CN103570010A - Preparation method of graphene powder material - Google Patents
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- CN103570010A CN103570010A CN201310487255.0A CN201310487255A CN103570010A CN 103570010 A CN103570010 A CN 103570010A CN 201310487255 A CN201310487255 A CN 201310487255A CN 103570010 A CN103570010 A CN 103570010A
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Abstract
The invention discloses a preparation method of a graphene powder material. The preparation method comprises the following steps of (1) adding graphite oxide into an organic alkaline solution, and carrying out ultrasonic dispersion to obtain a graphene dispersing solution; (2) adding an organic borohydride into the graphene dispersing solution obtained in the step (1), carrying out solid-liquid separation after stirring, and drying to obtain the graphene powder material. The graphene powder material prepared by using the preparation method of the graphene powder material, disclosed by the invention, has favorable dispersibility and stability in polar solvents such as water, methanol, ethanol, dimethyl formamide and the like, the concentration of the dispersing solution can be up to 2-5mg/ml, and no sediments are generated after the graphene powder material is stored for 4-6 months; the graphene powder material contains few impurities and has potential application values in the fields such as materials, energy, biological sensing, electronics, electrochemistry, solar cells and the like; the preparation method disclosed by the invention has the advantages of mild reaction condition, simple process, short period, low graphene impurity content, high efficiency, economy, environment friendliness and the like, and is easy to realize large-scale production.
Description
Technical field
The invention belongs to Graphene technical field, be specifically related to a kind of preparation method of graphene powder material.
Background technology
Graphene is a kind of Two-dimensional Carbon material, and each carbon atom is with sp
2the mode that hydridization forms covalent linkage is connected with other 3 carbon atoms, is then arranged as cellular lattice.The basic structural unit of Graphene is benzene six-ring the most stable in organic materials, its theoretic throat is only 0.35nm, it is the thinnest two-dimensional material of finding at present, the monoatomic layer structures shape that it is special it there is abundant and novel physical phenomenon, make Graphene show the physics and chemistry character of many excellences.The tensile strength of Graphene can reach 50～200GPa, and Young's modulus can reach 1TPa, is more than 100 times of steel, is the material with high specific strength that can prepare at present; Its carrier mobility reaches 1.5 * 10
4cm
2v
-1s
-1, be current 2 times of the known indium antimonide material with high mobility, be 10 times of commercial silicon chip mobility, under given conditions, its mobility even can be up to 2.5 * 10
5cm
2v
-1s
-1; The thermal conductivity of Graphene can reach 5 * 10
3wm
-1k
-1, be adamantine 3 times; In addition, Graphene also has the special propertys such as room temperature quantum hall effect (Hall effect) and room-temperature ferromagnetic.These excellent specific properties of Graphene make it can be used for mechanical strength, elasticity, antifatigue and many other that preparation has a superelevation to have the polymer composite of excellent properties, all have a wide range of applications in addition in fields such as electricity, the energy, bio-sensings.
Yet the physical and chemical performance of Graphene excellence is the character based on mono-layer graphite sheet; When constructing graphene-based matrix material, the high dispersing of Graphene in matrix is to prepare the key of high performance composite.But, due to the high specific surface area of Graphene and strong van der Waals interaction between layers, cause graphene film interlayer to be easy to reunite or be again stacked to graphite-structure; And due to graphite this in water and organic solvent in neither dispersion, thereby limited it, further apply.Therefore, high effective and modified or grapheme modified powder body material how, enables to be applied to become in actual production the important topic of current Graphene research.
At present, the method for preparing Graphene mainly adopts physical method and chemical process.Wherein, physical method originates from the Geim of Manchester university leader study group adopts mechanically peel method to prepare graphene film (the Novoselov K.S. that maximum width can reach 10 μ m for 2004; Geim A.K.; Morozov S.V.; Jiang D.; Zhang Y.; Dubonos S.V.; Grigorieva I.V.; Firsov A.A.Science, 2004,306 (5696): 666-670).But, this method poor repeatability, productive rate is also very low, is not suitable for large-scale production and application.Chemical process is prepared the chemical reduction that the main method of Graphene is graphite oxide, generally by high-power ultrasonic, first realize peeling off of graphite oxide, for fear of graphene oxide, in reduction process, occur to reunite again, in preparing the process of Graphene, to add polymer, tensio-active agent, ionic liquid or other stablizers, by polymer winding, SURFACTANT ADSORPTION or electrostatic repulsion, cause the space obstacle between graphene layer, thereby prepare stable graphene dispersing solution.Utilize the chemical reduction of graphite oxide to prepare Graphene, there is the advantages such as production cost is low, operating procedure is simple, experiment condition is gentle, be relatively applicable to large-scale production.But profit is prepared Graphene in this way, in products obtained therefrom, there is a large amount of auxiliary agent impurity (polymer, tensio-active agent or other stablizers), have a strong impact on the further application of Graphene; And the Graphene finally obtaining, after being dried, is easily reunited, dispersed variation, powder dispersion concentration is 0.1～0.3mg/ml only, far can not meet the requirement of application.
Patent US2000303706 discloses and has utilized alkaline reducing agent as hydrazine hydrate or sodium borohydride reduction graphite oxide, can obtain having the graphene dispersing solution of favorable dispersity; And if in non-basic solution, reduce, the graphene dispersing solution after reduction can produce serious reunion and cannot obtain homodisperse dispersion liquid.The people such as Guo Shouwu, in 2010 patent (CN201010613212.9), react the graphite oxide aqueous solution with oxammonium hydrochloride, utilize ammoniacal liquor to control the pH value of reaction system, have successfully obtained the graphene dispersing solution of favorable dispersity.More than research shows, reduction-oxidation graphite under alkaline condition can obtain the Graphene of favorable dispersity.But because extent of exfoliation is too little, cause reaction time oversize.Subsequently, people (Che J., the Shen L. such as Che J., Xiao Y., Journal of Materials Chemistry, 2010,20,1722-1727) find, in intensive polar solvent, in dimethyl formamide, utilize quadrol to do dispersion agent and reductive agent, though can a step realize reduction and the dispersion of graphite oxide, simplify preparation technology, but exist, disperseed the low deficiency of concentration.The people such as Li Xin also disclose a kind of method of preparing Graphene in 2012 in patent (CN201210152803.X), and applicant is ultrasonic oxidation graphite in sodium hydroxide solution, has obtained the Graphene of favorable dispersity; But exist the high and Graphene of temperature of reaction in solvent middle and high concentration bad dispersibility, the incomplete problem of reducing, seriously limited the widespread use of Graphene.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of graphene powder material, solves graphene dispersing solution concentration Graphene low, that reduction not exclusively causes in prior art and applies limited problem.
In order to realize above object, the technical solution adopted in the present invention is: a kind of preparation method of graphene powder material, comprises the following steps:
1) graphite oxide is added in organic bases solution, ultrasonic dispersion, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add organic boron hydride, after stirring, carry out solid-liquid separation, dry, obtain.
Organic bases described in step 1) is tetraalkyl ammonium hydroxide, and its general molecular formula is:
[N(C
nH
2n+1)
4]OH，
Wherein, n is 1,2,3 or 4.
The mass percentage concentration of described organic bases solution is 10%～40%.
The consumption of described organic bases solution is: the organic bases solution of 1～10ml for every 100mg graphite oxide.
Described in step 1), ultrasonic power is 100～400W, and the ultrasonic time is 10～120min.
The general molecular formula of the hydride of organic boron step 2) is:
[N(C
nH
2n+1)
4]BH
4，
Wherein, n is 1,2,3 or 4.
The consumption of described organic boron hydride is: the organic boron hydride of 0.1～1ml for every 100mg graphite oxide.
The method of solid-liquid separation step 2) is that millipore filtration suction filtration or high speed centrifugation are separated.
The aperture of described millipore filtration is 0.1～0.45 μ m.The rotating speed of described high speed centrifugation separation is 10000～20000rpm.
Step 2) described in, be dried as lyophilize or vacuum-drying.
Described cryodesiccated temperature is-20～-5 ℃, and be 10～48h time of drying; Described vacuum drying temperature is 20～50 ℃, and be 48～120h time of drying.
In the preparation method of graphene powder material of the present invention, described graphite oxide is made by improved oxidation style, Brodie method, Staudenmaier method, Hummers method or improved Hummers method.Described improved oxidation style is to take graphite as carbon source, and the vitriol oil and phosphoric acid are solvent and pro-oxidant, and potassium permanganate is oxygenant, prepares graphite oxide.
Known based on research background, when reduced graphene, controlling alkaline environment is an essential condition that successfully realizes Graphene reduction.But the inorganic reagent of current control alkaline environment is generally ammoniacal liquor and sodium hydroxide (potassium), but owing to existing inorganic cation and laminate electrostatic force too strong, causes peeling off rear Graphene and easily reunite; Organic reagent is generally quadrol, but due to a little less than quadrol alkalescence, its molecular volume is larger, enters graphite oxide interlayer resistance larger, cause Graphene to peel off effect bad, can only realize the dispersion of the Graphene of lower concentration.How to choose a base molecule with suitable construction, can not only easily enter graphite oxide interlayer, realize graphite oxide and peel off; And the electrostatic force of positively charged ion and laminate can not be too strong in base molecule structure, can not be too a little less than, just in time can stop reassociating of Graphene laminate.
The preparation method of graphene powder material of the present invention, utilize organic bases for stripper, organic boron hydride be reductive agent, assisting ultrasonic has realized peeling off and reducing of graphite oxide under gentle condition, obtains graphene powder material; Innovation of the present invention is to choose has the cationic organic bases of large alkane as stripper, alkaline environment is not only provided, and large alkane cation group and Coulomb repulsion and the buffer action between laminate in its structure, make graphite oxide in reduction, can not there is the stacking again between laminate, the phenomenon that the radius of having avoided using system that inorganic reducing agent is brought into causes Graphene laminate to reassemble too by force compared with little positively charged ion and Graphene laminate reactive force, and then obtained the graphene dispersing solution of favorable dispersity; Gained graphene powder material shows good dispersiveness and stability at polar solvent in as water, methyl alcohol, ethanol, dimethyl formamide equal solvent, and dispersion liquid concentration can, up to 2～5mg/ml, be deposited and without precipitation, occur for 4～6 months; In addition, prepared graphene powder material is when further applying, because the electrostatic force of the macoradical alkane positively charged ion of introducing on its laminate and Graphene laminate is not very strong, can be substituted by group that in system, other reactive forces are stronger or molecule and become " leaving away " group, thereby can in Graphene compound system, not introduce impurity, in fields such as material, the energy, bio-sensing, electronics, electrochemistry, solar cells, there is potential using value; Preparation method's reaction conditions of the present invention is gentle, and technique is simple, and the cycle is short, has the advantages such as efficient, economy, environmental protection, and is easy to accomplish scale production.
Accompanying drawing explanation
Fig. 1 is the dispersed experimental observation figure of embodiment 4 gained graphene powder materials, and wherein the solvent of (a) is water, and solvent (b) is methyl alcohol, and solvent (c) is dimethyl formamide, and solvent (d) is dimethyl sulfoxide (DMSO);
Fig. 2 is the transmission electron microscope picture of comparative example gained graphene oxide powder body material;
Fig. 3 is the transmission electron microscope picture of embodiment 4 gained graphene powder materials;
Fig. 4 is the ultraviolet-visible absorption spectroscopy figure of embodiment 6 and comparative example gained powder body material, and wherein (a) is graphite oxide, is (b) comparative example gained graphene oxide, is (c) embodiment 6 gained graphene powder materials;
Fig. 5 is the XPS wide range scintigram of embodiment 7 and comparative example gained powder body material, and wherein (a) is graphite oxide, is (b) embodiment 7 gained graphene powder materials;
Fig. 6 is the X-ray diffractogram of embodiment 12 and comparative example gained powder body material, and wherein (a) is graphite, is (b) graphite oxide, is (c) embodiment 12 gained graphene powder materials;
Fig. 7 is the Raman spectrogram of embodiment 14 and comparative example gained powder body material, and wherein (a) is graphite, is (b) graphite oxide, is (c) embodiment 14 gained graphene powder materials.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Graphite oxide used in embodiment 1～15 is prepared by improved oxidation style, is specially: by natural flake graphite and KMnO
4join successively dense H
2sO
4/ H
3pO
4volume ratio is in the mixing solutions of 9:1, then by water-bath, is controlled reactant is heated to 40 ℃, and stir 6h; In system, add the H that water, mass concentration are 30% successively
2o
2solution; Reaction finishes rear filtered while hot, and the salt acid elution that is 5% by mass concentration, until SO
4 2-remove completely; Centrifugal rear collection bottom settlings is then dried 24 hours at 60 ℃, the final graphite oxide that obtains brown.
Embodiment 1
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 50ml mass concentration is in 10% tetramethyl ammonium hydroxide solution, ultrasonic dispersion, and ultrasonic power is 400W, ultrasonic time is 60min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetramethyl-hydroboration ammonia, under room temperature condition, stir 3h, adopt the millipore filtration of 0.45 μ m to carry out after suction filtration, under-20 ℃ of conditions, carry out lyophilize, time of drying, 10h, obtained graphene powder material.
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 50ml mass concentration is in 20% tetraethyl ammonium hydroxide solution, ultrasonic dispersion, and ultrasonic power is 300W, ultrasonic time is 60min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetraethyl-hydroboration ammonia, under room temperature condition, stir 3h, adopt the millipore filtration of 0.1 μ m to carry out after suction filtration, under-10 ℃ of conditions, carry out lyophilize, time of drying, 24h, obtained graphene powder material.
Embodiment 3
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 50ml mass concentration is in 30% TPAOH solution, ultrasonic dispersion, and ultrasonic power is 200W, ultrasonic time is 60min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrapropyl hydroboration ammonia, under room temperature condition, stir 3h, adopt the millipore filtration of 0.22 μ m to carry out after suction filtration, under-5 ℃ of conditions, carry out lyophilize, time of drying, 48h, obtained graphene powder material.
Embodiment 4
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 50ml mass concentration is in 40% TBAH solution, ultrasonic dispersion, and ultrasonic power is 100W, ultrasonic time is 60min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrabutyl hydroboration ammonia, under room temperature condition, stir 3h, adopt the millipore filtration of 0.1 μ m to carry out after suction filtration, under-20 ℃ of conditions, carry out lyophilize, time of drying, 10h, obtained graphene powder material.
Embodiment 5
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 100ml mass concentration is in 40% TBAH solution, ultrasonic dispersion, and ultrasonic power is 100W, ultrasonic time is 30min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrabutyl hydroboration ammonia, under room temperature condition, stir 3h, adopt the millipore filtration of 0.1 μ m to carry out after suction filtration, under 5 ℃ of conditions, carry out vacuum-drying, time of drying, 120h, obtained graphene powder material.
Embodiment 6
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 10ml mass concentration is in 40% TBAH solution, ultrasonic dispersion, and ultrasonic power is 400W, ultrasonic time is 20min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrabutyl hydroboration ammonia, under room temperature condition, stir 3h, adopt the millipore filtration of 0.1 μ m to carry out after suction filtration, under 10 ℃ of conditions, carry out vacuum-drying, time of drying, 80h, obtained graphene powder material.
Embodiment 7
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 50ml mass concentration is in 40% TBAH solution, ultrasonic dispersion, and ultrasonic power is 400W, ultrasonic time is 10min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrabutyl hydroboration ammonia, under room temperature condition, stir 3h, adopt the millipore filtration of 0.1 μ m to carry out after suction filtration, under 20 ℃ of conditions, carry out vacuum-drying, time of drying, 48h, obtained graphene powder material.
Embodiment 8
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 50ml mass concentration is in 20% TBAH solution, ultrasonic dispersion, and ultrasonic power is 400W, ultrasonic time is 30min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 1ml tetrabutyl hydroboration ammonia, under room temperature condition, stir 3h, adopt the millipore filtration of 0.1 μ m to carry out after suction filtration, under-20 ℃ of conditions, carry out lyophilize, time of drying, 10h, obtained graphene powder material.
Embodiment 9
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 100ml mass concentration is in 10% tetramethyl ammonium hydroxide solution, ultrasonic dispersion, and ultrasonic power is 400W, ultrasonic time is 60min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 10ml tetramethyl-hydroboration ammonia, under room temperature condition, stir 3h, adopt the rotating speed of 10000rpm to carry out centrifugation, taking precipitate carries out lyophilize under-20 ℃ of conditions, time of drying, 10h, obtained graphene powder material.
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 100ml mass concentration is in 20% tetraethyl ammonium hydroxide solution, ultrasonic dispersion, and ultrasonic power is 400W, ultrasonic time is 60min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetraethyl-hydroboration ammonia, under room temperature condition, stir 3h, adopt the rotating speed of 15000rpm to carry out centrifugation, taking precipitate carries out lyophilize under-20 ℃ of conditions, time of drying, 10h, obtained graphene powder material.
Embodiment 11
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 100ml mass concentration is in 30% TPAOH solution, ultrasonic dispersion, and ultrasonic power is 400W, ultrasonic time is 30min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrabutyl hydroboration ammonia, under room temperature condition, stir 3h, adopt the rotating speed of 20000rpm to carry out centrifugation, taking precipitate carries out lyophilize under-20 ℃ of conditions, time of drying, 10h, obtained graphene powder material.
Embodiment 12
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 50ml mass concentration is in 40% TBAH solution, ultrasonic dispersion, and ultrasonic power is 200W, ultrasonic time is 30min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrabutyl hydroboration ammonia, under room temperature condition, stir 3h, adopt the rotating speed of 20000rpm to carry out centrifugation, taking precipitate carries out lyophilize under-20 ℃ of conditions, time of drying, 10h, obtained graphene powder material.
Embodiment 13
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 50ml mass concentration is in 40% TBAH solution, ultrasonic dispersion, and ultrasonic power is 200W, ultrasonic time is 30min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrabutyl hydroboration ammonia, under room temperature condition, stir 3h, adopt the rotating speed of 20000rpm to carry out centrifugation, taking precipitate carries out vacuum-drying under 10 ℃ of conditions, time of drying, 80h, obtained graphene powder material.
Embodiment 14
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added to 50ml mass concentration is in 40% TBAH solution, ultrasonic dispersion, and ultrasonic power is 400W, ultrasonic time is 10min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrabutyl hydroboration ammonia, under room temperature condition, stir 3h, adopt the rotating speed of 20000rpm to carry out centrifugation, taking precipitate carries out vacuum-drying under 20 ℃ of conditions, time of drying, 48h, obtained graphene powder material.
Comparative example
The preparation method of the graphene oxide powder body material of this comparative example, be specially: it is in 40% TBAH solution that 1g graphite oxide is added to 50ml mass concentration, ultrasonic dispersion, ultrasonic power is 100W, ultrasonic time is 60min, obtains graphene oxide dispersion liquid.
Experimental example 1
This experimental example carries out dispersiveness experiment to embodiment 4 gained graphene powder materials.Experimental technique is: water intaking, methyl alcohol, dimethyl formamide, each 5ml of dimethyl sulfone are as solvent, being placed in respectively label is (a) and (b), (c), (d) clear-glass bottle, respectively add again 15mg embodiment 4 gained graphene powder materials, after ultrasonic 1h disperses, standing, observe supernatant fluid color and layering situation and take pictures, as shown in Figure 1.Found that, embodiment 4 gained graphene powder materials can stable dispersion in dimethyl formamide and methyl-sulphoxide more than 6 months, can stable dispersion in water about 4 months, and can stable dispersion in methyl alcohol 3 months, and do not produce precipitation.Dispersed experimental result shows, graphene powder material of the present invention has good dispersiveness in intensive polar solvent.
Experimental example 2
This experimental example carries out transmission electron microscope observing to embodiment 4 gained graphene powder materials, comparative example gained graphene oxide dispersion liquid.Comparative example gained graphene oxide dispersion liquid is directly dripped after dilution after drying on copper mesh and observe, as shown in Figure 2.Get a certain amount of embodiment 4 gained graphene powder dispersion of materials in methyl alcohol, after ultrasonic 1h, drip on copper mesh, after drying, carry out transmission electron microscope observing, as shown in Figure 3.Found that: the graphene oxide after peeling off and graphene powder all present laminated structure, in laminated structure, have a lot of folding lines; Difference is, the sheet surfaces of Graphene is compared with graphene oxide surface transparent, surface is " totally " also more, this is owing to adopting organic bases when peeling off oxidized graphite flake layer, aid in and ultrasonicly can make graphite oxide partial reduction, but because organic bases reductibility is poor, its surface is not thoroughly reduced; After further employing organic boron hydride reduction, graphene sheet layer reduction ratio is more thorough, the surface comparison " totally " that seems; And the graphene film interlayer after reduction is owing to there being the isolation of large alkane ion, lamella does not occur that after reduction multilayer reunites.Transmissioning electric mirror test result shows, employing organic bases is stripper, and organic boron hydride is reductive agent, aids in ultrasonicly, on the basis of peeling off, can realize reduction and the dispersion of Graphene.
Experimental example 3
This experimental example carries out ultraviolet-visible absorption spectroscopy analysis to embodiment 6 gained graphene powder materials.Testing method: get respectively a certain amount of graphite oxide, embodiment 6 gained graphene powder dispersion of materials in water, after ultrasonic 1h, get upper strata liquid after standing 1h and carry out UV, visible light absorption test; Directly get comparative example gained graphene oxide dispersion liquid and test, result as shown in Figure 4.On comparison diagram 4, three spectral line of absorption can be found out, (curve a) has occurred the characteristic peak of graphite oxide to graphite oxide at 230nm and 291nm place; And adopt organic bases directly peel off and assisting ultrasonic after in the graphene oxide dispersion liquid (curve b) that obtains, also this two absorption peaks have still been retained, but peak is compared with graphite oxide by force and has been weakened a lot, although stripper energy partial reduction graphene oxide laminate for light is described, reduction not yet completely; And after organic boron hydride reduction (curve c), the absorption peak completely dissolve at 230nm and 291nm place, the substitute is the charateristic avsorption band that has occurred Graphene at 270nm place, the reducing power that organic bases is described is limited, compare with document mineral alkali reductibility, add the organic bases can only partial reduction graphene oxide laminate, essentially further add organic hydroborate, thoroughly reduction obtain graphene dispersing solution.
Experimental example 4
This experimental example carries out xps energy spectrum analysis to embodiment 7 gained graphene powder materials, and result as shown in Figure 5.XPS by contrast graphite oxide and graphene powder, can find out the C on Graphene
1Speak by force will be far above graphite oxide, and O
1speak to obviously be weaker than graphite oxide by force, obviously, resulting grapheme material under organic bases and organic boron hydride acting in conjunction condition, in Graphene, C/O ratio will, far above graphite oxide, illustrate and successfully realize deoxidation treatment; In the power spectrum of the graphene powder of peeling off in addition,, there is N
1Speak, illustrates between organic cation in organic bases and organic boron hydride and Graphene laminate and has electrostatic force, and be retained.According to Energy disperaive quantitative analysis, nitrogen element atomic percentage conc is only 1.3%; Other methods that adopt organic surface active agents or macromolecule stabilizer to prepare Graphene of explanation and document are compared, and the resulting Graphene foreign matter content of the method is extremely low.
Experimental example 5
This experimental example carries out X-ray diffraction analysis to embodiment 12 gained graphene powder materials, and result as shown in Figure 6.By contrast graphite (curve a), the XRD result of graphite oxide (curve b) and graphene powder (curve c), can find out, the structure of graphene powder and graphite and graphite oxide make a big difference, it has lost the ordered structure of graphite and graphite oxide, but only near being 24 °, 2 θ angles there is a very little diffraction peak, show that Graphene reunion degree under powder state is little, still kept a dispersiveness preferably; Further prove the method that this invention proposes, can next step realize the dispersion of the reduction of Graphene at mild conditions.
Experimental example 6
This experimental example carries out Raman spectrum analysis to embodiment 14 gained graphene powder materials, and result as shown in Figure 7.Raman spectrum can be the indication probe of carbon-based material microtexture, thereby is widely used in graphite and relevant modified graphite Material Field.By contrast graphite (curve a), the Raman result (Fig. 7) of graphite oxide (curve b) and graphene powder (curve c), can find out, all there is D band and the G band of feature in graphite, graphite oxide and graphene powder; Contrast G band strength, graphite oxide, due to oxidation, has been introduced a large amount of oxy radicals on laminate, cause its D band strength obviously to strengthen; And graphene powder prepared by the method proposing with the present invention, due to the minimizing of oxy radical, G band strength obviously will be with higher than D, show in reduction process, the ordered structure of graphite is recovered, and defect content reduces, and has further confirmed the generation of graphene-structured.
Claims (10)
1. a preparation method for graphene powder material, is characterized in that: comprise the following steps:
1) graphite oxide is added in organic bases solution, ultrasonic dispersion, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add organic boron hydride, after stirring, carry out solid-liquid separation, dry, obtain.
2. the preparation method of graphene powder material according to claim 1, is characterized in that: organic bases described in step 1) is tetraalkyl ammonium hydroxide, and its general molecular formula is:
[N(C
nH
2n+1)
4]OH，
Wherein, n is 1,2,3 or 4.
3. the preparation method of graphene powder material according to claim 1 and 2, is characterized in that: the mass percentage concentration of described organic bases solution is 10%～40%.
4. the preparation method of graphene powder material according to claim 3, is characterized in that: the consumption of described organic bases solution is: the organic bases solution of 1～10ml for every 100mg graphite oxide.
5. the preparation method of graphene powder material according to claim 1, is characterized in that: described in step 1), ultrasonic power is 100～400W, and the ultrasonic time is 10～120min.
6. the preparation method of graphene powder material according to claim 1, is characterized in that: step 2) described in the general molecular formula of organic boron hydride be:
[N(C
nH2
n+1)
4]BH
4，
Wherein, n is 1,2,3 or 4.
7. according to the preparation method of the graphene powder material described in claim 1 or 6, it is characterized in that: the consumption of described organic boron hydride is: the organic boron hydride of 0.1～1ml for every 100mg graphite oxide.
8. the preparation method of graphene powder material according to claim 1, is characterized in that: step 2) described in the method for solid-liquid separation be that millipore filtration suction filtration or high speed centrifugation are separated.
9. the preparation method of graphene powder material according to claim 1, is characterized in that: step 2) described in be dried as lyophilize or vacuum-drying.
10. the preparation method of graphene powder material according to claim 9, is characterized in that: described cryodesiccated temperature is-20～-5 ℃, and be 10～48h time of drying; Described vacuum drying temperature is 20～50 ℃, and be 48～120h time of drying.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787326A (en) * | 2014-03-06 | 2014-05-14 | 南开大学 | Preparation method of grapheme material with three-dimensional network structure |
| CN104030279A (en) * | 2014-06-16 | 2014-09-10 | 上海交通大学 | Method for preparing graphene through acetylacetone reduction |
| CN105460922A (en) * | 2015-11-29 | 2016-04-06 | 福建医科大学 | Partially reduced GO (graphene oxide) fluorescence resonance energy transfer nano-probe and preparation method thereof |
| CN105712345A (en) * | 2016-03-23 | 2016-06-29 | 中南大学 | Method for preparing graphene powder |
| CN108165016A (en) * | 2018-01-19 | 2018-06-15 | 林荣铨 | A kind of preparation method of modified graphene heat-conducting silicone grease |
| CN108584933A (en) * | 2018-07-15 | 2018-09-28 | 石梦成 | A kind of fluorinated graphene prepared by ionic liquid stripping |
| CN110194450A (en) * | 2019-05-13 | 2019-09-03 | 四川欧迅能源工程科技有限公司 | A kind of preparation method of graphene composite material |
| CN110482538A (en) * | 2019-08-26 | 2019-11-22 | 上海利物盛纳米科技有限公司 | A kind of preparation method of the graphene oxide of controllable pH |
| CN112960670A (en) * | 2021-04-23 | 2021-06-15 | 安徽工业大学 | Edge hydroxylation modified graphene and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787326A (en) * | 2014-03-06 | 2014-05-14 | 南开大学 | Preparation method of grapheme material with three-dimensional network structure |
| CN103787326B (en) * | 2014-03-06 | 2015-06-17 | 南开大学 | Preparation method of grapheme material with three-dimensional network structure |
| CN104030279A (en) * | 2014-06-16 | 2014-09-10 | 上海交通大学 | Method for preparing graphene through acetylacetone reduction |
| CN105460922A (en) * | 2015-11-29 | 2016-04-06 | 福建医科大学 | Partially reduced GO (graphene oxide) fluorescence resonance energy transfer nano-probe and preparation method thereof |
| CN105712345A (en) * | 2016-03-23 | 2016-06-29 | 中南大学 | Method for preparing graphene powder |
| CN108165016A (en) * | 2018-01-19 | 2018-06-15 | 林荣铨 | A kind of preparation method of modified graphene heat-conducting silicone grease |
| CN108584933A (en) * | 2018-07-15 | 2018-09-28 | 石梦成 | A kind of fluorinated graphene prepared by ionic liquid stripping |
| CN110194450A (en) * | 2019-05-13 | 2019-09-03 | 四川欧迅能源工程科技有限公司 | A kind of preparation method of graphene composite material |
| CN110482538A (en) * | 2019-08-26 | 2019-11-22 | 上海利物盛纳米科技有限公司 | A kind of preparation method of the graphene oxide of controllable pH |
| CN112960670A (en) * | 2021-04-23 | 2021-06-15 | 安徽工业大学 | Edge hydroxylation modified graphene and preparation method thereof |
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