CN110282619A - A kind of method that graphene oxide is peeled off in the reduction of lithium assisted microwave synthesis dilatometry - Google Patents
A kind of method that graphene oxide is peeled off in the reduction of lithium assisted microwave synthesis dilatometry Download PDFInfo
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- CN110282619A CN110282619A CN201910539112.7A CN201910539112A CN110282619A CN 110282619 A CN110282619 A CN 110282619A CN 201910539112 A CN201910539112 A CN 201910539112A CN 110282619 A CN110282619 A CN 110282619A
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- lithium
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- graphene oxide
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
Abstract
The present invention relates to nano-carbon material preparation field, the method for specifically a kind of lithium assisted microwave synthesis dilatometry reduction peeling graphene oxide.The preparation of lithium assisted microwave synthesis reduced graphene is to be ultrasonically treated, it is completed under conditions of air blast drying and microwave heating, in microwave heating heating process, oxygen-containing functional group on graphene oxide falls off to be released for gas, generate pressure, cause that thermal expansion occurs and peels off between graphene layer, the graphene of high quality is prepared under low-temperature atmosphere-pressure.In microwave heating process, the decomposition rate of oxygen-containing functional group is bigger than the diffusion rate for generating gas in graphene oxide, and producing can overcome the combined Van der Waals force of graphene sheet layer, to realize reduction and removing.And lithium is more advantageous to the peeling of graphene sheet layer in the presence of original electronic structure has been broken.This preparation method simple process, preparation speed is fast, at low cost, can be mass-produced, and product is black floccule.
Description
Technical field
The present invention relates to nano-carbon material preparation field, oxidation is peeled off in specifically a kind of lithium assisted microwave synthesis dilatometry reduction
The method of graphene.
Background technique
Graphene is composed of the carbon atom that six side's honeycomb lattices arrange, and has excellent electricity, optics, calorifics and machine
Tool performance is a kind of ideal carbon nanomaterial.The application study of graphene is being risen, include low-cost desalination,
High-strength composite load-bearing material, high frequency transistor, solar battery, sensor, catalysis, lithium ion battery and supercapacitor etc.
All various aspects have broad application prospects.Therefore the graphene for preparing high quality is imperative.Graphene can be by expanding stone
Ink is prepared by ultrasound removing or ball milling, but degree of thermal expansion and the lamellar spacing therefore obtained are by graphite type and swelling agent
Insertion process influence, lamellar spacing is generally thicker, it is difficult to obtain the graphene of single layer or few layer.
Conventional dilatometry needs to carry out at high temperature under high pressure, needs more harsh preparation condition, and energy consumption is high,
Product is few, therefore wants to prepare largely, and it is imperative to start new preparation method for the graphene of high quality.
Summary of the invention
It is using graphene oxide as raw material, through ultrasound the purpose of the present invention is being directed to problems of the existing technology
Processing, dipping, microwave heating, quickly prepare the graphite of high quality under lower temperature, smaller energy consumption.
The present invention is achieved by the following technical solutions: a kind of lithium assisted microwave synthesis dilatometry reduction peeling graphite oxide
The method of alkene, comprising the following steps:
Lithium salts is dissolved in deionized water, is stirred evenly, after then graphene oxide powder and lithium salt solution are mixed evenly
It is ultrasonically treated 30min, the mixed solution after ultrasound is placed in vacuum drying oven drying, before obtaining lithium assisted microwave synthesis reduced graphene
Drive body；Then the grinding of lithium assisted microwave synthesis reduced graphene presoma is placed in corundum crucible with cover, is put into micro-wave oven
Vacuum pump is opened in storehouse, until microwave furnace pressure is -0.05MPa, is opened micro-wave oven cooling circulating water, is opened microwave switch, adjusts
Power is saved, in-furnace temperature is made to reach 200 DEG C；Microwave is closed after seeing the lid pop-up of corundum crucible by the visual windows of micro-wave oven
Switch after in-furnace temperature naturally cools to 50 DEG C, closes cooling circulating water, is passed through after nitrogen to furnace pressure restores to normal pressure and beats
Open the cabin door, obtains lithium assisted microwave synthesis reduced graphene.
As the further improvement of technical solution of the present invention, temperature in the vacuum drying oven is 65 DEG C, and drying time is
12h。
As the further improvement of technical solution of the present invention, the mass ratio of the lithium salts and graphene oxide powder is 1:10.
As the further improvement of technical solution of the present invention, the lithium salts is lithium nitrate or lithium carbonate.
There is apparent advance compared with the background technology, the present invention, using graphene oxide as raw material, on abundant graphene
Oxygen-containing functional group abundant makes oxygen-containing functional group resolve into carbon monoxide or carbon dioxide, contains in graphene oxide by heating
The decomposition rate of oxygen functional group is bigger than the diffusion rate for generating gas, produces to overcome and is combined together graphene sheet layer
Van der Waals force so that graphene layer is expanded and peeled off, to realize reduction and removing.Due to the lesser size of lithium and spy
Different electronic structure, is inserted between graphene layer, changes the electronic structure of graphene, reduces attraction between layers
Power is more advantageous to the removing of graphene layer, while may be implemented to be rapidly heated using microwave heating.This preparation method technique is first
Into data are accurately full and accurate, and preparation speed is fast, and simple process and low cost can be mass-produced, and product is the cotton-shaped object of black, electricity
Mirror is shown as very thin yarn shape structure, and specific surface area is about the octuple of graphene oxide, and product purity is high, be highly desirable,
Method that is extensive and quickly preparing high-quality graphene.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the graphene transmission electron microscope picture of lithium auxiliary law preparation, is known in figure: graphene is transparent yarn shape structure,
Fold is existed simultaneously.Show that the material is very thin, graphene oxide is peeled off by successfully reduction.
Fig. 2 is graphene oxide, the nitrogen adsorption desorption song of microwave reduction graphene and lithium assisted microwave synthesis reduced graphene
Line comparison diagram, known in figure: the graphene after the reduction of lithium assisted microwave synthesis has higher gas absorption amount.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
Technical solution of the present invention is described in detail with reference to the accompanying drawing.
The chemical substance material used when specific implementation are as follows: graphite, potassium permanganate, sodium nitrate, lithium nitrate, lithium carbonate, salt
Acid, the concentrated sulfuric acid, hydrogen peroxide, deionized water prepare dosage with gram, milliliter, centimetre3For measurement unit.
Graphite: C solid 2g ± 0.001g
Potassium permanganate: KMnO4Solid 7g ± 0.001g
Sodium nitrate: NaNO3Solid 1.2g ± 0.001g
Lithium nitrate: LiNO3•H2O solid 0.010g ± 0.001g
Lithium carbonate: Li2CO3Solid 0.010g ± 0.001g
Hydrochloric acid: HCl, 37% liquid 300mL ± 10mL of mass percent concentration
The concentrated sulfuric acid: H2SO4Liquid 100mL ± 10mL
Hydrogen peroxide: H2O2, 30% liquid 50mL ± 10mL of concentration of volume percent
Deionized water: H2± 50 mL of 3000 mL of O liquid
The preparation method is as follows:
(1), graphene oxide is prepared
1. configuring aqueous hydrochloric acid solution
10 mL of hydrochloric acid ± 0.001mL, 190 mL of deionized water ± 0.001mL are measured, is added in beaker, stirring 3min makes to mix
Uniformly, aqueous hydrochloric acid solution is obtained；
2. preparing graphite oxide
It measures 40mL ± 0.001mL concentrated sulfuric acid to be added into 250mL beaker, for use；
2g ± 0.001g graphite powder is weighed, for use；
1.2g ± 0.001g sodium nitrate is weighed, for use；
7g ± 0.001g potassium permanganate is weighed, for use；
Beaker equipped with the concentrated sulfuric acid is placed in ice-water bath and is stirred, while load weighted graphite powder and sodium nitrate solid is added, is stirred
It is slowly added to load weighted potassium permanganate solid after mixing 5min, control temperature is no more than 20 DEG C, is warming up to 35 DEG C after stirring 5min
Constant temperature stirs 3h, and point 5 addition 250mL deionized waters are eventually adding 30% hydrogen peroxide of 50mL ± 0.001mL, continue to stir
It is filtered while hot after 5min；
3. washing, dry graphite oxide
Filter cake is rinsed twice with aqueous hydrochloric acid solution, after deionized water flushes three times, filter cake is put into 60 DEG C of vacuum oven
Dry 20h；
4. preparing graphene oxide suspension
0.2g ± 0.001g graphite oxide is weighed, is put into beaker；
200mL ± 0.001mL deionized water is measured, addition is placed in the beaker of graphite oxide, is sufficiently stirred, then ultrasonication
1h obtains graphene oxide suspension；
5. filtering, being dry
Graphene oxide suspension after ultrasonic treatment is placed in the Buchner funnel of bottle,suction, is carried out with three layers of middling speed qualitative filter paper
It filters, remaining product filter cake on filter paper, filtrate liquid is evacuated in filter flask；
Filter cake is put into 60 DEG C of vacuum oven and dries 12h；
(2), preparation prepares lithium assisted microwave synthesis reduced graphene
The preparation of lithium assisted microwave synthesis reduced graphene is to be ultrasonically treated, and is completed under conditions of air blast drying and microwave heating
, in microwave heating heating process, the oxygen-containing functional group on graphene oxide falls off to be released for gas, is generated pressure, is caused
Thermal expansion occurs between graphene layer and peels off.In the present invention, used micro-wave oven is the limited public affairs of the outstanding full microwave equipment in Nanjing
Take charge of the NJZ4-3 type microwave high-temperature agglomerating plant of purchase.Commercially available graphene oxide can also be used described in preparation method when presoma
The graphene oxide powder that powder or other preparation methods prepare.
Prepare presoma:
0.1000g ± 0.001g graphene oxide powder is weighed, it is spare to be put into 10mL beaker；
0.0100g ± 0.001g lithium salts (lithium nitrate or lithium carbonate) is weighed, is dissolved in 3mL ± 0.001mL deionized water, stirring is equal
It is even；
Graphene oxide powder is mixed with above-mentioned solution, is ultrasonically treated 30 minutes after mixing evenly；
Mixed solution after ultrasound is put into 65 degree of vacuum drying ovens, is taken out after 12 hours and collects presoma.
Grinding:
The lithium assisted microwave synthesis reduced graphene presoma agate mortar prepared, pestle are ground；
Microwave thermal expansion:
It weighs ground lithium assisted microwave synthesis reduced graphene presoma and is put into corundum crucible with cover, be put into storehouse in micro-wave oven, adjust
Whole position obtains infrared temperature probe and accurately tests crucible and sample temperature；
Vacuum pump is opened, is microwave furnace pressure about -0.05MPa；
Micro-wave oven cooling cycle water installations are opened, microwave switch is opened, regulation power makes it be rapidly heated to 200 degree or so；
Microwave switch is closed after seeing that crucible cover bullet goes out from visual windows, starts to cool down；
Cooling circulating water is closed after in-furnace temperature is down to 50 degree, is passed through after nitrogen restores normal pressure to furnace pressure and opens cabin
Door takes out sample；
It saves, record
The lithium assisted microwave synthesis reduced graphene of preparation is weighed and is recorded, is fitted into sample sack, posts label, marked with date is placed in
In drier, closed preservation；
(3), test, analysis and characterization
Test, analysis and characterization are carried out to the pattern of the graphene of preparation, Chemical Physics performance；
Morphology analysis is carried out to sample with transmission electron microscope；
Conclusion: lithium assisted microwave synthesis reduced graphene is loose cotton-shaped black powder, and product purity is up to 99.5%, under transmission electron microscope
Transparent yarn shape structure is presented, shows the thickness degree for having very thin；
Specific surface area test is carried out to sample with nitrogen adsorption desorption；
Conclusion: the specific surface area of lithium assisted microwave synthesis reduced graphene significantly increases, and is 472 m2/ g is approximately three times of graphene oxide
With six times.
(4), microwave reduction graphene is prepared
It is as a comparison sample to prepare microwave reduction graphene, preparation method is identical as above-mentioned steps (1)-(2), in step (2)
It is added without lithium salts.Following table is graphene oxide, the ratio table of microwave reduction graphene and lithium assisted microwave synthesis reduced graphene
The data summarizations table such as face.
Known in table: comparing graphene oxide, the ratio table of microwave reduction graphene and lithium assisted microwave synthesis reduced graphene
Area significantly increases, and respectively may be about four times and eight times of graphene oxide.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (5)
1. a kind of method that graphene oxide is peeled off in the reduction of lithium assisted microwave synthesis dilatometry, which comprises the following steps:
Lithium salts is dissolved in deionized water, is stirred evenly, after then graphene oxide powder and lithium salt solution are mixed evenly
It is ultrasonically treated 30min, the mixed solution after ultrasound is placed in vacuum drying oven drying, before obtaining lithium assisted microwave synthesis reduced graphene
Drive body；Then the grinding of lithium assisted microwave synthesis reduced graphene presoma is placed in corundum crucible with cover, is put into micro-wave oven
Vacuum pump is opened in storehouse, until microwave furnace pressure is -0.05MPa, is opened micro-wave oven cooling circulating water, is opened microwave switch, adjusts
Power is saved, in-furnace temperature is made to reach 200 DEG C；Microwave is closed after seeing the lid pop-up of corundum crucible by the visual windows of micro-wave oven
Switch after in-furnace temperature naturally cools to 50 DEG C, closes cooling circulating water, is passed through after nitrogen to furnace pressure restores to normal pressure and beats
Open the cabin door, obtains lithium assisted microwave synthesis reduced graphene.
2. a kind of method that graphene oxide is peeled off in the reduction of lithium assisted microwave synthesis dilatometry according to claim 1, special
Sign is that the temperature in the vacuum drying oven is 65 DEG C, drying time 12h.
3. a kind of method that graphene oxide is peeled off in the reduction of lithium assisted microwave synthesis dilatometry according to claim 1 or 2,
It is characterized in that, the mass ratio of the lithium salts and graphene oxide powder is 1:10.
4. a kind of method that graphene oxide is peeled off in the reduction of lithium assisted microwave synthesis dilatometry according to claim 1 or 2,
It is characterized in that, the lithium salts is lithium nitrate or lithium carbonate.
5. a kind of method that graphene oxide is peeled off in the reduction of lithium assisted microwave synthesis dilatometry according to claim 3, special
Sign is that the lithium salts is lithium nitrate or lithium carbonate.
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| CN201910539112.7A CN110282619B (en) | 2019-06-20 | 2019-06-20 | Method for reducing and peeling graphene oxide by lithium-assisted microwave thermal expansion method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111463028A (en) * | 2020-04-09 | 2020-07-28 | 陕西科技大学 | rGO-L iOH micro-spring/wood composite electrode material, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502611A (en) * | 2011-11-15 | 2012-06-20 | 东南大学 | Method for rapidly preparing graphene in large quantities by utilizing graphite oxides |
| CN108622887A (en) * | 2017-03-17 | 2018-10-09 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of swollen quick-fried method for preparing graphene of microwave |
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- 2019-06-20 CN CN201910539112.7A patent/CN110282619B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502611A (en) * | 2011-11-15 | 2012-06-20 | 东南大学 | Method for rapidly preparing graphene in large quantities by utilizing graphite oxides |
| CN108622887A (en) * | 2017-03-17 | 2018-10-09 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of swollen quick-fried method for preparing graphene of microwave |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111463028A (en) * | 2020-04-09 | 2020-07-28 | 陕西科技大学 | rGO-L iOH micro-spring/wood composite electrode material, and preparation method and application thereof |
| CN111463028B (en) * | 2020-04-09 | 2021-06-29 | 陕西科技大学 | rGO-LiOH micro-spring/wood composite electrode material and preparation method and application thereof |
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