CN103570010B - A kind of preparation method of graphene powder material - Google Patents
A kind of preparation method of graphene powder material Download PDFInfo
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- CN103570010B CN103570010B CN201310487255.0A CN201310487255A CN103570010B CN 103570010 B CN103570010 B CN 103570010B CN 201310487255 A CN201310487255 A CN 201310487255A CN 103570010 B CN103570010 B CN 103570010B
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Abstract
The invention discloses a kind of preparation method of graphene powder material, comprise the following steps: 1) graphite oxide is added in organic alkali solution, ultrasonic disperse, obtains graphene dispersing solution; 2) in step 1) gained graphene dispersing solution, add organic boron hydride, carry out solid-liquid separation, drying after stirring, to obtain final product.The preparation method of graphene powder material of the present invention, gained graphene powder material shows good dispersiveness and stability in polar solvent is as water, methyl alcohol, ethanol, dimethyl formamide equal solvent, dispersion liquid concentration up to 2 ~ 5mg/ml, can be deposited and occur without precipitation for 4 ~ 6 months; Impurities is few, has potential using value in fields such as material, the energy, bio-sensing, electronics, electrochemistry, solar cells; Preparation method's reaction conditions of the present invention is gentle, and technique is simple, and the cycle is short, and Graphene foreign matter content is low, has the advantages such as efficient, economy, environmental protection, and is easy to accomplish scale production.
Description
Technical field
The invention belongs to technical field of graphene, 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 found at present, its special monoatomic layer structures shape it there is the abundant and physical phenomenon of novelty, 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 most high specific strength can prepared at present; Its carrier mobility reaches 1.5 × 10
4cm
2v
-1s
-1, be known at present 2 times with the indium antimonide materials of most high mobility, be 10 times of commercial silicon chip mobility, under given conditions, its mobility even can 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 preparing mechanical strength, elasticity, antifatigue and many other with 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.
But the physical and chemical performance of Graphene excellence is the character based on mono-layer graphite sheet; When constructing graphene-based matrix material, Graphene high dispersing in the base prepares the key of high performance composite.But the specific surface area high due to Graphene and van der Waals interaction strong between layers, cause graphene film interlayer to be easy to reunite or be again stacked to graphite-structure; And this neither disperses in water He in organic solvent due to graphite, thus limit it and further apply.Therefore, how high effective and modified or grapheme modified powder body material, enables to be applied to the important topic becoming the research of current Graphene in actual production.
At present, the method preparing Graphene mainly adopts physical method and chemical process.Wherein, physical method originates from study group's employing mechanically peel legal system in 2004 of Manchester university Geim leader for obtaining graphene film (the Novoselov K.S. that maximum width can reach 10 μm; 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.The main method that chemical process prepares Graphene is the chemical reduction of graphite oxide, generally by high-power ultrasonic, first realize the stripping of graphite oxide, in order to avoid graphene oxide occurs to reunite in reduction process again, polymer, tensio-active agent, ionic liquid or other stablizers will be added in the process preparing Graphene, by polymer winding, SURFACTANT ADSORPTION or electrostatic repulsion, cause the space obstacle between graphene layer, thus 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 prepares Graphene in this way, there is a large amount of auxiliary agent impurity (polymer, tensio-active agent or other stablizers) in products obtained therefrom, have a strong impact on the further application of Graphene; And the Graphene finally obtained after the drying, easily reunites, dispersed variation, powder dispersion concentration only 0.1 ~ 0.3mg/ml, far can not meet the requirement of application.
Patent US2000303706 discloses and utilizes alkaline reducing agent as hydrazine hydrate or sodium borohydride reduction graphite oxide, can obtain the graphene dispersing solution with favorable dispersity; And if reduce in non-alkaline solution, the graphene dispersing solution after reduction can produce serious reunion and cannot obtain homodisperse dispersion liquid.The graphite oxide aqueous solution and oxammonium hydrochloride, in 2010 patent (CN201010613212.9), react by the people such as Guo Shouwu, utilize ammoniacal liquor to control the pH value of reaction system, successfully obtain the graphene dispersing solution of favorable dispersity.More than research shows, reduction-oxidation graphite in the basic conditions, can obtain the Graphene of favorable dispersity.But because extent of exfoliation is too little, cause reaction time oversize.Subsequently, the people such as CheJ. (Che J., Shen L., Xiao Y., Journal of Materials Chemistry, 2010,20,1722-1727) find, in intensive polar solvent in dimethyl formamide, quadrol is utilized to do dispersion agent and reductive agent, though a step reduction and the dispersion of graphite oxide can be realized, simplify preparation technology, but there is the low deficiency of dispersion concentration.The people such as Li Xin also disclosed a kind of method preparing Graphene in 2012 in patent (CN201210152803.X), and applicant is ultrasonic oxidation graphite in sodium hydroxide solution, obtains the Graphene of favorable dispersity; But there is high and Graphene high density bad dispersibility, the incomplete problem of reducing in a solvent of temperature of reaction, seriously limit the widespread use of Graphene.
Summary of the invention
The object of this invention is to provide a kind of preparation method of graphene powder material, solve the Graphene that graphene dispersing solution concentration in prior art is low, reduction not exclusively causes and apply 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 alkali solution, ultrasonic disperse, obtain graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add organic boron hydride, carry out solid-liquid separation, drying after stirring, to obtain final product.
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 alkali solution is 10% ~ 40%.
The consumption of described organic alkali solution is: the organic alkali solution of every 100mg graphite oxide 1 ~ 10ml.
Power ultrasonic described in step 1) is 100 ~ 400W, and the ultrasonic time is 10 ~ 120min.
Step 2) described in the general molecular formula of organic boron hydride be:
[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 every 100mg graphite oxide 0.1 ~ 1ml.
Step 2) described in the method for solid-liquid separation be that millipore filtration suction filtration or high speed centrifugation are separated.
The aperture of described millipore filtration is 0.1 ~ 0.45 μm.The rotating speed that described high speed centrifugation is separated is 10000 ~ 20000rpm.
Step 2) described in dry be lyophilize or vacuum-drying.
Described cryodesiccated temperature is-20 ~-5 DEG C, and time of drying is 10 ~ 48h; Described vacuum drying temperature is 20 ~ 50 DEG C, and time of drying is 48 ~ 120h.
In the preparation method of graphene powder material of the present invention, described graphite oxide is obtained by the Hummers method of the oxidation style improved, Brodie method, Staudenmaier method, Hummers method or improvement.The oxidation style of described improvement 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 the essential condition successfully realizing Graphene reduction.But the inorganic reagent of current control alkaline environment is generally ammoniacal liquor and sodium hydroxide (potassium), but too strong owing to there is inorganic cation and laminate electrostatic force, cause peeling off rear Graphene and easily reunite; Organic reagent is generally quadrol, but due to quadrol alkalescence weak, its molecular volume is comparatively large, enters graphite oxide interlayer resistance comparatively large, causes the peeling effect of Graphene bad, can only realize the dispersion of the Graphene of lower concentration.How to choose the base molecule that has suitable construction, can not only easily enter graphite oxide interlayer, realize graphite oxide and peel off; And the electrostatic force of base molecule structure cationic and laminate can not be too strong, can not be too weak, just in time can stop reassociating of Graphene laminate.
The preparation method of graphene powder material of the present invention, utilizes that organic bases is stripper, organic boron hydride is reductive agent, assisting ultrasonic, achieves stripping and the reduction of graphite oxide under mild conditions, obtains graphene powder material; Innovation of the present invention is to choose has the cationic organic bases of large alkane as stripper, provide not only alkaline environment, and Coulomb repulsion in its structure between large alkane cation group and laminate and buffer action, make graphite oxide while reduction, the stacking again between laminate can not be there is, avoid and use inorganic reducing agent institute to bring the less positively charged ion of the radius of system into and Graphene laminate reactive force causes the phenomenon that Graphene laminate reassembles too by force, and then obtain the graphene dispersing solution of favorable dispersity; Gained graphene powder material shows good dispersiveness and stability in polar solvent is as water, methyl alcohol, ethanol, dimethyl formamide equal solvent, and dispersion liquid concentration up to 2 ~ 5mg/ml, can be deposited and occur without precipitation for 4 ~ 6 months; In addition, prepared graphene powder material is when applying further, because the electrostatic force of macoradical alkane positively charged ion that its laminate is introduced and Graphene laminate is not very strong, can be substituted by the stronger group of other reactive forces in system or molecule and become " leaving away " group, thus impurity can not be introduced in graphene complex system, 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 material, and wherein the solvent of (a) is water, and the solvent of (b) is methyl alcohol, and the solvent of (c) is dimethyl formamide, and the solvent of (d) is dimethyl sulfoxide (DMSO);
Fig. 2 is the transmission electron microscope picture of comparative example gained graphene oxide powder material;
Fig. 3 is the transmission electron microscope picture of embodiment 4 gained graphene powder material;
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, and (b) is comparative example gained graphene oxide, and (c) is embodiment 6 gained graphene powder material;
Fig. 5 is the XPS wide range scintigram of embodiment 7 and comparative example gained powder body material, and wherein (a) is graphite oxide, and (b) is embodiment 7 gained graphene powder material;
Fig. 6 is the X-ray diffractogram of embodiment 12 and comparative example gained powder body material, and wherein (a) is graphite, and (b) is graphite oxide, and (c) is embodiment 12 gained graphene powder material;
Fig. 7 is the Raman spectrogram of embodiment 14 and comparative example gained powder body material, and wherein (a) is graphite, and (b) is graphite oxide, and (c) is embodiment 14 gained graphene powder material.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Graphite oxide used in embodiment 1 ~ 15 is prepared by the oxidation style improved, and is specially: by natural flake graphite and KMnO
4join dense H successively
2sO
4/ H
3pO
4volume ratio is in the mixing solutions of 9:1, then controls reactant to be heated to 40 DEG C by water-bath, and stirs 6h; In system, add water successively, mass concentration is the H of 30%
2o
2solution; Reaction terminates rear filtered while hot, and is the salt acid elution of 5% by mass concentration, until SO
4 2-remove completely; Collected after centrifugation bottom settlings, then at 60 DEG C dry 24 hours, the graphite oxide of final 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 50ml mass concentration is in the tetramethyl ammonium hydroxide solution of 10%, ultrasonic disperse, and ultrasonic power is 400W, and ultrasonic time is 60min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetramethyl-hydroboration ammonia, stir 3h under room temperature condition, after adopting the millipore filtration of 0.45 μm to carry out suction filtration, under-20 DEG C of conditions, carry out lyophilize, time of drying, 10h, obtained graphene powder material.
Embodiment 2
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added 50ml mass concentration is in the tetraethyl ammonium hydroxide solution of 20%, ultrasonic disperse, and ultrasonic power is 300W, and ultrasonic time is 60min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetraethyl-hydroboration ammonia, stir 3h under room temperature condition, after adopting the millipore filtration of 0.1 μm to carry out suction filtration, under-10 DEG C 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 50ml mass concentration is in the TPAOH solution of 30%, ultrasonic disperse, and ultrasonic power is 200W, and ultrasonic time is 60min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrapropyl hydroboration ammonia, stir 3h under room temperature condition, after adopting the millipore filtration of 0.22 μm to carry out suction filtration, under-5 DEG C 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 50ml mass concentration is in the TBAH solution of 40%, ultrasonic disperse, and ultrasonic power is 100W, and ultrasonic time is 60min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrabutyl hydroboration ammonia, stir 3h under room temperature condition, after adopting the millipore filtration of 0.1 μm to carry out suction filtration, under-20 DEG C 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 100ml mass concentration is in the TBAH solution of 40%, ultrasonic disperse, and ultrasonic power is 100W, and ultrasonic time is 30min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrabutyl hydroboration ammonia, stir 3h under room temperature condition, after adopting the millipore filtration of 0.1 μm to carry out suction filtration, under 5 DEG C 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 10ml mass concentration is in the TBAH solution of 40%, ultrasonic disperse, and ultrasonic power is 400W, and ultrasonic time is 20min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrabutyl hydroboration ammonia, stir 3h under room temperature condition, after adopting the millipore filtration of 0.1 μm to carry out suction filtration, under 10 DEG C 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 50ml mass concentration is in the TBAH solution of 40%, ultrasonic disperse, and ultrasonic power is 400W, and ultrasonic time is 10min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 5ml tetrabutyl hydroboration ammonia, stir 3h under room temperature condition, after adopting the millipore filtration of 0.1 μm to carry out suction filtration, under 20 DEG C 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 50ml mass concentration is in the TBAH solution of 20%, ultrasonic disperse, and ultrasonic power is 400W, and ultrasonic time is 30min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add 1ml tetrabutyl hydroboration ammonia, stir 3h under room temperature condition, after adopting the millipore filtration of 0.1 μm to carry out suction filtration, under-20 DEG C 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 100ml mass concentration is in the tetramethyl ammonium hydroxide solution of 10%, ultrasonic disperse, and ultrasonic power is 400W, and ultrasonic time is 60min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, 10ml tetramethyl-hydroboration ammonia is added, stir 3h under room temperature condition, adopt the rotating speed of 10000rpm to carry out centrifugation, taking precipitate carries out lyophilize under-20 DEG C of conditions, time of drying, 10h, obtained graphene powder material.
Embodiment 10
The preparation method of the graphene powder material of the present embodiment, comprises the following steps:
1) 1g graphite oxide being added 100ml mass concentration is in the tetraethyl ammonium hydroxide solution of 20%, ultrasonic disperse, and ultrasonic power is 400W, and ultrasonic time is 60min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, 5ml tetraethyl-hydroboration ammonia is added, stir 3h under room temperature condition, adopt the rotating speed of 15000rpm to carry out centrifugation, taking precipitate carries out lyophilize under-20 DEG C 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 100ml mass concentration is in the TPAOH solution of 30%, ultrasonic disperse, and ultrasonic power is 400W, and ultrasonic time is 30min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, 5ml tetrabutyl hydroboration ammonia is added, stir 3h under room temperature condition, adopt the rotating speed of 20000rpm to carry out centrifugation, taking precipitate carries out lyophilize under-20 DEG C 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 50ml mass concentration is in the TBAH solution of 40%, ultrasonic disperse, and ultrasonic power is 200W, and ultrasonic time is 30min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, 5ml tetrabutyl hydroboration ammonia is added, stir 3h under room temperature condition, adopt the rotating speed of 20000rpm to carry out centrifugation, taking precipitate carries out lyophilize under-20 DEG C 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 50ml mass concentration is in the TBAH solution of 40%, ultrasonic disperse, and ultrasonic power is 200W, and ultrasonic time is 30min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, 5ml tetrabutyl hydroboration ammonia is added, stir 3h under room temperature condition, adopt the rotating speed of 20000rpm to carry out centrifugation, taking precipitate carries out vacuum-drying under 10 DEG C 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 50ml mass concentration is in the TBAH solution of 40%, ultrasonic disperse, and ultrasonic power is 400W, and ultrasonic time is 10min, obtains graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, 5ml tetrabutyl hydroboration ammonia is added, stir 3h under room temperature condition, adopt the rotating speed of 20000rpm to carry out centrifugation, taking precipitate carries out vacuum-drying under 20 DEG C of conditions, time of drying, 48h, obtained graphene powder material.
Comparative example
The preparation method of the graphene oxide powder material of this comparative example, be specially: 1g graphite oxide being added 50ml mass concentration is in the TBAH solution of 40%, ultrasonic disperse, and ultrasonic power is 100W, ultrasonic time is 60min, obtains graphene oxide dispersion.
Experimental example 1
This experimental example carries out dispersiveness experiment to embodiment 4 gained graphene powder material.Experimental technique is: water intaking, methyl alcohol, dimethyl formamide, each 5ml of dimethyl sulfone are as solvent, being placed in label is respectively (a) and (b), (c), (d) clear-glass bottle, respectively add 15mg embodiment 4 gained graphene powder material again, after ultrasonic 1h disperses, leave standstill, observe supernatant fluid color and delamination and take pictures, as shown in Figure 1.Found that, embodiment 4 gained graphene powder material Absorbable organic halogens in dimethyl formamide and methyl-sulphoxide disperses more than 6 months, and in water, Absorbable organic halogens disperses about 4 months, and Absorbable organic halogens disperses 3 months in methyl alcohol, and does 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 material, comparative example gained graphene oxide dispersion.Comparative example gained graphene oxide dispersion is directly dripped after dilution after drying on copper mesh and observe, as shown in Figure 2.Getting a certain amount of embodiment 4 gained graphene powder material is dispersed in methyl alcohol, after ultrasonic 1h, drips on copper mesh, carries out transmission electron microscope observing, as shown in Figure 3 after drying.Found that: the graphene oxide after stripping and graphene powder all present laminated structure, laminated structure has a lot of folding line; Difference is, the sheet surfaces of Graphene is transparent compared with surface of graphene oxide, surface is " totally " also more, this is owing to adopting organic bases peeling off oxidized graphite flake layer while, aid in and ultrasonicly can make graphite oxide partial reduction, but because organic bases reductibility is poor, its surface is not thoroughly reduced; After adopting organic boron hydride reduction further, graphene sheet layer reduction ratio is comparatively thorough, and surface seems and compares " totally "; And the graphene film interlayer after reduction is owing to existing the isolation of large alkane ion, lamella does not occur that after reduction multilayer is reunited.Transmissioning electric mirror test result shows, employing organic bases is stripper, and organic boron hydride is reductive agent, aids in ultrasonic, 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 material.Testing method: get a certain amount of graphite oxide respectively, embodiment 6 gained graphene powder material is dispersed in water, after ultrasonic 1h, gets upper liquid after leaving standstill 1h and carries out ultravioletvisible absorption test; Directly get comparative example gained graphene oxide dispersion to 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 at 230nm and 291nm place to graphite oxide; And adopt organic bases directly to peel off and after assisting ultrasonic in the graphene oxide dispersion (curve b) that obtains, also this two absorption peaks are still remained, but peak weakens by force a lot compared with graphite oxide, although light stripper energy partial reduction graphene oxide laminate is described, reduce not yet completely; And after organic boron hydride reduction (curve c), the absorption peak completely dissolve at 230nm and 291nm place, the substitute is and occurred the charateristic avsorption band of Graphene at 270nm place, illustrate that the reducing power of organic bases is limited, compared with document mineral alkali reductibility, adding organic bases can only partial reduction graphene oxide laminate, requiredly adds organic hydroborate further, thoroughly reduction could obtain graphene dispersing solution.
Experimental example 4
This experimental example carries out xps energy spectrum analysis to embodiment 7 gained graphene powder material, and result as shown in Figure 5.By contrasting the XPS of graphite oxide and graphene powder, can find out, the C on Graphene
1Speak by force will far above graphite oxide, and O
1speak obviously to be weaker than graphite oxide by force, obviously, obtain under organic bases and organic boron hydride acting in conjunction condition grapheme material, in Graphene, C/O ratio far above graphite oxide, will illustrate and successfully achieve deoxidation treatment; In addition, there is N in the power spectrum of the graphene powder of stripping
1Speak, illustrates to there is electrostatic force between organic cation in organic bases and organic boron hydride and Graphene laminate, and has been retained.According to Energy disperaive quantitative analysis, nitrogen Elements Atom percentage composition is only 1.3%; Illustrate that other adopt organic surface active agent or macromolecule stabilizer to prepare compared with the method for Graphene with document, the method obtain Graphene foreign matter content extremely low.
Experimental example 5
This experimental example carries out X-ray diffraction analysis to embodiment 12 gained graphene powder material, 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 loses the ordered structure of graphite and graphite oxide, but be only near 24 °, occurred a very little diffraction peak in 2 θ angles, show that Graphene reunion degree under powder state is little, still maintain a dispersiveness preferably; Further demonstrate the method that this invention proposes, a step can realize the dispersion of the reduction of Graphene in a mild condition.
Experimental example 6
This experimental example carries out Raman spectrum analysis to embodiment 14 gained graphene powder material, and result as shown in Figure 7.Raman spectrum can be the instruction probe of carbon-based material microtexture, is thus widely used in graphite and relevant modified graphite Material Field.By contrast graphite (curve a), the Raman results (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, laminate introduces a large amount of oxy radicals, causes its D band strength obviously to strengthen; And with graphene powder prepared by the method that the present invention proposes, due to the minimizing of oxy radical, G band strength is obviously higher than D band, show in reduction process, the ordered structure of graphite is recovered, and defect content reduces, and further demonstrate that the generation of graphene-structured.
Claims (9)
1. a preparation method for graphene powder material, is characterized in that: comprise the following steps:
1) graphite oxide is added in organic alkali solution, ultrasonic disperse, obtain graphene dispersing solution;
2) in step 1) gained graphene dispersing solution, add organic boron hydride, carry out solid-liquid separation, drying after stirring, to obtain final product;
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.
2. the preparation method of graphene powder material according to claim 1, is characterized in that: the mass percentage concentration of described organic alkali solution is 10% ~ 40%.
3. the preparation method of graphene powder material according to claim 2, is characterized in that: the consumption of described organic alkali solution is: the organic alkali solution of every 100mg graphite oxide 1 ~ 10ml.
4. according to the preparation method of the graphene powder material described in claim 1, it is characterized in that: power ultrasonic described in step 1) is 100 ~ 400W, the ultrasonic time is 10 ~ 120min.
5., according to the preparation method of the graphene powder material described in claim 1, it is characterized in that: step 2) described in the general molecular formula of organic boron hydride be:
[N(C
nH
2n+1)
4]BH
4，
Wherein, n is 1,2,3 or 4.
6. the preparation method of the graphene powder material according to claim 1 or 5, is characterized in that: the consumption of described organic boron hydride is: the organic boron hydride of every 100mg graphite oxide 0.1 ~ 1ml.
7., according to the preparation method of the graphene powder material described in claim 1, it 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.
8., according to the preparation method of the graphene powder material described in claim 1, it is characterized in that: step 2) described in dry be lyophilize or vacuum-drying.
9. the preparation method of graphene powder material described according to Claim 8, it is characterized in that: described cryodesiccated temperature is-20 ~-5 DEG C, time of drying is 10 ~ 48h; Described vacuum drying temperature is 20 ~ 50 DEG C, and time of drying is 48 ~ 120h.
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| CN104030279A (en) * | 2014-06-16 | 2014-09-10 | 上海交通大学 | Method for preparing graphene through acetylacetone reduction |
| CN105460922B (en) * | 2015-11-29 | 2017-10-20 | 福建医科大学 | Partial reduction graphene oxide FRET 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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| CN102583351A (en) * | 2012-02-29 | 2012-07-18 | 中国科学院宁波材料技术与工程研究所 | Preparation method of fewer-layer graphene |
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| 石墨烯的氧化还原法制备及结构表征;杨勇辉等;《无机化学学报》;20101130;第26卷(第11期);2083-2090 * |
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