CN107986267A - The method and its heating furnace that a kind of redox graphene powder upgrading is modified - Google Patents
The method and its heating furnace that a kind of redox graphene powder upgrading is modified Download PDFInfo
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- CN107986267A CN107986267A CN201711120982.8A CN201711120982A CN107986267A CN 107986267 A CN107986267 A CN 107986267A CN 201711120982 A CN201711120982 A CN 201711120982A CN 107986267 A CN107986267 A CN 107986267A
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Abstract
The present invention relates to technical field of graphene, more specifically, is related to method and its heating furnace that a kind of redox graphene powder upgrading is modified.Thermal reduction reformation is carried out to redox graphene using fluidized bed reaction method, continue redox graphene manufacturing process route, with reference to graphene sheet layer fault location under CVD deposition technology and high temperature, there are the characteristics of avtive spot, defect mending and reconstruction processing are carried out to redox graphene, the integrality of its molecule crystallographic texture is improved, and then improves its thermal conductivity characteristic.The heating furnace includes furnace body and the inner tube with sieve, said inner tube is arranged in furnace body, heating unit is equipped between the furnace body and inner tube, said inner tube one end is communicated with gas exhaust piping, the inner tube other end is communicated with air inlet pipeline, the air inlet pipeline is equipped with air inlet, and the gas exhaust piping is equipped with air bleeding valve and vacuum pump.Technical method technique provided by the invention is simple, has larger industrialization promotion potentiality.
Description
Technical field
The present invention relates to technical field of graphene, more specifically, is related to a kind of redox graphene powder upgrading and changes
The method and its heating furnace of property.
Background technology
Graphene has excellent electricity, optics, physics, chemistry and architectural characteristic, has a wide range of applications.Especially
It is the quasi- two-dimensional structure and the big pi bond of delocalization of six membered ring, its perfect cystal is possessed the electron transfer of up to 20000cm/ (Vs)
The room temperature plane thermal conductivity of rate and more than 5000W/mK, has high application value in thermoelectricity functional material.To current
Untill, common graphene preparation method has mechanical stripping method, chemical vapour deposition technique, silicon carbide epitaxial growth method, liquid phase stripping
From graphite method, graphene oxide reduction method.But for the use in practice, it inexpensive, large-scale can prepare high-quality
Graphene is vital.In these methods, graphene oxide reduction method has that production cost is low, extensive preparation letter
Singly, the characteristics of yield is high, is a kind of effective ways for substantially meeting above-mentioned requirements.Graphene oxide reduction method is natural scale stone
Ink is by Hummer, and the methods of Brodie, Staudenmaier synthesizes graphite oxide on a large scale, then through high temperature puffing or ultrasound
Graphene oxide is made in stripping, then obtains redox graphene powder or slurry through electronation.
Preparing graphene oxide restoring method at present mainly includes chemical reduction method, high-energy ray radiation method, solvent heat
Reduction method etc..As patent CN201510073801.5 disclose it is a kind of be catalyzed redox graphene method, first based on oxidation
The salting-out effect of graphene, metal salt solution is added in graphene oxide water solution, is formed cotton-shaped suspended matter, is then added
NH3BH3, at room temperature NH is catalyzed using the metallic particles restored3BH3Hydrolysis is so as in surface of graphene oxide release
Go out the nascent hydrogen atom with high reproducibility, by hydrogen atom come redox graphene, this chemical reduction method method technique
Simply, chemical reagent of low cost, but being used during chemical reduction method, such as ammonia borine, hydrazine hydrate, sodium borohydride, benzene
Hydrazine and hydroquinone etc., easily produce serious environmental pollution.Patent CN201610412825.3 discloses a kind of hydrophobe
The preparation method of the controllable redox graphene of property, the controllable reduction-oxidation graphite of hydrophobe is prepared using solvent thermal reaction
Alkene slurry, this solvothermal method prepares process environment close friend, green high-efficient, without adding any reducing agent, but to reality
It is stringent to test condition requirement, it is impossible to realize industrialization and continuous production.Patent CN201710218841.3 discloses a kind of triggering
The preparation method of the microwave radiation technology high-quality redox graphene of mode utilizes redox graphene, Graphene powder or iron
Cobalt nickel etc.Race's metal etc. triggers material and graphene oxide thin layer together, under conditions of microwave radiation, through triggering agent and
The collective effect of microwave, is reduced graphene oxide, and this high-energy ray radiation is stringent to experiment condition requirement, and can limit
The size and uniformity of sample.Patent CN201610599766.5 discloses the side that a kind of one-step method prepares redox graphene
Method, will be directly added into metal reduction reaction in graphene oxide slurry, in same reactor a step realize from crystalline flake graphite to
The preparation of redox graphene, although this high-temperature hydrogen reduction method will not pollute environment, this process must
It must carry out under the high temperature conditions.
The common initiating process prepared as redox graphene is that intercalation product made of natural flake graphite aoxidizes
Graphite.The reaction can to inside graphite six membered ring structure produce oxidation, by-C=C- double bonds be oxidized to epoxy-functional,
Carbonyl and carboxyl.The former makes double bond become single key structure through reducing hydrogenation, and the latter is directly broken double bond, and then six membered ring structure
Destroyed with big pi bond, destroyed the microstructure that graphene sheet layer realizes super-high heat-conductive electric conductivity, reduce its performance
Index.The above problem is that all redox graphene syntheti c routes can not avoid, and the improvement in all disclosed patents is equal
In terms of concentrating on the efficiency of restoring method and the raising of reducing degree, the quantity of control oxygen-containing functional group is only capable of, can not be effectively
Remove the oxygen-containing functional group that graphene oxide contains, while the six membered ring knot inside the graphene sheet layer to being produced by oxidizing process
Structure destruction is helpless, can not repair singly-bound and double bond fracture defect caused by initially oxidation intercalation.
The content of the invention
In the presence of overcoming the shortcomings of the prior art, the present invention provides a kind of redox graphene powder upgrading and changes
The method and its heating furnace of property, solve presently commercially available redox graphene material structure defect is more, thermal conductivity is low etc.
Problem.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
Redox graphene powder, is added the inner tube of heating furnace by a kind of method that redox graphene powder upgrading is modified
In, argon gas 20-60min is passed through into the inner tube of heating furnace under normal pressure to replace inner air, keeps normal in inner tube after displacement
Pressure, can improve replacement result by vacuumizing the method for applying argon gas if necessary.
Heating furnace starts to warm up while is passed through argon gas；When furnace temperature reaches 400 DEG C, kept the temperature；Be passed through after insulation argon gas and
Hydrogen mixed gas stream, while 750 DEG C are warming up to the speed of 5-20 DEG C/min, kept the temperature；Be passed through after insulation argon gas, hydrogen and
Methane mixed gas, duration of ventilation 10-90min, is then shut off hydrogen and methane gas, retains argon gas to stablize shape of the material in stove
State；
Material is heated to 1000 DEG C in argon gas with the programming rate of 5-10 DEG C/min, keeps the temperature 40min, is then protected in inert gas
The lower Temperature fall of shield obtains the graphene powder after upgrading processing to room temperature.
The redox graphene powder refers to graphene oxide material after reduction treatment, micro- by a diameter of 5-30
The form the few-layer graphene alkene composition of rice, wherein the graphene less than 3 layers is more than 90%；Diameter is more than 10 in redox graphene powder
The material of micron is more than 70%, its real density is about 1.06g/cm3。
The purity requirement of the argon gas, hydrogen, methane is more than 99.99%；Volume ratio between argon gas and hydrogen mixed gas
For 70：10-30, the volume ratio between argon gas, hydrogen and methane mixed gas are 30-50：20-40：10-30.
The CVD reaction time using the oxygen content in redox graphene as with reference to index, according to 1g oxygen atoms 1600-
The normal pressure methane throughput setting of 2000ml, you can ensure to obtain thermal conductivity compared with the preferable graphite ene product of performance.
The heating furnace includes furnace body and the inner tube with sieve, said inner tube and is arranged in furnace body, the furnace body with it is interior
Be equipped with heating unit between pipe, said inner tube one end is communicated with gas exhaust piping, and the inner tube other end is communicated with air inlet pipeline, it is described into
Air pipe is equipped with air inlet, and the gas exhaust piping is equipped with air bleeding valve and vacuum pump.
The sieve has two, and is arranged in inner tube, and the sieve is 300 mesh high temperature resistant sieves.
Said inner tube is quartz glass inner tube or corundum inner tube.
Temperature thermocouple is equipped with said inner tube, easy to understand and control temperature in inner tube.
Said inner tube is connected with gas exhaust piping and air inlet pipeline respectively by sealing block, and inner tube removes air inlet pipeline and exhaust pipe
Sealed outside road to keep air-tightness.
The heating furnace can set microwave to heat by microwave radiation technology or plasma asistance in air inlet and material lower floor position
Or plasma heating device.
Compared with prior art, the advantageous effect of present invention is that：
The method and its heating furnace that a kind of redox graphene powder upgrading of the present invention is modified, utilize fluidized bed reaction method pair
Redox graphene carries out thermal reduction reformation, continues the process route of graphite oxide-high temperature puffing-high-temperature hydrogen reduction,
With reference to graphene sheet layer fault location under CVD deposition technology and high temperature there are the characteristics of avtive spot, to the oxygen of high-temperature hydrogen reduction
Graphite alkene carries out defect mending processing by CVD reactivities carbon atom, and the graphene powder defect after processing is decreased obviously,
Oxygen-containing functional group hydroxyl and carbonyl significantly decline.The present invention makes graphite by the reactant state of vertical heater and control boiling-like
Alkene is not susceptible to bonding for lamella during CVD and grows carbon distribution；Make oxygen reduction fossil by using carbon atom thermal activation principle
Black alkene produces reactivity site in defective locations, is then reacted using CVD, the active atoms of carbon of pyrolysis is deposited in active sites
To reduce the fault of construction of graphene, its thermoelectricity capability is improved；Pyroprocess after being reacted by CVD, further promotes pyrolysis
The graphitization of carbon is reset, and improves molecule crystallographic texture integrality；Can when industrializing and amplifying by reacting high temperature inert gas
To be recycled, to reduce energy consumption and cost.Present invention process is simple, equipment disposal ability is strong, is easy to implement work
Industry is amplified and continuous production is transformed, duty parameter is easily controllable.
Brief description of the drawings
Fig. 1 is the structure diagram of heating furnace of the present invention；
Wherein：1 is furnace body, and 2 be sieve, and 3 be inner tube, and 4 be heating unit, and 5 be gas exhaust piping, and 6 be air inlet pipeline, and 7 be air inlet
Mouthful, 8 be air bleeding valve, and 9 be vacuum pump, and 10 be sealing block, and 11 be temperature thermocouple.
Embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work
Embodiment, belongs to the scope of protection of the invention.
A kind of method that redox graphene powder upgrading is modified, using fluidized bed reaction method to reduction-oxidation graphite
Alkene carries out thermal reduction reformation.Redox graphene powder is added in the inner tube of heating furnace, under normal pressure into heating furnace
Argon gas 20-60min is passed through in pipe to replace inner air, normal pressure is kept in inner tube after displacement；Heating furnace is with 0.5-5 DEG C/min's
Speed starts to warm up, while is passed through argon gas with the flow of 30-100ml/min, material is kept pico- boiling sample tumbling state；Stove
When temperature reaches 400 DEG C, insulation 30min is carried out；Argon gas and hydrogen mixed gas stream are passed through after insulation, while with the speed of 5-20 DEG C/min
Degree is warming up to 750 DEG C, carries out insulation 10min；Argon gas, hydrogen and methane blended are passed through with the flow of 25-40ml/min after insulation
Gas, duration of ventilation 10-90min, is then shut off hydrogen and methane gas, retains argon gas to stablize state of the material in stove；Material
1000 DEG C are heated to the programming rate of 5-10 DEG C/min in argon gas, keeps the temperature 40min, it is then natural under inert gas shielding
Cool to room temperature and obtain the graphene powder after upgrading processing.
The redox graphene powder refers to graphene oxide material after reduction treatment, micro- by a diameter of 5-30
The form the few-layer graphene alkene composition of rice, wherein the graphene less than 3 layers is more than 90%；Diameter is more than 10 in redox graphene powder
The material of micron is more than 70%, its real density is about 1.06g/cm3。
In the present embodiment, the purity requirement of the argon gas, hydrogen, methane is more than 99.99%；Argon gas is mixed with hydrogen
Volume ratio between gas is 70：10-30, the volume ratio between argon gas, hydrogen and methane mixed gas are 30-50：20-40：10-
30。
In the present embodiment, the CVD reaction time is using the oxygen content in redox graphene as with reference to index, according to
The normal pressure methane throughput setting of 1g oxygen atoms 1600-2000ml, it is ensured that obtain thermal conductivity compared with the preferable graphene of performance
Product.
As shown in Figure 1, the heating furnace that a kind of redox graphene powder upgrading is modified includes furnace body 1 and with sieve 2
Inner tube 3, said inner tube 3 is arranged in furnace body 1, and heating unit 4, said inner tube 3 one are equipped between the furnace body 1 and inner tube 3
End is communicated with gas exhaust piping 5, and 3 other end of inner tube is communicated with air inlet pipeline 6, and the air inlet pipeline 6 is equipped with three air inlets 7,
Each air inlet 7 is connected with air inlet pipeline 6.The gas exhaust piping 5 is equipped with air bleeding valve 8 and vacuum pump 9.
In the present embodiment, the sieve 2 has two, and is arranged in inner tube 3, and the sieve 2 is the resistance to height of 300 purposes
Warm sieve,
In the present embodiment, said inner tube 3 is quartz glass inner tube or corundum inner tube, inner tube diameter 40mm.
In the present embodiment, temperature thermocouple 11 is equipped with said inner tube 3, easy to understand and control temperature in inner tube 3.Can
To use temperature controller in the prior art, temperature controller is connected with temperature thermocouple 11 and heating unit 4, so that according to
Temperature control heating unit 4.Heating unit 4 can use the existing components such as heating tape.
In the present embodiment, said inner tube 3 is connected with gas exhaust piping 5 and air inlet pipeline 6 respectively by sealing block 10, inner tube
3 seal to keep air-tightness in addition to gas exhaust piping 5 and air inlet pipeline 6.
In the present embodiment, the heating furnace can be by microwave radiation technology or plasma asistance, in air inlet and material lower floor
Position sets microwave heating or plasma heating device.It can promote the decomposition and activation of methane, improve oxygen-containing official on graphene
Removal efficiency and CVD deposition efficiency can be rolled into a ball.
In the present embodiment, sample draws the oxygen-containing function in graphene powder after processing before and after the processing for infrared spectrum analysis
Group's hydroxyl and carbonyl significantly decline；Raman spectrum analysis sample before and after the processing, graphene powder G peaks become and come to a point by force after processing
It is sharp, illustrate that graphene defect is decreased obviously；Graphene powder tabletting（φ 20mm, thickness 0.2mm, density 2.05g/cm3）Side
Block resistance value drops to 42-500m Ω/ from 3-10 Ω/；25 DEG C of test temperature, specific heat capacity 0.75, the thermal conductivity factor of tabletting
480W/mK is increased to from 240W/mK
Only presently preferred embodiments of the present invention is explained in detail above, but the present invention is not limited to above-described embodiment, at this
In the knowledge that field those of ordinary skill possesses, various changes can also be made on the premise of present inventive concept is not departed from
Change, various change should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of method that redox graphene powder upgrading is modified, it is characterised in that add redox graphene powder
In the inner tube for entering heating furnace, argon gas 20-60min is passed through into the inner tube of heating furnace under normal pressure to replace inner air, is replaced
Afterwards normal pressure is kept in inner tube；
Heating furnace starts to warm up while is passed through argon gas；When furnace temperature reaches 400 DEG C, kept the temperature；Argon gas and hydrogen are passed through after insulation
Mixed airflow, while 750 DEG C are warming up to the speed of 5-20 DEG C/min, kept the temperature；Argon gas, hydrogen and methane are passed through after insulation
Gaseous mixture, duration of ventilation 10-90min, is then shut off hydrogen and methane gas, retains argon gas to stablize state of the material in stove；
Material is heated to 1000 DEG C in argon gas with the programming rate of 5-10 DEG C/min, keeps the temperature 40min, is then protected in inert gas
The lower Temperature fall of shield obtains the graphene powder after upgrading processing to room temperature.
2. the method that a kind of redox graphene powder upgrading according to claim 1 is modified, it is characterised in that described
Redox graphene powder refers to graphene oxide material after reduction treatment, by form the few-layer graphene 5-30 microns a diameter of
Alkene forms, wherein the graphene less than 3 layers is more than 90%；Material of the diameter more than 10 microns is more than in redox graphene powder
70%, its real density is about 1.06g/cm3。
3. the method that a kind of redox graphene powder upgrading according to claim 1 is modified, it is characterised in that heating
Stove is started to warm up with the speed of 0.5-5 DEG C/min, while is passed through argon gas with the flow of 30-100ml/min, material is kept pico-
Seethe with excitement sample tumbling state.
4. the method that a kind of redox graphene powder upgrading according to claim 1 is modified, it is characterised in that furnace temperature
When reaching 400 DEG C, soaking time 30min；When being warming up to 750 DEG C, soaking time 10min.
5. the method that a kind of redox graphene powder upgrading according to claim 1 is modified, it is characterised in that argon gas
Volume ratio between hydrogen mixed gas is 70：10-30, the volume ratio between argon gas, hydrogen and methane mixed gas are 30-50：
20-40：10-30.
6. the heating furnace that method uses according to claim 1, it is characterised in that：The heating furnace includes furnace body（1）And band
There is sieve（2）Inner tube（3）, said inner tube（3）It is arranged on furnace body（1）It is interior, the furnace body（1）With inner tube（3）Between be equipped with plus
Thermal（4）, said inner tube（3）One end is communicated with gas exhaust piping（5）, inner tube（3）The other end is communicated with air inlet pipeline（6）, institute
State air inlet pipeline（6）It is equipped with air inlet（7）, the gas exhaust piping（5）It is equipped with air bleeding valve（8）And vacuum pump（9）.
7. the heating furnace that method uses according to claim 6, it is characterised in that：The sieve（2）There are two, and be respectively provided with
In inner tube（3）It is interior, the sieve（2）For 300 mesh sieve nets.
8. the heating furnace that method uses according to claim 6, it is characterised in that：Said inner tube（3）For quartz glass inner tube
Or corundum inner tube.
9. the heating furnace that method uses according to claim 6, it is characterised in that：Said inner tube（3）It is interior to be equipped with thermometric thermoelectricity
It is even（11）, easy to understand and control inner tube（3）Interior temperature.
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Cited By (6)
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| CN110078057A (en) * | 2019-04-02 | 2019-08-02 | 华东师范大学 | A kind of the redox graphene and preparation method of low-resistivity |
| CN110155991A (en) * | 2019-04-24 | 2019-08-23 | 华东师范大学 | A kind of preparation method of redox graphene and nitrogen-doped graphene |
| CN110482548A (en) * | 2019-09-04 | 2019-11-22 | 中国科学院山西煤炭化学研究所 | A method of removing super capacitor active carbon oxygen-containing functional group |
| CN111697226A (en) * | 2020-06-23 | 2020-09-22 | 内蒙古中科四维热管理材料有限公司 | Preparation method of oily conductive agent slurry and electrode plate and assembly method of battery |
| CN113104843A (en) * | 2021-04-20 | 2021-07-13 | 雷索新材料(苏州)有限公司 | Graphene and preparation method thereof |
| CN114538426A (en) * | 2022-03-04 | 2022-05-27 | 深圳石墨烯创新中心有限公司 | Preparation method of graphene |
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Application publication date: 20180504 |