CN104445169A - Method for preparing grapheme by means of aqueous phase cutting and stripping - Google Patents
Method for preparing grapheme by means of aqueous phase cutting and stripping Download PDFInfo
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Abstract
The invention relates to a method for preparing grapheme by means of aqueous phase cutting and stripping. The method comprises the following steps: 1) performing intercalation treatment on graphite serving as a raw material to prepare a graphite intercalation compound; 2) adding a certain amount of active substances, and cutting a graphite interlamination compound under a certain condition; and 3) centrifuging or filtering mixed liquid subjected to cutting treatment to prepare a high-concentration grapheme sizing agent or a filter cake which can be dispersed again. According to the method, the cutting operation is carried out by using low-cost reagents at a room temperature; because of low energy consumption, no pollution and high efficiency, the prepared graphene nanolamellas can be widely applied to the fields of energy storage and conversion, catalysis, various types of composite materials, paintings, conductive ink and the like.
Description
Technical field
The invention belongs to technical field of graphene preparation; relate to a kind of aqueous phase and shear the method peeled off and prepare Graphene; be specifically related to the method by shearing treatment, peeling off graphite in aqueous becomes Graphene, finally realizes the preparation method of the less energy-consumption of Graphene, high yield and mass-producing.
Background technology
As a kind of two desirable materials, Graphene more and more becomes the focus of current scientific research.Graphene is the essential structure unit of natural graphite, and lamellar spacing is only 0.335 nm, and it has high mechanical moduli (1.0 TPa), thermal conductivity (5300 W/m.K), specific surface area (2630 m
2/ g) and charge mobility (250,000 cm
2/ V.s), in fields such as polymer composites, energy and material, telecommunications, there is broad prospect of application.Therefore, low cost, high yield prepare the prerequisite that high-quality graphene becomes commercial applications, are also key challenges of research work.Together with interacting pile up each other by π-π and Van der Waals force between graphene sheet layer.Simultaneously, the height inertia of graphenic surface also makes them can only be dispersed in limited solvent (as N-Methyl pyrrolidone NMP, N, dinethylformamide DMF, dichlorobenzene etc.) realize low Graphene content dispersion (as 0.7 mg/mL, weight fraction about 7 × 10
-4wt%), even if again disperse after concentrated, Graphene also only can realize the stable dispersion (weight fraction is about 2.6-2.8 wt%) of 26-28 mg/mL Graphene (Langmuir, 2011,27,9077 – 9082) in NMP.Interaction between layers stronger between graphene sheet layer makes ultrasonic stripping in a solvent often can only realize lower charge stripping efficiency.Such as, even if adopt 45 kHz, 23 W ultrasonic device process 460 hours, its final single-layer graphene is relative to productive rate also only 4 wt% of starting material graphite.
Up to now, although countries in the world have proposed the preparation method of various Graphene, comprise the method for redox and mechanically peel, all these methods still need be improved in following.First, the high-quality graphene technology of preparing that can be mass-produced in the urgent need to.But existing graphene preparation technology relates to the reduction of graphene oxide more, the graphene film damage layer that this technological line relates to and the reduction of consequent performance, realize scale operation for it and application proposes challenge.
On the other hand, enhancing productivity, reducing costs also is an indispensable influence factor.But high-level efficiency and low cost technology of preparing in fact all mean brief production process route and cold operation.Existing technology is many need through long-time pyrographite intercalation or stripping of expanding, and the Graphene after stripping still needs through repeatedly washing, and then obtains graphene powder through spraying or lyophilize.Not only energy consumption is high for such preparation process, technical process is tediously long; And, obtained minimum (the <0.3 g/cm of graphene powder packing density
3), powder product dispersive ability is in a solvent limited, and (such as, Graphene stable dispersion concentration is in organic solvent less than 3 wt%, Accounts of Chemical Research, 2013,46 (1), 14-22.), make it apply and transport very difficult.
Summary of the invention
A kind of aqueous phase is the object of the present invention is to provide to shear the method peeled off and prepare Graphene.
Graphene productive rate prepared by the inventive method can reach more than 40% (relative to starting material graphite).Further, complete, the specific conductivity of Graphene crystalline network can reach 1.7 × 10
4more than S/m.Present method can be scattered in alkaline aqueous solution or by simple solid-liquid separation (as filtered) obtained low solvent Graphene filter cake or wet/dry powder body higher than the Graphene content of 10 wt% (> 100 mg/mL) is undertaken storing and transporting (still keeping the form peeled off very well, be easy to again be scattered in solvent), be very easy to the further use of Graphene.
The present invention adopts following technical scheme to realize:
Aqueous phase shears the method peeled off and prepare Graphene, and concrete steps are as follows:
(1) adopted by raw graphite the method for chemical oxidation intercalation or electrochemical intercalation to carry out intercalation processing, make intercalator enter graphite layers, prepare graphite intercalation compound, be beneficial to completing of stripping process; Wherein: described intercalator component be in sulfuric acid, nitric acid, perchloric acid, phosphoric acid, hydrogen peroxide, potassium permanganate, potassium bichromate, iron trichloride, chromium trioxide, ammonium persulphate, formic acid, acetic acid, oxalic acid, bromine, chlorine, iodine chloride, iodine bromide IBr, ozone or oxygen more than one;
(2) graphite intercalation compound and active substance are added to the water, under shearing action, process 10 minutes-20 hours, obtain graphene suspension or the dispersion liquid of stripping; The consumption of described active substance is 0.01-10 times of raw graphite quality, and the add-on of water is 5-1000 times of raw graphite quality;
(3) graphene suspension step (2) obtained or dispersion liquid filter through centrifugal or filter screen (cloth), make solid-liquid separation, obtain Graphene thickener or filter cake.
In the present invention, described in step (1), raw graphite is natural graphite, synthetic graphite or expanded graphite.
In the present invention, adopt in step (1) intercalator intercalation object to be to weaken the Interaction between layers between graphite flake layer, the intercalation being again beneficial to follow-up alkaline matter enters (driving due to chemical potential difference inside and outside interlayer) and in the absorption (forming charged graphene sheet layer by Charger transfer) of graphenic surface.Various intercalator all can adopt, as long as can expand interlayer distance.It is pointed out that the intercalated graphite adopting different intercalator to obtain is differentiated, can be single order intercalated graphite, also can be multistage intercalated graphite.Such as, the vitriol oil and potassium permanganate intercalator, the vitriol oil and concentrated nitric acid intercalator cause single order intercalation, and namely each graphene sheet layer is separated by one deck intercalator; Concentrated nitric acid, concentrated nitric acid and strong phosphoric acid, the vitriol oil and strong phosphoric acid intercalator then may produce high-order intercalated graphite, make the final Graphene peeled off may occur the mixture of individual layer, multilayer (or few layer) graphene-structured.Intercalator can be the vitriol oil and concentrated nitric acid mixture, the vitriol oil and potassium permanganate mixture, the vitriol oil and potassium bichromate mixture, the vitriol oil and ammonium persulphate mixture, the vitriol oil and chromium trioxide mixture, the vitriol oil and sulphur trioxide, the vitriol oil and chlorine, the vitriol oil and ozone (ozone and oxygen mixed gas), the vitriol oil and formic acid mixtures, the vitriol oil and acetate mixture, the vitriol oil and strong phosphoric acid mixture, the vitriol oil and hydrogen peroxide mixture, concentrated nitric acid, concentrated nitric acid and potassium permanganate mixture, concentrated nitric acid and potassium bichromate mixture, concentrated nitric acid and hydrogen peroxide mixture, concentrated nitric acid and strong phosphoric acid mixture etc. are oxidized intercalator.In actual mechanical process, adoptable intercalator is of a great variety, just exemplifies part intercalator here.Intercalation behavior and the final intercalated graphite structure formed of various intercalator have been comparatively complete summary (Russian Chemical Bulletin in the survey article published, 2005,54 (8): 1749-1767), they all can be applicable to the preparation of the graphite intercalation compound in the present invention.The above-mentioned intercalator kind listed can select one of them to carry out intercalation, also can be the arbitrary combination between them, but be not limited thereto.
In the present invention, active substance described in step (2) is one in sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, salt of wormwood, Quilonum Retard, sodium bicarbonate, saleratus, lithium bicarbonate, ammonium hydroxide, tetrabutylammonium or industrial soda or arbitrary combination between them, its consumption be the 0.2-5 of raw graphite quality doubly.
In the present invention, the add-on of water described in step (2) is 10-100 times of raw graphite quality.
In the present invention, the shearing treatment described in step (2) refers to and adopts shear to carry out shearing treatment to graphitiferous intercalation compound suspension liquid of aqueous phase.Shearing rate is 1000-100000 rev/min.
In the present invention, the centrifugation described in step (2) refers to and adopts the rotating speed of 200-10000 rev/min to concentrate the graphene suspension after ultrasonic stripping, can obtain high Graphene content thickener after removing supernatant liquid.Depend on centrifugal rotational speed, in thickener, Graphene content can control, the preparation of low Graphene content thickener is allowed under the slow speed of revolution, even the high density thickener that high rotating speed prepares also can keep good individual layer or few layer graphene form very well, and be easy to again by the graphene suspension of the obtained various concentration of dilution.
Filter type described in step (2) refers to and directly removes the aqueous solution by shearing the graphene suspension after peeling off by filter screen (cloth), gained filter cake can carry out transport and next step operation easily, and to pile up be relative loose to the lamella formed, can not cause and again again be piled into graphite-structure and cannot be dispersed.Such as, only again they need can be scattered in solvent by mechanical stirring (adopting ultrasonic wave added if desired), and aqueous phase or the organic phase thickener of various concentration can be obtained.When intercalated graphite is single order intercalated graphite, the single-layer graphene (relative to raw graphite) that productive rate is more than 60% can be obtained; When intercalated graphite is second order above intercalated graphite, can obtain productive rate is more than 60% individual layer and few layer (number of plies is less than or equal to 10) Graphene mixture (relative to raw graphite).
In the present invention, the Graphene slurry described in step (3) and Graphene filter cake can disperse in a solvent again again.
For the various problems that prior art exists, the present inventor is through long-term Researching and practicing, propose technical scheme of the present invention, the program can realize high-level efficiency, low cost, the individual layer of mass-producing or the preparation of few layer graphene nanoscale twins, especially the shearing lift-off technology route proposed here has good industrialization, the practical prospect of scale operation, solve Graphene low cost, key issue prepared by mass-producing, for realizing Graphene in every field (as matrix material, coating, conductive ink, flexible electronic, lithium cell, the energy storage materials such as ultracapacitor) in widespread use provide effective way.
Beneficial effect of the present invention is: the technical process short (high-level efficiency) that the present invention proposes, the mass-producing aqueous phase technology of preparing of energy consumption low (being normal-temperature operation substantially).By the introducing of shearing action, not only can cause the stripping of graphene sheet layer, and can greatly lower turnout and cost.In addition, the reagent that present method adopts is all commercially available cheap reagent, and the solvent in preparation process is easy to reclaim.And; obtained graphene product unprecedented high concentration (can be greater than 10 wt%; > 100 mg/mL) be scattered in water; also can be made into the Graphene filter cake or powder that are easy to again disperse, effectively achieve low cost prepared by high-quality graphene mass-producing, high-level efficiency, environment friendly and storage, transport and use problem.
Accompanying drawing explanation
Fig. 1 peels off transmission electron microscope (TEM) image of rear Graphene;
Fig. 2 peels off scanning electronic microscope (SEM) image of rear Graphene.
Embodiment
Below by way of specific examples, technical scheme of the present invention is described.Should be appreciated that, one or more steps that the present invention mentions are not repelled also there is other method and step before and after described combination step, or can also insert other method and step between these specifically mentioned steps.Should also be understood that these examples are only not used in for illustration of the present invention to limit the scope of the invention.Except as otherwise noted, the numbering of various method steps is only the object differentiating various method steps, but not for restriction each method ordering or limit practical range of the present invention, the change of its relativeness or adjustment, under the condition without substantial technological content alteration, when being also considered as the enforceable category of the present invention.
Embodiment 1:
By 200 milliliters of vitriol oils (98%) and 10 grams of potassium permanganate (purity >95%), 10 grams of crystalline graphite powder (particle diameter is 500 microns or 35 orders, carbon content >95%) Homogeneous phase mixing, hierarchy of control temperature is lower than 35
oc, it, after 2 hours, slowly adds in 1000 milliliters of frozen water by continuously stirring, and removes reaction heat in time, avoids system temperature too high.Then add 20 milliliters of hydrogen peroxide and stir 5 minutes, after filtration, obtaining graphite intercalation compound.
The graphite intercalation compound (wet) obtained after filtration is mixed with 10 grams of sodium hydroxide and 250 ml waters.Adopt shearing stirrer (power 500 W) 18, after processing 50 minutes under 000 turn/min, obtain black graphene suspension.Under the condition of 10000 revs/min, after centrifugal 10 minutes, supernatant liquid is gone to obtain the aqueous phase thickener of high single-layer graphene content the dark solution obtained.Compared to graphite raw material, individual layer and few layer graphene mixture productive rate are greater than 60%.Transmission electron microscope photo (Fig. 1) and the electron scanning micrograph (Fig. 2) of graphene film confirm its good peeling effect.After compacting film forming, adopting four point probe conductivity measuring instrument to obtain graphene film specific conductivity is 1.5 × 10
4s/m.
Embodiment 2
By 100 milliliters of oleums (containing 20% sulphur trioxide), 5 milliliters of hydrogen peroxide and 10 grams of crystalline graphite powder (particle diameter is 500 microns) Homogeneous phase mixing, hierarchy of control temperature is lower than 35
oc, it, after 2 hours, slowly adds in 1000 milliliters of frozen water by continuously stirring, notes removing mixture heat in time, avoiding system temperature too high.Then add 20 milliliters of hydrogen peroxide and stir 5 minutes, after filtration, obtaining graphite intercalation compound.
The graphite intercalation compound (wet) obtained after filtration is mixed with 10 grams of sodium hydroxide and 250 ml waters.Adopt shearing stirrer (power 500 W) 18, after processing 50 minutes under 000 turn/min, obtain black graphene suspension.Under the condition of 10000 revs/min, after centrifugal 10 minutes, supernatant liquid is gone to obtain the aqueous phase thickener of high single-layer graphene content the dark solution obtained.Compared to graphite raw material, individual layer and few layer graphene mixture productive rate are greater than 60%.After compacting film forming, adopting four point probe conductivity measuring instrument to obtain graphene film specific conductivity is 1.5 × 10
4s/m.
Embodiment 3
30 grams of ammonium persulphates, 200 milliliters of vitriol oils (98%) are mixed with 10 grams of crystalline graphite powders (particle diameter is 500 microns), it slowly adds after 6 hours in 1000 milliliters of frozen water by stirring at room temperature, notes removing mixture heat in time, avoiding system temperature too high.Then add 20 milliliters of hydrogen peroxide and stir 5 minutes, after filtration, obtaining graphite intercalation compound.
The graphite intercalation compound (wet) obtained after filtration is mixed with 10 grams of sodium hydroxide and 250 ml waters.Adopt shearing stirrer (power 500 W) 18, after processing 50 minutes under 000 turn/min, obtain black graphene suspension.Under the condition of 10000 revs/min, after centrifugal 10 minutes, supernatant liquid is gone to obtain the aqueous phase thickener of high single-layer graphene content the dark solution obtained.Compared to graphite raw material, individual layer and few layer graphene mixture productive rate are greater than 60%.After compacting film forming, adopting four point probe conductivity measuring instrument to obtain graphene film specific conductivity is 1.5 × 10
4s/m.
Embodiment 4
100 milliliters of vitriol oils (sulfuric acid content 98%), 50 milliliters of concentrated nitric acids (nitric acid content 98%) are mixed with crystalline graphite powder (particle diameter is 500 microns), stirring at room temperature was filtered after 1 hour, and add in oxalic acid solution and soak 1 hour, filter and pour into fast in 500 milliliters of aqueous solution containing 20 grams of sodium hydroxide.Adopt shearing stirrer (power 500 W) 18, after processing 50 minutes under 000 turn/min, obtain black graphene suspension.Under the condition of 10000 revs/min, after centrifugal 10 minutes, go supernatant liquid to obtain the aqueous phase thickener of high Graphene content the dark solution obtained, in this thickener, alkene is still with individual layer and few layer graphene state dispersion.Compared to graphite raw material, individual layer and few layer graphene mixture productive rate are greater than 50%.
Embodiment 5
By 200 milliliters of vitriol oils (98%) and 10 grams of potassium permanganate (purity >95%), 10 grams of crystalline graphite powder (particle diameter is 500 microns or 35 orders, carbon content >95%) Homogeneous phase mixing, hierarchy of control temperature is lower than 35
oc, it, after 2 hours, slowly adds in 1000 milliliters of frozen water by continuously stirring, notes removing mixture heat in time, avoiding system temperature too high.Then add 20 milliliters of hydrogen peroxide and stir 5 minutes, after filtration, obtaining graphite intercalation compound.
The graphite intercalation compound (wet) obtained after filtration is mixed with 50 grams of sodium hydroxide and 250 ml waters.Adopt shearing stirrer (power 500 W) 18, after processing 50 minutes under 000 turn/min, obtain black graphene suspension.Under the condition of 10000 revs/min, after centrifugal 10 minutes, supernatant liquid is gone to obtain the aqueous phase thickener of high single-layer graphene content the dark solution obtained.Compared to graphite raw material, individual layer and few layer graphene mixture productive rate are greater than 60%.After compacting film forming, adopting four point probe conductivity measuring instrument to obtain graphene film specific conductivity is 1.5 × 10
4s/m.
Embodiment 6
By 200 milliliters of vitriol oils (98%) and 10 grams of potassium permanganate (purity >95%), 10 grams of crystalline graphite powder (particle diameter is 500 microns or 35 orders, carbon content >95%) Homogeneous phase mixing, hierarchy of control temperature is lower than 35
oc, it, after 2 hours, slowly adds in 1000 milliliters of frozen water by continuously stirring, notes removing mixture heat in time, avoiding system temperature too high.Then add 20 milliliters of hydrogen peroxide and stir 5 minutes, after filtration, obtaining graphite intercalation compound.
The graphite intercalation compound (wet) obtained after filtration is mixed with 10 grams of potassium hydroxide and 250 ml waters.Adopt shearing stirrer (power 500 W) 18, after processing 50 minutes under 000 turn/min, obtain black graphene suspension.Under the condition of 10000 revs/min, after centrifugal 10 minutes, supernatant liquid is gone to obtain the aqueous phase thickener of high single-layer graphene content the dark solution obtained.Compared to graphite raw material, individual layer and few layer graphene mixture productive rate are greater than 60%.After compacting film forming, adopting four point probe conductivity measuring instrument to obtain graphene film specific conductivity is 1.5 × 10
4s/m.
Embodiment 7
By 200 milliliters of vitriol oils (98%) and 10 grams of potassium permanganate (purity >95%), 10 grams of crystalline graphite powder (particle diameter is 500 microns or 35 orders, carbon content >95%) Homogeneous phase mixing, hierarchy of control temperature is lower than 35
oc, it, after 2 hours, slowly adds in 1000 milliliters of frozen water by continuously stirring, notes removing mixture heat in time, avoiding system temperature too high.Then add 20 milliliters of hydrogen peroxide and stir 5 minutes, after filtration, obtaining graphite intercalation compound.
The graphite intercalation compound (wet) obtained after filtration is mixed with 10 grams of potassium hydroxide and 250 ml waters.Adopt shearing stirrer (power 500 W) 8, after processing 50 minutes under 000 turn/min, obtain black graphene suspension.Under the condition of 10000 revs/min, after centrifugal 10 minutes, supernatant liquid is gone to obtain the aqueous phase thickener of high single-layer graphene content the dark solution obtained.Compared to graphite raw material, individual layer and few layer graphene mixture productive rate are greater than 50%.After compacting film forming, adopting four point probe conductivity measuring instrument to obtain graphene film specific conductivity is 1.5 × 10
4s/m.
Embodiment 8
By 200 milliliters of vitriol oils (98%) and 10 grams of potassium permanganate (purity >95%), 10 grams of crystalline graphite powder (particle diameter is 500 microns or 35 orders, carbon content >95%) Homogeneous phase mixing, hierarchy of control temperature is lower than 35
oc, it, after 2 hours, slowly adds in 1000 milliliters of frozen water by continuously stirring, notes removing mixture heat in time, avoiding system temperature too high.Then add 20 milliliters of hydrogen peroxide and stir 5 minutes, after filtration, obtaining graphite intercalation compound.
The graphite intercalation compound (wet) obtained after filtration is mixed with 10 grams of potassium hydroxide and 250 ml waters.Adopt shearing stirrer (power 500 W) 18, after processing 180 minutes under 000 turn/min, obtain black graphene suspension.Under the condition of 10000 revs/min, after centrifugal 10 minutes, supernatant liquid is gone to obtain the aqueous phase thickener of high single-layer graphene content the dark solution obtained.Compared to graphite raw material, individual layer and few layer graphene mixture productive rate are greater than 70%.After compacting film forming, adopting four point probe conductivity measuring instrument to obtain graphene film specific conductivity is 1.5 × 10
4s/m.
Embodiment 9
By 200 milliliters of vitriol oils (98%) and 10 grams of potassium permanganate (purity >95%), 10 grams of crystalline graphite powder (particle diameter is 500 microns or 35 orders, carbon content >95%) Homogeneous phase mixing, hierarchy of control temperature is lower than 35
oc, it, after 2 hours, slowly adds in 1000 milliliters of frozen water by continuously stirring, notes removing mixture heat in time, avoiding system temperature too high.Then add 20 milliliters of hydrogen peroxide and stir 5 minutes, after filtration, obtaining graphite intercalation compound.
The graphite intercalation compound (wet) obtained after filtration is mixed with 10 grams of sodium hydroxide and 100 ml waters.Adopt shearing stirrer (power 500 W) 18, after processing 50 minutes under 000 turn/min, obtain black graphene suspension.Under the condition of 10000 revs/min, after centrifugal 10 minutes, supernatant liquid is gone to obtain the aqueous phase thickener of high single-layer graphene content the dark solution obtained.Compared to graphite raw material, individual layer and few layer graphene mixture productive rate are greater than 60%.After compacting film forming, adopting four point probe conductivity measuring instrument to obtain graphene film specific conductivity is 1.5 × 10
4s/m.
Embodiment 10
By 200 milliliters of vitriol oils (98%) and 10 grams of potassium permanganate (purity >95%), 10 grams of crystalline graphite powder (particle diameter is about 50 microns, carbon content >95%) Homogeneous phase mixing, hierarchy of control temperature is lower than 35
oc, it, after 2 hours, slowly adds in 1000 milliliters of frozen water by continuously stirring, notes removing mixture heat in time, avoiding system temperature too high.Then add 20 milliliters of hydrogen peroxide and stir 5 minutes, after filtration, obtaining graphite intercalation compound.
The graphite intercalation compound (wet) obtained after filtration is mixed with 10 grams of sodium hydroxide and 100 ml waters.Adopt shearing stirrer (power 500 W) 18, after processing 50 minutes under 000 turn/min, obtain black graphene suspension.Under the condition of 10000 revs/min, after centrifugal 10 minutes, supernatant liquid is gone to obtain the aqueous phase thickener of high single-layer graphene content the dark solution obtained.Compared to graphite raw material, individual layer and few layer graphene mixture productive rate are greater than 60%.After compacting film forming, adopting four point probe conductivity measuring instrument to obtain graphene film specific conductivity is 1.5 × 10
4s/m.
Embodiment 11
By 200 milliliters of vitriol oils (98%) and 30 grams of potassium permanganate (purity >95%), 10 grams of crystalline graphite powder (particle diameter is 500 microns or 35 orders, carbon content >95%) Homogeneous phase mixing, hierarchy of control temperature is lower than 35
oc, it, after 2 hours, slowly adds in 1000 milliliters of frozen water by continuously stirring, notes removing mixture heat in time, avoiding system temperature too high.Then add 20 milliliters of hydrogen peroxide and stir 5 minutes, after filtration, obtaining graphite intercalation compound.
The graphite intercalation compound (wet) obtained after filtration is mixed with 10 grams of sodium hydroxide and 250 ml waters.Adopt shearing stirrer (power 500 W) 18, after processing 50 minutes under 000 turn/min, obtain black graphene suspension.Under the condition of 10000 revs/min, after centrifugal 10 minutes, supernatant liquid is gone to obtain the aqueous phase thickener of high single-layer graphene content the dark solution obtained.Compared to graphite raw material, individual layer and few layer graphene mixture productive rate are greater than 60%.After compacting film forming, adopting four point probe conductivity measuring instrument to obtain graphene film specific conductivity is 1.5 × 10
4s/m.
Embodiment 12
By 200 milliliters of vitriol oils (98%) and 30 grams of potassium permanganate (purity >95%), 10 grams of crystalline graphite powder (particle diameter is 500 microns or 35 orders, carbon content >95%) Homogeneous phase mixing, hierarchy of control temperature is lower than 35
oc, it, after 2 hours, slowly adds in 1000 milliliters of frozen water by continuously stirring, notes removing mixture heat in time, avoiding system temperature too high.Then add 20 milliliters of hydrogen peroxide and stir 5 minutes, after filtration, obtaining graphite intercalation compound.
The graphite intercalation compound (wet) obtained after filtration is mixed with 10 grams of sodium hydroxide and 250 ml waters.Adopt shearing stirrer (power 500 W) 18, after processing 50 minutes under 000 turn/min, obtain black graphene suspension.Under the condition of 5000 revs/min, after centrifugal 10 minutes, supernatant liquid is gone to obtain the aqueous phase thickener of high single-layer graphene content the dark solution obtained.Compared to graphite raw material, individual layer and few layer graphene mixture productive rate are greater than 60%.After compacting film forming, adopting four point probe conductivity measuring instrument to obtain graphene film specific conductivity is 1.5 × 10
4s/m.
Comparative example 1
The 2 grams of graphite intercalation compounds adopting embodiment 1 method to prepare are scattered in (not containing alkaline matters such as sodium hydroxide) in 100 ml deionized water, with shearing stirrer (power 500 W) 18,50 minutes are processed under 000 turn/min, only the graphene sheet layer of minute quantity is stripped, compared to starting material graphite, it is peeled off productive rate and is less than 1%.
Comparative example 2
Directly in the aqueous sodium hydroxide solution of pH=14, adopt shearing stirrer (power 500 W) 18 crystalline flake graphite (particle size about 500 microns), after processing 50 minutes under 000 turn/min, only the graphene sheet layer of minute quantity is stripped, and compared to starting material graphite, it is peeled off productive rate and is less than 2%.
Comparative example 3
Employing 10 grams of expanded graphite alkene are scattered in the 100 ml deionized water solution containing sodium hydroxide (pH=14), reflux is after 60 minutes, shearing stirrer (power 500 W) is 1, after processing 30 minutes under 000 turn/min, obtain homogeneous phase dark solution, centrifugal removing supernatant liquid obtains Graphene thickener.Graphene sheet layer mean thickness is greater than 5 nm, the graphene sheet layer that thickness is less than 3 nanometers relative to the productive rate of raw material expanded graphite powder lower than 30%.
Comparative example 4
The compound between graphite layers of the 2 grams of sulfuric acid intercalations adopting embodiment 1 method to prepare is scattered in the 100 ml deionized water solution containing sodium hydroxide (pH=14), reflux is after 60 minutes, do not adopt any ultrasonic or shearing treatment method, product is still almost macroscopic large chip architecture.Centrifugal removing supernatant liquid obtains black precipitate, does not almost have Graphene to produce.
Claims (7)
1. aqueous phase shears the method peeled off and prepare Graphene, it is characterized in that concrete steps are as follows:
(1) adopted by raw graphite the method for chemical oxidation intercalation or electrochemical intercalation to carry out intercalation processing, make intercalator enter graphite layers, prepare graphite intercalation compound, be beneficial to completing of stripping process; Wherein: described intercalator component be in sulfuric acid, nitric acid, perchloric acid, phosphoric acid, hydrogen peroxide, potassium permanganate, potassium bichromate, iron trichloride, chromium trioxide, ammonium persulphate, formic acid, acetic acid, oxalic acid, bromine, chlorine, iodine chloride, iodine bromide IBr, ozone or oxygen more than one;
(2) graphite intercalation compound and active substance are added to the water, under shearing action, process 10 minutes-20 hours, obtain graphene suspension or the dispersion liquid of stripping; The consumption of described active substance is 0.01-10 times of raw graphite quality, and the add-on of water is 5-1000 times of raw graphite quality;
(3) graphene suspension step (2) obtained or dispersion liquid filter through centrifugal or filter screen (cloth), make solid-liquid separation, obtain Graphene thickener or filter cake.
2. method according to claim 1, is characterized in that described in step (1), raw graphite is natural graphite, synthetic graphite or expanded graphite.
3. method according to claim 1, it is characterized in that active substance described in step (2) is one in sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, salt of wormwood, Quilonum Retard, sodium bicarbonate, saleratus, lithium bicarbonate, ammonium hydroxide, tetrabutylammonium or industrial soda or arbitrary combination between them, its consumption be the 0.2-5 of raw graphite quality doubly.
4. method according to claim 1, is characterized in that the add-on of water described in step (2) is 10-100 times of raw graphite quality.
5. method according to claim 1, it is characterized in that the shearing treatment described in step (2) refers to and adopt shear to carry out shearing treatment to graphitiferous intercalation compound suspension liquid of aqueous phase, shearing rate is 1000-100000 rev/min.
6. method according to claim 1, it is characterized in that the centrifugation described in step (2) refers to adopts the rotating speed of 200-10000 rev/min to concentrate the graphene suspension after ultrasonic stripping, can obtain high Graphene content thickener after removing supernatant liquid.
7. method according to claim 1, is characterized in that the Graphene slurry described in step (3) and Graphene filter cake can disperse in a solvent again again.
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| CN105800598A (en) * | 2016-02-26 | 2016-07-27 | 无锡吉仓纳米材料科技有限公司 | Method for preparing graphene by cutting intercalation method |
| CN105948028A (en) * | 2016-05-06 | 2016-09-21 | 成都新柯力化工科技有限公司 | Method for preparation of graphene precursor by internal mixer peeling and graphene precursor |
| CN106082180A (en) * | 2016-06-06 | 2016-11-09 | 南通伟德动力电池研究所（普通合伙） | A kind of acid intercalated graphite and Ammonium persulfate. are the method that raw material manufactures Graphene |
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| WO2017084561A1 (en) * | 2015-11-16 | 2017-05-26 | 复旦大学 | Preparation method for large-size graphene oxide or graphene |
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| CN109775696A (en) * | 2019-03-14 | 2019-05-21 | 西南科技大学 | Semi-dry Process at Room Temperature prepares expanded graphite and wet process removing prepares graphene method |
| CN111232964A (en) * | 2020-01-19 | 2020-06-05 | 北京石墨烯研究院 | Graphene wafer transfer method, graphene wafer and bubbling system |
| CN113683084A (en) * | 2021-08-24 | 2021-11-23 | 洛阳师范学院 | Preparation method of functionalized few-layer graphene |
| CN114275820A (en) * | 2022-01-11 | 2022-04-05 | 南通金仕达超微阻燃材料有限公司 | NiFe2O4One-pot preparation method of few-layer graphite broadband wave-absorbing powder material |
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| CN106554010A (en) * | 2015-09-25 | 2017-04-05 | 苏州烯时代石墨烯科技有限公司 | The method of preparation of industrialization big size graphene |
| WO2017084561A1 (en) * | 2015-11-16 | 2017-05-26 | 复旦大学 | Preparation method for large-size graphene oxide or graphene |
| CN105800598A (en) * | 2016-02-26 | 2016-07-27 | 无锡吉仓纳米材料科技有限公司 | Method for preparing graphene by cutting intercalation method |
| CN107215867A (en) * | 2016-03-22 | 2017-09-29 | 中国科学院金属研究所 | A kind of method that serialization prepares graphene oxide microplate |
| CN105948028A (en) * | 2016-05-06 | 2016-09-21 | 成都新柯力化工科技有限公司 | Method for preparation of graphene precursor by internal mixer peeling and graphene precursor |
| CN106082180A (en) * | 2016-06-06 | 2016-11-09 | 南通伟德动力电池研究所（普通合伙） | A kind of acid intercalated graphite and Ammonium persulfate. are the method that raw material manufactures Graphene |
| CN108622887A (en) * | 2017-03-17 | 2018-10-09 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of swollen quick-fried method for preparing graphene of microwave |
| CN108622887B (en) * | 2017-03-17 | 2020-04-14 | 郑州新世纪材料基因组工程研究院有限公司 | Method for preparing graphene through microwave puffing |
| CN107285302B (en) * | 2017-08-17 | 2020-05-26 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene |
| CN107285302A (en) * | 2017-08-17 | 2017-10-24 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of graphene |
| CN107572515A (en) * | 2017-09-30 | 2018-01-12 | 湖南国盛石墨科技有限公司 | The preparation method of inflatable micro crystal graphite |
| CN107445158A (en) * | 2017-09-30 | 2017-12-08 | 湖南国盛石墨科技有限公司 | The swollen expansion process of micro crystal graphite |
| CN109666350A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of waterborne conductive coating and preparation method thereof containing highly conductive graphene |
| CN109666350B (en) * | 2017-10-16 | 2021-06-29 | 山东欧铂新材料有限公司 | Water-based conductive coating containing high-conductivity graphene and preparation method thereof |
| CN108165016A (en) * | 2018-01-19 | 2018-06-15 | 林荣铨 | A kind of preparation method of modified graphene heat-conducting silicone grease |
| CN108585634A (en) * | 2018-05-04 | 2018-09-28 | 砺剑防务技术集团有限公司 | Boron nitride fire-resistant anticorrosion paint and preparation method thereof |
| CN109775696A (en) * | 2019-03-14 | 2019-05-21 | 西南科技大学 | Semi-dry Process at Room Temperature prepares expanded graphite and wet process removing prepares graphene method |
| CN111232964A (en) * | 2020-01-19 | 2020-06-05 | 北京石墨烯研究院 | Graphene wafer transfer method, graphene wafer and bubbling system |
| CN113683084A (en) * | 2021-08-24 | 2021-11-23 | 洛阳师范学院 | Preparation method of functionalized few-layer graphene |
| CN114275820A (en) * | 2022-01-11 | 2022-04-05 | 南通金仕达超微阻燃材料有限公司 | NiFe2O4One-pot preparation method of few-layer graphite broadband wave-absorbing powder material |
| CN114275820B (en) * | 2022-01-11 | 2023-12-01 | 南通金仕达高精实业股份有限公司 | NiFe 2 O 4 One-pot preparation method of few-layer graphite broadband wave-absorbing powder material |
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