares multi-layer graphene.

Background technology

Graphene is a kind of excellent two-dimentional multifunctional material, with excellent power, hot property, high damping characteristic and Good solid lubrication performance, it is with important application prospects in the advanced manufacturing technologies such as aerospace, nuclear energy field.At present The preparation method of report graphene is mainly the following, but respectively has disadvantage：（1）Mechanical stripping method is simple for process, but its yield It is extremely low；（2）Oxidation-reduction method is more efficiently produced on a large scale, but largely can lead to environmental pollution and most using high concentration acid solution Residual oxygen functional group can destroy the crystal structure etc. of graphene in final product；（3）Epitaxial growth method and chemical vapour deposition technique pair Equipment and prepare environment（High temperature high vacuum）It is required that high, complex process etc. is chiefly used in preparing graphene film.Therefore, how Efficiently, low cost, the preparation graphene powder material of green low toxicity have obtained the very big concern and research of global material scholar.Its In, utilize magnesium powder and CO₂Greenhouse gases reaction synthesizing graphite alkene material has many advantages, such as：（1）Magnesium powder and CO₂It is cheap, come Source is extensive, greatly reduces the manufacturing cost of graphene；（2）Simple for process, operability is strong；（3）Product postprocessing is simple, because This, which is expected to become a kind of extensive preparation reliable method of graphene powder material of industrialization.

Metal magnesium powder is placed in high temperature furnace, is risen under argon gas protection environment by document one, 103332681 A of Chinese patent CN Temperature is to target temperature（500~650 DEG C）, then pass to CO₂/ Ar mixed gas induces reaction, then the cooling in argon gas, obtains black Color powder, then pickling is up to graphene.

Document two, Chinese patent CN 103112844A light magnesium by magnesium metal and two in the beaker equipped with carbon dioxide Carbon dioxide reaction, and obtained reaction product is subjected to quenching treatment in different medium, then remove magnesium in mixture and Magnesia, washing, drying obtain graphene.

Document three, 106115675 A of Chinese patent CN disclose a kind of preparation method of mesoporous graphene：By magnesium powder and Magnesia powder mixes, and is put into sealed pressure vessel and is embedded to tungsten filament, is then passed through CO₂Gas applies electric current to tungsten filament and causes gold Belong to magnesium powder and CO₂Reaction obtains black powder, and mesoporous grapheme material is obtained after overpickling and freeze-drying.

By studying and judging discovery to above-mentioned document：Directly utilize magnesium powder and CO₂Reaction haves the shortcomings that reaction is insufficient（Document Two）；Even if incomplete if 500~650 DEG C of reactions of high temperature（Document one）.

Invention content

It is an object of the invention to be the existing metal magnesium powder of solution and CO₂Directly reaction is incomplete, graphene low output Problem provides a kind of self-propagating synthesis technique that can be used for industrialized production graphene powder material with practical value and side Method.

A kind of method that self-propagating high-temperature prepares multi-layer graphene, it is characterised in that be as follows：

Step 1, magnesium chips is poured into the tiling of strip corundum Noah's ark, the granularity requirements of magnesium chips are in 100~200 mesh, the thickness for the layer that tiles Degree is 3~5 mm；The thickness of meticulous or excessively thick magnesium powder, the layer that tiles can all influence the formation of combustion wave during self-propagating synthesis And sprawling, and finally influence the quality and quantity of product；

Step 2, the corundum Noah's ark for being loaded with magnesium chips is placed in self-propagating synthesis stove, embedment length and the comparable spiral shape of corundum Noah's ark Molybdenum filament, molybdenum filament both ends connect synthetic furnace electrode；It is required that the length of molybdenum filament is suitable with corundum Noah's ark, it can ensure any place in this way Magnesium powder can light and react abundant, increase substantially the yield of graphene；

Step 3, self-propagating synthesis stove is sealed, electrode both ends connect electric welding machine welding gun；Self-propagating synthesis stove air inlet pipe is connected to CO₂Gas Bottle, is passed through CO₂, fill row 3 times, exclude the interference of air, and be finally passed through the CO that pressure value is 0.2~0.5 MPa₂Gas；

Step 4, switch for electric welder is opened, electric current is added to 60~80 A, is maintained 5~15 seconds；It is observed from self-propagating synthesis stove Magnesium powder is ignited and vigorous combustion, this process can continue 30s or so, while can hear the sound of corundum Noah's ark fracture； Welder power stove natural cooling to be synthesized is closed, fluffy black powder is collected；

Step 5, black powder is placed in the hydrochloric acid solution that mass fraction is 5%~10%, ultrasonic vibration cleans 10~12h, goes Except oxidation magnesium addition；

Step 6, step 5 gained black suspension is filtered, it is neutral that distilled water flushing to pH value, which is used in combination, dries to obtain target product Graphene；

Step 7, X-ray diffractometer is utilized（XRD）, scanning electron microscope（SEM）And transmission electron microscope（TEM）Technology pair Purity, pattern and the number of plies of prepared target product graphene are characterized.

The grain size of heretofore described magnesium chips, thickness, the shape of crucible and molybdenum filament length all can be to magnesium powder and CO₂'s The extent of reaction generates tremendous influence.

The method of the invention have required equipment it is simple, it is simple for process, at low cost, can mass production, prepared material Expect that purity is high, while the CO in air can be efficiently used₂The advantages that greenhouse gases, extensive raw material sources.

Description of the drawings

Fig. 1 is the XRD diagram piece of graphene powder prepared by embodiment 1.

Fig. 2 is the raman spectrum of graphene powder prepared by embodiment 1.

Fig. 3 is the Electronic Speculum pattern picture after graphene powder prepared by embodiment 1 is ultrasonically treated.

Fig. 4 is the transmission electron microscope shape appearance figure piece of graphene powder prepared by embodiment 1.

Specific implementation mode

Embodiment 1

The magnesium chips of 100~200 mesh of granularity, quality 2g is poured into strip corundum Noah's ark to pave, thickness is in 2 mm；By corundum Noah's ark It is placed in self-propagating synthesis stove, embedment length and the comparable spiral shape molybdenum filament of corundum Noah's ark, both ends connection electrode in magnesium chips；It is close Self-propagating synthesis stove is sealed, CO is passed through₂Gas, fills row 3 times, is finally passed through CO₂Gas is to 0.2MPa；It is connected to electric current using electric welding machine, It is maintained 5 seconds in 80A, lighting magnesium powder makes itself and CO₂Gas reaction collects target product and utilizes 5% dilute hydrochloric acid ultrasound clear after cooling 10h is washed, distilled water flushing, suction filtration dry to obtain target product 0.33g.

Embodiment 2

The magnesium chips of 100~200 mesh of granularity, quality 5g is poured into strip corundum Noah's ark to pave, thickness is in 4 mm；By corundum Noah's ark It is placed in self-propagating synthesis stove, embedment length and the comparable spiral shape molybdenum filament of corundum Noah's ark, both ends connection electrode in magnesium chips；It is close Self-propagating synthesis stove is sealed, CO is passed through₂Gas, fills row 3 times, is finally passed through CO₂Gas is to 0.3 MPa；It is connected to electricity using electric welding machine Stream maintains 10 seconds in 70A, and lighting magnesium powder makes itself and CO₂Gas reaction is collected target product and is surpassed using 5% dilute hydrochloric acid after cooling Sound cleans 12h, and distilled water flushing, suction filtration dry to obtain target product 0.86g.

Claims

1. a kind of method that self-propagating high-temperature prepares multi-layer graphene, it is characterised in that the specific steps are：By granularity 100~200 Purpose magnesium chips pours into strip corundum Noah's ark and paves, and thickness is maintained between 3~5 mm；The corundum Noah's ark for being loaded with magnesium chips is placed in In self-propagating synthesis stove, embedment length and the comparable spiral shape molybdenum filament of corundum Noah's ark, both ends connection electrode in magnesium chips；Sealing is certainly Synthetic furnace is spread, CO is passed through₂Gas fills row to exclude the interference of air, then proceedes to be passed through CO first₂Gas；Utilize electric welding machine It is connected to electric current, lighting magnesium powder makes itself and CO₂Gas reaction is collected target product and is cleaned by ultrasonic using dilute hydrochloric acid, steamed after cooling Distilled water cleaning filters, the drying i.e. multi-layer graphene of acquisition high-purity.

2. the method as described in claim 1, it is characterised in that CO described in self-propagating synthesis stove₂The pressure of gas be 0.2~ 0.5 MPa。

3. the method as described in claim 1, it is characterised in that the condition for lighting magnesium powder is to maintain 5~15 in 60~80A Second.

4. the method as described in claim 1, it is characterised in that the mass fraction of the dilute hydrochloric acid is 5%~10%.

5. the method as described in claim 1, it is characterised in that the time that the dilute hydrochloric acid is cleaned by ultrasonic is 10~12h.

6. the method as described in claim 1, it is characterised in that it is neutrality that the distilled water, which is cleaned to pH value,.