CN109292757A - A kind of graphene and preparation method thereof - Google Patents
A kind of graphene and preparation method thereof Download PDFInfo
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- CN109292757A CN109292757A CN201811381707.6A CN201811381707A CN109292757A CN 109292757 A CN109292757 A CN 109292757A CN 201811381707 A CN201811381707 A CN 201811381707A CN 109292757 A CN109292757 A CN 109292757A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- 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
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- 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
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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
Abstract
The invention discloses a kind of graphenes and preparation method thereof, and the mixture of magnesium metal and magnesia is put into container；Under the protection of argon atmosphere, the temperature in container is risen to 400-900 DEG C with the heating rate of 1-15 DEG C/min, temperature is passed through CO into container after reaching peak2Gas；To vessel insulation 10-180min, stop being passed through CO later2Container is cooled to room temperature by gas under the protection of argon atmosphere, and black powder is made；Appropriate amount of acid is added in black powder, sufficiently after reaction, is sufficiently washed with deionized water to neutrality, graphene is made after drying.A kind of graphene of the present invention and preparation method thereof, using magnesium reduction process, is passed through CO in the mixture of magnesium metal and porous magnesia2Carry out high-temperature calcination, prepare high-specific surface area, high conductivity rich in mesoporous energy storage graphene.The advantages that present invention has process simple, and processing equipment requirement is low, and raw material sources are wide, and price is low, treatment process environmental sound, and can be realized industrialized production.
Description
Technical field
The present invention relates to electrode of super capacitor carbon material field, in particular to a kind of graphene and preparation method thereof.
Background technique
Graphene is a kind of individual layer laminated structure material being made of carbon atom, because of its high intensity, high heat conductance, highly conductive
The advantages that property and high-specific surface area, receives the extensive attention of researcher.Graphene Theory Conductivity is up to 106S/cm, theory are led
Hot property is up to 5300W/ (m K), while they have high specific surface area (- 103m2/ g magnitude), these properties show
Sp2 nano-sized carbon is a kind of excellent electrochemical energy storage materials, is expected to become battery and electrode material for super capacitor of new generation.Mesh
The preceding method for preparing graphene mainly has: micromechanics stripping method, redox chemistry stripping method, solvent-thermal method, outside plane of crystal
Epitaxial growth, surface of SiC graphitization method, chemical vapour deposition technique etc., however, existing method has what can not be mass produced to lack
Point, most common solvent-thermal method use natural graphite, potassium permanganate, and the concentrated sulfuric acid and concentrated nitric acid prepare graphene, have it is at high cost,
Aftertreatment technology is complicated and the problem of easily causing environmental pollution.
Summary of the invention
The object of the present invention is to provide a kind of graphene and preparation method thereof, process is simple, equipment requirement is low, being capable of scale
Change prepares graphene, graphene obtained specific surface area with higher and conductivity.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of graphene and preparation method thereof, comprising the following steps:
(1) mixture of magnesium metal and magnesia is put into container；
(2) under the protection of argon atmosphere, the temperature in the container is risen to by 400-900 with the heating rate of 1-15 DEG C/min
DEG C, temperature is passed through CO into the container after reaching peak2Gas；
(3) to the vessel insulation 10-180min, stop being passed through CO later2Gas will be described under the protection of argon atmosphere
Container is cooled to room temperature, and black powder is made；
(4) appropriate amount of acid is added in the black powder, sufficiently after reaction, is sufficiently washed with deionized water to neutrality, after drying
Graphene is made.
Preferably, the magnesia is porous magnesia.
It is highly preferred that the porous magnesia is to MgCO3•3H2In O, argon gas is passed through with the flow of 250ml/min, together
When MgCO heated with the rate of heat addition of 10 DEG C/min3•3H2O to 500 DEG C, and it is obtained after heat preservation 1 hour.
It is further preferred that the MgCO3•3H2O is the Na by 1mol/L2CO3The MgCl of solution and 1mol/L2Solution
After being mutually mixed reaction with the mass ratio of 1:1, with ethanol washing 3-5 times, after being dried in vacuum environment with 40-50 DEG C of temperature
It is obtained.
Preferably, the mixture of magnesium metal and magnesia, be by mass ratio be 1:8 magnesium metal and magnesia in mortar
Made from grinding after 10-40min.
Preferably, in the container, the flow for being passed through argon gas is 60-120ml/min；After temperature reaches peak, it is passed through
CO2Flow be 100-140ml/min, while the flow for being passed through argon gas is reduced into 40-60ml/min.
Preferably, the acid being added in the black powder is the hydrochloric acid of 1-3mol/L.
Preferably, it in step (4), is dried in vacuum oven with 25-40 DEG C of temperature.
A kind of graphene is made by above-mentioned preparation method.
Due to the application of the above technical scheme, compared with the prior art, the invention has the following advantages: a kind of stone of the present invention
Black alkene and preparation method thereof is passed through CO in the mixture of magnesium metal and porous magnesia using magnesium reduction process2Carry out high temperature
Calcining, prepare high-specific surface area, high conductivity rich in mesoporous energy storage graphene.The present invention has process simple, and processing is set
It is standby to require low, the advantages that raw material sources are wide, and price is low, treatment process environmental sound, and can be realized industrialized production.It solves
The existing method for preparing graphene can not be mass produced, is at high cost, aftertreatment technology is complicated and easily causes environmental pollution
Problem.
The present invention further has the advantage that
Compared with conventional chemical vapor deposition and the graphene preparation methods such as chemical stripping method, preparation method of the present invention is simple, at
Sheet is cheap, favorable reproducibility, is easy to apply；
The grapheme material of preparation has very high specific surface area, and specific surface area is up to 600-1500m2/g；
Graphene obtained is the excellent electrode material of supercapacitor, and conductivity is higher than 5000S/m, be used as lithium ion battery,
When the conductive material of lithium-air battery and other batteries, it is better than other conductive additives.
Detailed description of the invention
Attached drawing 1-4 is the scanning electron microscope (SEM) photograph of graphene made from embodiment 1.
Specific embodiment
Technical solution of the present invention is further elaborated below with reference to specific embodiment.
Embodiment 1
(1) by the Na of 100ml 1mol/L2CO3100ml 1mol/L MgCl is added in solution2In solution, after stirring 30min, filter out
Sediment and with ethanol washing 4 times, to completely remove Na+Ion；Product is put into vacuum oven, 40 DEG C at a temperature of
MgCO is made in drying3•3H2O。
(2) to MgCO3•3H2In O, argon gas is passed through with the flow of 250ml/min, while adding with the rate of heat addition of 10 DEG C/min
Hot MgCO3•3H2O to 500 DEG C, and after heat preservation 1 hour, porous magnesia is made.
(3) by porous magnesia obtained in magnesium metal and step (2) with the mass ratio of 1:8 the ground and mixed in mortar
It after 30min, is put into high temperature furnace, argon gas is passed through with the flow of 80ml/min, under the protection of argon atmosphere, with 5 DEG C/min liter
Warm rate rises to 650 DEG C；CO is passed through after temperature reaches 650 DEG C2Gas, CO2The flow of gas is 120ml/min, while by argon
The flow of gas reduces to 60ml/min；Then to vessel insulation 30min, stop being passed through CO later2Gas, in the protection of argon atmosphere
Under, it is cooled to room temperature, black powder is made in container.
(4) hydrochloric acid that 1mol/L is added in black powder obtained in step (3) measures solution sufficiently after reaction
PH value is 5；Sufficiently washed to neutrality, be put into vacuum oven with deionized water, 25 DEG C at a temperature of dry, be made graphite
Alkene.
It is the scanning electron microscope (SEM) photograph of porous graphene obtained in embodiment 1 referring to shown in Fig. 1-4.It can be apparent in Fig. 1
The whole figure pattern for finding out the graphene formed under magnesium oxide template by magnesium thermit, can be with after Fig. 2 and Fig. 3 amplification
Find out, graphene obtained has similar netted lamellar structure, forms biggish mesh, graphene between lamella interconnection
For lamella size in 1-5 microns, lamella edge is irregular, while having phenomena such as part curling.It can in Fig. 4 of amplification 80K
To observe that sheet surfaces have the Facial Features such as the apparent intraformational folding of graphene.
Embodiment 2
(1) by the Na of 100ml 1mol/L2CO3100ml 1mol/L MgCl is added in solution2In solution, after stirring 50min, filter out
Sediment and with ethanol washing 4 times, to completely remove Na+Ion；Product is put into vacuum oven, 50 DEG C at a temperature of
MgCO is made in drying3•3H2O。
(2) to MgCO3•3H2In O, argon gas is passed through with the flow of 250ml/min, while adding with the rate of heat addition of 10 DEG C/min
Hot MgCO3•3H2O to 500 DEG C, and after heat preservation 1 hour, porous magnesia is made.
(3) by porous magnesia obtained in magnesium metal and step (2) with the mass ratio of 1:8 the ground and mixed in mortar
It after 40min, is put into high temperature furnace, argon gas is passed through with the flow of 60ml/min, under the protection of argon atmosphere, with 3 DEG C/min liter
Warm rate rises to 750 DEG C；CO is passed through after temperature reaches 750 DEG C2Gas, CO2The flow of gas is 100ml/min, while by argon
The flow of gas reduces to 50ml/min；Then to vessel insulation 40min, stop being passed through CO later2Gas, in the protection of argon atmosphere
Under, it is cooled to room temperature, black powder is made in container.
(4) hydrochloric acid that 3mol/L is added in black powder obtained in step (3) measures solution sufficiently after reaction
PH value is 3；Sufficiently washed to neutrality, be put into vacuum oven with deionized water, 40 DEG C at a temperature of dry, be made graphite
Alkene.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand the contents of the present invention and be implemented, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the scope of protection of the present invention.
Claims (9)
1. a kind of graphene and preparation method thereof, it is characterised in that: the following steps are included:
(1) mixture of magnesium metal and magnesia is put into container；
(2) under the protection of argon atmosphere, the temperature in the container is risen to by 400-900 with the heating rate of 1-15 DEG C/min
DEG C, temperature is passed through CO into the container after reaching peak2Gas；
(3) to the vessel insulation 10-180min, stop being passed through CO later2Gas, under the protection of argon atmosphere, by the appearance
Device is cooled to room temperature, and black powder is made；
(4) appropriate amount of acid is added in the black powder, sufficiently after reaction, is sufficiently washed with deionized water to neutrality, after drying
Graphene is made.
2. a kind of graphene according to claim 1 and preparation method thereof, it is characterised in that: the magnesia is porous oxygen
Change magnesium.
3. a kind of graphene according to claim 2 and preparation method thereof, it is characterised in that: the porous magnesia be by
To MgCO3•3H2In O, argon gas is passed through with the flow of 250ml/min, while MgCO is heated with the rate of heat addition of 10 DEG C/min3•
3H2O to 500 DEG C, and it is obtained after heat preservation 1 hour.
4. a kind of graphene according to claim 3 and preparation method thereof, it is characterised in that: the MgCO3•3H2O be by
The Na of 1mol/L2CO3The MgCl of solution and 1mol/L2After solution is mutually mixed reaction with the mass ratio of 1:1, with ethanol washing 3-5
It is secondary, with obtained after 40-50 DEG C of temperature drying in vacuum environment.
5. a kind of graphene according to claim 1 and preparation method thereof, it is characterised in that: magnesium metal and magnesia it is mixed
Object is closed, is obtained after grinding 10-40min in mortar by magnesium metal and magnesia that mass ratio is 1:8.
6. a kind of graphene according to claim 1 and preparation method thereof, it is characterised in that: in the container, be passed through argon
The flow of gas is 60-120ml/min；After temperature reaches peak, it is passed through CO2Flow be 100-140ml/min, while will lead to
The flow for entering argon gas reduces to 40-60ml/min.
7. a kind of graphene according to claim 1 and preparation method thereof, it is characterised in that: add in the black powder
The acid entered is the hydrochloric acid of 1-3mol/L.
8. a kind of graphene according to claim 1 and preparation method thereof, it is characterised in that: dry in vacuum in step (4)
Dry case is dried with 25-40 DEG C of temperature.
9. a kind of graphene is made by preparation method of any of claims 1-8.
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Cited By (3)
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| CN109835884A (en) * | 2019-03-27 | 2019-06-04 | 王奉瑾 | A method of graphene is prepared using liquid metal alkali |
| CN110817839A (en) * | 2019-12-06 | 2020-02-21 | 华南师范大学 | Method for reducing carbon dioxide into porous carbon material, porous carbon material and application |
| CN111003704A (en) * | 2019-12-20 | 2020-04-14 | 上海昱瓴新能源科技有限公司 | Preparation method and application of three-dimensional graphene lithium ion battery ultra-fast charging negative electrode material |
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| CN109835884A (en) * | 2019-03-27 | 2019-06-04 | 王奉瑾 | A method of graphene is prepared using liquid metal alkali |
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| CN110817839A (en) * | 2019-12-06 | 2020-02-21 | 华南师范大学 | Method for reducing carbon dioxide into porous carbon material, porous carbon material and application |
| CN110817839B (en) * | 2019-12-06 | 2021-10-08 | 华南师范大学 | Method for reducing carbon dioxide into porous carbon material, porous carbon material and application |
| CN111003704A (en) * | 2019-12-20 | 2020-04-14 | 上海昱瓴新能源科技有限公司 | Preparation method and application of three-dimensional graphene lithium ion battery ultra-fast charging negative electrode material |
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