CN104787758B - Method for preparing graphene on large scale - Google Patents
Method for preparing graphene on large scale Download PDFInfo
- Publication number
- CN104787758B CN104787758B CN201510186396.8A CN201510186396A CN104787758B CN 104787758 B CN104787758 B CN 104787758B CN 201510186396 A CN201510186396 A CN 201510186396A CN 104787758 B CN104787758 B CN 104787758B
- Authority
- CN
- China
- Prior art keywords
- graphene
- compound
- ultrasound wave
- expansion
- metal ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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, relates in particular to a kind of method of prepare with scale Graphene, the method energy
Enough single batches produce hundreds of kilograms of high-quality graphene product.
Background technology
Since being found from 2004, Graphene receives much concern as a kind of new carbon.It is it is a kind of completely bysp 2 The thickness that the carbon atom of hydridization is constituted is only the quasi- two dimensional crystal material of monoatomic layer or several monoatomic layers, with height
The excellent performance such as light transmission and electric conductivity, high-specific surface area, high intensity and pliability, it is expected to high-performance nanometer electronic device,
The fields such as photoelectric device, gas sensor, composite, field emmision material and energy stores obtain extensively applies.But, it is high-quality
Inexpensive, a large amount of preparation of amount Graphene is still faced adverse conditions, and constrains the development and application of the material.
At present, the definition of the grapheme material that academia is accepted extensively is：Graphite of the carbon atom number of plies within 10 layers is thin
Piece, its thickness is below 3.5 nanometers.For this purpose, China Patent No. " 201110282370.5 " discloses " one on May 2nd, 2012
Plant the method for preparing high-quality graphene ", its technical scheme is the graphite intercalation with halogen or metal halide as intercalator
Compound is raw material, carries out expansion and ultrasound is peeled off in a solvent, so as to obtain high-quality stone in oxalic acid or hydrogenperoxide steam generator
Black alkene.The characteristic property index of graphene product obtained by this method is：3-8 layers of the number of plies of graphene film（Thickness be 1-
2.5 nanometer）, 5-50 microns of lateral dimension, carbon-to-oxygen ratio 30-120,5 wt% of impurity content.But the method can only realize list
The preparation of the high-quality graphene of batch hectogram level.
With the expansion of Graphene application, the demand of Graphene is increasingly increased, in order to obtain higher production
Ability, it is necessary to be amplified to realize the yield of the hundreds of feather weight of single batch to above-mentioned technology.But at single batch material
The increase of reason amount, occurs in that the following problem for having a strong impact on production effect in amplification process：
Firstth, above-mentioned patent mainly uses the metal ion (M for being present in graphite layersx+) catalyzing hydrogen peroxide is in interlayer
Decompose and produce oxygen (O2) expansion peel off graphite obtain Graphene, when expansion reaction starts, metal ion is only existed
In graphite layers, react based on effectively decomposing；With the carrying out of reaction, interlayer metal ion is gradually dissolved in liquid phase, when
When the concentration of metal ion increases to a certain extent, the aggravation of decomposition can be caused, is particularly being prepared in a large number（Single batch system
Standby hundreds of kilograms Graphene）When, the increase of inventory causes the amount of metal ion from graphite layers dissolution huge, on the contrary thing
Increasing for material also cause metal ion diffusion hindered in the solution, but as the inflation fluid in above-mentioned patent is oxalic acid or peroxide
Change hydrogen solution, the inflation fluid can not be acted upon to the metal ion in solution, this results in local invalid and decomposes aggravation so that
The working substance Mass lost of expansion reaction is participated in, causes the underexpansion of intercalated graphite raw material, the expansion generation to graphite is unfavorable
Affect, so as to cannot scale obtain high-quality Graphene.Secondth, after peeling off, intercalator is difficult to remove completely, causes gained
Impurity content in graphene product is too high（5 — 10 wt%）, and subsequent applications are had undesirable effect.3rd, obtain
Graphene number of plies majority concentrates on 7-9 layers, the quality and poor-performing of graphene product.4th, ultrasound wave is peeled off needs in a large number
Organic solvent or various surfactants aqueous solution or organic solution, cause the production cost of Graphene higher.5th, stone
When ink peels off into Graphene, specific surface area is increased dramatically, simultaneously because the weak oxide effect in expansion reaction so that Graphene table
Face is with negative charge, thus metal ion positively charged in easy absorption intercalator and solution, due to process during a large amount of preparation
The increase of inventory, these metal ions are difficult to remove by simple washing, thus result in metal in gained graphene product
The increase of ion concentration.The presence of a large amount of metal ions can be adversely affected to the application of Graphene.Although pickling can have
Effect removes metal ion, but a large amount of pickling can also cause Heavy environmental pollution while cost is increased.
The content of the invention
It is an object of the invention to solve the above-mentioned problems in the prior art, there is provided a kind of prepare with scale Graphene
Method, using the present invention after, be obtained in that single batch volume of production up to hundreds of kilograms of high-quality graphene product.
For achieving the above object, the technical solution used in the present invention is as follows：
A kind of method of prepare with scale Graphene, it is characterised in that comprise the following steps：
A, graphite intercalation compound powder body is added in composite expanded liquid, is then carried out under conditions of 20-50 °C
Expansion reaction 2-6 hours, obtains the quasiflake graphite alkene aggregation liquid suspension for expanding；
B, to quasiflake graphite alkene aggregation liquid suspension carry out filtration treatment, obtain quasiflake graphite alkene aggregation；
C, complexing of metal ion agent and water washing quasiflake graphite alkene aggregation are adopted successively, complexing of metal ion agent washing
After the completion of and water washing after the completion of be required to carry out filtration treatment to quasiflake graphite alkene aggregation, finally obtain pH value for 6-8
Quasiflake graphite alkene aggregation wet feed；
D, the quasiflake graphite alkene aggregation wet feed after washing is added in compound stripper carries out at ultrasonic wave concussion
Reason 0.5-20 hours, realizes peeling off, and makes graphene dispersion form graphene solution in compound stripper；
E, the moisture removed using expansion drying or cryodesiccated method in graphene solution, obtain graphene powder,
The moisture of graphene powder is less than 5wt%.
The composite expanded liquid is to be uniformly mixed following components by mass percentage：Hydrogenperoxide steam generator 75-
90%, complexing of metal ion agent 1-10%, acidity-basicity regulator 2-5%, surface tension modifier 0.5-5%, remaining is water.
The concentration of the hydrogenperoxide steam generator is 20-30%.
In the composite expanded liquid complexing of metal ion agent be sodium potassium tartrate tetrahydrate, sodium pyrophosphate, disodium edta,
One or more in oxalic acid, oxalates, sodium gluconate, ethylenediamine tetraacetic methene sodium phosphate, diethanolamine, triethanolamine is answered
Close, the acidity-basicity regulator be hydrochloric acid, sulphuric acid, phosphoric acid, formic acid, acetic acid, ethanedioic acid, ammonia, sodium hydroxide, potassium hydroxide,
One or more in ethylenediamine, sodium bicarbonate it is compound, the surface tension modifier be methanol, ethanol, propanol, butanol,
One or more in ethyl acetate it is compound.
The compound stripper is to be uniformly mixed following components by mass percentage：Complexing of metal ion agent 5-
20%, surface tension modifier 1-5%, remaining is water.
Complexing of metal ion agent in the compound stripper is sodium potassium tartrate tetrahydrate, sodium pyrophosphate, sodium ethylene diamine tetracetate
One or more in salt, sodium gluconate, ethylenediamine tetraacetic methene sodium phosphate, oxalic acid, oxalates, diethanolamine, triethanolamine
It is compound, surface tension modifier is methanol, ethanol, propanol, sodium lauryl sulphate, dodecylbenzene sodium sulfonate, hexadecane
One or more in base trimethylammonium bromide, fluorocarbon surfactant it is compound.
Graphite intercalation compound treating capacity in step a per 1 ton of composite expanded liquid is 9-15Kg.
Gained graphene powder in step e, the number of plies of its graphene film are less than 7 layers, 1-5 microns of lateral dimension, carbon
Than 20-100, impurity content is less than 2wt% to oxygen.
Gained graphene powder in step e, the number of plies of its graphene film is 1-5 layers, 2-4 microns of lateral dimension,
Carbon-to-oxygen ratio 25-80.
Step a carries out expansion reaction by expansion gear, and the expansion gear includes expansion drum and rabbling mechanism, institute
State, the chuck bottom is provided with hot water or steam inlet, and top is provided with hot water or steam goes out
Mouthful, the rabbling mechanism includes motor and shaft, and the motor is fixed on expansion drum top, and the shaft is set by motor
Put at the middle part of expansion drum.
The chuck is formed by the housing combination that expansion drum and fixation are wrapped on expansion drum outer surface.
The chuck bottom is provided with discharge port, and discharge port is located at the lower section of hot water or steam inlet.
The expansion drum top is provided with taper top, and solid-phase material charge door, liquid phase material are provided with the taper top
Charge door, water inlet and exhaust outlet, the bottom of the expansion drum are provided with drain hole, and displaying blowing is connected with the drain hole
Valve.
The quantity of the exhaust outlet is to be each equipped with axial flow blower in two, and two exhaust outlets.
Four symmetrical fixtures are provided with the outer wall of the expansion drum.
Step d is peeled off by ultrasound wave stripping off device, and the ultrasound wave stripping off device includes peeling off tank and many
Root ultrasound wave vibrating bar, many described ultrasound wave vibrating bars are vertically fixed in stripping tank, and many ultrasound wave vibrating bars exist
It is distributed in polycyclic in same frontal plane of projection.
Many described ultrasound wave vibrating bars are vertical layered to be arranged in stripping tank, the lower end of upper strata ultrasound wave vibrating bar with
The upper end dislocation of lower floor's ultrasound wave vibrating bar is intersecting, and the quantity of ultrasound wave vibrating bar is the ultrasound wave vibrating bar number of plies on every ring
Integral multiple.
The quantity all same of every layer of ultrasound wave vibrating bar in the stripping tank, and per layer of ultrasound wave vibrating bar is uniformly arranged
Peel off in tank.
Side wall and bottom in the stripping tank is provided with compressed-air atomizer.
Under the present invention is also in liquid phase soaking conditionses, using the metal ion (M for being present in graphite layersx+) catalysis peroxide
Change hydrogen and decompose generation oxygen (O in interlayer2) expansion peel off graphite obtain Graphene（As shown in Figure 1）, its core is anti-
Should be：
, but the present invention can be in expansion reaction and washing process appoplexy involving the collateral
Close the metal ion in solution.In terms of its concrete mechanism of action is mainly reflected in three below：One is expansion reaction, anti-in expansion
Should be initial, metal ion exists only in graphite layers, reacts based on effectively decomposing, with carrying out and the graphite flake layer of reaction
Peel off, interlayer metal ion is gradually dissolved in liquid phase, and the now complexing of metal ion agent complexation in composite expanded liquid is dissolved into
Metal ion in solution so as to lose catalysis activity, so as to reach the effect for suppressing decomposition and promoting effectively decomposition, enters
And the quasiflake graphite alkene aggregation of high level expansion is obtained, two is carrying out washing treatment, washs vermiform using complexing of metal ion agent
Graphene aggregation, removes the metal ion in quasiflake graphite alkene aggregation.Three is lift-off processing, enters one in stripping process
Step removes the metal ion in quasiflake graphite alkene aggregation.Wherein, using the composite expanded liquid of above-mentioned specific components, Neng Goushi
The effective process of hundreds of kilograms of graphite intercalation compounds of existing single batch, is washed using complexing of metal ion agent, being capable of complexation graphite
The metal ion of interlayer, so as to improve the preparation quality of Graphene, using the compound stripper of specific components, being capable of further network
Dissociate during co oscillation the metal ion for.Three coordinates, it becomes possible to realize that single batch produces hundreds of kilograms of high-quality stone
Black alkene product.
Implementation of the present invention using expansion gear：Pass through liquid phase material charge door and water inlet first in proportion to swollen
Raw material, the good quantitative composite expanded liquid of configuration is added then to add stone by solid-phase material charge door into expansion drum in swell
Black intercalation compound powder, graphite intercalation compound are floated on after being contacted with composite expanded liquid on liquid level, start to expand reaction,
The reaction is static process（Gather heat of reaction, accelerate the carrying out of reaction）, touch the graphite intercalation chemical combination of composite expanded liquid
Thing first participates in reaction, but with the carrying out of reaction, material bed increasingly thicker, upper materials cannot touch multiple by siphonage
Inflation fluid is closed, is now needed startup motor control shaft to mix the solid-liquid phase materials in expansion drum, is about stirred a few minutes
Afterwards, stop stirring, continue reaction, until graphite intercalation compound reacts completely.Can produce the multiple short time in course of reaction big
Steam can be discharged in time by amount steam by axial flow blower.Hot water or steam circulation need to be passed through during reaction in chuck, it is ensured that multiple
Temperature time opening stirring in OK range, course of reaction of inflation fluid is closed, allows solid-liquid phase materials to be fully contacted, reaction terminates
Afterwards, show baiting valve in opening, after solid-liquid phase materials are all discharged, cleaning expansion top tank structure.
Using it is an advantage of the current invention that：
First, the present invention is due to adding complexing of metal ion during expansion reaction, carrying out washing treatment and lift-off processing
Agent, therefore, it is possible to the metal ion of positively charged is converted into negatively charged metal complex ion, effectively suppresses metal ion to exist
The absorption of graphenic surface, i.e., suppress decomposition while promoting and effectively decomposing, and only single batch does not produce hundreds of kilograms
The manufacture of Graphene provides powerful guarantee, moreover it is possible to make the content of impurity metal ion in graphene product be reduced to 0.5-
2wt%。
2nd, the present invention in, the complexing of metal ion agent in composite expanded liquid can with complexation be dissolved into the metal in solution from
Son so as to lose catalysis activity, reaches the effect for suppressing decomposition, and acidity-basicity regulator is used for the soda acid for adjusting extender
Degree, can optimize the complexation effect of chelating agent, and surface tension modifier is used to adjust infiltration of the stripper to graphite and Graphene
Property, to promote diffusion of the extender to graphite layers, and then promote effective decomposition reaction.Metal ion network in compound stripper
Mixture further complexation graphite layers can dissociate the metal ion for, compared with prior art, using above-mentioned specific components
Composite expanded liquid and compound stripper can improve the expansion uniformity of graphite and reduce percentage of impurity in large-scale production, so as to
The graphene product number of plies of final acquisition is made less than 10 layers, and has focused largely on 1-5 layers.In addition, if hydrogenperoxide steam generator
Concentration is less than 20%, the response time will be caused long and reaction is insufficient；If the concentration of hydrogenperoxide steam generator is higher than 30%, deposit again
In reaction aggravation, the safety problem such as uncontrollable is reacted, therefore the concentration of hydrogenperoxide steam generator is set as into 20-30%, both protected
Mildness and the safety of reaction have been demonstrate,proved, the adequacy of reaction has been in turn ensure that.
3rd, present invention production single batch graphene product is relative to raw graphite（Not comprising intercalator quality）Yield it is high
In 90%, have the advantages that the production time is short and raw material availability is high.
4th, present invention expansion stripping process hardly destroys the structure of Graphene, can farthest retain Graphene
Structure and electricity and mechanical property.
5th, it is this feature of static reaction process that the present invention is directed to graphite intercalation compound with the reaction of composite expanded liquid,
It is specific that rabbling mechanism and chuck are provided with expansion drum.Wherein, chuck can make the composite expanded liquid in expansion drum keep certain
Temperature, the persistence and adequacy for expansion reaction provide powerful guarantee；By hot water or steam are passed through in chuck come
The temperature of composite expanded liquid is kept, there is pollution-free, reusable edible, low cost and high insulating effect.Rabbling mechanism
Interval stirring power graphite intercalation compound is fully contacted in expansion process with composite expanded liquid so that graphite intercalation
The expansion reaction of compound is more abundant, is conducive to shortening the time of expansion reaction.Although prior art also has various knot
The agitator of structure, but those agitators are persistence stirrings, therefore, rabbling mechanism is combined to be formed with jacketed expansion drum
Expansion gear there is novelty and unexpected effect.
6th, in the present invention, chuck is formed by the housing combination that expansion drum and fixation are wrapped on expansion drum outer surface, the knot
Structure not only causes the sealing of chuck more preferably, also so that the heat transfer effect of hot water or steam is more preferable in chuck.
7th, in the present invention, be conducive to quickly removing Yu Shui in chuck and miscellaneous by being arranged on the discharge port of chuck bottom
Matter, using more convenient.
8th, in the present invention, expansion drum top arranges taper top, and taper top makes expansion drum space bigger, and is disposed thereon
Exhaust outlet coordinate, be prevented from produce steam loss everywhere, be more beneficial for aerofluxuss.In addition, in charging, by independent
The charging of solid-phase material charge door, liquid phase material charge door and water inlet, can avoid each solid-liquid phase materials before into expansion drum
Mixing, is conducive to the addition of precise control solid-liquid phase materials.
9th, in the present invention, as expansion reaction high water time can produce substantial amounts of gas, therefore two axial flow blower energy are passed through
The velocity of discharge of gas is further speeded up enough.
Tenth, in the present invention, by four symmetrical fixtures being arranged on expansion tank wall, be conducive to the fast of expansion drum
Speed is fixed.
11, in the present invention, many ultrasound wave vibrating bars peeled off in tank are distributed in polycyclic in same frontal plane of projection,
Ultrasonic power density in tank body can be increased with Omnidirectional radiation tank interior, material is peeled off so as to improve single batch
Amount.
12, in the present invention, many vertical layered being arranged on of ultrasound wave vibrating bar are peeled off in tank, and ultrasound wave shakes on every ring
The quantity of dynamic rod is the integral multiple of the ultrasound wave vibrating bar number of plies, and the structure causes ultrasound wave vibrating bar peeling off the ultrasonic spoke in tank
Penetrate effect and stability is more preferable, improve the quality of the peeling effect and final products obtained therefrom of material.Compared with prior art, surpass
The structure that the layering of acoustic vibration rod is arranged not only further increases the amount that single batch peels off material, also reduces the body for peeling off tank
Product and floor space, have the advantages that easy for installation and practical.And the lower end of upper strata ultrasound wave vibrating bar and lower floor's ultrasound
The upper end dislocation of ripple vibrating head is intersecting, then can avoid the white space without ultrasonic radiation occur in stripping tank.
13, in the present invention, every layer of ultrasound wave vibrating bar is uniformly arranged the structure peeled off in tank so that peel off in tank
Portion, middle part are identical with the ultrasonic radiation effect of bottom, i.e., when scale processes material, can at short notice fully by material
It is completely exfoliated, is conducive to improving the quality of graphene product.
14, in the present invention, by the nozzle jet compression air for peeling off pot sidewall and bottom, can be to peeling off in tank
Material plays rolling effect, had both improve peeling effect of the ultrasound wave to material, and had reduced splitting time again,
15, in the present invention Graphene low production cost, impact very little of the whole course of reaction to environment, and waste liquid
Processing cost is low.
16, the graphene film number of plies of graphene powder obtained by the present invention is adopted for 1-5 layers, lateral dimension 2-4
Micron, carbon-to-oxygen ratio 25-80, its quality is far better than the existing skill for being " 201110282370.5 " as representative with China Patent No.
The quality of graphene powder obtained in art.
17, replace the alcohols stripper of high cost by the compound stripper of the low surfactant of alternative costs, to swollen
After swollen reaction, gained quasiflake graphite alkene aggregation carries out ultrasonic wave concussion stripping, and the low cost for realizing graphene powder is raw
Produce.
Description of the drawings
Fig. 1 is expansion release mechanism schematic diagram of the graphite intercalation compound in composite expanded liquid：（a）Graphite intercalation
Compound is added in hydrogenperoxide steam generator；（b）Hydrogen peroxide decomposes generation oxygen under the catalytic action of graphite layers metal ion
Gas（O2）；（c）Graphene sheet layer peeling-off Graphene for obtaining monolithic in the presence of oxygen expansion；
Graphene powder obtained by Fig. 2 large-scale productions；
The transmission electron microscope pattern of Fig. 3 large-scale production Graphenes；
The thermogravimetric curve of Fig. 4 large-scale production Graphenes；
Main structure diagrams of the Fig. 5 for embodiment 6；
Fig. 6 is the main structure diagram of expansion drum in embodiment 6；
Fig. 7 is the overlooking the structure diagram of expansion drum in embodiment 6；
Fig. 8 is the main structure diagram of stripping tank in embodiment 7；
Fig. 9 is the overlooking the structure diagram of stripping tank in embodiment 7；
Figure 10 is the structural representation of ultrasound wave vibrating bar in embodiment 7；
It is labeled as in figure：1st, expansion drum, 2, chuck, 3, import, 4, outlet, 5, motor, 6, shaft, 7, shell, 8, row
Drain port, 9, taper top, 10, solid-phase material charge door, 11, liquid phase material charge door, 12, water inlet, 13, exhaust outlet, 14, blowing
Mouthful, 15, fixture, 16, peel off tank, 17, ultrasound wave vibrating bar, 18, nozzle.
Specific embodiment
Embodiment 1
A kind of method of prepare with scale Graphene, comprises the following steps：
A, graphite intercalation compound powder body is added in composite expanded liquid, is then carried out under conditions of 20-50 °C
Expansion reaction 2-6 hours, obtains the quasiflake graphite alkene aggregation liquid suspension of high level expansion, wherein, per 1 ton of composite expanded liquid
Graphite intercalation compound treating capacity be 9-15Kg；
B, to quasiflake graphite alkene aggregation liquid suspension carry out filtration treatment, obtain quasiflake graphite alkene aggregation；
C, complexing of metal ion agent and water washing quasiflake graphite alkene aggregation are adopted successively, complexing of metal ion agent washing
After the completion of and water washing after the completion of be required to carry out filtration treatment to quasiflake graphite alkene aggregation, finally obtain pH value for 6-8
Quasiflake graphite alkene aggregation wet feed；
D, the quasiflake graphite alkene aggregation wet feed after washing is proportionally added into ultrasound wave is carried out in compound stripper
Concussion is processed 0.5-20 hours, realizes peeling off, and makes graphene dispersion form graphene solution in compound stripper, wherein, it is compacted
Worm shape Graphene aggregation wet feed is 1 with the mass ratio of compound stripper：5—25；
E, the moisture removed using expansion drying or cryodesiccated method in graphene solution, obtain graphene powder,
The moisture of graphene powder is less than 5wt%.
In the present embodiment, the composite expanded liquid is to be uniformly mixed following components by mass percentage：Peroxidating
Hydrogen solution 75-90%, complexing of metal ion agent 1-10%, acidity-basicity regulator 2-5%, surface tension modifier 0.5-5%, its
Yu Weishui.Wherein, the concentration of hydrogenperoxide steam generator is 20-30%.Further, the metal ion network in the composite expanded liquid
Mixture is the compound of sodium potassium tartrate tetrahydrate, sodium pyrophosphate and disodium edta, and the acidity-basicity regulator is hydrochloric acid and sulfur
Sour is compound, and the surface tension modifier is the compound of methanol, ethanol and propanol.
In the present embodiment, the compound stripper is to be uniformly mixed following components by mass percentage：Metal from
Sub- chelating agent 5-20%, surface tension modifier 1-5%, remaining is water.Further, the metal in the compound stripper from
Sub- chelating agent is the compound of sodium potassium tartrate tetrahydrate, sodium pyrophosphate, disodium edta and sodium gluconate, surface tension adjustment
Agent is the compound of methanol and ethanol.
In the present embodiment, the pH value of quasiflake graphite alkene aggregation wet feed be according to the pH value of wash filtrate determining,
If the pH value of wash filtrate is 6-8, the pH value of the moisture adsorbed in illustrating quasiflake graphite alkene aggregation wet feed also exists
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, lateral dimension
For 1-5 microns, carbon-to-oxygen ratio is 20-100, and impurity content is less than 2wt%.
Embodiment 2
A kind of method of prepare with scale Graphene, comprises the following steps：
A, graphite intercalation compound powder body is added in composite expanded liquid, then carries out expanding under conditions of 25 °C anti-
Answer 3 hours, obtain the quasiflake graphite alkene aggregation liquid suspension of high level expansion, wherein, per the graphite intercalation of 1 ton of composite expanded liquid
Compound treatment amount is 9Kg；
B, to quasiflake graphite alkene aggregation liquid suspension carry out filtration treatment, obtain quasiflake graphite alkene aggregation；
C, complexing of metal ion agent and water washing quasiflake graphite alkene aggregation are adopted successively, complexing of metal ion agent washing
After the completion of and water washing after the completion of be required to carry out filtration treatment to quasiflake graphite alkene aggregation, finally obtain pH value for 6-8
Quasiflake graphite alkene aggregation wet feed；
D, the quasiflake graphite alkene aggregation wet feed after washing is proportionally added into ultrasound wave is carried out in compound stripper
Concussion is processed 0.5 hour, realizes peeling off, and makes graphene dispersion form graphene solution in compound stripper, wherein, vermiform
Graphene aggregation wet feed is 1 with the mass ratio of compound stripper：5；
E, the moisture removed using expansion drying or cryodesiccated method in graphene solution, obtain graphene powder,
The moisture of graphene powder is less than 5wt%.
In the present embodiment, the composite expanded liquid is to be uniformly mixed following components by mass percentage：Concentration is
20% hydrogenperoxide steam generator 90%, complexing of metal ion agent 5%, acidity-basicity regulator 2%, surface tension modifier 2%, remaining is
Water.Further, the complexing of metal ion agent is the compound of oxalic acid and oxalates, and the acidity-basicity regulator is phosphoric acid, first
Acid and acetic acid it is compound, the surface tension modifier is the compound of propanol and butanol.
In the present embodiment, the compound stripper is to be uniformly mixed following components by mass percentage：Metal from
Sub- chelating agent 5%, surface tension modifier 5%, remaining is water.Further, the complexing of metal ion in the compound stripper
Agent is the compound of sodium gluconate, ethylenediamine tetraacetic methene sodium phosphate and oxalic acid, and surface tension modifier is propanol, dodecyl sulfur
Sour sodium and dodecylbenzene sodium sulfonate it is compound.
It is in the present embodiment, by taking 4 parts of same amount of graphite intercalation compounds as an example, made using the above-mentioned special parameters of Jing respectively
Composite expanded liquid expansion process 40min, 60min, 100min and 120min, following experimental result can be obtained：
Again respectively with single batch 100Kg, 200 Kg, 300 Kg, 350 Kg, 500 Kg graphite intercalation compounds as raw material,
Jing after said method process, high-quality graphene product, specific experiment parameter tool following table is obtained：
Embodiment 3
A kind of method of prepare with scale Graphene, comprises the following steps：
A, graphite intercalation compound powder body is added in composite expanded liquid, then carries out expanding under conditions of 35 °C anti-
Answer 4 hours, obtain the quasiflake graphite alkene aggregation liquid suspension of high level expansion, wherein, per the graphite intercalation of 1 ton of composite expanded liquid
Compound treatment amount is 11Kg；
B, to quasiflake graphite alkene aggregation liquid suspension carry out filtration treatment, obtain quasiflake graphite alkene aggregation；
C, complexing of metal ion agent and water washing quasiflake graphite alkene aggregation are adopted successively, complexing of metal ion agent washing
After the completion of and water washing after the completion of be required to carry out filtration treatment to quasiflake graphite alkene aggregation, finally obtain pH value for 6-8
Quasiflake graphite alkene aggregation wet feed；
D, the quasiflake graphite alkene aggregation wet feed after washing is proportionally added into ultrasound wave is carried out in compound stripper
Concussion is processed 8 hours, realizes peeling off, and makes graphene dispersion form graphene solution in compound stripper, wherein, vermiform stone
Black alkene aggregation wet feed is 1 with the mass ratio of compound stripper：15；
E, the moisture removed using expansion drying or cryodesiccated method in graphene solution, obtain graphene powder,
The moisture of graphene powder is less than 5wt%.
In the present embodiment, the composite expanded liquid is to be uniformly mixed following components by mass percentage：Concentration is
24% hydrogenperoxide steam generator 85%, complexing of metal ion agent 2%, acidity-basicity regulator 3%, surface tension modifier 0.5%, remaining
For water.Further, the complexing of metal ion agent is the compound of oxalates and sodium gluconate, and the acidity-basicity regulator is
Ethanedioic acid and ammonia it is compound, the surface tension modifier is the compound of ethanol, propanol and butanol.
In the present embodiment, the compound stripper is to be uniformly mixed following components by mass percentage：Metal from
Sub- chelating agent 11%, surface tension modifier 2%, remaining is water.Further, the complexing of metal ion in the compound stripper
Agent is the compound of sodium gluconate, ethylenediamine tetraacetic methene sodium phosphate and oxalic acid, and surface tension modifier is propanol, dodecyl sulfur
Sour sodium and dodecylbenzene sodium sulfonate it is compound.
It is in the present embodiment, by taking 4 parts of same amount of graphite intercalation compounds as an example, made using the above-mentioned special parameters of Jing respectively
Composite expanded liquid expansion process 40min, 60min, 100min and 120min, following experimental result can be obtained：
Again respectively with single batch 100Kg, 200 Kg, 300 Kg, 350 Kg, 500 Kg graphite intercalation compounds as raw material,
Jing after said method process, high-quality graphene product, specific experiment parameter tool following table is obtained：
Embodiment 4
A kind of method of prepare with scale Graphene, comprises the following steps：
A, graphite intercalation compound powder body is added in composite expanded liquid, then carries out expanding under conditions of 45 °C anti-
Answer 5 hours, obtain the quasiflake graphite alkene aggregation liquid suspension of high level expansion, wherein, per the graphite intercalation of 1 ton of composite expanded liquid
Compound treatment amount is 13Kg；
B, to quasiflake graphite alkene aggregation liquid suspension carry out filtration treatment, obtain quasiflake graphite alkene aggregation；
C, complexing of metal ion agent and water washing quasiflake graphite alkene aggregation are adopted successively, complexing of metal ion agent washing
After the completion of and water washing after the completion of be required to carry out filtration treatment to quasiflake graphite alkene aggregation, finally obtain pH value for 6-8
Quasiflake graphite alkene aggregation wet feed；
D, the quasiflake graphite alkene aggregation wet feed after washing is proportionally added into ultrasound wave is carried out in compound stripper
Concussion is processed 15 hours, realizes peeling off, and makes graphene dispersion form graphene solution in compound stripper, wherein, vermiform
Graphene aggregation wet feed is 1 with the mass ratio of compound stripper：20；
E, the moisture removed using expansion drying or cryodesiccated method in graphene solution, obtain graphene powder,
The moisture of graphene powder is less than 5wt%.
In the present embodiment, the composite expanded liquid is to be uniformly mixed following components by mass percentage：Concentration is
27% hydrogenperoxide steam generator 80%, complexing of metal ion agent 8%, acidity-basicity regulator 5%, surface tension modifier 5%, remaining is
Water.Further, the complexing of metal ion agent is compound, the acid-base value of ethylenediamine tetraacetic methene sodium phosphate and diethanolamine
Regulator is the compound of sodium hydroxide and potassium hydroxide, and the surface tension modifier is the compound of butanol and ethyl acetate.
In the present embodiment, the compound stripper is to be uniformly mixed following components by mass percentage：Metal from
Sub- chelating agent 20%, surface tension modifier 1%, remaining is water.Further, the complexing of metal ion in the compound stripper
Agent is the compound of oxalates and diethanolamine, and surface tension modifier is dodecylbenzene sodium sulfonate and cetyl trimethyl bromine
Change the compound of ammonium.
It is in the present embodiment, by taking 4 parts of same amount of graphite intercalation compounds as an example, made using the above-mentioned special parameters of Jing respectively
Composite expanded liquid expansion process 40min, 60min, 100min and 120min, following experimental result can be obtained：
Again respectively with single batch 100Kg, 200 Kg, 300 Kg, 350 Kg, 500 Kg graphite intercalation compounds as raw material,
Jing after said method process, high-quality graphene product, specific experiment parameter tool following table is obtained：
Embodiment 5
A kind of method of prepare with scale Graphene, comprises the following steps：
A, graphite intercalation compound powder body is added in composite expanded liquid, then carries out expanding under conditions of 50 °C anti-
Answer 6 hours, obtain the quasiflake graphite alkene aggregation liquid suspension of high level expansion, wherein, per the graphite intercalation of 1 ton of composite expanded liquid
Compound treatment amount is 15Kg；
B, to quasiflake graphite alkene aggregation liquid suspension carry out filtration treatment, obtain quasiflake graphite alkene aggregation；
C, complexing of metal ion agent and water washing quasiflake graphite alkene aggregation are adopted successively, complexing of metal ion agent washing
After the completion of and water washing after the completion of be required to carry out filtration treatment to quasiflake graphite alkene aggregation, finally obtain pH value for 6-8
Quasiflake graphite alkene aggregation wet feed；
D, the quasiflake graphite alkene aggregation wet feed after washing is proportionally added into ultrasound wave is carried out in compound stripper
Concussion is processed 20 hours, realizes peeling off, and makes graphene dispersion form graphene solution in compound stripper, wherein, vermiform
Graphene aggregation wet feed is 1 with the mass ratio of compound stripper：25；
E, the moisture removed using expansion drying or cryodesiccated method in graphene solution, obtain graphene powder,
The moisture of graphene powder is less than 5wt%.
In the present embodiment, the composite expanded liquid is to be uniformly mixed following components by mass percentage：Concentration is
30% hydrogenperoxide steam generator 75%, complexing of metal ion agent 10%, acidity-basicity regulator 4%, surface tension modifier 2%, remaining is
Water.Further, the complexing of metal ion agent is the compound of diethanolamine and triethanolamine, and the acidity-basicity regulator is second
Diamidogen and sodium bicarbonate it is compound, the surface tension modifier is the compound of ethanol and ethyl acetate.
In the present embodiment, the compound stripper is to be uniformly mixed following components by mass percentage：Metal from
Sub- chelating agent 16%, surface tension modifier 4%, remaining is water.Further, the complexing of metal ion in the compound stripper
Agent is the compound of oxalates, diethanolamine and triethanolamine, and surface tension modifier is cetyl trimethylammonium bromide and fluorine
Carbon surface active agent it is compound.
It is in the present embodiment, by taking 4 parts of same amount of graphite intercalation compounds as an example, made using the above-mentioned special parameters of Jing respectively
Composite expanded liquid expansion process 40min, 60min, 100min and 120min, following experimental result can be obtained：
Again respectively with single batch 100Kg, 200 Kg, 300 Kg, 350 Kg, 500 Kg graphite intercalation compounds as raw material,
Jing after said method process, high-quality graphene product, specific experiment parameter tool following table is obtained：
Embodiment 6
A kind of expansion gear that expansion reaction is carried out for graphite intercalation compound, including expansion drum 1 and rabbling mechanism, institute
State and on expansion drum 1, be provided with chuck 2,2 bottom of the chuck is provided with hot water or steam inlet 3, top is provided with hot water or steaming
Vapor outlet 4, the rabbling mechanism include motor 5 and shaft 6, and the motor 5 is fixed on 1 top of expansion drum, the shaft 6
The middle part of expansion drum 1 is arranged on by motor 5.
Further, the chuck 2 combined by the shell 7 that expansion drum 1 and fixation are wrapped on 1 outer surface of expansion drum and
Into.Further, 2 bottom of the chuck is provided with discharge port 8, and discharge port 8 is located at the lower section of hot water or steam inlet 3.
In the present embodiment, four symmetrical fixtures 15 are provided with the outer wall of the expansion drum 1, on the expansion drum 1
Portion is provided with taper top 9, and solid-phase material charge door 10, liquid phase material charge door 11, water inlet 12 are provided with the taper top 9
With two exhaust outlets 13, in two exhaust outlets 13, axial flow blower is each equipped with, the bottom of the expansion drum 1 is provided with drain hole
14, displaying baiting valve is connected with the drain hole 14.
In the present embodiment, the shell 7 is that an overall sheet material compacting is formed, and is weldingly fixed on the outer surface of expansion drum 1.
In the present embodiment, 1 main material of expansion drum adopts S31603, Q235B, wherein inwall contacting material part to adopt
S31603。
In the present embodiment, the chuck 2 also directly on 1 wall of expansion drum can open up inner chamber and be formed.
During work, raw material is added in proportion into expansion drum 1 by liquid phase material charge door 11 and water inlet 12 first, is matched somebody with somebody
Quantitative composite expanded liquid is put, graphite intercalation compound powder has been added into expansion drum 1 by solid-phase material charge door 10 then
End, graphite intercalation compound are floated on after being contacted with composite expanded liquid on liquid level, start to expand reaction, and the reaction is static mistake
Journey（Gather heat of reaction, accelerate the carrying out of reaction）, touch composite expanded liquid graphite intercalation compound first participate in reaction, but
With the carrying out of reaction, material bed increasingly thicker, upper materials cannot touch composite expanded liquid by siphonage, now need
Start the control shaft 6 of motor 5 to mix the solid-liquid phase materials in expansion drum 1, allow solid-liquid phase materials to be fully contacted, about stir
After mixing a few minutes, stop stirring, continue reaction, until graphite intercalation compound reacts completely.Can repeatedly in short-term in course of reaction
Between produce a large amount of steam, in time steam can be discharged by axial flow blower.Hot water need to be passed through in chuck 2 during reaction or steam is followed
Ring, it is ensured that the temperature of composite expanded liquid shows baiting valve in OK range after reaction terminates in opening, will be solid-liquid phase materials complete
After portion discharges, 1 inwall of expansion drum is cleaned.
Embodiment 7
A kind of ultrasound wave stripping off device for preparing Graphene, including tank 16 and Duo Gen ultrasound wave vibrating bars 17 are peeled off,
Many described ultrasound wave vibrating bars 17 are vertically fixed in stripping tank 16, and many ultrasound wave vibrating bars 17 are in same orthographic projection
It is distributed in polycyclic in face.
In the present embodiment, many described ultrasound wave vibrating bars 17 are vertical layered to be arranged in stripping tank 16, upper strata ultrasound
The lower end of ripple vibrating head 17 intersect with the upper end dislocation of lower floor ultrasound wave vibrating bar 17, and often on ring ultrasound wave vibrating bar 17 number
Amount is the integral multiple of 17 number of plies of ultrasound wave vibrating bar.
In the present embodiment, the quantity all same for peeling off every layer of ultrasound wave vibrating bar 17 in tank 16, and per layer of ultrasound
Ripple vibrating head 17 is uniformly arranged in stripping tank 16.
In the present embodiment, the side wall peeled off in tank 16 and bottom are provided with compressed-air atomizer 18.
During work：Appropriate compound stripper is added in tank 16 to peeling off first, then by quasiflake graphite alkene aggregation wet feed
Add and peel off in tank 16, be then turned on supersonic vibration rod power supply and start supersound process, while passing through 18 jet compression air of nozzle
Burst agitation material, after the completion for the treatment of that material is peeled off, pass hull closure power supply opens discharge hole for discharge.
Claims (11)
1. a kind of method of prepare with scale Graphene, it is characterised in that comprise the following steps：
A, graphite intercalation compound powder body is added in composite expanded liquid, then carries out expanding under conditions of 20-50 DEG C anti-
Answer 2-6 hours, obtain the quasiflake graphite alkene aggregation liquid suspension for expanding；
B, to quasiflake graphite alkene aggregation liquid suspension carry out filtration treatment, obtain quasiflake graphite alkene aggregation；
C, complexing of metal ion agent and water washing quasiflake graphite alkene aggregation are adopted successively, complexing of metal ion agent washing is completed
Afterwards be required to carry out filtration treatment to quasiflake graphite alkene aggregation after the completion of water washing, finally obtain pH value for 6-8 it is compacted
Worm shape Graphene aggregation wet feed；
D, the quasiflake graphite alkene aggregation wet feed after washing is added in compound stripper carries out ultrasonic wave concussion process
0.5-20 hours, realize peeling off, make graphene dispersion graphene solution be formed in compound stripper；
E, the moisture removed using expansion drying or cryodesiccated method in graphene solution, obtain graphene powder, graphite
The moisture of alkene powder body is less than 5wt%；
The composite expanded liquid is to be uniformly mixed following components by mass percentage：Hydrogenperoxide steam generator 75-90%, gold
Category ionic complexing agent 1-10%, acidity-basicity regulator 2-5%, surface tension modifier 0.5-5%, remaining is water；
Step d is peeled off by ultrasound wave stripping off device, and the ultrasound wave stripping off device includes peeling off tank（16）With it is many
Root ultrasound wave vibrating bar（17）, described many ultrasound wave vibrating bars（17）Stripping tank is fixed on vertically（16）It is interior, and many super
Acoustic vibration rod（17）It is distributed in polycyclic in same frontal plane of projection；
Many described ultrasound wave vibrating bars（17）It is vertical layered to be arranged on stripping tank（16）It is interior, upper strata ultrasound wave vibrating bar（17）
Lower end and lower floor's ultrasound wave vibrating bar（17）Upper end dislocation it is intersecting, and per ring on ultrasound wave vibrating bar（17）Quantity be super
Acoustic vibration rod（17）The integral multiple of the number of plies.
2. a kind of method of prepare with scale Graphene as claimed in claim 1, it is characterised in that：The hydrogenperoxide steam generator
Concentration be 20-30%.
3. a kind of method of prepare with scale Graphene as claimed in claim 1 or 2, it is characterised in that：It is described composite expanded
Complexing of metal ion agent in liquid is sodium potassium tartrate tetrahydrate, sodium pyrophosphate, disodium edta, oxalic acid, oxalates, gluconic acid
Compound, the acidity-basicity regulator of one or more in sodium, ethylenediamine tetraacetic methene sodium phosphate, diethanolamine, triethanolamine
Be hydrochloric acid, sulphuric acid, phosphoric acid, formic acid, acetic acid, ethanedioic acid, ammonia, sodium hydroxide, potassium hydroxide, ethylenediamine, in sodium bicarbonate
One or more compound, the surface tension modifier are methanol, ethanol, propanol, butanol, the one kind or many in ethyl acetate
That what is planted is compound.
4. a kind of method of prepare with scale Graphene as claimed in claim 1, it is characterised in that：The compound stripper is
Following components is uniformly mixed by mass percentage：Complexing of metal ion agent 5-20%, surface tension modifier 1-5%,
Remaining is water.
5. a kind of method of prepare with scale Graphene as claimed in claim 4, it is characterised in that：In the compound stripper
Complexing of metal ion agent be sodium potassium tartrate tetrahydrate, sodium pyrophosphate, disodium edta, sodium gluconate, ethylenediamine tetramethyl
Fork sodium phosphate, oxalic acid, oxalates, diethanolamine, one or more in triethanolamine compound, surface tension modifier is first
Alcohol, ethanol, propanol, sodium lauryl sulphate, dodecylbenzene sodium sulfonate, cetyl trimethylammonium bromide, fluorocarbon surface are lived
Property agent in one or more compound.
6. a kind of method of prepare with scale Graphene as claimed in claim 1, it is characterised in that：Per 1 ton in step a
The graphite intercalation compound treating capacity of composite expanded liquid is 9-15Kg.
7. a kind of method of prepare with scale Graphene as claimed in claim 1, it is characterised in that：Gained in step e
Graphene powder, the number of plies of its graphene film is 1-5 layers, 2-4 microns of lateral dimension, carbon-to-oxygen ratio 25-80.
8. a kind of method of prepare with scale Graphene as claimed in claim 1, it is characterised in that：Step a is by swollen
Swollen device carries out expansion reaction, and the expansion gear includes expansion drum（1）And rabbling mechanism, the expansion drum（1）On be provided with
Chuck（2）, the chuck（2）Bottom is provided with hot water or steam inlet（3）, top is provided with hot water or steam (vapor) outlet（4）, institute
Stating rabbling mechanism includes motor（5）And shaft（6）, the motor（5）It is fixed on expansion drum（1）Top, the shaft（6）
By motor（5）It is arranged on expansion drum（1）Middle part.
9. a kind of method of prepare with scale Graphene as claimed in claim 8, it is characterised in that：The expansion drum（1）On
Portion is provided with taper top（9）, the taper top（9）On be provided with solid-phase material charge door（10）, liquid phase material charge door（11）、
Water inlet（12）And exhaust outlet（13）, the expansion drum（1）Bottom be provided with drain hole（14）, the drain hole（14）Upper connection
There is upper displaying baiting valve.
10. a kind of method of prepare with scale Graphene as claimed in claim 1, it is characterised in that：The stripping tank（16）
Interior every layer of ultrasound wave vibrating bar（17）Quantity all same, and per layer of ultrasound wave vibrating bar（17）It is uniformly arranged stripping tank（16）
It is interior.
A kind of 11. methods of prepare with scale Graphene as claimed in claim 1, it is characterised in that：The stripping tank（16）
Interior side wall and bottom are provided with compressed-air atomizer（18）.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510186396.8A CN104787758B (en) | 2015-04-20 | 2015-04-20 | Method for preparing graphene on large scale |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510186396.8A CN104787758B (en) | 2015-04-20 | 2015-04-20 | Method for preparing graphene on large scale |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104787758A CN104787758A (en) | 2015-07-22 |
| CN104787758B true CN104787758B (en) | 2017-05-03 |
Family
ID=53553013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510186396.8A Active CN104787758B (en) | 2015-04-20 | 2015-04-20 | Method for preparing graphene on large scale |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104787758B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107673335B (en) * | 2017-01-04 | 2019-03-05 | 柯良节 | Graphene preparation method based on the reaction of multiphase quantum self coupling |
| BR112019025349B1 (en) | 2017-06-27 | 2023-10-17 | Ecolab Usa Inc | METHOD FOR TREATING WASHING CLOTHES, AND WASHING CLOTHING ADDITIVE COMPOSITION |
| 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 |
| 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 |
Citations (5)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2015
- 2015-04-20 CN CN201510186396.8A patent/CN104787758B/en active Active
Patent Citations (5)
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104787758A (en) | 2015-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104787758B (en) | Method for preparing graphene on large scale | |
| CN104860300B (en) | Graphene preparation method | |
| CN104787759B (en) | A kind of impurity-removing method in graphene preparation process | |
| CN105006375A (en) | Nitrogen and phosphor co-doped porous carbon nanotube, and preparation method and application thereof | |
| CN106044763B (en) | A method of preparing graphene powder at room temperature | |
| CN105836807B (en) | A kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide and its preparation method and application | |
| KR20150122316A (en) | A method and apparatus for manufacturing graphite oxide dispersion liquid with high production yield rate and reproducibility | |
| CN108217733A (en) | A kind of preparation method of carbon-manganese dioxide composite material | |
| CN103204490B (en) | Preparation method of iron trioxide/carbon yolk-eggshell nano-composite structure | |
| CN111320150A (en) | Method for preparing hexagonal boron nitride nanosheets by ion insertion ultrasonic stripping of alkali metal salt | |
| CN105347340A (en) | Preparation method of graphene oxide | |
| CN102942185A (en) | Method for preparing nano-scale white carbon black product | |
| CN106166495A (en) | A kind of sulfur doping oxygen-starved TiO2the preparation method of photocatalyst | |
| CN106672957A (en) | Method for preparing graphene oxide according to Fenton oxidation method | |
| CN107082416B (en) | A method of graphene is prepared based on ozone oxidation | |
| CN101891164B (en) | Method for purifying cubic boron nitride | |
| CN109569318A (en) | The preparation method of porous structure graphene oxide ultrafiltration membrane | |
| CN107281998A (en) | Modified magnetic alumina adsorbant and its preparation method and application | |
| CN105206812B (en) | The method that one step hydro thermal method prepares carbon coating type LiFePO4 | |
| CN106587045A (en) | Production process of graphene oxide | |
| CN104828818B (en) | The efficient intercalation stripping means and low order graphite intercalation compound and micron thin-walled porous expanded graphite of a kind of micron graphite thin slice | |
| CN108862259A (en) | A kind of graphene production method and device | |
| CN107899560A (en) | The preparation method of graphene titanium dioxide composite photocatalyst | |
| CN105480965A (en) | Preparation method of graphene | |
| CN204588708U (en) | One prepares Graphene expansion reaction device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |