CN104787758A - Method for preparing graphene on large scale - Google Patents
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- CN104787758A CN104787758A CN201510186396.8A CN201510186396A CN104787758A CN 104787758 A CN104787758 A CN 104787758A CN 201510186396 A CN201510186396 A CN 201510186396A CN 104787758 A CN104787758 A CN 104787758A
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Abstract
The invention discloses a method for preparing graphene on a large scale. The method comprises the following steps: a, adding graphite intercalation compound powder into compound expanding liquid, and performing expansion reaction to obtain an expanded vermicular graphene aggregate suspension; b, filtering the vermicular graphene aggregate suspension to obtain a vermicular graphene aggregate; c, washing the vermicular graphene aggregate by using a metal ion complexing agent and water sequentially to obtain a vermicular graphene aggregate wet material with the PH value of 6-8; d, adding the vermicular graphene aggregate wet material washed by water into a compound stripping liquid, and performing ultrasonic oscillation for 0.5-20 hours so as to disperse graphene into the compound stripping liquid to form a graphene solution; e, removing water from the graphene solution by a flash drying or freeze drying method to obtain graphene powder. After adoption of the method, a high-quality graphene product with the single batch production being up to hundreds of kilograms can be obtained.
Description
Technical field
The present invention relates to field of graphene, relate in particular to a kind of method that Graphene is prepared in mass-producing, the method can single batch produce the high-quality graphene product of hundreds of kilograms.
Background technology
Since being found from 2004, Graphene receives much concern as a kind of new carbon.It is a kind of completely by
sp 2 the thickness of the carbon atom formation of hydridization is only the accurate two dimensional crystal material of monoatomic layer or several monoatomic layer, there is the performance that high light transmittance and electroconductibility, high-specific surface area, high strength and snappiness etc. are excellent, be expected to obtain widespread use in fields such as high-performance nanometer electronic device, photoelectric device, gas sensor, matrix material, field emmision material and stored energies.But low cost, a large amount of preparation of high-quality graphene are still faced adverse conditions, and constrain the development and apply of this material.
At present, the grapheme material that academia accepts extensively is defined as: the graphite flake of the carbon atom number of plies within 10 layers, its thickness is below 3.5 nanometers.For this reason, China Patent No. " 201110282370.5 " disclosed " a kind of method preparing high-quality graphene " on May 2nd, 2012, its technical scheme is for raw material with halogen or the metal halide graphite intercalation compound that is intercalator, in oxalic acid or superoxol, carry out expansion and ultrasonic stripping in a solvent, thus obtain high-quality graphene.The characteristic property index of graphene product obtained by this method is: the number of plies 3-8 layers (thickness is 1-2.5 nanometers) of graphene film, lateral dimension 5-50 microns, carbon-to-oxygen ratio 30-120, foreign matter content 5 wt%.But the method can only realize the preparation of the high-quality graphene of single batch of hectogram level.
Along with the expansion of Graphene Application Areas, the demand of Graphene being increased day by day, in order to obtain higher throughput, just needing the output amplifying to realize single batch of hundreds of feather weight to above-mentioned technology.But due to the increase of single batches treatment capacity, in amplification process, there is the following problem having a strong impact on production effect:
The first, above-mentioned patent mainly utilizes the metal ion (M being present in graphite layers
x+) catalyzing hydrogen peroxide decomposes at interlayer and to produce oxygen (O
2) expansion peel off graphite obtain Graphene, when expansion reaction starts, metal ion is only present in graphite layers, reacts effectively to be decomposed into master, along with the carrying out of reaction, interlayer metal ion is dissolved in liquid phase gradually, when the concentration of metal ion increases to a certain degree, the aggravation of decomposition can be caused, particularly when a large amount of preparation the Graphene of hundreds of kilograms (single batch preparation), the increase of inventory, cause from the amount of metal ion of graphite layers stripping huge, otherwise increasing of material also makes metal ion diffusion hindered in the solution, but because the inflation fluid in above-mentioned patent is oxalic acid or superoxol, this inflation fluid can not be processed the metal ion in solution, this just causes local invalid to decompose aggravation, make the working substance Mass lost participating in expansion reaction, cause the underexpansion of intercalated graphite raw material, the expansion of graphite is had a negative impact, thus mass-producing cannot obtain high-quality Graphene.The second, after peeling off, intercalator is difficult to remove completely, causes the foreign matter content in gained graphene product too high (5-10 wt%), and causes detrimentally affect to subsequent applications.Three, the Graphene number of plies majority obtained concentrates on 7-9 layers, and the quality and performance of graphene product is poor.Four, ultrasonic wave peels off the aqueous solution or organic solution that need a large amount of organic solvents or various tensio-active agent, causes the production cost of Graphene higher.Five, when graphite peels off into Graphene, specific surface area sharply increases, simultaneously due to the weak oxide effect in expansion reaction, make graphenic surface with negative charge, thus easily metal ion positively charged in intercalator and solution is adsorbed, the increase of handled thing doses during owing to preparing in a large number, these metal ions are difficult to, by simply washing removal, therefore cause the increase of metal ion content in gained graphene product.The existence of a large amount of metal ion can cause disadvantageous effect to the application of Graphene.Although pickling effectively can remove metal ion, a large amount of pickling also can cause Heavy environmental pollution while increase cost.
Summary of the invention
The object of the invention is to solve the above-mentioned problems in the prior art, provide a kind of mass-producing to prepare the method for Graphene, after adopting the present invention, the high-quality graphene product that single batch of turnout reaches hundreds of kilograms can be obtained.
For achieving the above object, the technical solution used in the present invention is as follows:
A method for Graphene is prepared in mass-producing, it is characterized in that comprising the following steps:
A, graphite intercalation compound powder is joined in composite expanded liquid, then under the condition of 20-50 ° of C, carry out expansion reaction 2-6 hours, obtain the quasiflake graphite alkene aggregate suspension expanded;
B, filtration treatment is carried out to quasiflake graphite alkene aggregate suspension, obtain quasiflake graphite alkene aggregate;
C, successively employing complexing of metal ion agent and water washing quasiflake graphite alkene aggregate, complexing of metal ion agent washed after and water washing complete after all need to carry out filtration treatment to quasiflake graphite alkene aggregate, finally obtain the quasiflake graphite alkene aggregate wet feed that pH value is 6-8;
D, the quasiflake graphite alkene aggregate wet feed after washing is joined in compound stripping liquid and carries out ultrasonic oscillation process 0.5-20 hours, realize peeling off, make graphene dispersion form graphene solution in compound stripping liquid;
E, the moisture adopted in expansion drying or cryodesiccated method removal graphene solution, obtain graphene powder, the moisture content of graphene powder is less than 5wt%.
Described composite expanded liquid be by following component by mass percentage Homogeneous phase mixing form: superoxol 75-90%, complexing of metal ion agent 1-10%, acidity-basicity regulator 2-5%, surface tension modifier 0.5-5%, all the other are water.
The concentration of described superoxol is 20-30%.
In described composite expanded liquid, complexing of metal ion agent is Seignette salt, trisodium phosphate, disodium edta, oxalic acid, oxalate, Sunmorl N 60S, ethylenediamine tetraacetic methene sodium phosphate, diethanolamine, one or more compound in trolamine, described acidity-basicity regulator is hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, ammoniacal liquor, sodium hydroxide, potassium hydroxide, quadrol, one or more compound in sodium bicarbonate, described surface tension modifier is methyl alcohol, ethanol, propyl alcohol, butanols, one or more compound in ethyl acetate.
Described compound stripping liquid be by following component by mass percentage Homogeneous phase mixing form: complexing of metal ion agent 5-20%, surface tension modifier 1-5%, all the other are water.
Complexing of metal ion agent in described compound stripping liquid is one or more the compound in Seignette salt, trisodium phosphate, disodium edta, Sunmorl N 60S, ethylenediamine tetraacetic methene sodium phosphate, oxalic acid, oxalate, diethanolamine, trolamine, and surface tension modifier is one or more the compound in methyl alcohol, ethanol, propyl alcohol, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, cetyl trimethylammonium bromide, fluorocarbon surfactant.
In described step a, the graphite intercalation compound treatment capacity of every 1 ton of composite expanded liquid is 9-15Kg.
Gained graphene powder in described step e, the number of plies of its graphene film is less than 7 layers, lateral dimension 1-5 microns, and carbon-to-oxygen ratio 20-100, foreign matter content is less than 2wt%.
Gained graphene powder in described step e, the number of plies of its graphene film is 1-5 layers, lateral dimension 2-4 microns, carbon-to-oxygen ratio 25-80.
Described step a carries out expansion reaction by expansion gear, described expansion gear comprises expansion drum and stirring mechanism, described expansion drum is provided with chuck, described chuck bottom is provided with hot water or steam inlet, top is provided with hot water or vapour outlet, described stirring mechanism comprises motor and stir shaft, and described motor is fixed on expansion drum top, and described stir shaft is arranged on the middle part of expansion drum by motor.
The housing combination that described chuck is rolled on expansion drum outside surface by expansion drum and fixed packet forms.
Be provided with escape orifice bottom described chuck, escape orifice is positioned at the below of hot water or steam inlet.
Described expansion drum top is provided with taper top, and described taper top is provided with solid-phase material charging opening, liquid phase material charging opening, water-in and exhaust outlet, the bottom of described expansion drum is provided with drain hole, this drain hole is connected with displaying baiting valve.
The quantity of described exhaust outlet is two, and is all equipped with aerofoil fan in two exhaust outlets.
The outer wall of described expansion drum is provided with four symmetrical mounting blocks.
Described steps d is peeled off by ultrasonic wave stripping off device, described ultrasonic wave stripping off device comprises peels off tank and Duo Gen ultrasound wave vibrating bar, many described ultrasound wave vibrating bars are vertically fixed on to be peeled off in tank, and many ultrasound wave vibrating bar distributions in polycyclic in same frontal plane of projection.
Many described ultrasound wave vibrating bars are vertical layered to be arranged on and to peel off in tank, and the lower end of upper strata ultrasound wave vibrating bar misplaces crossing with the upper end of lower floor's ultrasound wave vibrating bar, and often on ring the quantity of ultrasound wave vibrating bar be the integral multiple of the ultrasound wave vibrating bar number of plies.
In described stripping tank, the quantity of every layer of ultrasound wave vibrating bar is all identical, and the ultrasound wave vibrating bar of every layer is evenly arranged in stripping tank.
Sidewall in described stripping tank and bottom are provided with compressed-air atomizer.
The present invention is equally under liquid phase soaking conditions, utilizes the metal ion (M being present in graphite layers
x+) catalyzing hydrogen peroxide decomposes at interlayer and to produce oxygen (O
2) expansion peel off graphite obtain Graphene (as shown in Figure 1), its core reaction is:
, but the present invention can metal ion in expansion reaction and washing process in complex solution.Its concrete mechanism of action is mainly reflected in following three aspects: one is expansion reaction, initial in expansion reaction, metal ion is only present in graphite layers, reaction is to be effectively decomposed into master, along with the carrying out of reaction and the stripping of graphite flake layer, interlayer metal ion is dissolved in liquid phase gradually, complexing of metal ion agent complexing now in composite expanded liquid is dissolved into the metal ion in solution, it is made to lose catalytic activity, thus reach the effect suppressing decomposition and promote effectively to decompose, and then obtain the quasiflake graphite alkene aggregate of high level expansion, two is carrying out washing treatment, adopt complexing of metal ion agent washing quasiflake graphite alkene aggregate, remove the metal ion in quasiflake graphite alkene aggregate.Three is lift-off processing, removes the metal ion in quasiflake graphite alkene aggregate in stripping process further.Wherein, adopt the composite expanded liquid of above-mentioned specific components, effective process of single batch of hundreds of kilograms of graphite intercalation compounds can be realized, adopt complexing of metal ion agent washing, can the metal ion of complexing graphite layers, thus improve the preparation quality of Graphene, adopt the compound stripping liquid of specific components, can dissociate in further complexing oscillatory process the metal ion.Three coordinates, and just can realize the high-quality graphene product that single batch is produced hundreds of kilograms.
The present invention uses the implementation method of expansion gear: first in expansion drum, add raw material in proportion by liquid phase material charging opening and water-in, configure quantitative composite expanded liquid, then in expansion drum, graphite intercalation compound powder is added by solid-phase material charging opening, graphite intercalation compound floats on liquid level after contacting with composite expanded liquid, start to expand reaction, this reaction is that static process (gathers heat of reaction, the carrying out of accelerated reaction), the graphite intercalation compound touching composite expanded liquid first participates in reaction, but along with the carrying out of reaction, material bed more and more thicker, upper materials cannot touch composite expanded liquid by syphonic effect, now need starter motor to control stir shaft to mix the solid liquid phase material in expansion drum, after about stirring several minutes, stop stirring, continue reaction, until graphite intercalation compound complete reaction.In reaction process, repeatedly the short period of time produces a large amount of steam in meeting, is discharged by steam in time by aerofoil fan.Need pass into hot water or steam cycle in chuck during reaction, ensure that the temperature of composite expanded liquid is in OK range, in reaction process, time opening stirs, allow solid liquid phase material fully contact, after reaction terminates, open displaying baiting valve, after solid liquid phase material is all discharged, cleaning expansion drum inwall.
Employing the invention has the advantages that:
One, the present invention owing to all adding complexing of metal ion agent in expansion reaction, carrying out washing treatment and lift-off processing process, therefore, it is possible to the metal ion of positively charged is converted into electronegative metal complex ion, effective suppression metal ion is in the absorption of graphenic surface, namely while promotion is effectively decomposed, decomposition is suppressed, be not only single batch of manufacture of producing hundreds of kilograms of Graphenes and provide powerful guarantee, the content of impurity metal ion in graphene product can also be made to be reduced to 0.5-2wt%.
Two, in the present invention, complexing of metal ion agent in composite expanded liquid complexing can be dissolved into metal ion in solution, it is made to lose catalytic activity, reach the effect suppressing decomposition, acidity-basicity regulator, for adjusting the potential of hydrogen of swelling agent, can optimize the complexing effect of complexing agent, and surface tension modifier is for adjusting the wetting property of stripping liquid to graphite and Graphene, to promote that swelling agent is to the diffusion of graphite layers, and then promote effective decomposition reaction.Complexing of metal ion agent in compound stripping liquid can further complexing graphite layers to dissociate the metal ion; compared with prior art; adopt the composite expanded liquid of above-mentioned specific components and compound stripping liquid can improve the expansion homogeneity of graphite when large-scale production and reduce trash content; thus make the final graphene product number of plies obtained lower than 10 layers, and mostly concentrate on 1-5 layers.In addition, if the concentration of superoxol is lower than 20%, the reaction times will be caused long insufficient with reaction; If the concentration of superoxol is higher than 30%, there is again reaction aggravation, react the safety problem such as uncontrollable, therefore the concentration of superoxol is set as 20-30%, has both ensure that mildness and the security of reaction, in turn ensure that the adequacy of reaction.
Three, manufacture order of the present invention batch graphene product is relative to the productive rate of raw graphite (not comprising intercalator quality) higher than 90%, has the advantage that the production time is short and raw material availability is high.
Four, the present invention's stripping process that expands destroys the structure of Graphene hardly, farthest can retain the structure of Graphene and electricity and mechanical property.
Five, the reaction that the present invention is directed to graphite intercalation compound and composite expanded liquid is this feature of static reaction process, specificly on expansion drum, is provided with stirring mechanism and chuck.Wherein, chuck can make the composite expanded liquid in expansion drum keep certain temperature, for the persistence of expansion reaction and adequacy provide powerful guarantee; Keep the temperature of composite expanded liquid by passing into hot water or steam in chuck, have pollution-free, reusable edible, cost are low and the advantage of high insulating effect.The interval stirring power of stirring mechanism makes graphite intercalation compound fully contact in expansion process with composite expanded liquid, thus makes the expansion reaction of graphite intercalation compound more abundant, is conducive to the time shortening expansion reaction.Although prior art also has the agitation vat of various structure, those agitation vats are all that persistence stirs, and therefore, stirring mechanism and jacketed expansion drum are combined the expansion gear formed and has novelty and unexpected effect.
Six, in the present invention, the housing combination that chuck is rolled on expansion drum outside surface by expansion drum and fixed packet forms, and this structure not only makes the sealing of chuck better, also makes the heat transmission effect of hot water or steam in chuck better.
Seven, in the present invention, water and impurity more than being conducive to removing in chuck fast by the escape orifice be arranged on bottom chuck, use more convenient.
Eight, in the present invention, expansion drum top arranges taper top, and taper top makes expansion drum space larger, coordinates, the steam that can prevent loss everywhere, be more conducive to exhaust with exhaust outlet disposed thereon.In addition, when reinforced, by independently solid-phase material charging opening, liquid phase material charging opening and water-in are reinforced, each solid liquid phase material can be avoided to enter expansion drum forward slip value, be conducive to the add-on accurately controlling solid liquid phase material.
Nine, in the present invention, because expansion reaction time of high water can produce a large amount of gas, the velocity of discharge of gas can therefore be accelerated further by two aerofoil fans.
Ten, in the present invention, by being arranged on the symmetrical mounting block of on expansion drum outer wall four, the fixing fast of expansion drum is conducive to.
11, in the present invention, the many ultrasound wave vibrating bars distribution in polycyclic in same frontal plane of projection in tank is peeled off, can Omnidirectional radiation tank interior, increase ultrasonic power density in tank body, thus improve the amount that single batch is peeled off material.
12, in the present invention, many vertical layered being arranged on of ultrasound wave vibrating bar are peeled off in tank, and the quantity of ultrasound wave vibrating bar is the integral multiple of the ultrasound wave vibrating bar number of plies on every ring, this structure make ultrasound wave vibrating bar the ultrasonic radiation effect peeled off in tank and stability better, improve the peeling effect of material and the quality of final products obtained therefrom.Compared with prior art, the structure that ultrasound wave vibrating bar layering is arranged not only further increases the amount that single batch is peeled off material, also reduces the volume and floor space of peeling off tank, has easy for installation and practical advantage.And the lower end of upper strata ultrasound wave vibrating bar misplaces crossing with the upper end of lower floor ultrasound wave vibrating bar, then can avoid peeling off in tank the white space occurred without ultrasonic radiation.
13, in the present invention; every layer of ultrasound wave vibrating bar evenly arranges the structure peeled off in tank; make to peel off tank internal upper part, middle part is identical with the ultrasonic radiation effect of bottom; namely when mass-producing material handling; fully material can be peeled off completely at short notice, be conducive to the quality improving graphene product.
14, in the present invention, by peeling off the nozzle ejection pressurized air of pot sidewall and bottom, rolling effect can be played to the material peeled off in tank, both having improve the peeling effect of ultrasonic wave to material, additionally reduced splitting time,
15, in the present invention, the production cost of Graphene is low, and whole reaction process is very little on the impact of environment, and the processing cost of waste liquid is low.
16, the graphene film number of plies of the graphene powder obtained by the present invention is adopted to be 1-5 layers, lateral dimension 2-4 microns, carbon-to-oxygen ratio 25-80, it is the quality of the graphene powder that prior art that " 201110282370.5 " are representative obtains that its quality is better than far away with China Patent No..
17, replace by the tensio-active agent compound stripping liquid that alternative costs are low the alcohols stripping liquid that cost is high, ultrasonic oscillation stripping is carried out to gained quasiflake graphite alkene aggregate after expansion reaction, achieves the low cost production of graphene powder.
Accompanying drawing explanation
Fig. 1 is the expansion release mechanism schematic diagram of graphite intercalation compound in composite expanded liquid: (a) graphite intercalation compound joins in superoxol; B () hydrogen peroxide decomposes generation oxygen (O2) under the katalysis of graphite layers metal ion; Occur under c effect that () graphene sheet layer expands at oxygen to peel off the Graphene obtaining monolithic;
The graphene powder of Fig. 2 large-scale production gained;
The transmission electron microscope pattern of Fig. 3 large-scale production Graphene;
The thermogravimetric curve of Fig. 4 large-scale production Graphene;
Fig. 5 is the main TV structure schematic diagram of embodiment 6;
Fig. 6 is the main TV structure schematic diagram of expansion drum in embodiment 6;
Fig. 7 is the plan structure schematic diagram of expansion drum in embodiment 6;
Fig. 8 is the main TV structure schematic diagram peeling off tank in embodiment 7;
Fig. 9 is the plan structure schematic diagram peeling off tank in embodiment 7;
Figure 10 is the structural representation of ultrasound wave vibrating bar in embodiment 7;
Be labeled as in figure: 1, expansion drum, 2, chuck, 3, import, 4, export, 5, motor, 6, stir shaft, 7, shell, 8, escape orifice, 9, taper top, 10, solid-phase material charging opening, 11, liquid phase material charging opening, 12, water-in, 13, exhaust outlet, 14, drain hole, 15, mounting block, 16, tank is peeled off, 17, ultrasound wave vibrating bar, 18, nozzle.
Embodiment
Embodiment 1
A method for Graphene is prepared in mass-producing, comprises the following steps:
A, graphite intercalation compound powder is joined in composite expanded liquid, then under the condition of 20-50 ° of C, expansion reaction 2-6 hours is carried out, obtain the quasiflake graphite alkene aggregate suspension of high level expansion, wherein, the graphite intercalation compound treatment capacity of every 1 ton of composite expanded liquid is 9-15Kg;
B, filtration treatment is carried out to quasiflake graphite alkene aggregate suspension, obtain quasiflake graphite alkene aggregate;
C, successively employing complexing of metal ion agent and water washing quasiflake graphite alkene aggregate, complexing of metal ion agent washed after and water washing complete after all need to carry out filtration treatment to quasiflake graphite alkene aggregate, finally obtain the quasiflake graphite alkene aggregate wet feed that pH value is 6-8;
D, the quasiflake graphite alkene aggregate wet feed after washing is joined in proportion in compound stripping liquid and carries out ultrasonic oscillation process 0.5-20 hours, realize peeling off, graphene dispersion is made to form graphene solution in compound stripping liquid, wherein, the mass ratio of quasiflake graphite alkene aggregate wet feed and compound stripping liquid is 1:5-25;
E, the moisture adopted in expansion drying or cryodesiccated method removal graphene solution, obtain graphene powder, the moisture content of graphene powder is less than 5wt%.
In the present embodiment, described composite expanded liquid be by following component by mass percentage Homogeneous phase mixing form: superoxol 75-90%, complexing of metal ion agent 1-10%, acidity-basicity regulator 2-5%, surface tension modifier 0.5-5%, all the other are water.Wherein, the concentration of superoxol is 20-30%.Further, complexing of metal ion agent in described composite expanded liquid is the compound of Seignette salt, trisodium phosphate and disodium edta, described acidity-basicity regulator is the compound of hydrochloric acid and sulfuric acid, and described surface tension modifier is the compound of methyl alcohol, ethanol and propyl alcohol.
In the present embodiment, described compound stripping liquid be by following component by mass percentage Homogeneous phase mixing form: complexing of metal ion agent 5-20%, surface tension modifier 1-5%, all the other are water.Further, the complexing of metal ion agent in described compound stripping liquid is the compound of Seignette salt, trisodium phosphate, disodium edta and Sunmorl N 60S, and surface tension modifier is the compound of methyl alcohol and ethanol.
In the present embodiment, the pH value of quasiflake graphite alkene aggregate wet feed determines according to the pH value of wash filtrate, if the pH value of wash filtrate is 6-8, then illustrates that the pH value of the moisture adsorbed in quasiflake graphite alkene aggregate wet feed is also between 6-8.
In the present embodiment, the experiment proved that, the number of plies of the graphene film of gained graphene powder is less than 7 layers, and lateral dimension is 1-5 microns, and carbon-to-oxygen ratio is 20-100, and foreign matter content is less than 2wt%.
Embodiment 2
A method for Graphene is prepared in mass-producing, comprises the following steps:
A, graphite intercalation compound powder is joined in composite expanded liquid, then under the condition of 25 ° of C, expansion reaction 3 hours is carried out, obtain the quasiflake graphite alkene aggregate suspension of high level expansion, wherein, the graphite intercalation compound treatment capacity of every 1 ton of composite expanded liquid is 9Kg;
B, filtration treatment is carried out to quasiflake graphite alkene aggregate suspension, obtain quasiflake graphite alkene aggregate;
C, successively employing complexing of metal ion agent and water washing quasiflake graphite alkene aggregate, complexing of metal ion agent washed after and water washing complete after all need to carry out filtration treatment to quasiflake graphite alkene aggregate, finally obtain the quasiflake graphite alkene aggregate wet feed that pH value is 6-8;
D, the quasiflake graphite alkene aggregate wet feed after washing is joined in proportion in compound stripping liquid and carries out ultrasonic oscillation process 0.5 hour, realize peeling off, graphene dispersion is made to form graphene solution in compound stripping liquid, wherein, the mass ratio of quasiflake graphite alkene aggregate wet feed and compound stripping liquid is 1:5;
E, the moisture adopted in expansion drying or cryodesiccated method removal graphene solution, obtain graphene powder, the moisture content of graphene powder is less than 5wt%.
In the present embodiment, described composite expanded liquid be by following component by mass percentage Homogeneous phase mixing form: concentration is the superoxol 90% of 20%, complexing of metal ion agent 5%, acidity-basicity regulator 2%, surface tension modifier 2%, and all the other are water.Further, described complexing of metal ion agent is the compound of oxalic acid and oxalate, and described acidity-basicity regulator is the compound of phosphoric acid, formic acid and acetic acid, and described surface tension modifier is the compound of propyl alcohol and butanols.
In the present embodiment, described compound stripping liquid be by following component by mass percentage Homogeneous phase mixing form: complexing of metal ion agent 5%, surface tension modifier 5%, all the other are water.Further, the complexing of metal ion agent in described compound stripping liquid is the compound of Sunmorl N 60S, ethylenediamine tetraacetic methene sodium phosphate and oxalic acid, and surface tension modifier is the compound of propyl alcohol, sodium lauryl sulphate and Sodium dodecylbenzene sulfonate.
In the present embodiment, for the graphite intercalation compound of 4 parts of identical amounts, use respectively through the composite expanded liquid expansion process 40min obtained by above-mentioned special parameter, 60min, 100min and 120min, following experimental result can be obtained:
Again respectively with single batch of 100Kg, 200 Kg, 300 Kg, 350 Kg, 500 Kg graphite intercalation compounds for raw material, after aforesaid method process, high-quality graphene product can be obtained, specific experiment parameter tool following table:
Embodiment 3
A method for Graphene is prepared in mass-producing, comprises the following steps:
A, graphite intercalation compound powder is joined in composite expanded liquid, then under the condition of 35 ° of C, expansion reaction 4 hours is carried out, obtain the quasiflake graphite alkene aggregate suspension of high level expansion, wherein, the graphite intercalation compound treatment capacity of every 1 ton of composite expanded liquid is 11Kg;
B, filtration treatment is carried out to quasiflake graphite alkene aggregate suspension, obtain quasiflake graphite alkene aggregate;
C, successively employing complexing of metal ion agent and water washing quasiflake graphite alkene aggregate, complexing of metal ion agent washed after and water washing complete after all need to carry out filtration treatment to quasiflake graphite alkene aggregate, finally obtain the quasiflake graphite alkene aggregate wet feed that pH value is 6-8;
D, the quasiflake graphite alkene aggregate wet feed after washing is joined in proportion in compound stripping liquid and carries out ultrasonic oscillation process 8 hours, realize peeling off, graphene dispersion is made to form graphene solution in compound stripping liquid, wherein, the mass ratio of quasiflake graphite alkene aggregate wet feed and compound stripping liquid is 1:15;
E, the moisture adopted in expansion drying or cryodesiccated method removal graphene solution, obtain graphene powder, the moisture content of graphene powder is less than 5wt%.
In the present embodiment, described composite expanded liquid be by following component by mass percentage Homogeneous phase mixing form: concentration is the superoxol 85% of 24%, complexing of metal ion agent 2%, acidity-basicity regulator 3%, surface tension modifier 0.5%, and all the other are water.Further, described complexing of metal ion agent is the compound of oxalate and Sunmorl N 60S, and described acidity-basicity regulator is the compound of oxalic acid and ammoniacal liquor, and described surface tension modifier is the compound of ethanol, propyl alcohol and butanols.
In the present embodiment, described compound stripping liquid be by following component by mass percentage Homogeneous phase mixing form: complexing of metal ion agent 11%, surface tension modifier 2%, all the other are water.Further, the complexing of metal ion agent in described compound stripping liquid is the compound of Sunmorl N 60S, ethylenediamine tetraacetic methene sodium phosphate and oxalic acid, and surface tension modifier is the compound of propyl alcohol, sodium lauryl sulphate and Sodium dodecylbenzene sulfonate.
In the present embodiment, for the graphite intercalation compound of 4 parts of identical amounts, use respectively through the composite expanded liquid expansion process 40min obtained by above-mentioned special parameter, 60min, 100min and 120min, following experimental result can be obtained:
Again respectively with single batch of 100Kg, 200 Kg, 300 Kg, 350 Kg, 500 Kg graphite intercalation compounds for raw material, after aforesaid method process, high-quality graphene product can be obtained, specific experiment parameter tool following table:
Embodiment 4
A method for Graphene is prepared in mass-producing, comprises the following steps:
A, graphite intercalation compound powder is joined in composite expanded liquid, then under the condition of 45 ° of C, expansion reaction 5 hours is carried out, obtain the quasiflake graphite alkene aggregate suspension of high level expansion, wherein, the graphite intercalation compound treatment capacity of every 1 ton of composite expanded liquid is 13Kg;
B, filtration treatment is carried out to quasiflake graphite alkene aggregate suspension, obtain quasiflake graphite alkene aggregate;
C, successively employing complexing of metal ion agent and water washing quasiflake graphite alkene aggregate, complexing of metal ion agent washed after and water washing complete after all need to carry out filtration treatment to quasiflake graphite alkene aggregate, finally obtain the quasiflake graphite alkene aggregate wet feed that pH value is 6-8;
D, the quasiflake graphite alkene aggregate wet feed after washing is joined in proportion in compound stripping liquid and carries out ultrasonic oscillation process 15 hours, realize peeling off, graphene dispersion is made to form graphene solution in compound stripping liquid, wherein, the mass ratio of quasiflake graphite alkene aggregate wet feed and compound stripping liquid is 1:20;
E, the moisture adopted in expansion drying or cryodesiccated method removal graphene solution, obtain graphene powder, the moisture content of graphene powder is less than 5wt%.
In the present embodiment, described composite expanded liquid be by following component by mass percentage Homogeneous phase mixing form: concentration is the superoxol 80% of 27%, complexing of metal ion agent 8%, acidity-basicity regulator 5%, surface tension modifier 5%, and all the other are water.Further, described complexing of metal ion agent is the compound of ethylenediamine tetraacetic methene sodium phosphate and diethanolamine, and described acidity-basicity regulator is the compound of sodium hydroxide and potassium hydroxide, and described surface tension modifier is the compound of butanols and ethyl acetate.
In the present embodiment, described compound stripping liquid be by following component by mass percentage Homogeneous phase mixing form: complexing of metal ion agent 20%, surface tension modifier 1%, all the other are water.Further, the complexing of metal ion agent in described compound stripping liquid is the compound of oxalate and diethanolamine, and surface tension modifier is the compound of Sodium dodecylbenzene sulfonate and cetyl trimethylammonium bromide.
In the present embodiment, for the graphite intercalation compound of 4 parts of identical amounts, use respectively through the composite expanded liquid expansion process 40min obtained by above-mentioned special parameter, 60min, 100min and 120min, following experimental result can be obtained:
Again respectively with single batch of 100Kg, 200 Kg, 300 Kg, 350 Kg, 500 Kg graphite intercalation compounds for raw material, after aforesaid method process, high-quality graphene product can be obtained, specific experiment parameter tool following table:
Embodiment 5
A method for Graphene is prepared in mass-producing, comprises the following steps:
A, graphite intercalation compound powder is joined in composite expanded liquid, then under the condition of 50 ° of C, expansion reaction 6 hours is carried out, obtain the quasiflake graphite alkene aggregate suspension of high level expansion, wherein, the graphite intercalation compound treatment capacity of every 1 ton of composite expanded liquid is 15Kg;
B, filtration treatment is carried out to quasiflake graphite alkene aggregate suspension, obtain quasiflake graphite alkene aggregate;
C, successively employing complexing of metal ion agent and water washing quasiflake graphite alkene aggregate, complexing of metal ion agent washed after and water washing complete after all need to carry out filtration treatment to quasiflake graphite alkene aggregate, finally obtain the quasiflake graphite alkene aggregate wet feed that pH value is 6-8;
D, the quasiflake graphite alkene aggregate wet feed after washing is joined in proportion in compound stripping liquid and carries out ultrasonic oscillation process 20 hours, realize peeling off, graphene dispersion is made to form graphene solution in compound stripping liquid, wherein, the mass ratio of quasiflake graphite alkene aggregate wet feed and compound stripping liquid is 1:25;
E, the moisture adopted in expansion drying or cryodesiccated method removal graphene solution, obtain graphene powder, the moisture content of graphene powder is less than 5wt%.
In the present embodiment, described composite expanded liquid be by following component by mass percentage Homogeneous phase mixing form: concentration is the superoxol 75% of 30%, complexing of metal ion agent 10%, acidity-basicity regulator 4%, surface tension modifier 2%, and all the other are water.Further, described complexing of metal ion agent is the compound of diethanolamine and trolamine, and described acidity-basicity regulator is the compound of quadrol and sodium bicarbonate, and described surface tension modifier is the compound of ethanol and ethyl acetate.
In the present embodiment, described compound stripping liquid be by following component by mass percentage Homogeneous phase mixing form: complexing of metal ion agent 16%, surface tension modifier 4%, all the other are water.Further, the complexing of metal ion agent in described compound stripping liquid is the compound of oxalate, diethanolamine and trolamine, and surface tension modifier is the compound of cetyl trimethylammonium bromide and fluorocarbon surfactant.
In the present embodiment, for the graphite intercalation compound of 4 parts of identical amounts, use respectively through the composite expanded liquid expansion process 40min obtained by above-mentioned special parameter, 60min, 100min and 120min, following experimental result can be obtained:
Again respectively with single batch of 100Kg, 200 Kg, 300 Kg, 350 Kg, 500 Kg graphite intercalation compounds for raw material, after aforesaid method process, high-quality graphene product can be obtained, specific experiment parameter tool following table:
Embodiment 6
A kind of expansion gear carrying out expansion reaction for graphite intercalation compound, comprise expansion drum 1 and stirring mechanism, described expansion drum 1 is provided with chuck 2, described chuck 2 bottom is provided with hot water or steam inlet 3, top is provided with hot water or vapour outlet 4, described stirring mechanism comprises motor 5 and stir shaft 6, and described motor 5 is fixed on expansion drum 1 top, and described stir shaft 6 is arranged on the middle part of expansion drum 1 by motor 5.
Further, the shell 7 that described chuck 2 is rolled on expansion drum 1 outside surface by expansion drum 1 and fixed packet combines.Further, be provided with escape orifice 8 bottom described chuck 2, escape orifice 8 is positioned at the below of hot water or steam inlet 3.
In the present embodiment, the outer wall of described expansion drum 1 is provided with four symmetrical mounting blocks 15, described expansion drum 1 top is provided with taper top 9, described taper top 9 is provided with solid-phase material charging opening 10, liquid phase material charging opening 11, water-in 12 and two exhaust outlets 13, all aerofoil fan is equipped with in two exhaust outlets 13, the bottom of described expansion drum 1 is provided with drain hole 14, and this drain hole 14 is connected with displaying baiting valve.
In the present embodiment, described shell 7 is that an overall sheet material compacting forms, and is weldingly fixed on the outside surface of expansion drum 1.
In the present embodiment, the main material of expansion drum 1 adopts S31603, Q235B, and wherein contact internal walls material parts adopts S31603.
In the present embodiment, described chuck 2 also directly can be offered inner chamber and be formed on expansion drum 1 wall.
During work, first in expansion drum 1, raw material is added in proportion by liquid phase material charging opening 11 and water-in 12, configure quantitative composite expanded liquid, then in expansion drum 1, graphite intercalation compound powder is added by solid-phase material charging opening 10, graphite intercalation compound floats on liquid level after contacting with composite expanded liquid, start to expand reaction, this reaction is that static process (gathers heat of reaction, the carrying out of accelerated reaction), the graphite intercalation compound touching composite expanded liquid first participates in reaction, but along with the carrying out of reaction, material bed more and more thicker, upper materials cannot touch composite expanded liquid by syphonic effect, the solid liquid phase material now needing starter motor 5 to control in stir shaft 6 pairs of expansion drums 1 mixes, solid liquid phase material is allowed fully to contact, after about stirring several minutes, stop stirring, continue reaction, until graphite intercalation compound complete reaction.In reaction process, repeatedly the short period of time produces a large amount of steam in meeting, is discharged by steam in time by aerofoil fan.Hot water or steam cycle need be passed in chuck 2 during reaction, ensure that the temperature of composite expanded liquid is in OK range, after reaction terminates, open displaying baiting valve, after solid liquid phase material is all discharged, cleaning expansion drum 1 inwall.
Embodiment 7
A kind of ultrasonic wave stripping off device for the preparation of Graphene, comprise and peel off tank 16 and Duo Gen ultrasound wave vibrating bar 17, described many ultrasound wave vibrating bars 17 are vertically fixed on to be peeled off in tank 16, and many ultrasound wave vibrating bar 17 distributions in polycyclic in same frontal plane of projection.
In the present embodiment, vertical layered being arranged on of described many ultrasound wave vibrating bars 17 is peeled off in tank 16, the lower end of upper strata ultrasound wave vibrating bar 17 misplaces crossing with the upper end of lower floor ultrasound wave vibrating bar 17, and on every ring, the quantity of ultrasound wave vibrating bar 17 is integral multiples of ultrasound wave vibrating bar 17 number of plies.
In the present embodiment, in described stripping tank 16, the quantity of every layer of ultrasound wave vibrating bar 17 is all identical, and the ultrasound wave vibrating bar 17 of every layer is evenly arranged in stripping tank 16.
In the present embodiment, the sidewall in described stripping tank 16 and bottom are provided with compressed-air atomizer 18.
During work: first add appropriate compound stripping liquid in stripping tank 16, again quasiflake graphite alkene aggregate wet feed is added and peel off in tank 16, then open ultrasonic vibration rod power supply and start supersound process, simultaneously by nozzle 18 jet compression air burst agitation material, after material has been peeled off, closing device power supply, opens discharge hole for discharge.
Claims (14)
1. a method for Graphene is prepared in mass-producing, it is characterized in that comprising the following steps:
A, graphite intercalation compound powder is joined in composite expanded liquid, then under the condition of 20-50 ° of C, carry out expansion reaction 2-6 hours, obtain the quasiflake graphite alkene aggregate suspension expanded;
B, filtration treatment is carried out to quasiflake graphite alkene aggregate suspension, obtain quasiflake graphite alkene aggregate;
C, successively employing complexing of metal ion agent and water washing quasiflake graphite alkene aggregate, complexing of metal ion agent washed after and water washing complete after all need to carry out filtration treatment to quasiflake graphite alkene aggregate, finally obtain the quasiflake graphite alkene aggregate wet feed that pH value is 6-8;
D, the quasiflake graphite alkene aggregate wet feed after washing is joined in compound stripping liquid and carries out ultrasonic oscillation process 0.5-20 hours, realize peeling off, make graphene dispersion form graphene solution in compound stripping liquid;
E, the moisture adopted in expansion drying or cryodesiccated method removal graphene solution, obtain graphene powder, the moisture content of graphene powder is less than 5wt%.
2. the method for Graphene is prepared in a kind of mass-producing as claimed in claim 1; it is characterized in that: described composite expanded liquid be by following component by mass percentage Homogeneous phase mixing form: superoxol 75-90%; complexing of metal ion agent 1-10%; acidity-basicity regulator 2-5%; surface tension modifier 0.5-5%, all the other are water.
3. the method for Graphene is prepared in a kind of mass-producing as claimed in claim 2, it is characterized in that: the concentration of described superoxol is 20-30%.
4. the method for Graphene is prepared in a kind of mass-producing as claimed in claim 2 or claim 3, it is characterized in that: in described composite expanded liquid, complexing of metal ion agent is Seignette salt, trisodium phosphate, disodium edta, oxalic acid, oxalate, Sunmorl N 60S, ethylenediamine tetraacetic methene sodium phosphate, diethanolamine, one or more compound in trolamine, described acidity-basicity regulator is hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, ammoniacal liquor, sodium hydroxide, potassium hydroxide, quadrol, one or more compound in sodium bicarbonate, described surface tension modifier is methyl alcohol, ethanol, propyl alcohol, butanols, one or more compound in ethyl acetate.
5. the method for Graphene is prepared in a kind of mass-producing as claimed in claim 1 or 2; it is characterized in that: described compound stripping liquid be by following component by mass percentage Homogeneous phase mixing form: complexing of metal ion agent 5-20%; surface tension modifier 1-5%, all the other are water.
6. the method for Graphene is prepared in a kind of mass-producing as claimed in claim 5; it is characterized in that: the complexing of metal ion agent in described compound stripping liquid is one or more the compound in Seignette salt, trisodium phosphate, disodium edta, Sunmorl N 60S, ethylenediamine tetraacetic methene sodium phosphate, oxalic acid, oxalate, diethanolamine, trolamine, and surface tension modifier is one or more the compound in methyl alcohol, ethanol, propyl alcohol, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, cetyl trimethylammonium bromide, fluorocarbon surfactant.
7. the method for Graphene is prepared in a kind of mass-producing as claimed in claim 1, it is characterized in that: in described step a, the graphite intercalation compound treatment capacity of every 1 ton of composite expanded liquid is 9-15Kg.
8. the method for Graphene is prepared in a kind of mass-producing as claimed in claim 1, it is characterized in that: gained graphene powder in described step e, and the number of plies of its graphene film is 1-5 layers, lateral dimension 2-4 microns, carbon-to-oxygen ratio 25-80.
9. the method for Graphene is prepared in a kind of mass-producing as claimed in claim 1, it is characterized in that: described step a carries out expansion reaction by expansion gear, described expansion gear comprises expansion drum (1) and stirring mechanism, described expansion drum (1) is provided with chuck (2), described chuck (2) bottom is provided with hot water or steam inlet (3), top is provided with hot water or vapour outlet (4), described stirring mechanism comprises motor (5) and stir shaft (6), described motor (5) is fixed on expansion drum (1) top, described stir shaft (6) is arranged on the middle part of expansion drum (1) by motor (5).
10. the method for Graphene is prepared in a kind of mass-producing as claimed in claim 9; it is characterized in that: described expansion drum (1) top is provided with taper top (9); described taper top (9) is provided with solid-phase material charging opening (10), liquid phase material charging opening (11), water-in (12) and exhaust outlet (13); the bottom of described expansion drum (1) is provided with drain hole (14), and (14) are connected with displaying baiting valve to this drain hole.
The method of Graphene is prepared in 11. a kind of mass-producings as described in claim 1,9 or 10; it is characterized in that: described steps d is peeled off by ultrasonic wave stripping off device; described ultrasonic wave stripping off device comprises peels off tank (16) and many ultrasound wave vibrating bars (17); described many ultrasound wave vibrating bars (17) are vertically fixed on to be peeled off in tank (16), and many ultrasound wave vibrating bar (17) distributions in polycyclic in same frontal plane of projection.
The method of Graphene is prepared in 12. a kind of mass-producings as claimed in claim 11; it is characterized in that: vertical layered being arranged on of described many ultrasound wave vibrating bars (17) is peeled off in tank (16); the lower end of upper strata ultrasound wave vibrating bar (17) misplaces crossing with the upper end of lower floor's ultrasound wave vibrating bar (17), and on every ring, the quantity of ultrasound wave vibrating bar (17) is the integral multiple of ultrasound wave vibrating bar (17) number of plies.
The method of Graphene is prepared in 13. a kind of mass-producings as claimed in claim 12; it is characterized in that: (in 16, the quantity of every layer of ultrasound wave vibrating bar (17) is all identical, and the ultrasound wave vibrating bar of every layer (17) is evenly arranged in stripping tank (16) for described stripping tank.
The method of Graphene is prepared in 14. a kind of mass-producings as claimed in claim 11, it is characterized in that: the sidewall in described stripping tank (16) and bottom are provided with compressed-air atomizer (18).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107500279A (en) * | 2017-08-04 | 2017-12-22 | 湖南国盛石墨科技有限公司 | A kind of batch prepares the method and its production system of graphene |
| CN107673335A (en) * | 2017-01-04 | 2018-02-09 | 柯良节 | Graphene preparation method based on the reaction of multiphase quantum self coupling |
| CN110127689A (en) * | 2019-05-05 | 2019-08-16 | 陈让珠 | The production method of silicone oil phase graphene |
| US10472596B2 (en) | 2017-06-27 | 2019-11-12 | Ecolab Usa Inc. | Non-phosphorous transition metal control in laundry applications |
| CN112299402A (en) * | 2019-07-30 | 2021-02-02 | 中国石油化工股份有限公司 | Stripping method of graphite intercalation substance, graphene prepared by stripping method and application of graphene in composite fiber |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
| CN102627273A (en) * | 2012-04-19 | 2012-08-08 | 常州第六元素材料科技股份有限公司 | Purifying process for graphene material of energy storing device |
| CN102744028A (en) * | 2012-06-21 | 2012-10-24 | 泰州巨纳新能源有限公司 | Industrial large-scale reaction vessel for preparing graphene |
| CN102910624A (en) * | 2012-11-08 | 2013-02-06 | 南京师范大学 | Preparation method of high-yield graphene without defects |
| CN104058396A (en) * | 2014-07-14 | 2014-09-24 | 复旦大学 | Method for preparing large-size high-quality graphene with controllable number of layers |
| CN104118875A (en) * | 2014-07-30 | 2014-10-29 | 江苏捷峰高科能源材料股份有限公司 | Method and special device for cleaning active carbon of supercapacitor |
-
2015
- 2015-04-20 CN CN201510186396.8A patent/CN104787758B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
| CN102627273A (en) * | 2012-04-19 | 2012-08-08 | 常州第六元素材料科技股份有限公司 | Purifying process for graphene material of energy storing device |
| CN102744028A (en) * | 2012-06-21 | 2012-10-24 | 泰州巨纳新能源有限公司 | Industrial large-scale reaction vessel for preparing graphene |
| CN102910624A (en) * | 2012-11-08 | 2013-02-06 | 南京师范大学 | Preparation method of high-yield graphene without defects |
| CN104058396A (en) * | 2014-07-14 | 2014-09-24 | 复旦大学 | Method for preparing large-size high-quality graphene with controllable number of layers |
| CN104118875A (en) * | 2014-07-30 | 2014-10-29 | 江苏捷峰高科能源材料股份有限公司 | Method and special device for cleaning active carbon of supercapacitor |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107673335A (en) * | 2017-01-04 | 2018-02-09 | 柯良节 | Graphene preparation method based on the reaction of multiphase quantum self coupling |
| KR20190007031A (en) * | 2017-01-04 | 2019-01-21 | 량제 커 | A method for producing graphene based on a polyphase quantum bonding reaction |
| EP3486213A4 (en) * | 2017-01-04 | 2019-08-21 | Or, Leung Chit | Method for preparing graphene based on multi-phase quantum self-coupling reaction |
| KR102173421B1 (en) | 2017-01-04 | 2020-11-03 | 량제 커 | Graphene manufacturing method based on multiphase quantum self-bonding reaction |
| US10472596B2 (en) | 2017-06-27 | 2019-11-12 | Ecolab Usa Inc. | Non-phosphorous transition metal control in laundry applications |
| CN107500279A (en) * | 2017-08-04 | 2017-12-22 | 湖南国盛石墨科技有限公司 | A kind of batch prepares the method and its production system of graphene |
| CN107500279B (en) * | 2017-08-04 | 2020-04-07 | 湖南国盛石墨科技有限公司 | Method for preparing graphene in batches and production system thereof |
| CN110127689A (en) * | 2019-05-05 | 2019-08-16 | 陈让珠 | The production method of silicone oil phase graphene |
| CN112299402A (en) * | 2019-07-30 | 2021-02-02 | 中国石油化工股份有限公司 | Stripping method of graphite intercalation substance, graphene prepared by stripping method and application of graphene in composite fiber |
| CN112299402B (en) * | 2019-07-30 | 2022-03-11 | 中国石油化工股份有限公司 | Stripping method of graphite intercalation substance, graphene prepared by stripping method and application of graphene in composite fiber |
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