CN103435030B - A kind of preparation facilities of Graphene and method - Google Patents
A kind of preparation facilities of Graphene and method Download PDFInfo
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- CN103435030B CN103435030B CN201310290472.0A CN201310290472A CN103435030B CN 103435030 B CN103435030 B CN 103435030B CN 201310290472 A CN201310290472 A CN 201310290472A CN 103435030 B CN103435030 B CN 103435030B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000012429 reaction media Substances 0.000 claims abstract description 83
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 239000012530 fluid Substances 0.000 claims abstract description 28
- 239000012043 crude product Substances 0.000 claims abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 31
- 235000011089 carbon dioxide Nutrition 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 230000004087 circulation Effects 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001273 butane Substances 0.000 claims description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 238000001035 drying Methods 0.000 abstract description 4
- 230000003534 oscillatory effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 20
- 230000035484 reaction time Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000000746 purification Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001007 puffing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a kind of preparation facilities and method of Graphene.This device comprises: the first reactor, the second reactor, the first agitator, the second agitator and pneumavalve.The method comprises the following steps: make Graphite Powder 99 and dispersion agent enter the first reactor; Passing into reaction medium to the first reactor makes it form supercutical fluid, and Graphite Powder 99 is reacted, and obtains the reacted Graphite Powder 99 of the first reactor; Regulate pneumavalve, the reacted Graphite Powder 99 of the first reactor and dispersion agent is made to enter the second reactor of normal pressure, pass into reaction medium to the second reactor makes it form supercutical fluid simultaneously, Graphite Powder 99 is reacted, obtain the reacted Graphite Powder 99 of the second reactor, after cycle alternation reaction, obtain Graphene crude product; After Graphene crude product cleaning-drying, obtain Graphene.The preparation method of Graphene of the present invention utilizes the performance of supercutical fluid, and by the feature that two reactor oscillatory types react, prepares the Graphene of high quality, high yield.
Description
Technical field
The present invention relates to a kind of preparation facilities and method of Graphene, belong to the technical field of graphene in field of nanometer material technology.
Background technology
Since being found from Graphene in 2004, just enjoyed the generally favor from physics and Material Field investigator always.Graphene is a kind of bi-dimensional cellular shape crystalline network carbonaceous material tightly packed by monolayer carbon atom.Although Graphene only has a carbon atomic layer thickness, and is one the thinnest in known materials, but unusual rigid.Graphene is also the material that current known conductive is outstanding.In addition, Graphene also has the performance of many excellences: as higher Young's modulus, thermal conductivity, huge specific surface area etc.Due to the property of Graphene, it is all widely used in electronics, optics, magnetics, biomedicine, sensor, energy storage etc.And how to prepare high quality, the Graphene of high yield become the most popular research topic in this area.
At present, the method preparing Graphene mainly comprises following several: oxidation reduction process, chemical Vapor deposition process, mechanically peel method, epitaxial growth method, solvent stripping method etc.But oxidation reduction process need experience the oxidising process of graphite, and Graphite Powder 99 easily introduces a large amount of defects in the process of oxidation, is but difficult to repair these defects completely, so be difficult to prepare high-quality Graphene during reduction.The preparation condition harshness of chemical Vapor deposition process and epitaxial growth method, complicated operation, apparatus expensive, be thus difficult to carry out scale operation.The complex operation of mechanically peel method, the amount of each product obtained is little and cost is very high, is unfavorable for extensive preparation.Although solvent stripping method can prepare high-quality Graphene, there is the shortcoming that productive rate is low, and be unfavorable for industrializing implementation.
As can be seen here, develop a kind of preparation facilities and method of novel Graphene, be still one of this area problem demanding prompt solution.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of preparation facilities and method of Graphene.The preparation method of Graphene of the present invention utilizes the performance of supercutical fluid, and by the feature that two reactor oscillatory types react, prepares the Graphene of high quality, high yield.
For reaching above-mentioned purpose, the invention provides a kind of preparation facilities of Graphene, it at least comprises: the first reactor, the second reactor, the first agitator, the second agitator and pneumavalve;
Described first reactor is connected by pipeline with described second reactor, and this pipeline is provided with described pneumavalve;
Described first reactor is connected with described first agitator;
Described second reactor is connected with described second agitator.
According to the specific embodiment of the present invention, preferably, the preparation facilities of above-mentioned Graphene also comprises tensimeter and temperature controller.Described tensimeter is connected to the first reactor and the second reactor, in order to control the pressure in reaction process.Described temperature controller is connected to the first reactor and the second reactor, in order to control the temperature in reaction process.
In the preparation facilities of Graphene of the present invention, what can also comprise valve (safety valve, control valve etc.) and material enters pipeline, those skilled in the art can according to practical situation to the position of valve and number, and material enters the position of pipeline and number adjusts.
In addition, in preparation facilities of the present invention, the title of the first reactor and the second reactor is only to make statement more clear, not distinct therebetween, can be the autoclave that this area routine uses.The title of the first agitator and the second agitator is also only to make statement more clear, not distinct therebetween, can be the agitator that this area routine uses.
The present invention also provides a kind of preparation method of Graphene, and it is the method adopting the preparation facilities of above-mentioned Graphene to be prepared, and the method at least comprises the following steps:
A, make Graphite Powder 99 and dispersion agent enter the first reactor, then open the first agitator;
B, regulate temperature in the first reactor to temperature of reaction, reaction medium is passed into again in the first reactor, regulate pressure in the first reactor to reaction pressure, make described reaction medium reach supercritical state and form supercutical fluid, stop passing into reaction medium, Graphite Powder 99 reacts under the effect of supercutical fluid, when reaching the reaction times of the first reactor, obtain the reacted Graphite Powder 99 of the first reactor, stop the first agitator, regulate pressure in the first reactor to normal pressure, and make reaction medium discharge the first reactor, then regulate temperature in the second reactor to temperature of reaction,
C, regulate pneumavalve, the reacted Graphite Powder 99 of described first reactor and dispersion agent is made to enter the second reactor by pipeline, simultaneously, reaction medium is passed in the second reactor, and open the second agitator, regulate pressure in the second reactor to reaction pressure, make described reaction medium reach supercritical state and form supercutical fluid, stop passing into reaction medium, Graphite Powder 99 reacts under the effect of supercutical fluid, when reaching the reaction times of the second reactor, obtain the reacted Graphite Powder 99 of the second reactor, i.e. Graphene crude product, stop the second agitator, regulate pressure in the second reactor to normal pressure, and make reaction medium discharge the second reactor (now, can think that Graphite Powder 99 has carried out 0.5 circulation between the first reactor and the second reactor),
D, described Graphene crude product carried out clean, after drying, obtain described Graphene.
In above-mentioned preparation method, described Graphite Powder 99 just can mix with dispersion agent before entering the first reactor, also can mix under agitation after entering the first reactor.
In above-mentioned preparation method, preferably, the stirring velocity of described first agitator and described second agitator is 100-500r/min.Further, the stirring velocity of described first agitator and described second agitator can be the same or different, as long as meet above-mentioned scope.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method also comprises step C-1: after step c, regulate pneumavalve, the reacted Graphite Powder 99 of described second reactor and dispersion agent is made to enter the first reactor by pipeline, simultaneously, reaction medium is passed in the first reactor, and open the first agitator, regulate pressure in the first reactor to reaction pressure, make described reaction medium reach supercritical state and form supercutical fluid, stop passing into reaction medium, Graphite Powder 99 reacts under the effect of supercutical fluid, when reaching the reaction times of the first reactor, obtain the reacted Graphite Powder 99 of the first reactor, i.e. Graphene crude product, stop the first agitator, regulate pressure in the first reactor to normal pressure, and make reaction medium discharge the first reactor (now, can think that Graphite Powder 99 has carried out 1 circulation between the first reactor and the second reactor).
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method also comprises step C-2: after step C-1, repeat step C and step C-1 once or several times, make Graphite Powder 99 and dispersion agent circulating reaction between the first reactor and the second reactor, obtain the reacted Graphite Powder 99 of the first reactor or the reacted Graphite Powder 99 of the second reactor, i.e. Graphene crude product.Wherein, describedly repeat step C and step C-1 once or several times, refer to: repeat step C, repeat step C and step C-1, repeat a step C and step C-1 after repeat step C etc. again, finally obtain the reacted Graphite Powder 99 of the first reactor or the reacted Graphite Powder 99 of the second reactor.
As can be seen here, in the preparation process in accordance with the present invention, Graphite Powder 99 and dispersion agent can be made between the first reactor and the second reactor, to carry out N or N+0.5 circulation, to prepare Graphene crude product.After reacting in a kettle., probably there is the Graphite Powder 99 of 5%-10% (with the total mass of described Graphite Powder 99 for benchmark) to generate Graphene at every turn.Those skilled in the art can adjust the number of times of circulation according to actual needs.Preferably, N is the integer (as N=0, then cycle index is 0.5 time) of 0-20, and that is, the number of times that Graphite Powder 99 and dispersion agent carry out circulating between the first reactor and the second reactor is 0.5-20 time.More preferably, the number of times that Graphite Powder 99 and dispersion agent carry out circulating between the first reactor and the second reactor is 2.5-10 time.
In above-mentioned preparation method, it should be noted that, carry out reacted Graphite Powder 99 at the first reactor to be all called " the reacted Graphite Powder 99 of the first reactor " at every turn, carry out reacted Graphite Powder 99 at the second reactor at every turn and be all called " the reacted Graphite Powder 99 of the second reactor "; But, in fact, to enter the first reactor reacted " the reacted Graphite Powder 99 of the first reactor " not identical for homogeneous (for the first time, second time etc.), and to enter the second reactor reacted " the reacted Graphite Powder 99 of the second reactor " not identical yet for homogeneous (for the first time, second time etc.).In the present invention, be only to make statement more succinct, clear and definite, so use above-mentioned address.And " the reacted Graphite Powder 99 of the first reactor " and " the reacted Graphite Powder 99 of the second reactor " is in fact the crude product of Graphene.
In above-mentioned preparation method, when regulating pneumavalve, because the pressure just carried out in the reactor of reaction is high pressure, and the pressure in another reactor is normal pressure, and thus Graphite Powder 99 and dispersion agent can be pressed into another reactor.And regulate pneumavalve, the Graphite Powder 99 of nearly more than 90% and dispersion agent can be pressed into another reactor, and efficiency is very high at every turn, remaining Graphite Powder 99 and dispersion agent can think the reasonable error reacted.
In above-mentioned preparation method, the reaction medium entering the first reactor is identical with the reaction medium entering the second reactor, preferably, described reaction medium comprises the combination of one or more in the mixture (mass ratio of butane and butylene can be 1:0.1-1:10) of the mixture (mass ratio of carbonic acid gas and nitrogen can be 1:0.1-1:10) of the mixture (mass ratio of carbonic acid gas and water can be 1:0.1-1:10) of carbonic acid gas, carbonic acid gas and water, carbonic acid gas and nitrogen, butane and butylene, toluene and benzene.More preferably, described reaction medium is carbonic acid gas.
In above-mentioned preparation method, preferably, described dispersion agent comprises the combination of one or more in dinitrophenol(DNP), dimethyl formamide and sodium laurylsulfonate.
In above-mentioned preparation method, preferably, the mass ratio of described Graphite Powder 99 and described dispersion agent is 1:0.1-1:10.
In above-mentioned preparation method, preferably, the mass ratio of the reaction medium and Graphite Powder 99 that enter the first reactor or the second reactor is each time 1:1-1:3.And the consumption entering the reaction medium of reactor can be the same or different at every turn, as long as meet aforementioned proportion.
In the preparation process in accordance with the present invention, the reaction pressure in the first reactor and the second reactor, temperature of reaction and reaction times determine according to the kind of reaction medium, emergent pressure, critical temperature.For reaction medium of the present invention, in above-mentioned preparation method, preferably, the reaction pressure in described first reactor is 10-300 normal atmosphere, temperature of reaction is 30-400 DEG C, and the reaction times of described first reactor is 10 minutes to 120 minutes.In addition, preferably, the reaction pressure in described second reactor is 10-300 normal atmosphere, and temperature of reaction is 30-400 DEG C, and the reaction times of described second reactor is 10 minutes to 120 minutes.And the reaction pressure in described first reactor and described second reactor, temperature of reaction and reaction times can be the same or different.
In above-mentioned preparation method, preferably, described Graphite Powder 99 is the Graphite Powder 99 after purification process; More preferably, described purification process at least comprises ultrasonic cleaning.Before carrying out preparation method of the present invention, Graphite Powder 99 can be carried out purification process, this purification process can comprise ultrasonic cleaning, and the ultrasonic frequency of this ultrasonic cleaning, power and ultrasonic cleaning time can carry out conventional adjustment by those skilled in the art according to practical situation.Such as, hyperacoustic frequency can be 40KHz, and power can be 150W, and the ultrasonic cleaning time can be 5-10min.In addition, except ultrasonic cleaning, conventional other purification process modes used can also to be used in chemical treatment or this area to carry out purification process to Graphite Powder 99, to remove dephasign material wherein and impurity element.
In above-mentioned preparation method, ethanol can be adopted to the cleaning of Graphene crude product.The number of times of washing and each consumption can carry out conventional selection and adjustment by those skilled in the art.Can be oven drying to the drying of Graphene crude product after washing, drying temperature be 80-100 DEG C, and the time is 12h.
The present invention is by adopting dispersion agent and supercutical fluid, and the circulation of Graphite Powder 99 between two reactors (two reactor oscillatory type reactions) prepares the Graphene of high quality, high yield.Wherein, dispersion agent plays dissemination, makes Graphite Powder 99 be in suspended state; Supercutical fluid plays stripping effect, and enters into the process of another reactor at Graphite Powder 99 from a reactor, and pressure promptly declines to a great extent, and make Graphite Powder 99 puffing be Graphene, the charge stripping efficiency of Graphite Powder 99 is higher, and the productive rate of Graphene is higher.
Preparation facilities and the method for Graphene of the present invention have the following advantages: 1, Graphite Powder 99 carries out circulating reaction between two reactors, every secondary response probably has the Graphite Powder 99 of 5%-10% (with the total mass of described Graphite Powder 99 for benchmark) to generate Graphene, and repeatedly reaction makes the productive rate of Graphene be improved; 2, utilize the property of supercutical fluid, the Graphene that defect is few, quality is high can be prepared; 3, preparation process is simple, cost is low, processing ease, and can realize continuous production, and having can the broad prospect of application of scale operation.
Accompanying drawing explanation
Fig. 1 is the structural representation of the preparation facilities of the Graphene of embodiment 1.
Fig. 2 is the atomic power electron micrograph of the Graphene product of embodiment 2.
Fig. 3 is the atomic power electron micrograph of the Graphene product of embodiment 3.
Fig. 4 is the low power transmission electron microscope photo of the Graphene product of embodiment 3.
Fig. 5 is the high power transmission electron microscope photo of the Graphene product of embodiment 3.
Fig. 6 is the atomic power electron micrograph of the Graphene product of embodiment 4.
Primary clustering nomenclature:
First reactor 1 second reactor 2 first agitator 3 second agitator 4
First tensimeter 5 second tensimeter 6 first temperature controller 7 second temperature controller 8
Pneumavalve 9 under meter 10 reaction medium enters pipeline 11
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
The present embodiment provides a kind of preparation facilities of Graphene, as shown in Figure 1, it at least comprises: the first reactor 1, second reactor 2, first agitator 3, second agitator 4, first tensimeter 5, second tensimeter 6, first temperature controller 7, second temperature controller 8, pneumavalve 9, under meter 10, reaction medium enter pipeline 11 and other connection lines and multiple valve;
Described first reactor 1 is connected by pipeline with described second reactor 2, and this pipeline is provided with described pneumavalve 9;
Described first reactor 1 is connected with described first agitator 3;
Described second reactor 2 is connected with described second agitator 4;
It is that two depot sidings are connected to described first reactor 1 and described second reactor 2 that described reaction medium enters pipeline 11 bifurcated, and described under meter 10 be positioned at described reaction medium enter pipeline 11 bifurcated before pipeline on, the reaction medium that described first tensimeter 5 is connected near described first reactor 1 by pipeline enters on the pipeline after pipeline 11 bifurcated, the reaction medium that second tensimeter 6 is connected near described second reactor 2 by pipeline enters on the pipeline after pipeline 11 bifurcated
Described first temperature controller 7 is connected with described first reactor 1 by pipeline;
Described second temperature controller 8 is connected with described second reactor 2 by pipeline.
It should be noted that, reaction medium enters pipeline 11 except the one end be connected with the first reactor 1, second reactor 2, and the other end can be connected to the storing unit of reaction medium; If reaction medium is one matter, then the other end that reaction medium enters pipeline 11 can be directly connected in the storing unit (as carbon dioxide storage tank etc.) of this reaction medium; If reaction medium is mixture, then reaction medium enters the other end of pipeline 11 can bifurcated be also the storing unit (as carbon dioxide storage tank and nitrogen storage tank etc.) that two depot sidings are connected to two kinds of materials in this mixture, and two kinds of materials in this mixture enter in pipeline 11 at reaction medium and carry out being mixed to form mixture reaction medium.
In addition, in the device of the present embodiment, " first " uses with the word of " second " is only to make statement more clear, not distinct between " first " and the same instruments representated by " second ".
Embodiment 2
The present embodiment provides a kind of preparation method of Graphene, and it is the method adopting the preparation facilities of the Graphene of embodiment 1 to be prepared, and the method comprises the following steps:
A, Graphite Powder 99 is carried out ultrasonic cleaning, the frequency of this ultrasonic cleaning is 40KHz, and power is 150W, and the ultrasonic cleaning time is 5-10min, obtains the Graphite Powder 99 after purifying;
B, the Graphite Powder 99 after purifying to be mixed with the mass ratio of 1:5 with sodium lauryl sulphate (dispersion agent);
C, make the mixture of Graphite Powder 99 and dispersion agent enter the first reactor 1, then open the first agitator 3;
D, regulate the temperature to 40 in the first reactor 1 DEG C (temperature of reaction) and controlled by the first temperature controller 7, enter pipeline 11 by reaction medium again and pass into carbonic acid gas (reaction medium in the first reactor 1, the ratio of itself and Graphite Powder 99 is 1:1), and adopt under meter 10 to control the flow of carbonic acid gas, regulate pressure to 80 normal atmosphere (reaction pressure) in the first reactor 1 and controlled by the first tensimeter 5, make carbonic acid gas reach supercritical state and form supercutical fluid, stop passing into carbonic acid gas, Graphite Powder 99 reacts under the effect of supercritical co, reach the 60min(reaction times) time, obtain the Graphite Powder 99 after the first reactor reaction 1, stop the first agitator 3, regulate pressure in the first reactor 1 to normal pressure, and make carbonic acid gas discharge the first reactor 1, then the temperature to 40 DEG C in the second reactor 2 is regulated,
E, regulate pneumavalve 9, the reacted Graphite Powder 99 of described first reactor 1 and dispersion agent is made to enter the second reactor 2 by pipeline, simultaneously, enter pipeline 11 by reaction medium and pass into carbonic acid gas (reaction medium in the second reactor 2, the ratio of itself and Graphite Powder 99 is 1:1), and adopt under meter 10 to control the flow of carbonic acid gas, open the second agitator 4, regulate pressure to 80 normal atmosphere (reaction pressure) in the second reactor 2 and controlled by the first tensimeter 5, make carbonic acid gas reach supercritical state and form supercutical fluid, stop passing into carbonic acid gas, Graphite Powder 99 reacts under the effect of supercritical co, reach the 60min(reaction times) time, obtain the reacted Graphite Powder 99 of the second reactor 2, stop the second agitator 4, regulate pressure in the second reactor 2 to normal pressure, and make carbonic acid gas discharge the second reactor 2,
F, regulate pneumavalve 9, the reacted Graphite Powder 99 of described second reactor 2 and dispersion agent is made to enter the first reactor 1 by pipeline, simultaneously, enter pipeline 11 by reaction medium in the first reactor 1, pass into carbonic acid gas (ratio of itself and Graphite Powder 99 is 1:1), and adopt under meter 10 to control the flow of carbonic acid gas, open the first agitator 3, regulate pressure to 80 normal atmosphere in the first reactor 1 and controlled by the first tensimeter 5, make carbonic acid gas reach supercritical state and form supercutical fluid, stop passing into carbonic acid gas, Graphite Powder 99 reacts under the effect of supercritical co, when reaching 60min, obtain the reacted Graphite Powder 99 of the first reactor 1, stop the first agitator 3, regulate pressure in the first reactor 1 to normal pressure, and make carbonic acid gas discharge the first reactor 1, now, Graphite Powder 99 has carried out 1 circulation between the first reactor 1 and the second reactor 2,
G, a repetition step e and F repeat a step e again, make Graphite Powder 99 between the first reactor 1 and the second reactor 2, carry out 2.5 circulations, obtain Graphene crude product;
H, described Graphene crude product ethanol is cleaned after, in the baking oven of 80-100 DEG C, dry 12h, obtains described Graphene.
The Graphene product of atomic power electron microscope to gained is adopted to characterize, result as shown in Figure 2, is carried out calculating according to the known method of Fig. 2 and this area the Graphene that known Graphene product is less than 10 layers and is accounted for 62%(with the gross weight of described Graphene product for benchmark).Thus, the Graphene product of embodiment 2 has the advantage of high quality, high yield.
Embodiment 3
The present embodiment provides a kind of preparation method of Graphene, its method be prepared for the preparation facilities of the Graphene adopting embodiment 1, this preparation method is substantially identical with the preparation method of embodiment 2, and difference is: reaction medium is the mixture that carbonic acid gas and nitrogen mix with the mass ratio of 1:1; The mass ratio of Graphite Powder 99 and sodium lauryl sulphate is 1:1; The temperature of reaction of the first reactor and the second reactor is 40 DEG C, and reaction pressure is 80 normal atmosphere, and the reaction times is 30min; The cycle index of Graphite Powder 99 between the first reactor and the second reactor is 5 times.
Atomic power electron microscope and the Graphene product of transmission electron microscope to gained is adopted to characterize, its atomic power electron micrograph as shown in Figure 3, carries out calculating according to the known method of Fig. 3 and this area the Graphene that known Graphene product is less than 10 layers and accounts for 80%(with the gross weight of described Graphene product for benchmark); Its transmission electron microscope photo is as shown in Figures 4 and 5, clear by the number of plies of Fig. 4 and Fig. 5 known Graphene product, and most product is be less than the Graphene of 10 layers.Thus, the Graphene product of embodiment 3 has the advantage of high quality, high yield.
Embodiment 4
The present embodiment provides a kind of preparation method of Graphene, its method be prepared for the preparation facilities of the Graphene adopting embodiment 1, this preparation method is substantially identical with the preparation method of embodiment 2, and difference is: reaction medium is the mixture that butane and butylene mix with the mass ratio of 1:1; Dispersion agent is dimethyl formamide, and the mass ratio of Graphite Powder 99 and dimethyl formamide is 2:1; The temperature of reaction of the first reactor and the second reactor is 160 DEG C, and reaction pressure is 50 normal atmosphere, and the reaction times is 60min; The cycle index of Graphite Powder 99 between the first reactor and the second reactor is 6 times.
The Graphene product of atomic power electron microscope to gained is adopted to characterize, result as shown in Figure 6, carry out calculating according to the known method of Fig. 6 and this area the Graphene that known Graphene product is less than 10 layers and account for 70%(with the gross weight of described Graphene product for benchmark), thus, the Graphene product of embodiment 4 has the advantage of high quality, high yield.
Claims (1)
1. a preparation method for Graphene, the preparation facilities of its Graphene adopted comprises:
First reactor (1), the second reactor (2), the first agitator (3), the second agitator (4), the first tensimeter (5), the second tensimeter (6), the first temperature controller (7), the second temperature controller (8), pneumavalve (9), under meter (10), reaction medium enter pipeline (11) and other connection lines and multiple valve;
Described first reactor (1) is connected by pipeline with described second reactor (2), and this pipeline is provided with described pneumavalve (9);
Described first reactor (1) is connected with described first agitator (3);
Described second reactor (2) is connected with described second agitator (4);
It is that two depot sidings are connected to described first reactor (1) and described second reactor (2) that described reaction medium enters pipeline (11) bifurcated, and described under meter (10) be positioned at described reaction medium enter pipeline (11) bifurcated before pipeline on, the reaction medium that described first tensimeter (5) is connected near described first reactor (1) by pipeline enters on the pipeline after pipeline (11) bifurcated, the reaction medium that second tensimeter (6) is connected near described second reactor (2) by pipeline enters on the pipeline after pipeline (11) bifurcated,
Described first temperature controller (7) is connected with described first reactor (1) by pipeline;
Described second temperature controller (8) is connected with described second reactor (2) by pipeline;
The method is made up of following steps:
A, Graphite Powder 99 is carried out ultrasonic cleaning, the frequency of this ultrasonic cleaning is 40KHz, and power is 150W, and the ultrasonic cleaning time is 5-10min, obtains the Graphite Powder 99 after purifying;
B, the Graphite Powder 99 after purifying to be mixed with the mass ratio of 1:1 with dispersion agent sodium lauryl sulphate,
C, make the mixture of Graphite Powder 99 and dispersion agent enter the first reactor (1), then open the first agitator (3);
D, the temperature to 40 in the first reactor (1) DEG C is regulated also to be controlled by the first temperature controller (7), enter pipeline (11) by reaction medium again and in the first reactor (1), pass into mixture that carbonic acid gas and nitrogen mixes using the mass ratio of 1:1 as reaction medium, the mass ratio of itself and Graphite Powder 99 is 1:1, and adopt under meter (10) to control the flow of reaction medium, regulate pressure to 80 normal atmosphere in the first reactor (1) and controlled by the first tensimeter (5), make reaction medium reach supercritical state and form supercutical fluid, stop passing into reaction medium, Graphite Powder 99 reacts under the effect of supercutical fluid, when reaching 30min, obtain the first reactor (1) reacted Graphite Powder 99, stop the first agitator (3), regulate pressure in the first reactor (1) to normal pressure, and make reaction medium discharge the first reactor (1), then the temperature to 40 DEG C in the second reactor (2) is regulated,
E, regulate pneumavalve (9), the reacted Graphite Powder 99 of described first reactor (1) and dispersion agent is made to enter the second reactor (2) by pipeline, simultaneously, enter pipeline (11) by reaction medium and in the second reactor (2), pass into mixture that carbonic acid gas and nitrogen mixes using the mass ratio of 1:1 as reaction medium, the mass ratio of itself and Graphite Powder 99 is 1:1, and adopt under meter (10) to control the flow of carbonic acid gas, open the second agitator (4), regulate pressure to 80 normal atmosphere in the second reactor (2) and controlled by the second tensimeter (6), make reaction medium reach supercritical state and form supercutical fluid, stop passing into reaction medium, Graphite Powder 99 reacts under the effect of supercutical fluid, when reaching 30min, obtain the second reactor (2) reacted Graphite Powder 99, stop the second agitator (4), regulate pressure in the second reactor (2) to normal pressure, and make reaction medium discharge the second reactor (2),
F, regulate pneumavalve (9), the reacted Graphite Powder 99 of described second reactor (2) and dispersion agent is made to enter the first reactor (1) by pipeline, simultaneously, enter pipeline (11) by reaction medium and in the first reactor 1, pass into mixture that carbonic acid gas and nitrogen mixes using the mass ratio of 1:1 as reaction medium, the mass ratio of itself and Graphite Powder 99 is 1:1, and adopt under meter (10) to control the flow of reaction medium, open the first agitator (3), regulate pressure to 80 normal atmosphere in the first reactor (1) and controlled by the first tensimeter (5), make reaction medium reach supercritical state and form supercutical fluid, stop passing into reaction medium, Graphite Powder 99 reacts under the effect of supercutical fluid, when reaching 30min, obtain the first reactor (1) reacted Graphite Powder 99, stop the first agitator (3), regulate pressure in the first reactor (1) to normal pressure, and make reaction medium discharge the first reactor (1), now, Graphite Powder 99 has carried out 1 circulation between the first reactor (1) and the second reactor (2),
G, repeating step E and F, make Graphite Powder 99 between the first reactor (1) and the second reactor (2), carry out 5 circulations, obtain Graphene crude product;
H, described Graphene crude product ethanol is cleaned after, in the baking oven of 80-100 DEG C, dry 12h, obtains described Graphene;
Or be made up of following steps:
A, Graphite Powder 99 is carried out ultrasonic cleaning, the frequency of this ultrasonic cleaning is 40KHz, and power is 150W, and the ultrasonic cleaning time is 5-10min, obtains the Graphite Powder 99 after purifying;
B, the Graphite Powder 99 after purifying to be mixed with the mass ratio of 2:1 with dispersion agent dimethyl formamide,
C, make the mixture of Graphite Powder 99 and dispersion agent enter the first reactor (1), then open the first agitator (3);
D, the temperature to 160 in the first reactor (1) DEG C is regulated also to be controlled by the first temperature controller (7), enter pipeline (11) by reaction medium again and in the first reactor (1), pass into mixture that butane and butylene mix using the mass ratio of 1:1 as reaction medium, the mass ratio of itself and Graphite Powder 99 is 1:1, and adopt under meter (10) to control the flow of reaction medium, regulate pressure to 50 normal atmosphere in the first reactor (1) and controlled by the first tensimeter (5), make reaction medium reach supercritical state and form supercutical fluid, stop passing into reaction medium, Graphite Powder 99 reacts under the effect of supercutical fluid, when reaching 60min, obtain the first reactor (1) reacted Graphite Powder 99, stop the first agitator (3), regulate pressure in the first reactor (1) to normal pressure, and make reaction medium discharge the first reactor (1), then the temperature to 160 DEG C in the second reactor (2) is regulated,
E, regulate pneumavalve (9), the reacted Graphite Powder 99 of described first reactor (1) and dispersion agent is made to enter the second reactor (2) by pipeline, simultaneously, enter pipeline (11) by reaction medium and in the second reactor (2), pass into mixture that butane and butylene mix using the mass ratio of 1:1 as reaction medium, the mass ratio of itself and Graphite Powder 99 is 1:1, and adopt under meter (10) to control the flow of carbonic acid gas, open the second agitator (4), regulate pressure to 50 normal atmosphere in the second reactor (2) and controlled by the second tensimeter (6), make reaction medium reach supercritical state and form supercutical fluid, stop passing into reaction medium, Graphite Powder 99 reacts under the effect of supercutical fluid, when reaching 60min, obtain the second reactor (2) reacted Graphite Powder 99, stop the second agitator (4), regulate pressure in the second reactor (2) to normal pressure, and make reaction medium discharge the second reactor (2),
F, regulate pneumavalve (9), the reacted Graphite Powder 99 of described second reactor (2) and dispersion agent is made to enter the first reactor (1) by pipeline, simultaneously, enter pipeline (11) by reaction medium and in the first reactor 1, pass into mixture that butane and butylene mix using the mass ratio of 1:1 as reaction medium, the mass ratio of itself and Graphite Powder 99 is 1:1, and adopt under meter (10) to control the flow of reaction medium, open the first agitator (3), regulate pressure to 50 normal atmosphere in the first reactor (1) and controlled by the first tensimeter (5), make reaction medium reach supercritical state and form supercutical fluid, stop passing into reaction medium, Graphite Powder 99 reacts under the effect of supercutical fluid, when reaching 60min, obtain the first reactor (1) reacted Graphite Powder 99, stop the first agitator (3), regulate pressure in the first reactor (1) to normal pressure, and make reaction medium discharge the first reactor (1), now, Graphite Powder 99 has carried out 1 circulation between the first reactor (1) and the second reactor (2),
G, repeating step E and F, make Graphite Powder 99 between the first reactor (1) and the second reactor (2), carry out 6 circulations, obtain Graphene crude product;
H, described Graphene crude product ethanol is cleaned after, in the baking oven of 80-100 DEG C, dry 12h, obtains described Graphene.
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| CN106006626A (en) * | 2016-07-08 | 2016-10-12 | 张麟德 | Graphene material production device and system |
| CN106219526B (en) * | 2016-07-19 | 2018-11-27 | 福建翔丰华新能源材料有限公司 | A kind of method of purification of micro crystal graphite |
| CN106517168A (en) * | 2016-11-10 | 2017-03-22 | 中国石油大学(北京) | Device and method for preparing graphene by exfoliating graphite through quick pressure relief |
| CN107488891A (en) * | 2017-08-21 | 2017-12-19 | 中国石油大学(北京) | A kind of new function graphite alkene composite fibre and preparation method and application |
| CN111943182A (en) * | 2019-05-15 | 2020-11-17 | 英属维京群岛商艾格生科技股份有限公司 | Graphene powder and method for improving graphene defects |
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