CN106006611A - Method for efficiently preparing graphene oxide organic solution - Google Patents
Method for efficiently preparing graphene oxide organic solution Download PDFInfo
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- CN106006611A CN106006611A CN201610330573.XA CN201610330573A CN106006611A CN 106006611 A CN106006611 A CN 106006611A CN 201610330573 A CN201610330573 A CN 201610330573A CN 106006611 A CN106006611 A CN 106006611A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a method for efficiently preparing a graphene oxide organic solution. A target organic solvent is added to a graphene oxide aqueous solution with known concentration, water and the target organic solvent are separated with a solvent replacement method through distillation or fractionation, finally, a graphene oxide organic solution without water is ultrasonically dispersed, and the graphene oxide organic solution is obtained. The method has the advantages that the process is simple and the concentration and variety range of the organic solution is wide.
Description
Technical field
The invention belongs to a kind of method efficiently preparing graphene oxide organic solution.
Background technology
Graphene is that another after zero dimension fullerene, one-dimensional CNT, three-dimensional graphite has peculiar excellent properties
New Two Dimensional nano-carbon material, not only filled up material with carbon element from zero dimension to three-dimensional blank, and because of its have excellence heat,
Power, optical and electrical properties, be considered in terms of solaode, sensor, nanoelectronics, high-performance nanometer electronic device, composite wood
The fields such as material, field emmision material, gas sensor and energy storage have broad application prospects.But, Graphene is due to super
High specific surface area, the feature of powerful Van der Waals force, hydrophobic property and easily reunion limits it and extensively applies.
The appearance of the intermediate product graphene oxide that oxidation-reduction method prepares Graphene just solves the problems referred to above.Oxidation
Graphene is the derivatives of Graphene, is substantially the same with the structure of Graphene, is with the oxygen-containing functional group such as C=O, C-OH ,-COOH
Carbon atom in closely knit carbon wire side is combined the covalent bond type intercalation compound that the two-dimensional space formed infinitely extends.With graphite
Alkene is compared, and graphene oxide has more excellent performance.Not only there is good wettability and surface activity, and can be little
Peel off after molecule or polyalcohol intercalation, play the heaviest in terms of improving the combination properties such as the calorifics of material, electricity, mechanics
The effect wanted.
So far, researcher has been found that graphene oxide has following advantage: be current optimal catalyst carrier material
One of material；The graphene oxide that structure and Graphene are substantially the same has a large amount of hydrophilic functional groups not available for Graphene,
There is in biotic environment good dispersive property, high drug loading and certain slow release characteristic and drug effect such as significantly improves at the spy
Point, can overcome easily reuniting and the problem such as the drug action time is short, in medicine-carried system, biological detection, life when being used alone medicine
The biomedicine fields such as thing imaging, oncotherapy have a extensive future；Also it is the novel nano compounded mix of excellent performance, leads at photoelectricity
Territory has obvious application advantage；The graphite oxide obtaining surface-functionalized modification is restored also by chemical mode after modifying
Alkene has higher researching value.And the application of graphene oxide is main to be utilized as in liquid phase, particularly in organic system, main
Use and dried for graphene oxide water solution powder body or graphite oxide powder body are dispersed back in organic solution recycling
Mode be main.Chinese patent CN102746236A discloses one and prepares functional graphene oxide method, and this patent is logical
Cross after graphene oxide is carried out functionalization, promote graphene oxide dispersion in organic solvent.Concretely comprise the following steps
Under conditions of polyphosphoric acids is as catalyst, graphene oxide solution and the reagent being used for preparing functional graphene oxide are total to
Mixed process, makes the carboxyl functional group on graphene oxide lamella and the hydroxyl on o-hydroxy amine molecule and amino or o-phenylenediamine
Two amido functional group cyclizations on molecule, thus can introduce official's energy such as azoles or imidazoles on graphene oxide lamella
Group, and then promote and enhanced feature graphene oxide composite material solubility in organic facies.Patent CN102951632A is open
A kind of method preparing graphene oxide solution, specifically include graphite powder is mixed with oxidant carry out oxidation reaction generate oxidation
Graphite, and obtain graphite oxide powder through drying processes such as sucking filtration, the most under vacuum, by above-mentioned graphite oxide at 500-
Heat treatment at 800 DEG C, it is thus achieved that the preliminary graphene oxide powder peeled off, finally by the graphene oxide tentatively peeled off and dispersant
It is mixed and added in the organic solvents such as ethanol, through further ultrasonic acquisition graphene oxide solution.Patent CN103030807B
Disclose the in-situ inserted solution manufacturing method of graphene oxide benzimidazole dihydrochloride nanocomposite, in the method, important
Polyreaction raw material graphene oxide benzimidazole dihydrochloride solution preparation through the following steps that realize, first pass through improvement
Hummers method, oxidized intercalation, centrifuge washing obtains graphene oxide water solution, through 40-80 DEG C of drying, it is thus achieved that oxidation
Graphene powder, then graphite oxide powder body is scattered in in ethanol, acetone and other organic solvent, and under the conditions of carrying out ice-water bath
Supersound process obtain peel off graphene oxide organic solution.Above-mentioned patent is required to first graphene oxide water solution entered
Row is dried and obtains graphite oxide powder body, the most again graphite oxide powder body or pretreatment graphene oxide powder is dissolved into spy again
In fixed organic solvent, the method obtaining graphene oxide organic solution finally by ultrasonic disperse stripping.This not only can make
Graphene oxide organic solution preparation technology extends, dry run time consumption and energy consumption, and obtainable organic system scope is narrower.
As can be seen here, it is provided that a kind of technique is simple, organic solution wide ranges, the oxygen that can be connected mutually with current main-stream Graphene preparation technology
Functionalized graphene organic solution preparation method has very important significance.
Summary of the invention
It is an object of the invention to provide that a kind of technique is simple, concentration of organic solution and category wide efficiently prepare oxidation
The method of Graphene organic solution.
The present invention is by the graphene oxide water solution that obtains the commercially available of concentration known or chemical oxidation graft process
Add target organic solvent, then through simple distillation or fractional distillation, realize water by solvent displacement and separate with target organic solvent,
Finally by the graphene oxide organic solution of removal water in ultrasonic middle dispersion, graphene oxide organic solution can be obtained.
Owing to carrying out the most in the liquid phase in whole replacement process, and graphene oxide has typical quasi-two-dimensional space knot
Structure, thus graphene oxide does not occur to dissolve or chemical reaction in this liquid-phase system, but contain with C=O, C-OH ,-COOH etc.
Oxygen functional group carbon atom in closely knit carbon wire side is combined and forms the covalent bond type intercalation compound that two-dimensional space infinitely extends
Form is scattered in liquid phase, can't separate out.
To achieve these goals, the invention provides a kind of method efficiently preparing graphene oxide organic solution, logical
Cross techniques below scheme to realize:
(1) desirable oxidation Graphene organic solution determines, according to actual needs, determines desirable oxidation Graphene organic solution
Concentration b mg/ml and volume VB is totalml；
(2) according to concentration and the volume of step (1) desirable oxidation Graphene organic solution, requisite oxygen functionalized graphene water is determined
Concentration a of solution and volume VA is total, wherein, in the value theory of concentration a from the point of view of for arbitrary value, but in order to calculate and operate in reality
Convenient, this programme determines the concentration by market consultation existing product or dense according to document gained graphene oxide water solution
Degree is as the concentration known of graphene oxide water solution i.e. a mg/ml in this programme.
Volume VA is totalComputational methods and hypothesis are as follows:
To put it more simply, the volume of hypothesis solution does not change because adding solute graphene oxide, (i.e. partial molar volume is
Zero) the volume V of the graphene oxide solution that desired concn is a mg/ml, is calculated by formula 1A is total:
VA is total=VB is total* b/a formula 1
Wherein,
A is concentration mg/ml of graphene oxide water solution；
VA is totalVolume ml for the graphene oxide water solution that concentration is a mg/ml needed for configuration target organic solution；
B is concentration mg/ml of graphene oxide target organic solution；
VB is totalFor graphene oxide target organic solution volume ml
(3) according to step (2) result of calculation, measuring volume is VA is totalMl, concentration are that the graphene oxide of a mg/ml is water-soluble
Liquid, VB is totalMl target organic solvent adds in the container with agitator, and adjusting speed of agitator is 50～1000rpm, by two kinds of liquid
Body stirring mixing 10～30min, it is thus achieved that mixing liquid；
(4) step (3) gained mixing liquid is transferred in distillation or the distillation of fractionation apparatus or fractional distilling flask, in vacuum
Under the conditions of-0.04～-0.1MPa, adjust distillation or fractionation temperature ranges is 40～120 DEG C, and this temperature range should meet Jie
In under this vacuum condition, between azeotropic point (low boiling) and the boiling point (high boiling point) of organic solvent of water and organic solvent, this
A little boiling points can obtain by looking into boiling point substance table；When using rotary distillation or fractionating device, also needing to adjust rotating speed is 5-
60rpm；Starting distillation or fractional distillation, the water evaporated is back to after being condensed by condensing unit in accepter (bottle), until remaining
Remaining liquor capacity≤VB is totalMl and no longer have liquid till condensing unit is back to accepter (bottle)；
(5) step (4) will must be distilled or fractional distilling flask has gone the graphene oxide organic solution of moisture removal transfer to hold
In measuring bottle, supplement organic solvent until overall solution volume is VB is totalml；
(6) transferring in ultrasonic device by the graphene oxide organic solution of step (5) gained, employing power bracket is
Supersound process 10-1200s of 100-1200W, can obtain graphene oxide solution V that concentration is b mg/mlB is totalml。
Organic solution described in step (1) is the corresponding organic solvent selected according to application demand.Organic solvent is
Referring to the boiling point organic solvent higher than water, including having high-k (＞ 15～20), high dipole moment is (more than 8.34 × 10- 30C m) aprotic polar solvent or protonic solvent.Described protonic solvent includes but not limited to following solvent, and alcohols is such as
Hexalin, n-butyl alcohol, ethylene glycol, n-amyl alcohol, 1,2-propylene glycol, myristyl alcohol, 2-methyl isophthalic acid-propanol etc.；Amine such as ethylenediamine,
Ethanolamine, isopropanolamine etc.；Organic acid such as propanoic acid, acetic anhydride, butyric acid etc..Described aprotic polar solvent include but not limited to as
Lower solvent, ethers such as ethylene glycol diethyl ether, diamyl ether, diethylene glycol dimethyl ether, two hexyl ethers, methyl phenyl ethers anisole, butyl ether etc.；Halogenated hydrocarbon
Such as 1,1,2-trichloroethane, perchloroethylene, adjoin-chlorotoluene etc.；Ketone such as Ketohexamethylene, methyl butyl ketone etc.；Nitrogen-containing compound such as nitro
Ethane, pyridine, ethoxy quinoline etc.；Sulfoxide such as dimethyl sulfoxide etc.；Amide-type such as Methanamide, N,N-dimethylformamide, N-
Methyl pyrrolidone, DMAC N,N' dimethyl acetamide, hexamethyl phosphoric triamide etc..
Graphene oxide described in step (2) is the graphene oxide water solution prepared by chemical oxidation graft process, can
Obtained by existing method that is commercially available or that reported by document.As can refer to document Hummers, W.S.；Offeman, R.E., oxygen
The preparation of functionalized graphene, JACS .1985,80,1339 (Hummers, W.S.；Offeman,R.E.Preparation
Of graphite oxide.J.Am.Chem.Soc.1958,80,1339) described in by potassium chlorate, nitric acid, potassium permanganate or
The oxidizing graphite such as sulphuric acid prepares graphene oxide or the method for graphite oxide aqueous solution；Or other aoxidize graft process and prepare
Graphene oxide or graphite oxide aqueous solution may be applicable to this method.Wherein said graphene oxide includes but not limited to lead to
Cross Hummer method, Staudenmaier method or Brodie method and improved method thereof to crystalline flake graphite, highly oriented pyrolytic graphite or collection
Calculus ink, coal base graphitization raw material etc. carries out aoxidizing intercalation and the powder body that obtains or slurry.Described oxidation graft process include but not
It is limited to the methods such as following intercalation method, electrochemical intercalation, hot intercalation, organic solvent intercalation, ion insertion.
Step (3) described agitator includes turbine type agitator (the J640 type such as Zibo Danone chemical machinery company limited
Turbine type agitator, the SB90-284 type turbine type agitator of Yancheng City Huai Yu heating equipment company limited), propeller mixer
(such as the JBJ12-550-167/0.75 type propeller mixer of Pingyang County chemical machinery head factory, Wenzhou Ou Tai machine-building is limited
The B.KJ1-1.1/300-TX-300-1000S1 propeller mixer of company), flat-blade paddle agitator is (such as Wuxi true qualities environmental protection section
The PJ750 type flat-blade paddle agitator of skill company limited, the TY40 series flat paddle stirring of Hunan Zhong Lian ceramic machinery company limited
Machine), (such as the anchor agitator of Yancheng City water plant equipment company limited, Jiangsu Province's Yancheng City very joins electric power to anchor agitator
The anchor agitator of equipment company limited), helix(ribbon type) agitator (the J720 type helical-ribbon type such as Huaxing Speed Shift driving Machienry Factory, Zibo
Agitator, DJ160, DJ280 type helix(ribbon type) agitator of Botou City Zhi Cheng reductor company limited), magnetic stirring apparatus is (such as Beijing
The WIGGENS WHMIX induction magnetic of series of Sang Yi experimental apparatus institute drives agitator, and excellent Lay wins technology (Beijing) to be had
The JULABO-ACE multi position type magnetic stirring apparatus etc. of limit company), magnetic force heating stirrer (as Chinese mugwort card (Guangzhou) instrument and equipment limited
The IKA RET control-visc of company (IKA China) heats magnetic stirring apparatus, Louis business corporation agency's
Thermo Scientific heats magnetic stirring apparatus), hinging type agitator is (as Yancheng City creates heating equipment company limited
Hinging type agitator, Jining City is along the hinging type agitator of source plant equipment company limited), frequency conversion double layer agitator is (such as Yancheng
The frequency conversion double layer agitator of Huai Yu heating equipment company limited of city, the frequency conversion double layer stirring of Dezhou Li Yu mixing plant company limited
Device), side stir machine is (such as the CJB-5.5-260 type side stir machine of Zibo You Sheng Chemical Equipment Co., Ltd., Dezhou City
The TXL type side stir machine of De Kai deceleration transmission Machinery Co., Ltd., Shenzhen such as gram Science and Technology Ltd.'s CJB-3KW type side
Enter formula blender) etc..
Step (4) described distillation or fractionation apparatus such as normal pressure distillation apparatus is (such as General experimental science and technology investor group company limited
U.S.'s EE SimpleDist intelligent integrated distillation apparatus of agency, the MiniDIS of Grabner instrument company of AMETEK group is complete
Automatic distillation instrument etc.), (the French ISL AD1160 decompression such as Beijing first China's development in science and technology Limited Liability public affairs agency of decompression distillation apparatus
Distillation apparatus, the full glass vacuum distillation apparatus etc. that laboratory is independently built), normal pressure or decompression rotary distillation (evaporation) instrument (Ai Bei
The EV341 Rotary Evaporators of capital LabTech instrument limited company, the German Heidolph of the limited public agency of Tegent Technology
Hei-VAP Industrial Rotary Evaporators) etc.；Normal pressure or low pressure fractionating device are (such as Germany of Germany's
Pilodist PD 104 precise distillation apparatus, the 5201 precision fractionation towers etc. that Taizhou plain Jiangjiang glass apparatus factory produces) etc..
The condensing tube used in step (4) distillation or fractional distillation is according to mixing liquid boiling-point difference, selects suitable condensing tube
(straight cold finger, air set pipe (boiling-point difference is more than 150 DEG C), (boiling-point difference is more than 100 DEG C to spherical condensation tube, is less than or equal to
150 DEG C), (boiling-point difference is more than 10 DEG C, little for serpentine condenser (boiling-point difference is more than 50 DEG C, less than or equal to 100 DEG C) and thorn shape dephlegmator
In equal to 50 DEG C).
Step (6) described ultrasonic device includes that ultrasonic washing unit is (such as Dongguan City Pu Biao experiment equipment Science and Technology Ltd.
The digital adjustable ultrasonic washing unit of SPCC-6-HTD type, a SCQ-25-6 type sound man of virtue and ability for Shanghai Sheng Yan ultrasonic instrument company limited
Split type ultrasonic washer, the Britain PM1-300TD type ultrasonic cleaner of Shanghai Ling Chu enviromental protection instrument company limited agency
Deng), ultrasonic cell disruptor (the VOSHIN98-III type ultrasonic cell disruptor of Wuxi Wo Xin Instrument Ltd., north
Space Proview experimental facilities company limited Scientz-IID type ultrasonic cell disruptor is won in capital, and Tianjin Ao Tesaiensi instrument has
The UH-500B liquid crystal Ultrasonic cell smash etc. of limit company), energy-collecting ultrasonic equipment is (such as Nanjing following current Instrument Ltd. SL
Type energy-collecting ultrasonic emulsification dispersion system, the XO-1000F type energy-gathered ultrasonic material breast of Nanjing Xian Ou instrument manufacturing company limited
Change device etc.) etc. there is the equipment of ultrasound functions.
Specifically, above-mentioned steps (2) optimum condition is that in graphene oxide water solution, the preferred value of a is 8-16mg/ml；
Specifically, in above-mentioned steps (3), preferred agitator speed scope is 300-600rpm, and mixing time is 15-
20min；In this rotating speed and time range, while can efficiently ensureing there is preferable mixed effect, can reach saving energy
Consumption, reduces the purpose of production cost.
Specifically, above-mentioned steps (4) optimum condition be vacuum be-0.05～-0.08Mpa.
Specifically, above-mentioned steps (6) optimum condition be power bracket be 800-1000W, supersound process 100-300s.
The feature of the present invention and having the beneficial effects that:
(1) Preparation equipment of graphene oxide organic solution is simple, it is only necessary to simple stirring, distillation or fractionating device,
Ultrasonic, can realize, technical process is simple and is prone to industrialization amplification；
(2) this method can be with current main-stream oxidation-reduction method good being connected of Graphene preparation technology, it is not necessary to sets up new
Graphene oxide preparation technology；Preparing presoma is common graphene oxide water solution, it is not necessary to be dried by graphene oxide again
Dispersion, shortens technological process, it also avoid the energy loss in dry run；
(3) in the whole technical process of this method, it is not necessary to add any dispersant or other dispersing aiies, without to oxidation
Graphene is modified, can be organic molten by simply processing the graphene oxide that can directly obtain target organic solvent dissolving
Liquid, with other separation means, compares such as extraction, absorption etc., is not required to use other solvent beyond system components, thus ensures
New impurity will not be introduced；
(4) this method organic solution category is wide, can use any can dissolve each other and boiling point is higher than the organic of water with water
Solvent；Concentration range width, can obtain the various graphene oxide organic solutions that concentration is 0.1-30mg/mL and solve different application
Field is to different graphene oxide solution concentration and the demand of kind.
Accompanying drawing illustrates:
Fig. 1 is graphene oxide stereoscan photograph in embodiment 1
Fig. 2 is graphene oxide AFM electromicroscopic photograph in embodiment 1
Fig. 3 is graphene oxide solution 3D microphotograph in embodiment 1
Fig. 4 is pure DMF (a) and graphene oxide DMF solution (b) macroscopic view and Tyndall effect photo in embodiment 1
Fig. 5 is the sedimentation result picture after 3 months of the graphene oxide organic solution prepared by embodiment 1-5, and (a) is
Embodiment 1, (b) is embodiment 2, and (c) is embodiment 3, and (d) is embodiment 4, (e).For embodiment 5
Detailed description of the invention:
In order to describe technology contents and the effect of the present invention in detail, below with reference to be embodied as example (but be not limited to
Lower embodiment) and coordinate accompanying drawing to be explained.
Embodiment 1
(1) desirable oxidation Graphene organic solution determines.According to demand, determine required configuration be concentration be b=
0.01mg/ml, volume is VB is totalThe graphene oxide N of=1000ml, N dimethyl methylamine (DMF) solution:
(2) according to concentration and the volume of step (1) desirable oxidation Graphene organic solution, requisite oxygen functionalized graphene water is determined
The concentration a mg/ml and volume V of solutionA is totalml.In this embodiment, use and opened by improvement hummers method purchased from middle section charcoal is beautiful
The graphene oxide water solution sent out, accordingly it is determined that the concentration of the graphene oxide that concentration is 2mg/ml of charcoal U.S. of middle section is known
The concentration of graphene oxide water solution, i.e. a=2.
Requisite oxygen functionalized graphene aqueous solution volume VA is totalCalculating.To put it more simply, assume that the volume of solution is not because adding molten
Matter graphene oxide and change (i.e. partial molar volume is zero).The volume of required graphene oxide water solution is calculated by formula 1
VA is total。
VA is total=VB is total* b/a=0.01*1000/2ml=5ml formula 1
(3) according to step (2) result of calculation, the graphene oxide water solution of step (2) gained 2mg/ml is measured 5ml,
With 1000ml target organic solvent N, N dimethyl methylamine (DMF) is placed in the TY40 series of Hunan Zhong Lian ceramic machinery company limited
In flat paddle stirrer, adjusting the blender range of speeds is 150rpm, by two kinds of liquid agitation mixing 20min, it is thus achieved that initially mix
Close liquid；
(4) step (3) gained mixing liquid is transferred to the German Heidolph Hei-of the limited public agency of Tegent Technology
In VAP Industrial Rotary Evaporators, wherein evaporimeter condensing unit use serpentine condenser, adjust equipment vacuum degree be-
0.08Mpa, vapo(u)rizing temperature is 96 DEG C (now, the boiling point of water is 92 DEG C, and the boiling point of DMAC is 152.8 DEG C)；Adjust revolving bottle
Rotating speed is 10rpm, starts distillation, and the water evaporated is recovered to condense in sample collection bottle by condensing unit, until remaining
Liquor capacity≤1000ml, and no longer have water to be back to condense till sample collection bottle from condensing unit.
(5) step (4) will obtain the graphene oxide N having removed moisture removal in alembic, N dimethyl methylamine (DMF) solution
Transfer in volumetric flask, and supplementary target solvent N, N dimethyl methylamine (DMF) is until overall solution volume is 1000ml.
(6) by step (5) gained graphene oxide N, N dimethyl methylamine (DMF) solution transfers to Nanjing elder generation Europe instrument system
Make in the XO-1000F type energy-gathered ultrasonic material emulsator of company limited, the supersound process that ultrasonic power is 600W is set
1200s, can obtain the graphene oxide DMF solution 1000ml that concentration is 0.01mg/ml.Finally, the oxidation of certain volume is taken
Graphene N, N dimethyl methylamine (DMF) solution, it is accurate to 0.01ml, is placed in the weighing botle of constant weight that (quality is weighed and is accurate to
0.0001g), carefully shake, make test solution natural flow, in forming one layer of uniform thin film at the bottom of bottle.Place in drying baker, after drying
Taking-up is put in exsiccator, is cooled to room temperature, weighs, and can obtain solid content is 0.0104mg/ml.Gained desirable oxidation Graphene N,
It is 4% that the concentration value of N dimethyl methylamine (DMF) solution differs with theoretical value, i.e. less than ± 5%, meets and prepares standard-required.
Embodiment 2
(1) desirable oxidation Graphene organic solution determines.According to demand, determine required configuration be concentration be b=
0.1mg/ml, volume is VB is totalThe graphene oxide ethylenediamine solution of=500ml:
(2) according to concentration and the volume of step (1) desirable oxidation Graphene organic solution, determine and requisite oxygen functionalized graphene
The concentration a mg/ml and volume V of aqueous solutionA is totalml.In this embodiment, according to document Deoxygenation of
Exfoliated Graphite Oxide under Alkaline Conditions:A green route to graphene
Preparation.Advanced Materials, 2008,20 (23): 4490-4493. methods, determine that can obtain concentration is
The graphene oxide water solution of 0.5mg/ml；I.e. a=0.5.
Requisite oxygen functionalized graphene aqueous solution volume VA is totalCalculating.
In order to simplify calculating, it is assumed that the volume of solution does not changes (the most inclined mole of body because adding solute graphene oxide
Amass is zero).The volume V of required graphene oxide water solution is calculated by formula 1A is total。
VA is total=VB is total* b/a=0.1*500/0.5ml=100ml formula 1
Know according to above-mentioned formula and calculating, according to document Deoxygenation of Exfoliated Graphite
Oxide under Alkaline Conditions:A green route to graphene
Preparation.Advanced Materials, 2008,20 (23): 4490-4493. methods, prepare and obtain concentration and be
Graphene oxide water solution 100ml of 0.5mg/ml.
(3) according to step (2) result of calculation, the graphene oxide water solution of step (1) gained 0.5mg/ml is measured
100ml, is jointly positioned over 500ml target organic solvent ethylenediamine and has overlapped Yancheng City Huai Yu heating equipment company limited
In the beaker of frequency conversion double layer agitator, adjustment agitator speed is 800rpm, by two kinds of liquid agitation mixing 40min, it is thus achieved that just
Begin mixing liquid；
(4) step (3) gained mixing liquid is transferred to the U.S. of General experimental science and technology investor group company limited agency
In the alembic of EE SimpleDist intelligent integrated distillation apparatus, wherein condensing unit uses thorn shape dephlegmator, adjusts equipment true
Reciprocal of duty cycle is-0.06Mpa, and vapo(u)rizing temperature is 30 DEG C (now, the boiling point of water is 27 DEG C, and the boiling point of ethylenediamine is 39 DEG C)；Adjust rotation
The rotating speed of rolling bottle is 50rpm, starts distillation, and the water evaporated is recovered to condense in sample collection bottle by condensing unit, until
Remaining liquor capacity≤500ml and no longer have water from condensing unit be back to condense sample collection bottle.
(5) receiving flask has gone the graphene oxide ethylenediamine solution of moisture removal transfer to hold by step (4) must be distilled
In measuring bottle, and supplementary target solvent ethylenediamine to overall solution volume is 500ml.
(6) step (5) gained graphene oxide ethylenediamine solution is transferred to Wuxi Wo Xin Instrument Ltd.
In VOSHIN98-III type ultrasonic cell disruptor, supersound process 600s that ultrasonic power is 100W is set, can obtain dense
Degree is the graphene oxide ethylenediamine solution 500ml of 0.1mg/ml.Finally, the positive fourth of gained graphene oxide of certain volume is weighed
Alcoholic solution, is accurate to 0.01ml, is placed in the weighing botle of constant weight (quality is weighed and is accurate to 0.0001g), carefully shakes, make examination
Liquid natural flow, in forming one layer of uniform thin film at the bottom of bottle.Placing in drying baker, dried taking-up is put in exsiccator, cooling
To room temperature, weighing, can obtain solid content is 0.0990mg/ml.The concentration value of gained desirable oxidation Graphene ethylenediamine solution and reason
Opinion value difference is 1%, i.e. less than ± 5%, meets and prepares standard-required.
Embodiment 3
(1) desirable oxidation Graphene organic solution determines.According to demand, determine required configuration be concentration be b=2mg/
Ml, volume is VB is totalThe graphene oxide N of=200ml, N dimethyl acetamide (DMAC) solution.
(2) according to concentration and the volume of step (1) desirable oxidation Graphene organic solution, determine and requisite oxygen functionalized graphene
The concentration a mg/ml and volume V of aqueous solutionA is totalml.In this embodiment, have by buying Chinese Academy of Sciences's Chengdu organic chemistry
The TNWIGO type graphene oxide water solution of limit company, determines that the concentration of the graphene oxide that concentration is 10mg/ml is known
The concentration of graphene oxide water solution, i.e. a=10.
Requisite oxygen functionalized graphene aqueous solution volume VA is totalCalculating.
In order to simplify calculating, it is assumed that the volume of solution does not changes (the most inclined mole of body because adding solute graphene oxide
Amass is zero).The volume V of required graphene oxide water solution is calculated by formula 1A is total。
VA is total=VB is total* b/a=2*200/10ml=40ml formula 1
Know according to above-mentioned formula and calculating, buy the TNWIGO type concentration of Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences
For 10mg/ml graphene oxide water solution 40ml.
(3) according to step (2) result of calculation, the graphene oxide water solution of step (1) gained 10mg/ml is measured
40ml, with 200ml target organic solvent N, N dimethyl acetamide (DMAC) is placed in Zibo Danone chemical machinery company limited
In J640 type turbine type agitator, adjusting agitator speed scope is 50rpm, by two kinds of liquid agitation mixing 40min, it is thus achieved that just
Begin mixing liquid；
(4) step (3) gained mixing liquid is transferred to the France of China Tech skill Development Co., Ltd of Beijing elder generation agency
In the alembic of ISL AD1160 decompression distillation apparatus, wherein evaporimeter condensing unit uses serpentine condenser, adjusts equipment vacuum
Degree is-0.075Mpa, and vapo(u)rizing temperature is 96 DEG C (now, the boiling point of water is 92 DEG C, and the boiling point of DMAC is 156 DEG C)；Adjust and rotate
The rotating speed of bottle is 5rpm, starts distillation, and the water evaporated is recovered to condense in sample collection bottle by condensing unit, until remaining
Remaining liquor capacity≤200ml, and no longer have water till condensing unit is back to condense sample collection bottle.
(5) will obtain the graphene oxide N having removed moisture removal in alembic in step (4), N dimethyl acetamide (DMAC) is molten
Liquid is transferred in volumetric flask, and supplementary target solvent N, and N dimethyl acetamide (DMAC) is until overall solution volume is 200ml.
(6) by step (5) gained graphene oxide N, it is real that N dimethyl acetamide (DMAC) solution transfers to Dongguan City spectrum mark
Testing in the digital adjustable ultrasonic washing unit of SPCC-6-HTD type of equipment Science and Technology Ltd., arranging ultrasonic power is the super of 800W
Sonication 600s, can obtain the graphene oxide DMAC solution 200ml that concentration is 2mg/ml.Finally, the oxygen of certain volume is taken
Functionalized graphene N, N dimethyl acetamide (DMAC) solution, it is accurate to 0.01ml, is placed in the weighing botle of constant weight that (quality is weighed
It is accurate to 0.001g), carefully shake, make test solution natural flow, in forming one layer of uniform thin film at the bottom of bottle.Place in drying baker,
Dried taking-up is put in exsiccator, is cooled to room temperature, weighs, and can obtain solid content is 1.9846mg/ml.Gained target oxygen fossil
Ink alkene N, it is 0.77% that the concentration value of N dimethyl acetamide (DMAC) solution differs with theoretical value, i.e. less than ± 5%, meets
Prepare standard-required.
Embodiment 4
(1) desirable oxidation Graphene organic solution determines.According to demand, determine required configuration be concentration be b=15mg/
Ml, volume is VB is totalThe graphene oxide ethylene glycol diethyl ether solution of=100ml.
(2) according to concentration and the volume of step (1) desirable oxidation Graphene organic solution, determine and requisite oxygen functionalized graphene
The concentration a mg/ml and volume V of aqueous solutionA is totalml.In this embodiment 1, use the graphene oxide that in buying, section's charcoal is beautiful water-soluble
Liquid, determines that the concentration of the beautiful graphene oxide that concentration is 2mg/ml by improving the exploitation of hummers method of middle section charcoal is known
The concentration of graphene oxide water solution, i.e. a=2.
Requisite oxygen functionalized graphene aqueous solution volume VA is totalCalculating.
In order to simplify calculating, it is assumed that the volume of solution does not changes (the most inclined mole of body because adding solute graphene oxide
Amass is zero).The volume V of required graphene oxide water solution is calculated by formula 1A is total。
VA is total=VB is total* b/a=15*100/2ml=750ml formula 1
Therefore graphene oxide water solution 750ml of charcoal U.S. of section 2mg/ml in buying.
(3) according to step (4) result of calculation, the graphene oxide water solution of step (1) gained 2mg/ml is measured VA is total=
750ml, is jointly positioned over 100ml target organic solvent ethylene glycol diethyl ether and has overlapped Huaxing Speed Shift driving Machienry Factory, Zibo
J720 type helix(ribbon type) agitator beaker in, adjustment agitator speed is 500rpm, by two kinds of liquid agitation mixing 10min,
Obtain mixing liquid；
(4) step (3) gained mixing liquid is transferred to general GermanyPilodist PD104 accurate
In fractionating device, condensing unit uses fractionating column, and adjusting equipment vacuum degree is-0.1Mpa, and temperature is 35 DEG C of (now, boilings of water
Point is 31 DEG C, and the boiling point of ethylene glycol diethyl ether is 48 DEG C)；The rotating speed adjusting revolving bottle is 40rpm, starts fractional distillation, evaporates
Water is recovered to condense in sample collection bottle by condensing unit, until until remaining liquor capacity≤100ml and no longer having
Water is back to condense sample collection bottle from condensing unit.
(5) the graphene oxide ethylene glycol diethyl ether solution of moisture removal has been gone to transfer to by step (4) obtains in fractional distilling flask
In volumetric flask, and supplementary target organic solvent ethylene glycol diethyl ether to overall solution volume is 100ml.
(6) step (5) gained graphene oxide ethylene glycol diethyl ether solution is transferred to Beijing and win space Proview experimental facilities
In company limited Scientz-IID type ultrasonic cell disruptor, supersound process 500s that ultrasonic power is 1000W is set, i.e.
The graphene oxide ethylene glycol diethyl ether solution 100ml that concentration is 15mg/ml can be obtained.Finally, the oxidation of certain volume is weighed
Graphene ethylene glycol diethyl ether solution, is accurate to 0.01ml, is placed in the weighing botle of constant weight that (quality is weighed and is accurate to
0.001g), carefully shake, make test solution natural flow, in forming one layer of uniform thin film at the bottom of bottle.Place in drying baker, after drying
Taking-up is put in exsiccator, is cooled to room temperature, weighs, and can obtain solid content is 15.0250mg/ml.Gained desirable oxidation Graphene
It is 0.167% that the concentration value of ethylene glycol diethyl ether solution differs with theoretical value, i.e. less than ± 5%, meets and prepares standard-required.
Embodiment 5
(1) desirable oxidation Graphene organic solution determines.According to demand, determine required configuration be concentration be b=30mg/
Ml, volume is VB is totalThe graphene oxide butanol solution of=100ml.
(2) according to concentration and the volume of step (1) desirable oxidation Graphene organic solution, determine and requisite oxygen functionalized graphene
The concentration a mg/ml and volume V of aqueous solutionA is totalml.In this embodiment, according to document Preparation of graphite
Oxide.J.Am.Chem.Soc.1958,80,1339 methods, self-control concentration is the graphene oxide water solution of 8mg/ml, and
The concentration of the graphene oxide water solution known is 8mg/ml.
Requisite oxygen functionalized graphene aqueous solution volume VA is totalCalculating.
In order to simplify calculating, it is assumed that the volume of solution does not changes (the most inclined mole of body because adding solute graphene oxide
Amass is zero).The volume V of required graphene oxide water solution is calculated by formula 1A is total。
VA is total=VB is total* b/a=30*100/8ml=375ml formula 1
Know according to above-mentioned formula and calculating, according to document Preparation of graphite
Oxide.J.Am.Chem.Soc.1958,80,1339 methods, the graphene oxide that concentration is 8mg/ml of self-control 375ml is water-soluble
Liquid.
(3) according to step (2) result of calculation, the graphene oxide water solution of step (1) gained 8mg/ml is measured
375ml, is jointly positioned over 100ml target organic solvent n-butyl alcohol and has overlapped good card (Guangzhou) the instrument and equipment company limited that ends
In the beaker of the IKA RET control-visc heating magnetic stirring apparatus of (IKA China), adjusting agitator speed is
1000rpm, by two kinds of liquid agitation mixing 20min, it is thus achieved that mixing liquid；
(4) step (3) gained mixing liquid is transferred in the full glass vacuum distillation apparatus that laboratory is independently built, its
The condensing unit of middle vacuum distillation apparatus uses spherical condensation tube, and adjusting equipment vacuum degree is-0.06Mpa, and vapo(u)rizing temperature is 80
DEG C (now, the boiling point of water is 75 DEG C, and the boiling point of 1,2-PD is 158 DEG C)；The rotating speed adjusting revolving bottle is 60rpm, starts
Distillation, the water evaporated is recovered to condense in sample collection bottle by condensing unit, until remaining liquor capacity≤100ml
And no longer have water to be back to condense sample collection bottle from condensing unit.
(5) the graphene oxide butanol solution of moisture removal has been gone to transfer to volumetric flask by step (4) obtains in fractional distilling flask
In, and supplementary target solvent, n-butanol overall solution volume is 100ml.
(6) step (5) gained graphene oxide butanol solution is transferred to Nanjing following current Instrument Ltd. SL type gather
In energy ultrasonic emulsification disperse system, arranging supersound process 10s that ultrasonic power is 1200W, can obtain concentration is 30mg/ml's
Graphene oxide butanol solution 100ml.Finally, weigh the gained graphene oxide butanol solution of certain volume, be accurate to
0.01ml, is placed in the weighing botle of constant weight (quality is weighed and is accurate to 0.001g), carefully shakes, make test solution natural flow, in
The bottle end, forms one layer of uniform thin film.Placing in drying baker, dried taking-up is put in exsiccator, is cooled to room temperature, weighs, can
Obtaining solid content is 30.1292mg/ml.The concentration value of gained desirable oxidation Graphene butanol solution differs with theoretical value and is
4.3%, i.e. less than ± 5%, meet and prepare standard-required.
Table 1 embodiment 1-5 graphene oxide organic solution solid content value of calculation and measured value
Claims (29)
1. the method efficiently preparing graphene oxide organic solution, it is characterised in that comprise the steps:
(1) desirable oxidation Graphene organic solution determines, according to actual needs, determines the dense of desirable oxidation Graphene organic solution
Degree b mg/ml and volume VB is totalml；
(2) according to concentration and the volume of step (1) desirable oxidation Graphene organic solution, required graphene oxide water solution is determined
Concentration a and volume VA is total, volume VA is totalComputational methods and hypothesis are as follows:
To put it more simply, assume that the volume of solution does not changes because adding solute graphene oxide, calculating desired concn by formula 1 is
The volume V of the graphene oxide solution of a mg/mlA is total:
VA is total=VB is total* b/a formula 1
Wherein:
A is the concentration of graphene oxide water solution, mg/ml；
VA is totalFor the volume of graphene oxide water solution that concentration is a mg/ml, ml；
B is the concentration of graphene oxide target organic solution, mg/ml；
VB is totalFor graphene oxide target organic solution volume, ml；
(3) according to step (2) result of calculation, measuring volume is VA is totalMl, concentration are the graphene oxide water solution of a mg/ml, VB is total
Ml target organic solvent adds in the container with agitator, and adjusting speed of agitator is 50～1000rpm, by two kinds of liquid agitation
Mixing 10～30min, it is thus achieved that mixing liquid；
(4) step (3) gained mixing liquid is transferred in distillation or fractionation apparatus, is-0.04～-0.1 MPa in vacuum
Under the conditions of, adjust distillation or cut point, and this temperature range should meet under this vacuum condition, water and organic solvent
Between azeotropic point and the boiling point of organic solvent, starting distillation or fractional distillation, the water evaporated is back to after being condensed by condensing unit
In accepter, until remaining liquor capacity≤VB is totalMl, and no longer have liquid be back to accepter from condensing unit be
Only；
(5) must distill in step (4) or fractional distilling flask go the graphene oxide organic solution of moisture removal is supplemented organic molten
Agent is until overall solution volume is VB is totalml；
(6) the graphene oxide organic solution of step (5) gained being used power bracket is supersound process 10-of 100-1200W
1200s, i.e. obtains graphene oxide solution V that concentration is b mg/mlB is total ml。
A kind of method efficiently preparing graphene oxide organic solution the most as claimed in claim 1, it is characterised in that
Described in step (1), organic solution is the organic solvent that boiling point is higher than water.
A kind of method efficiently preparing graphene oxide organic solution the most as claimed in claim 2, it is characterised in that
Boiling point described in step (1) includes having high-k (＞ 15～20) higher than the organic solvent of water, and high dipole moment is (big
In 8.34 × 10-30C m) aprotic polar solvent or protonic solvent.
A kind of method efficiently preparing graphene oxide organic solution the most as claimed in claim 3, it is characterised in that
Described protonic solvent includes alcohols, amine or organic acid solvent.
A kind of method efficiently preparing graphene oxide organic solution the most as claimed in claim 4, it is characterised in that
Alcohols solvent described in step (1) be Hexalin, n-butyl alcohol, ethylene glycol, n-amyl alcohol, 1,2-propylene glycol, myristyl alcohol or
2-methyl isophthalic acid-propanol.
A kind of method efficiently preparing graphene oxide organic solution the most as claimed in claim 4, it is characterised in that
Described in step (1), amine solvent is ethylenediamine, ethanolamine, isopropanolamine.
A kind of method efficiently preparing graphene oxide organic solution the most as claimed in claim 4, it is characterised in that
Described in step (1), organic acid solvent is propanoic acid, acetic anhydride or butyric acid.
A kind of method efficiently preparing graphene oxide organic solution the most as claimed in claim 3, it is characterised in that
Described aprotic polar solvent includes the solvent of ethers, halogenated hydrocarbon, ketone, nitrogen-containing compound, sulfoxide or amide-type.
A kind of method efficiently preparing graphene oxide organic solution the most as claimed in claim 8, it is characterised in that
Described ether solvent is ethylene glycol diethyl ether, diamyl ether, diethylene glycol dimethyl ether, two hexyl ethers, methyl phenyl ethers anisole or butyl ether.
A kind of method efficiently preparing graphene oxide organic solution the most as claimed in claim 8, it is characterised in that described halogen
It is 1,1,2-trichloroethane, perchloroethylene or adjoin-chlorotoluene for varsol.
11. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 8, it is characterised in that described ketone
Kind solvent is Ketohexamethylene or methyl butyl ketone.
12. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 8, it is characterised in that described contain
Nitrogen compound solvent is nitroethane, pyridine or ethoxy quinoline.
13. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 8, it is characterised in that described Asia
Sulfoxide solvent is dimethyl sulfoxide.
14. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 8, it is characterised in that described acyl
Amine solvent is Methanamide, N,N-dimethylformamide, N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide or hexamethyl phosphoric acid
Disnalon (Ferrer)..
15. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 1, it is characterised in that step
(2) graphene oxide described in is the graphene oxide water solution prepared by chemical oxidation graft process.
16. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 15, it is characterised in that described
Chemical oxidation graft process includes electrochemical intercalation, hot intercalation, organic solvent intercalation, ion insertion method.
17. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 15, it is characterised in that described
Graphene oxide includes by Hummer method, Staudenmaier method or Brodie method and improved method thereof crystalline flake graphite,
Highly oriented pyrolytic graphite or kish, coal base graphitization raw material carries out aoxidizing intercalation and the powder body that obtains or slurry.
18. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 1, it is characterised in that step
(3) described agitator includes that turbine type agitator, propeller mixer, flat-blade paddle agitator, anchor agitator, helical-ribbon type stir
Device, magnetic stirring apparatus, magnetic force heating stirrer, hinging type agitator, frequency conversion double layer agitator or side stir machine.
19. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 18, it is characterised in that described
Turbine type agitator is the J640 type turbine type agitator of Zibo Danone chemical machinery company limited or the space heat supply of Yancheng City Huaihe River sets
The SB90-284 type turbine type agitator of standby company limited；Propeller mixer is the JBJ12-of Pingyang County chemical machinery head factory
550-167/0.75 type propeller mixer or the B.KJ1-1.1/300-TX-300-of Wenzhou Ou Tai Machinery Manufacturing Co., Ltd.
1000S1 propeller mixer；Flat-blade paddle agitator is the PJ750 type flat paddle stirring of Wuxi true qualities Environmental Protection Technology Co., Ltd
The TY40 flat paddle stirrer of series of device or Hunan Zhong Lian ceramic machinery company limited；Anchor agitator is Yancheng City water machinery
The anchor agitator of equipment company limited or the anchor agitator of Jiangsu Province Yancheng City Qi Lian power equipment company limited；Helical-ribbon type
Agitator is J720 type helix(ribbon type) agitator or the Botou City Zhi Cheng reductor company limited of Huaxing Speed Shift driving Machienry Factory, Zibo
DJ160, DJ280 type helix(ribbon type) agitator；Magnetic stirring apparatus is the WIGGENS WHMIX of Beijing Sang Yi experimental apparatus institute
The induction magnetic of series drives agitator or excellent Lay wins the JULABO-ACE multi position type magnetic agitation of technology (Beijing) company limited
Device；Magnetic force heating stirrer is the IKA RET control-visc of Chinese mugwort card (Guangzhou) instrument and equipment company limited (IKA China)
The Thermo Scientific of heating magnetic stirring apparatus or Louis business corporation agency heats magnetic stirring apparatus；Hinging type
Agitator is that Yancheng City creates the hinging type agitator of heating equipment company limited or Jining City along source plant equipment company limited
Hinging type agitator；Frequency conversion double layer agitator is frequency conversion double layer agitator or the moral of Yancheng City Huai Yu heating equipment company limited
The frequency conversion double layer agitator of Zhou Liyu mixing plant company limited；Side stir machine is Zibo You Sheng Chemical Equipment Co., Ltd.
CJB-5.5-260 type side stir machine, the TXL type side stir machine of Dezhou City De Kai deceleration transmission Machinery Co., Ltd.
Or Shenzhen such as gram Science and Technology Ltd. CJB-3KW type side stir machine.
20. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 1, it is characterised in that step
(4) adjust distillation or fractionation temperature ranges is 40～120 DEG C.
21. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 1, it is characterised in that step
(4), when using rotary distillation or fractionating device in, need to adjust rotating speed is 5-60rpm.
22. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 1, it is characterised in that step
(4) described distillation is air-distillation instrument, decompression distillation apparatus, normal pressure or decompression rotary distillation instrument；Fractionation apparatus is normal pressure or low pressure
Fractionating device.
23. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 22, it is characterised in that described
Air-distillation instrument is that U.S.'s EE SimpleDist intelligent integral of General experimental science and technology investor group company limited agency steams
Evaporate the full-automatic distillation apparatus of MiniDIS of instrument or Grabner instrument company of AMETEK group；Decompression distillation apparatus is Beijing elder generation China Tech
The French ISL AD1160 decompression distillation apparatus of skill development Limited Liability public affairs agency；Normal pressure or decompression rotary distillation instrument are Ai Beijing Lay
The EV341 Rotary Evaporators of Bai Taike instrument limited company or the German Heidolph of the limited public agency of Tegent Technology
Hei-VAP Industrial Rotary Evaporators；Normal pressure or low pressure fractionating device are the Pilodist of Germany of Germany PILODIST
The 5201 precision fractionation towers that PD 104 precise distillation apparatus or Taizhou plain Jiangjiang glass apparatus factory produce.
24. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 1, it is characterised in that step
(6) described ultrasonic device includes ultrasonic washing unit, ultrasonic cell disruptor, energy-collecting ultrasonic equipment.
25. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 24, it is characterised in that described
Ultrasonic washing unit is the digital adjustable ultrasonic waves for cleaning of SPCC-6-HTD type of Dongguan City Pu Biao experiment equipment Science and Technology Ltd.
Just environmental protection is insulted in machine, SCQ-25-6 type sound man of virtue and ability's Split type ultrasonic washer of Shanghai Sheng Yan ultrasonic instrument company limited or Shanghai
The Britain PM1-300TD type ultrasonic cleaner of Instrument Ltd. agency；Ultrasonic cell disruptor is Wuxi fertile letter instrument
Space Proview experimental facilities company limited Scientz-won by the VOSHIN98-III type ultrasonic cell disruptor of company limited, Beijing
The UH-500B liquid crystal supersonic cell of IID type ultrasonic cell disruptor or Tianjin Ao Tesaiensi Instrument Ltd. is pulverized
Instrument；Energy-collecting ultrasonic equipment is Nanjing following current Instrument Ltd. SL type energy-collecting ultrasonic emulsification dispersion system or Nanjing elder generation Europe instrument system
Make the XO-1000F type energy-gathered ultrasonic material emulsator of company limited.
26. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 1, it is characterised in that described step
Suddenly in (2) graphene oxide water solution, a is 8-16 mg/ml.
27. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 1, it is characterised in that described step
Suddenly in (3), agitator speed scope is 300-600rpm, and mixing time is 15-20min.
28. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 1, it is characterised in that described step
Suddenly (4) vacuum is-0.05～-0.08Mpa.
29. a kind of methods efficiently preparing graphene oxide organic solution as claimed in claim 1, it is characterised in that described step
Suddenly (6) ultrasonic power scope is 800-1000W, supersound process 100-300s.
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| CN109385139A (en) * | 2017-08-03 | 2019-02-26 | 深圳Tcl工业研究院有限公司 | The method of purification of zinc oxide base nano particle ink |
| CN109925981A (en) * | 2019-03-13 | 2019-06-25 | 太原理工大学 | A kind of preparation method of the graphene composite aerogel of high compression-strength |
| CN109971233A (en) * | 2019-04-10 | 2019-07-05 | 常州第六元素材料科技股份有限公司 | Graphene with high specific surface aggregation and preparation method thereof, graphene static conductive coating and preparation method thereof |
| CN113421617A (en) * | 2021-06-18 | 2021-09-21 | 广东佳纳能源科技有限公司 | Method for calculating solid content in process of preparing solid material by batch method and application thereof |
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| CN109385139A (en) * | 2017-08-03 | 2019-02-26 | 深圳Tcl工业研究院有限公司 | The method of purification of zinc oxide base nano particle ink |
| CN109385139B (en) * | 2017-08-03 | 2021-10-12 | 深圳Tcl工业研究院有限公司 | Purification method of zinc oxide-based nanoparticle ink |
| CN108264042A (en) * | 2018-02-24 | 2018-07-10 | 山西永东化工股份有限公司 | A kind of application of liquid phase enzymolysis production graphene oxide method and its graphene oxide |
| CN109925981A (en) * | 2019-03-13 | 2019-06-25 | 太原理工大学 | A kind of preparation method of the graphene composite aerogel of high compression-strength |
| CN109925981B (en) * | 2019-03-13 | 2022-02-11 | 太原理工大学 | Preparation method of graphene composite aerogel with high compressive strength |
| CN109971233A (en) * | 2019-04-10 | 2019-07-05 | 常州第六元素材料科技股份有限公司 | Graphene with high specific surface aggregation and preparation method thereof, graphene static conductive coating and preparation method thereof |
| CN113421617A (en) * | 2021-06-18 | 2021-09-21 | 广东佳纳能源科技有限公司 | Method for calculating solid content in process of preparing solid material by batch method and application thereof |
| CN113421617B (en) * | 2021-06-18 | 2022-03-11 | 广东佳纳能源科技有限公司 | Method for calculating solid content in process of preparing solid material by batch method and application thereof |
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