CN108101034A - A kind of device and method using microwave irradiation one-step method volume production graphene - Google Patents
A kind of device and method using microwave irradiation one-step method volume production graphene Download PDFInfo
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- CN108101034A CN108101034A CN201810050713.7A CN201810050713A CN108101034A CN 108101034 A CN108101034 A CN 108101034A CN 201810050713 A CN201810050713 A CN 201810050713A CN 108101034 A CN108101034 A CN 108101034A
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- reaction kettle
- graphite
- intercalator
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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
- C01B2204/02—Single layer graphene
Abstract
A kind of device and method using microwave irradiation one-step method volume production graphene, the equipment include reaction kettle, and kettle top is provided with microwave source, and the microwave source is connected with waveguide assembly and the waveguide assembly is extended into reaction kettle.The present invention only needs to select a kind of use in having the function of the oxidant seriously polluted or intercalator and the related intercalation of oxidation can be realized, significantly ambient pollution burden, and the oxidants such as relatively environment-friendly ferrate or intercalator can be chosen, technical process is pressurizeed without heating, the step of eliminating pretreatment, oxidation, intercalation, stripping, which include reducing, (one pot) of a step to be completed in a kettle, total time-consuming only needs 30min to one hours or so, energy charge is few, it is time saving and safe, realize a kind of process and equipment of environmentally friendly, safe and efficient volume production graphene.
Description
Technical field
The present invention relates to field of preparation of graphene, are specifically related to a kind of side of environmentally friendly, safe and efficient volume production graphene
Method and its equipment.
Background technology
Graphene has perfect two dimensional crystal structure, its lattice is the hexagon surrounded by six carbon atoms, thickness
For an atomic layer.By σ key connections between carbon atom, combination is sp2 hydridization, and it is extremely excellent that these σ keys impart graphene
Different mechanical property and structural rigidity.The hardness of graphene is 100 times or even to be also more than diamond stronger than best steel.In stone
In black alkene, there are one the p electronics of non-bonding, these p electronics can move freely each carbon atom in crystal, and move speed
Degree is up to the 1/300 of the light velocity, imparts the good electric conductivity of graphene.Graphene is the transparent conductive material of a new generation, can
Jian Guang areas, the transmitance of four layer graphenes is suitable with traditional ito thin film, and in other wave bands, the transmitance of four layer graphenes is remote
Far above ito thin film.
Graphene is the nano material that known world is most thin, most hard, it is almost fully transparent, is only absorbed
2.3% light；Thermal conductivity factor is up to 5300W/mK, and higher than carbon nanotubes and diamond, its electron mobility is more than under room temperature
15000cm2/Vs, but it is higher than carbon nanotubes or silicon crystal, and about 1 Ω m of resistivity, it is lower than copper or silver, for electricity in the world
The material of resistance rate minimum.Because its resistivity is extremely low, the speed of electron transfer is exceedingly fast, thus be expected to can be used to develop it is thinner, lead
Electric speed of new generation electronic component or transistor faster.Since graphene is substantially a kind of transparent, good conductor, also fit
It shares to manufacture transparent touch screen, even tabula rasa, solar cell.
The scientific circles that appear in of graphene have evoked huge great waves.It has been found that graphene has unusual lead
Electrical property, intensity and fabulous translucency beyond steel decades of times, its appearance are expected to trigger in hyundai electronics sciemtifec and technical sphere
One wheel revolution.In graphene, electronics can be migrated extremely efficiently, and traditional semiconductor and conductor, for example, silicon and copper it is remote
There is no graphene show must well.Due to the collision of electronics and atom, traditional semiconductor and conductor release one with the form of heat
A little energy, general computer chip wastes the electric energy of 72%-81% in this way within 2013, and graphene is then different, it
Electron energy will not be depleted, this makes it be provided with extraordinary good characteristic.
The performance of graphene uniqueness is closely related with its electronic band structure.It is using independent carbon atom as base, surrounding carbon is former
The gesture that son generates can calculate the energy level distribution of graphene as perturbation with the method for matrix.In dirac point (Dirac
Point) nearby it is unfolded, energy can be obtained and wave vector is (dispersion relation for being similar to photon) in a linear relationship, and pointed out in dirac
Existing singular point (singularity).This means near Fermi surface, the effective mass of electronics is zero in graphene, this is also explained
The properties such as the electricity of material uniqueness.
Due to the above-mentioned unusual calorifics of graphene, mechanics, electricity, the outstanding properties of Chemical Physics and fabulous steady
It is qualitative, therefore the method for preparing graphene becomes the emphasis studied in the industry.However, it is existing production graphene method, have with
Lower shortcoming：
1st, using PVD, CVD the methods of, yield is small, investment is big, condition is high.
2nd, chemical oxidization method need to be used to strong oxidizer and intercalator (KMnO4、H2SO4、HNO3Deng), heavy metal etc., meeting
Serious environmental pressure is caused, often produces 1T products, the backwash waste of 10T can be generated.Meanwhile HNO3Wait substances that can also bring quick-fried
Fried danger.
3rd, pre-processed, such as the technology that Zhejiang University is superb et al., with strong acid (H2SO4, HNO3) intercalator is used as,
Oxidation removes graphite, it is necessary to pre-process at low temperature for 24 hours.
Therefore, there are still the shortcomings that effective percentage is low, pollution is big, time-consuming, danger coefficient is high for existing method.
The content of the invention
To solve the above-mentioned problems, the present invention provides a kind of quick, environmental protection, the industrial scale of safe volume production graphene
Production method.
Technical solution of the present invention is as follows：
A kind of equipment using microwave irradiation one-step method volume production graphene, it is characterised in that including reaction kettle, the reaction
The kettle top of kettle is provided with microwave source, and the microwave source is connected with waveguide assembly and the waveguide assembly is extended into reaction kettle；Institute
State reaction kettle connection oxidant or the conveying device of intercalator and graphite.
The preferred microwave source is 2450Hz or 915Hz.
Preferred waveguide assembly gos deep into the depth of reaction kettle 1/2 to 4/5.
The preferred reaction kettle accommodates 0.5-1.5t raw materials, and reaction kettle material is enamel.
Further, the reaction kettle also connects accelerating agent and catalyst conveying device.
The reaction kettle further includes blender.
The conveying device of the oxidant or intercalator and graphite include the container of oxidant or intercalator, crystal vessel with
And the pipeline of the reaction kettle is led in the pre-mixing apparatus of two containers of connection, pre-mixing apparatus outlet connection.
Further include control microwave source and each device startup, the control device of end and operating parameter.
A kind of method using microwave irradiation one-step method volume production graphene, it is characterised in that using above equipment, first will
One of oxidant or intercalator are mixed into suspension with graphite, and then selectable addition oxidation catalyst and stripping promotes
Agent under normal temperature and pressure microwave irradiation, carries out oxidation intercalation and stripping, graphene oxide is made.
Further, after graphene oxide being made, the NMP of 3-5mg/ml is added, using microwave reduction into graphene.
The preferred oxidant is ferric acid salt or hydrogen peroxide.
The preferred intercalator is H2SO4, HNO3, FeCl3Or P2O5Middle one or more.
The amount of graphite is 5-15mg/ liters in the preferred suspension, and the amount of the oxidant or intercalator is graphite
3-10%.
The graphite is preferably the crystalline flake graphite or Delanium of 325 mesh.
The oxidation catalyst is rare earth or rare earth oxide such as cerium, and the stripping accelerating agent is naphthalene or naphthalene derivatives
Such as Kun, respective amount are the 0.5-1% of the quality of graphite raw material.
In the production of existing graphene, according to theoretical research and common cognition, using first aoxidized, intercalation, so
The means further removed afterwards not only need the oxidant and intercalator of substantial amounts of high pollution, but also need prolonged
Oxidation, intercalation pretreatment could carry out high temperature stripping.The present invention passes through the study found that due to existing in graphite microstructure itself
The active site of irregular structure in fact, in the presence of small amounts agent or intercalator, directly gives microwave irradiation,
Response can be generated by microwave irradiation as dipole because of active site, quick initiated oxidation intercalation further can be realized
It removes, so as to which the oxidation intercalation for simply realizing graphite to individual layer or few layer graphene oxide adds stripping process, on the one hand distinguishes
It is required in both existing oxidant and intercalator and prolonged pretreating process mode, the use of heavily contaminated substance significantly subtracts
It is few；Moreover, by microwave irradiation, the interior oxidation occurred of kettle, intercalation, stripping can be realized at normal temperatures and pressures, without external pressurized
Power and temperature.Further, the oxidant of selection and intercalator can be relatively environment-friendly type.
In general, the present invention has started in existing common oxidant and intercalator that only need to select a kind of use can be micro-
Amplitude can further choose the oxygen such as relatively environment-friendly ferrate according to the lower effect for realizing and aoxidizing related intercalation and finally removing
The step of ambient pollution burden is greatly decreased in agent or intercalator, and technical process pressurizes without heating, eliminates pretreatment, oxygen
Change, intercalation, stripping, which include reducing, (one pot) completion of a step, total time-consuming only to need 30min to one hours or so in a kettle, energy
Amount expends less, time saving and safe, realizes a kind of process and equipment of environmentally friendly, safe and efficient volume production graphene.It can add
The stripping accelerating agent chosen and oxidation catalyst of the invention is added further to promote preparation efficiency.In further reduction process
In, NMP dielectric constants are high, can preferentially be heated under microwave, generate reduction.
Description of the drawings
Fig. 1 is equipment schematic diagram of the embodiment of the present invention.
Each label lists as follows in figure：
1- reaction kettles, 2- waveguide assemblies, 3- suspensions, 4- control devices, 5- pre-mixing apparatus, 6- oxidants or intercalator
Container, 7- crystal vessels, 8- promote agent container, 9- catalyst containers；
M- blenders, A- microwave sources A, B- microwave source B.
Specific embodiment
In order to be better understood from the present invention, the present invention is further explained with reference to embodiment.
Embodiment 1
As shown in Figure 1, the equipment of the present embodiment includes reaction kettle 1,1t raw materials can be accommodated, 1 material of reaction kettle is enamel.Institute
The kettle top for stating reaction kettle is provided with microwave source A and microwave source B, is connected to waveguide assembly 2 and the waveguide assembly 2 extends into
1/2 height in reaction kettle 1；The reaction kettle 1 connects oxidant or the conveying device of intercalator and graphite, wherein the oxidation
The conveying device of agent or intercalator and graphite includes two container 6 of oxidant or intercalator, crystal vessel 7 and connection containers
Pre-mixing apparatus 5, the pre-mixing apparatus 5 outlet connection leads to the pipeline of the reaction kettle 1.The reaction kettle 1 also connects promotion
Agent container 8 and catalyst container 9.
The present embodiment further includes control microwave source and each device startup, the control device 4 of end and operating parameter.Specific fortune
During row, metering device and microwave irradiation reaction kettle 1 are subjected to raw antenatal exaination first, in order.By oxidant or intercalator
Container 6 in potassium ferrate oxidizing agent solution and the 250-450 mesh in crystal vessel 7 natural flake graphite first loading in mixture in advance
It puts in 5 and simply premixes, be then delivered in reaction kettle 1 and suspension 3 is mixed and made into deionized water, the amount of graphite in suspension 3
For 10mg/ liters, the amount of the potassium ferrate oxidant is the 3% of graphite, then is separately added into the cerium of graphite quality 0.5%
And naphthalene, start microwave source A and microwave source B, frequency 2450Hz, be placed in 900W power outputs 30min and individual layer oxygen is made
Graphite alkene.
Embodiment 2
Graphene oxide is prepared first, and for preparation process with embodiment 1, intercalator uses active principle as graphite quality
10% FeCl3, catalyst is the lanthana of graphite quality 1%, removes the anthracene that accelerating agent is graphite quality 1%.Then to anti-
The NMP that 4mg/ml is added in kettle 1 is answered, restarts microwave irradiation 1000W, is further existed using the selection heating mechanism of microwave
Single-layer graphene is reduced in 30min.
Embodiment 3
The present embodiment oxidant uses 5% hydrogen peroxide of the active principle for graphite quality, and catalyst is graphite quality 1%
Cerium oxide, remove accelerating agent be graphite quality 0.5% naphthalene, other steps are the same as embodiment 1 or 2.
Embodiment 4
Difference lies in the container not including accelerating agent and catalyst still can be small in 1-2 for the present embodiment and previous embodiment
When or so obtain product.
The foregoing is merely the preferable specific embodiment of the present invention, but protection scope of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in
Deng, such as the finely tuning of reactor volume, raw material additive amount, different oxidants or intercalator, other similar catalyst and rush
Into the replacement of agent and other feedstock transportations, storage and control device etc., should be covered by the protection scope of the present invention.Cause
This, protection scope of the present invention should be subject to the protection domain of claims.
Claims (10)
1. a kind of equipment using microwave irradiation one-step method volume production graphene, it is characterised in that including reaction kettle, the reaction kettle
Kettle top be provided with microwave source, the microwave source is connected with waveguide assembly and the waveguide assembly is extended into reaction kettle；It is described
Reaction kettle connects oxidant or the conveying device of intercalator and graphite.
2. equipment according to claim 1, it is characterised in that the microwave source is 2450Hz or 915Hz.
3. equipment according to claim 1, it is characterised in that the waveguide assembly gos deep into the depth of reaction kettle 1/2 to 4/5.
4. equipment according to claim 1, it is characterised in that the reaction kettle accommodates 0.5-1.5t raw materials, reaction kettle material
For enamel.
A kind of 5. method using microwave irradiation one-step method volume production graphene, it is characterised in that using any institutes of claim 1-4
Equipment is stated, one of oxidant or intercalator and graphite are mixed into suspension first, under normal temperature and pressure microwave irradiation, carries out oxygen
Change intercalation and stripping, graphene oxide is made.
6. according to the method described in claim 5, it is characterized in that after graphene oxide is made, NMP is added, using microwave also
Original is into graphene.
7. according to the method described in claim 5, it is characterized in that the oxidant or intercalator are ferric acid salt, dioxygen
Water, H2SO4, HNO3, FeCl3Or P2O5Middle one or more.
8. according to the method described in claim 5, it is characterized in that the amount of graphite is 5-15mg/ liter in the suspension, institute
The amount for stating oxidant or intercalator is the 3-10% of graphite.
9. according to the method described in claim 5, it is characterized in that the graphite is the crystalline flake graphite or artificial stone of 250-450 mesh
Ink.
10. according to the method described in claim 5, it is characterized in that oxidation catalyst is added in before microwave irradiation and removes promotion
Agent, the oxidation catalyst are rare earth or rare earth oxide, and the stripping accelerating agent is naphthalene or naphthalene derivatives, and respective amount is
The 0.5-1% of the quality of graphite raw material.
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| CN201810050713.7A CN108101034A (en) | 2018-01-18 | 2018-01-18 | A kind of device and method using microwave irradiation one-step method volume production graphene |
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| CN109336097A (en) * | 2018-09-07 | 2019-02-15 | 北京若水金枫科技有限公司 | A kind of preparation method and mass production device of graphene |
| CN113307259A (en) * | 2021-04-26 | 2021-08-27 | 高碑店市隆泰丰博石墨烯有限公司 | Microwave one-step dry-method graphene oxide mass production process |
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