CN104860300B - Graphene preparation method - Google Patents
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- CN104860300B CN104860300B CN201510186416.1A CN201510186416A CN104860300B CN 104860300 B CN104860300 B CN 104860300B CN 201510186416 A CN201510186416 A CN 201510186416A CN 104860300 B CN104860300 B CN 104860300B
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Abstract
The invention discloses a graphene preparation method comprising the following steps: a, graphite intercalation compound powder is added into a composite inflation fluid, and an inflation reaction is carried out under a temperature of 0-100 DEG C, such that inflated wormlike graphene aggregate suspension liquid is obtained; b, the wormlike graphene aggregate suspension liquid is subjected to a filtration treatment; c, the wormlike graphene aggregate is sequentially washed with a metal ion complexing agent and water, such that a wormlike graphene aggregate wet material with a pH value of 6-8 is obtained; d, the washed wormlike graphene aggregate wet material is added into water; an ultrasonic wave vibration treatment is carried out for 0.5-20h, such that stripping is realized and graphene is dispersed in water; and a graphene solution is obtained; and e, the water in the graphene solution is removed, such that graphene powder is obtained. With the method provided by the invention, hundreds of kilograms of a high-quality graphene product can be produced in one batch.
Description
Technical field
The present invention relates to field of graphene, relates in particular to a kind of preparation method of Graphene, the method can be criticized singly
The high-quality graphene product of secondary hundreds of kilograms of production.
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 high light transmittance
The performance excellent with electric conductivity, high-specific surface area, high intensity and pliability etc., it is expected in high-performance nanometer electronic device, phototube
The fields such as part, gas sensor, composite, field emmision material and energy stores obtain extensively application.But, high-quality graphite
Inexpensive, a large amount of preparations of alkene are still faced adverse conditions, and constrain the development and application of the material.
At present, the definition of the grapheme material that academia accepts 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 " disclosed " 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, expansion is carried out in oxalic acid or hydrogenperoxide steam generator and in a solvent ultrasound is peeled off, so as to obtain high-quality stone
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, the wt% of impurity content 5.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, particularly 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 because 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, intercalator is difficult to remove completely after peeling off, and 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, ultrasonic wave is peeled off needs in a large number
Organic solvent or various surfactants the 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 carries negative electrical charge, thus easily adsorbs metal ion positively charged in intercalator and solution, processes during due to a large amount of preparation
The increase of inventory, these metal ions are difficult to be removed 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 preparation side of Graphene
Method, using the present invention after, be obtained in that single batch output 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 preparation method of Graphene, it is characterised in that comprise the following steps：
A, graphite intercalation compound powder is added in composite expanded liquid, is then carried out under conditions of 0-100 °C
Expansion reaction, 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, successively using complexing of metal ion agent and water washing quasiflake graphite alkene aggregation, 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 to the water carry out ultrasonic oscillation process 0.5-20
Hour, realize peeling off, make graphene dispersion that graphene solution is formed in water；
E, the moisture removed using expansion drying or cryodesiccated method in graphene solution, obtain graphene powder,
The moisture of graphene powder is less than 5 wt %.
The composite expanded liquid is by mass percentage to be uniformly mixed following components：Hydrogenperoxide steam generator 60-
90%, complexing of metal ion agent 1-10%, acidity-basicity regulator 3-5%, surface tension modifier 0.5-5%, remaining is water.
The concentration of the hydrogenperoxide steam generator is 20-30%.
The complexing of metal ion agent be sodium potassium tartrate tetrahydrate, sodium pyrophosphate, disodium edta, oxalic acid, oxalates,
Compound, the soda acid of one or more in sodium gluconate, ethylenediamine tetraacetic methene sodium phosphate, diethanol amine, triethanolamine
Degree conditioning agent is hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, ethanedioic acid, ammoniacal liquor, NaOH, potassium hydroxide, ethylenediamine, carbonic acid
One or more in hydrogen sodium it is compound, the surface tension modifier is in methyl alcohol, ethanol, propyl alcohol, butanol, ethyl acetate
One or more compound.
Graphite intercalation compound treating capacity in step a per 1 ton of composite expanded liquid is 9-15Kg.
The time of expansion reaction is 2-5 hours in step a, and expansion temperature is 10-40 °C.
Gained graphene powder in step e, the number of plies of its graphene film is less than 10 layers, 1-5 microns of lateral dimension,
Carbon-to-oxygen ratio 20-120, impurity content is less than 2 wt%.
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 25-110.
Step a carries out expansion reaction by expansion gear, and the expansion gear includes expansion drum and rabbling mechanism, institute
State and be provided with expansion drum chuck, 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 is 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 ultrasonic wave stripping off device, and the ultrasonic 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
In polycyclic distribution 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 the metal ion in complex solution in expansion reaction and washing process.Its concrete mechanism of action is main
It is embodied in following two aspects：One is expansion reaction, and in expansion reaction initially, metal ion exists only in graphite layers, reaction
Based on effectively decomposing, with the stripping of the carrying out reacted and graphite flake layer, interlayer metal ion is gradually dissolved in liquid phase, this
When composite expanded liquid in complexing of metal ion agent complexing be dissolved into metal ion in solution so as to lose catalysis activity, from
And the effect for suppressing that decomposition and promotion are effectively decomposed is reached, and then the quasiflake graphite alkene aggregation of high level expansion is obtained,
Two is carrying out washing treatment, and using complexing of metal ion agent quasiflake graphite alkene aggregation is washed, and further removes quasiflake graphite alkene
Metal ion in aggregation.Wherein, using the composite expanded liquid of above-mentioned specific components, hundreds of kilograms of stones of single batch can be realized
The effective process of black intercalation compound, is washed using specific complexing of metal ion agent, can be complexed the metal of graphite layers from
Son, so as to improve the preparation quality of Graphene, both coordinate, it becomes possible to realize that single batch produces hundreds of kilograms of high-quality graphite
Alkene product.
The present invention uses the implementation of expansion gear：First by liquid phase material charge door and water inlet in proportion to swollen
Raw material, the good quantitative composite expanded liquid of configuration is added then to add stone into expansion drum by solid-phase material charge door in swell
Black intercalation compound powder, graphite intercalation compound floats on liquid level after contacting with composite expanded liquid, starts 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, now needs startup motor control shaft to mix the solid-liquid phase materials in expansion drum, about stirred a few minutes
Afterwards, stop stirring, continue to react, until graphite intercalation compound reacts completely.Can produce the multiple short time in course of reaction big
Amount steam, in time can be discharged 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, baiting valve is shown 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 adds complexing of metal ion agent during expansion reaction and in washing process, can be by band just
The metal ion of electricity is converted into negatively charged metal complex ion, effectively suppresses metal ion in the absorption of graphenic surface,
Suppress decomposition while promoting and effectively decomposing, only single batch does not produce the manufacture of hundreds of kilograms of Graphenes and provides
Powerful guarantee, moreover it is possible to which the content for making impurity metal ion in graphene product is reduced to 0.5-2%.In addition, and China Patent No.
Peel off in the aqueous solution or organic solution of organic solvent or various surfactants in " 201110282370.5 " and compare, this
The bright special nature for Graphene aggregation wet feed, significantly reduce by the way of being peeled off in the water production of Graphene into
This.
2nd, in the present invention, the complexing of metal ion agent in composite expanded liquid can be complexed the metal that is dissolved in solution from
Son so as to lose catalysis activity, reaches the effect for suppressing decomposition, and acidity-basicity regulator is used to adjust swelling agent and soda acid
Degree, can optimize the complexing effect of complexing agent, and surface tension modifier is used to adjusting composite expanded liquid to graphite and Graphene
Wellability, to promote diffusion of the swelling agent to graphite layers, and then promotes effective decomposition reaction.Compared with prior art, adopt
The enough degrees of expansion and uniformity that graphite is improved in large-scale production of the composite expanded liquid energy of specific components, so that finally obtaining
The graphene product number of plies be less than 10 layers, and have focused largely on 1-5 layers.
3rd, the composite expanded liquid in the present invention is by hydrogenperoxide steam generator 60-90%, complexing of metal ion agent 1-10%, acid
Alkalinity regulator 3-5%, surface tension modifier 0.5-5% and water are uniformly mixed by mass percentage, using above-mentioned each
Component and parameter can not only reduce the severe degree of the time of expansion reaction and reaction, additionally it is possible to the quasiflake graphite that reduction is obtained
The impurity content of alkene aggregation, so as to ensure that what is reacted is smoothed out, reaches preferable swelling state.But if exceeding above-mentioned ginseng
Number scope, then be likely to occur and do not react or react halfway problem.In addition, if the concentration of hydrogenperoxide steam generator is less than
20%, the reaction time will be caused long and reaction is insufficient；If the concentration of hydrogenperoxide steam generator is higher than 30%, reaction is there is again
Aggravation, reacts the safety problem such as uncontrollable, therefore the concentration of hydrogenperoxide steam generator is set as into 20-30%, both ensure that reaction
Stability and security, in turn ensure that the adequacy of reaction.
4th, in the present invention, expansion reaction overlong time will increase time cost, and expansion temperature is too low, and expansion will be caused anti-
Should be slow, temperature is too high, by the decomposition of aggravation hydrogen peroxide, therefore the time of expansion reaction is set to 2-5 hours, will be swollen
Swollen temperature is set to 10-40 °C, can either ensure the effect of expansion reaction, required for production single batch product is advantageously reduced again
Time.
5th, the present invention is this feature of static reaction process for graphite intercalation compound and 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 continuation 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 continuation stirrings, therefore, rabbling mechanism is combined with jacketed expansion drum to be formed
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 causes the heat transfer effect of hot water or steam in chuck more preferable.
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 exhaust.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, because expansion reaction high water time can produce substantial amounts of gas, therefore by two axial flow blower energy
Enough further speed up the velocity of discharge of gas.
Tenth, in the present invention, by four symmetrical fixtures being arranged on expansion tank wall, the fast of expansion drum is conducive to
Speed is fixed.
11, in the present invention, many ultrasound wave vibrating bars in tank are peeled off and are distributed in polycyclic in same frontal plane of projection,
Ultrasonic power density in tank body can be increased with Omnidirectional radiation tank interior, so as to improve single batch material is peeled off
Amount.
12, in the present invention, many vertical layered being arranged on of ultrasound wave vibrating bar are peeled off in tank, and ultrasonic 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 peeling effect of material and the quality of final products obtained therefrom.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 on 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, compressed air is sprayed by peeling off the nozzle of pot sidewall and bottom, can be to peeling off in tank
Material plays rolling effect, has both improve peeling effect of the ultrasonic wave to material, and splitting time is reduced again,
15, present invention production single batch graphene product is relative to raw graphite（Not comprising intercalator quality）Yield
Higher than 90%, have the advantages that the production time is short and raw material availability is high.
16, present invention expansion stripping process hardly destroys the structure of Graphene, can farthest retain graphite
The structure and electricity of alkene and mechanical property.
17, 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.
18, 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 25-110, 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.
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；
Fig. 5 is the main structure diagram of 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 that tank is peeled off in embodiment 7；
Fig. 9 is the overlooking the structure diagram that tank is peeled off 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 preparation method of Graphene, comprises the following steps：
A, graphite intercalation compound powder is proportionally added in composite expanded liquid, then in 0-100 °C of condition
Under carry out expansion reaction 2-5 hours, obtain high level expansion quasiflake graphite alkene aggregation liquid suspension, wherein, per 1 ton be combined
The graphite intercalation compound treating capacity of inflation fluid is 9-15Kg；
B, to quasiflake graphite alkene aggregation liquid suspension carry out filtration treatment, obtain quasiflake graphite alkene aggregation；
C, successively using complexing of metal ion agent and water washing quasiflake graphite alkene aggregation, 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 in water carrying out ultrasonic oscillation process
0.5-20 hours, realize peeling off, make graphene dispersion that graphene solution is formed in water, wherein, quasiflake graphite alkene aggregation
The ratio of wet feed and water is 1：5—1：100；
E, the moisture removed using expansion drying or cryodesiccated method in graphene solution, obtain graphene powder,
The moisture of graphene powder is less than 5 wt %.
In the present embodiment, the composite expanded liquid is by mass percentage to be uniformly mixed following components：Peroxidating
Hydrogen solution 60-90%, complexing of metal ion agent 1-10%, acidity-basicity regulator 3-5%, surface tension modifier 0.5-5%, its
Yu Weishui.Wherein, the concentration of hydrogenperoxide steam generator is 20-30%.Further, the complexing of metal ion agent is potassium tartrate
Sodium and sodium pyrophosphate it is compound, the acidity-basicity regulator is the compound of hydrochloric acid and sulfuric acid, and the surface tension modifier is first
Alcohol.
In the present embodiment, the pH value of quasiflake graphite alkene aggregation wet feed is the pH value according to washing filtrate determining,
If the pH value of washing filtrate is 6-8, the pH value for illustrating the moisture adsorbed in quasiflake graphite alkene aggregation wet feed also exists
Between 6-8.
In the present embodiment, in gained graphene powder, the number of plies of graphene film is less than 10 layers, 1-5 microns of lateral dimension,
Carbon-to-oxygen ratio 20-120, impurity content is less than 2 wt%.
Embodiment 2
A kind of preparation method of Graphene, comprises the following steps：
A, graphite intercalation compound powder is proportionally added in composite expanded liquid, is then entered under conditions of 20 °C
Row expansion reaction 2 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 is 9Kg；
B, to quasiflake graphite alkene aggregation liquid suspension carry out filtration treatment, obtain quasiflake graphite alkene aggregation；
C, successively using complexing of metal ion agent and water washing quasiflake graphite alkene aggregation, 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 in water carrying out ultrasonic oscillation process
0.5 hour, realize peeling off, make graphene dispersion that graphene solution is formed in water, wherein, quasiflake graphite alkene aggregation wet feed
It is 1 with the ratio of water：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 by mass percentage to be uniformly mixed following components：Concentration is
20% hydrogenperoxide steam generator 90%, complexing of metal ion agent 1%, acidity-basicity regulator 5%, surface tension modifier 0.5%, remaining
For water.Further, the complexing of metal ion agent is compound, the acid-base value regulation of disodium edta and oxalic acid
Agent is the compound of phosphoric acid, formic acid and acetic acid, and the surface tension modifier is the compound of ethanol and propyl alcohol.
It is made using the above-mentioned special parameters of Jing respectively by taking 4 parts of same amount of graphite intercalation compounds as an example in the present embodiment
Composite expanded liquid expansion process 40min, 60min, the 100min and 120min for obtaining, can obtain following experimental result：
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 is obtained, specific experiment parameter see the table below：
Embodiment 3
A kind of preparation method of Graphene, comprises the following steps：
A, graphite intercalation compound powder is proportionally added in composite expanded liquid, is then entered under conditions of 30 °C
Row expansion reaction 3 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 is 11Kg；
B, to quasiflake graphite alkene aggregation liquid suspension carry out filtration treatment, obtain quasiflake graphite alkene aggregation；
C, successively using complexing of metal ion agent and water washing quasiflake graphite alkene aggregation, 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 in water carrying out ultrasonic oscillation processes 8
Hour, realize peel off, make graphene dispersion that graphene solution is formed in water, wherein, quasiflake graphite alkene aggregation wet feed with
The ratio of water is 1：20；
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 by mass percentage to be uniformly mixed following components：Concentration is
24% hydrogenperoxide steam generator 85%, complexing of metal ion agent 5%, acidity-basicity regulator 3%, surface tension modifier 2%, remaining is
Water.Further, the complexing of metal ion agent is compound, the acidity-basicity regulator of disodium edta and oxalic acid
It is the compound of phosphoric acid, formic acid and acetic acid, the surface tension modifier is the compound of ethanol and propyl alcohol.
It is made using the above-mentioned special parameters of Jing respectively by taking 4 parts of same amount of graphite intercalation compounds as an example in the present embodiment
Composite expanded liquid expansion process 40min, 60min, the 100min and 120min for obtaining, can obtain following experimental result：
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 is obtained, specific experiment parameter see the table below：
Embodiment 4
A kind of preparation method of Graphene, comprises the following steps：
A, graphite intercalation compound powder is proportionally added in composite expanded liquid, is then entered under conditions of 30 °C
Row expansion reaction 4 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 is 13Kg；
B, to quasiflake graphite alkene aggregation liquid suspension carry out filtration treatment, obtain quasiflake graphite alkene aggregation；
C, successively using complexing of metal ion agent and water washing quasiflake graphite alkene aggregation, 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 in water carrying out ultrasonic oscillation process
15 hours, realize peeling off, make graphene dispersion that graphene solution is formed in water, wherein, quasiflake graphite alkene aggregation wet feed
It is 1 with the ratio of water：60；
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 by mass percentage to be uniformly mixed following components：Concentration is
27% hydrogenperoxide steam generator 80%, complexing of metal ion agent 8%, acidity-basicity regulator 5%, surface tension modifier 3.5%, remaining
For water.Further, the complexing of metal ion agent is compound, the acid-base value regulation of disodium edta and oxalic acid
Agent is the compound of phosphoric acid, formic acid and acetic acid, and the surface tension modifier is the compound of ethanol and propyl alcohol.
It is made using the above-mentioned special parameters of Jing respectively by taking 4 parts of same amount of graphite intercalation compounds as an example in the present embodiment
Composite expanded liquid expansion process 40min, 60min, the 100min and 120min for obtaining, can obtain following experimental result：
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 is obtained, specific experiment parameter see the table below：
Embodiment 5
A kind of preparation method of Graphene, comprises the following steps：
A, graphite intercalation compound powder is proportionally added in composite expanded liquid, is then entered under conditions of 40 °C
Row expansion reaction 5 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 is 15Kg；
B, to quasiflake graphite alkene aggregation liquid suspension carry out filtration treatment, obtain quasiflake graphite alkene aggregation；
C, successively using complexing of metal ion agent and water washing quasiflake graphite alkene aggregation, 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 in water carrying out ultrasonic oscillation process
20 hours, realize peeling off, make graphene dispersion that graphene solution is formed in water, wherein, quasiflake graphite alkene aggregation wet feed
It is 1 with the ratio of water：100；
E, the moisture removed using expansion drying or cryodesiccated method in graphene solution, obtain graphene powder,
The moisture of graphene powder is less than 5 wt %.
In the present embodiment, the composite expanded liquid is by mass percentage to be uniformly mixed following components：Concentration is
30% hydrogenperoxide steam generator 75%, complexing of metal ion agent 10%, acidity-basicity regulator 4%, surface tension modifier 5%, remaining is
Water.Further, the complexing of metal ion agent is compound, the acidity-basicity regulator of disodium edta and oxalic acid
It is the compound of phosphoric acid, formic acid and acetic acid, the surface tension modifier is the compound of ethanol and propyl alcohol.
It is made using the above-mentioned special parameters of Jing respectively by taking 4 parts of same amount of graphite intercalation compounds as an example in the present embodiment
Composite expanded liquid expansion process 40min, 60min, the 100min and 120min for obtaining, can obtain following experimental result：
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 is obtained, specific experiment parameter see the table below：
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 chuck 2 is provided with expansion drum 1, the bottom of the chuck 2 is provided with hot water or steam inlet 3, top is provided with hot water or steaming
Vapor outlet 4, the rabbling mechanism includes motor 5 and shaft 6, and the motor 5 is fixed on the top of expansion drum 1, the shaft 6
The middle part of expansion drum 1 is arranged on by motor 5.
Further, the chuck 2 combined by expansion drum 1 and the shell 7 that is wrapped on the outer surface of expansion drum 1 of fixation and
Into.Further, the bottom of the chuck 2 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, axial flow blower is each equipped with two exhaust outlets 13, the bottom of the expansion drum 1 is provided with drain hole
14, it is connected with displaying baiting valve on 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, the main material of expansion drum 1 adopts S31603, Q235B, wherein inwall contacting material part to adopt
S31603。
In the present embodiment, the chuck 2 also directly can open up inner chamber and be formed on the wall of expansion drum 1.
During work, first raw material is added into expansion drum 1 by liquid phase material charge door 11 and water inlet 12 in proportion, matched somebody with somebody
Quantitative composite expanded liquid is put, then graphite intercalation compound powder has been added into expansion drum 1 by solid-phase material charge door 10
End, graphite intercalation compound floats on liquid level after contacting with composite expanded liquid, starts 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, now need by siphonage
Start the control paddle 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 to react, until graphite intercalation compound reacts completely.Can repeatedly in short-term in course of reaction
Between produce a large amount of steam, by axial flow blower steam can be discharged in time.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 after reaction terminates, shows baiting valve in OK range in opening, solid-liquid phase materials are complete
After portion discharges, the inwall of expansion drum 1 is cleaned.
Embodiment 7
A kind of ultrasonic 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 the number of plies of ultrasound wave vibrating bar 17.
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：First appropriate water is added into stripping tank 16, then quasiflake graphite alkene aggregation wet feed is added into stripping
In tank 16, be then turned on ultrasonic vibration rod power supply start it is ultrasonically treated, while by nozzle 18 spray compressed air 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 (7)
1. a kind of preparation method of Graphene, it is characterised in that comprise the following steps：
A, graphite intercalation compound powder is added in composite expanded liquid, then carries out expanding under conditions of 0-100 DEG C anti-
Should, 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, successively using complexing of metal ion agent and water washing quasiflake graphite alkene aggregation, 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 to the water to carry out ultrasonic oscillation and processes 0.5-20 little
When, realize peeling off, make graphene dispersion that graphene solution is formed in water；
E, the moisture removed using expansion drying or cryodesiccated method in graphene solution, obtain graphene powder, graphite
The moisture of alkene powder is less than 5wt%；
The composite expanded liquid is by mass percentage to be uniformly mixed following components：Hydrogenperoxide steam generator 60-90%, gold
Category ionic complexing agent 1-10%, acidity-basicity regulator 3-5%, surface tension modifier 0.5-5%, remaining is water；
Step d is peeled off by ultrasonic wave stripping off device, and the ultrasonic 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）Vertically it is fixed on stripping tank（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 preparation method of Graphene as claimed in claim 1, it is characterised in that：The concentration of the hydrogenperoxide steam generator
For 20-30%.
3. a kind of preparation method of Graphene as claimed in claim 1 or 2, it is characterised in that：The complexing of metal ion agent
It is sodium potassium tartrate tetrahydrate, sodium pyrophosphate, disodium edta, oxalic acid, oxalates, sodium gluconate, ethylenediamine tetraacetic methene phosphorus
One or more in sour sodium, diethanol amine, triethanolamine it is compound, the acidity-basicity regulator be hydrochloric acid, sulfuric acid, phosphoric acid,
One or more in formic acid, acetic acid, ethanedioic acid, ammoniacal liquor, NaOH, potassium hydroxide, ethylenediamine, sodium acid carbonate it is compound,
The surface tension modifier is the compound of one or more in methyl alcohol, ethanol, propyl alcohol, butanol, ethyl acetate.
4. a kind of preparation method of Graphene as claimed in claim 1, it is characterised in that：It is compound swollen per 1 ton in step a
The graphite intercalation compound powder handling amount of swollen liquid is 9-15kg.
5. a kind of preparation method of Graphene as claimed in claim 1, it is characterised in that：Expansion reaction in step a
Time is 2-5 hours, and expansion temperature is 10-40 DEG C.
6. a kind of preparation method of Graphene as claimed in claim 1, it is characterised in that：Gained Graphene in step e
Powder, the number of plies of its graphene film is 1-5 layers, 2-4 microns of lateral dimension, carbon-to-oxygen ratio 25-110.
7. a kind of preparation method of Graphene as claimed in claim 1, it is characterised in that：Step a passes through expansion gear
Expansion reaction is carried out, 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）, it is described to stir
Mechanism is mixed including motor（5）And shaft（6）, the motor（5）It is fixed on expansion drum（1）Top, the shaft（6）Pass through
Motor（5）It is arranged on expansion drum（1）Middle part.
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| CN107673335B (en) * | 2017-01-04 | 2019-03-05 | 柯良节 | Graphene preparation method based on the reaction of multiphase quantum self coupling |
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