CN107857257A - The preparation method of single-layer graphene dispersion liquid - Google Patents
The preparation method of single-layer graphene dispersion liquid Download PDFInfo
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- CN107857257A CN107857257A CN201711185493.0A CN201711185493A CN107857257A CN 107857257 A CN107857257 A CN 107857257A CN 201711185493 A CN201711185493 A CN 201711185493A CN 107857257 A CN107857257 A CN 107857257A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 311
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 199
- 239000002356 single layer Substances 0.000 title claims abstract description 83
- 239000006185 dispersion Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- 239000007788 liquid Substances 0.000 title claims abstract description 60
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 118
- 239000010439 graphite Substances 0.000 claims abstract description 118
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 108
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000001257 hydrogen Substances 0.000 claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000002002 slurry Substances 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 239000002270 dispersing agent Substances 0.000 claims abstract description 44
- 239000008367 deionised water Substances 0.000 claims abstract description 37
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000012545 processing Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 239000007921 spray Substances 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims description 67
- 239000000243 solution Substances 0.000 claims description 53
- 238000010792 warming Methods 0.000 claims description 50
- 239000004744 fabric Substances 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- 239000010410 layer Substances 0.000 claims description 30
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 30
- -1 phthalic acid ester Chemical class 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 235000010344 sodium nitrate Nutrition 0.000 claims description 15
- 239000004317 sodium nitrate Substances 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012286 potassium permanganate Substances 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000004575 stone Substances 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 125000004423 acyloxy group Chemical group 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002885 octadecanoids Chemical class 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 21
- 238000005406 washing Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 238000001514 detection method Methods 0.000 description 13
- 238000007710 freezing Methods 0.000 description 13
- 230000008014 freezing Effects 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000002242 deionisation method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007613 slurry method Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention provides a kind of preparation method of single-layer graphene dispersion liquid, comprise the following steps：Natural flake graphite is provided, oxidation processes is carried out, prepares graphite oxide slurry；Deionized water is added in graphite oxide slurry, is peeled off by high-pressure homogeneous crusher machine, until obtaining the graphene oxide that average thickness is 0.4 0.7nm, average piece footpath is 0.8 10 μm；After graphene oxide is freeze-dried, it is passed through nitrogen and hydrogen mixture and carries out temperature programming processing, be cooled to room temperature, obtain single-layer graphene powder；Single-layer graphene powder is placed in spray mixer, ethanol solution to contain dispersant is used as spray, it is spray-dried under conditions of rotating speed is 300 1000rpm, temperature is 70 100 DEG C, after to be spray dried, continue stirring and obtain modified single-layer graphene powder；Modified single-layer graphene powder is dissolved in organic solvent for ultrasonic dispersion processing, obtains single-layer graphene dispersion liquid.
Description
Technical field
The invention belongs to graphene dispersing solution technical field, more particularly to a kind of preparation side of single-layer graphene dispersion liquid
Method.
Background technology
Graphene is a kind of material for the monatomic layer structure that hexagonal honeycomb lattice is made up of carbon atom, is had very excellent
Different conduction, heat conduction and mechanical performance, can be widely used in each field.But graphene is as a kind of two-dimensional nano material
Material, it is very easy to reunite, and graphene is changed into graphite-structure again after reuniting, it is difficult to play its unique performance.
Therefore how graphene uniform to be disperseed, is to solve current graphene application urgent problem.
Existing dispersion technology is broadly divided into two kinds, and first method is hydrophilic on graphite oxide surface grafting or oleophylic
Group, then peel off and be reduced into graphene, be prepared into the graphene dispersing solution or slurry being easily dispersed, but this preparation
Mode has that reactions steps are complicated, material loss is big, graphite oxide grafting not exclusively causes the shortcomings of scattered bad.Second of side
Method is to prepare graphene powder by way of redox or liquid phase stripping, is then directly added into dispersant and prepares graphene
Dispersion liquid or slurry, but graphene powder prepared by this method has just been reunited before scattered, reuses dispersant
Graphene powder can not be peeled away.
The content of the invention
It is an object of the invention to provide a kind of preparation method of single-layer graphene dispersion liquid, it is intended to solves existing individual layer stone
The problem of black alkene dispersion technology step is complicated, dispersion effect is bad.
The present invention is achieved in that a kind of preparation method of single-layer graphene dispersion liquid, comprises the following steps：
01. provides natural flake graphite, carries out oxidation processes, prepares graphite oxide slurry；
02. adds deionized water in the graphite oxide slurry, is peeled off by high-pressure homogeneous crusher machine, until being put down
The graphene oxide that equal thickness is 0.4-0.7nm, average piece footpath is 0.8-10 μm；The graphene oxide is freeze-dried
Afterwards, it is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture and carries out temperature programming processing, be cooled to room temperature, obtain single-layer graphene
Powder；
The single-layer graphene powder is placed in spray mixer by 03., and the ethanol solution to contain dispersant is used as spraying
Agent, it is spray-dried under conditions of rotating speed is 300-1000rpm, temperature is 70-100 DEG C, treats that the spray drying finishes
Afterwards, continue to be uniformly mixed, obtain modified single-layer graphene powder；Then it is the single-layer graphene powder of the modification is molten
In organic solvent, ultrasonic disperse processing, single-layer graphene dispersion liquid is obtained；
Wherein, the method for described program heating treatment is：The graphene oxide after freeze-drying is warming up to 150-
300 DEG C, keep 0.5-12h；600-800 DEG C is warming up to again, keeps 0.5-12h；1000-1200 DEG C is continuously heating to, is kept
0.5-12h。
Further, in step 01, the particle diameter of the natural flake graphite is 30-100 μm.
Further, in step 01, it is described prepare graphite oxide slurry method be：It is natural by 30-100 μm of 1-5 parts
Crystalline flake graphite and the sodium nitrate of 0.5-2.5 parts are dispersed in the concentrated sulfuric acid of 50-200 parts, and the Gao Meng of 3-15 parts is added under ice bath
Sour potassium, after reacting 0.5-4h, oil bath is warming up to 20-40 DEG C and continues to react 2-24h, adds the deionized water of 200-500 parts, and
Keep oil bath temperature to react 2-24h at 70-100 DEG C, be eventually adding hydrogen peroxide until reaction solution no longer produces bubble, stopping is anti-
Should；5% hydrochloric acid solution of 1000-2000 parts is added into mixed solution, is centrifuged, washed using filter cloth formula centrifuge,
Until slurry pH >=6, obtain graphite oxide slurry.
Further, the filter cloth mesh number of the filter cloth formula centrifuge is 8000-12000 mesh, centrifugal speed 3000-
12000rpm。
Further, in step 02, counted using the cumulative volume of the nitrogen and hydrogen mixture as 100%, the volume fraction content of hydrogen
For 1-8%；And/or the flow velocity of the nitrogen and hydrogen mixture is 10-100sccm.
Further, in step 02, the pressure of the high pressure homogenizer is 20000-70000psi.
Further, in step 03, the weight ratio of the single-layer graphene powder, dispersant and ethanol is 100-200:1-
5:10-20。
Further, in step 03, in the spray drying, the dispersant be phthalic acid ester, octadecanoid acid,
γ-methacryloxypropyl trimethoxy silane, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl three
At least one in (dioctyl phosphoric acid acyloxy) titanate esters, the oleic acid acyloxy of isopropyl two (dioctyl phosphoric acid acyloxy) titanate esters
Kind.
Further, in step 03, the organic solvent is ethanol, acetone, tetrahydrofuran, dimethylbenzene, ether, hexamethylene
At least one of alcohol, ethyl acetate.
And a kind of single-layer graphene dispersion liquid, the single-layer graphene dispersion liquid are prepared by the above method.
The preparation method of single-layer graphene dispersion liquid provided by the invention, ensure that the graphene of preparation from process route
Powder is single-layer graphene, and adds dispersant in single-layer graphene powder in a manner of spraying, is avoided graphite directly
The problem of alkene is added in solvent so as to cause to reunite with dispersant.The present invention is by reasonably controlling graphene film footpath size simultaneously
And optimization high temperature reduction process, make the graphene dispersing solution electrical and thermal conductivity performance of preparation more excellent.Specifically,
First, natural flake graphite is used as raw material, and after oxidized stripping, it is more can to obtain unit piece footpath oxy radical
Graphene oxide, so as to improve the dispersiveness in water.
Secondly, on the basis of natural flake graphite is used as raw material, the present invention uses high pressure homogenizer by graphite oxide
Peeled off, be broken for the graphene oxide of individual layer, and control the graphene oxide of individual layer thus may be used in the range of a stator footpath
To ensure that the single-layer graphene prepared still has good thermal conductivity.
Again, the graphene oxide after stripping is dried using freeze-drying mode by the present invention, by directly distilling
Graphene oxide after stripping is dried the mode of solvent, it is possible to prevente effectively from present in tradition suction filtration or drying mode
Graphene oxide piles up the problem of forming graphite oxide structure again.The present invention is handled using the temperature programming of segmented high-temperature reduction
Mode, graphene oxide is set progressively to slough oxy radical in a gaseous form in Temperature Programmed Processes.Due to the oxy radical
It is gaseous state in the process sloughed, therefore, the reunion of graphene oxide will not be caused, and can further strut single-layer graphene powder
Between spacing.In addition, temperature programming processing mode can avoid disposably causing thermal reduction reaction too fast temperature rise, enter
And cause graphene powder fly away everywhere and the oxy radical of graphene oxide removing it is insufficient the problem of.At high temperature simultaneously
Be passed through nitrogen and hydrogen mixture, can will likely undecomposed oxy radical reduced and repair its defect so that prepare list
Layer graphene powder has excellent electrical and thermal conductivity performance.
In addition, the present invention by single-layer graphene powder in the case where heat high-speed stirred, atomizing addition dispersant, can
So that dispersant is uniformly adhered to single-layer graphene powder surface, so as to ensure that final step graphene also will not the group of causing
It is poly-.
Single-layer graphene dispersion liquid prepared by the present invention, the graphene powder that preparation is ensure that from process route are individual layer
Graphene, and dispersant is added in single-layer graphene powder in a manner of spraying, avoid graphene and dispersant directly
The problem of adding in solvent so as to cause to reunite, while the present invention is by reasonably controlling graphene film footpath size and optimization high temperature
Reduction process, make the graphene dispersing solution electrical and thermal conductivity performance of preparation more excellent, the present invention passes through preferably suitable point in addition
It is more stable that powder enables the graphene of individual layer to disperse in a solvent.
Single-layer graphene dispersion liquid individual layer rate prepared by the present invention is high, and electrical and thermal conductivity performance is excellent, can high-concentration stable point
Dissipate, with polymer-polymer miscibility it is good the advantages that, can be widely applied to e-inks, film, electronic radiation and composite etc. neck
Domain, effective path is provided for the commercial application of graphene.
Embodiment
In order that technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only explaining
The present invention, it is not intended to limit the present invention.
The embodiments of the invention provide a kind of preparation method of single-layer graphene dispersion liquid, comprise the following steps：
S01., natural flake graphite is provided, oxidation processes is carried out, prepares graphite oxide slurry；
S02. deionized water is added in the graphite oxide slurry, is peeled off by high-pressure homogeneous crusher machine, until obtaining
The graphene oxide that average thickness is 0.4-0.7nm, average piece footpath is 0.8-10 μm；It is dry that the graphene oxide is subjected to freezing
After dry, it is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture and carries out temperature programming processing, be cooled to room temperature, obtain mono-layer graphite
Alkene powder；
S03. the single-layer graphene powder is placed in spray mixer, the ethanol solution to contain dispersant is used as spraying
Agent, it is spray-dried under conditions of rotating speed is 300-1000rpm, temperature is 70-100 DEG C, treats that the spray drying finishes
Afterwards, continue to be uniformly mixed, obtain modified single-layer graphene powder；Then it is the single-layer graphene powder of the modification is molten
In organic solvent, ultrasonic disperse processing, single-layer graphene dispersion liquid is obtained；
Wherein, the method for described program heating treatment is：The graphene oxide after freeze-drying is warming up to 150-
300 DEG C, keep 0.5-12h；600-800 DEG C is warming up to again, keeps 0.5-12h；1000-1200 DEG C is continuously heating to, is kept
0.5-12h。
Specifically, in above-mentioned steps S01, natural flake graphite is used as raw material, after oxidized stripping, can obtain unit
The more graphene oxide of piece footpath oxy radical, so as to improve the dispersiveness in water.Preferably, the natural flake graphite
Particle diameter is 30-100 μm.The natural flake graphite of preferable particle size, more small pieces can be cut into by redox mode
The oxidized graphite flake in footpath, it is set subsequently to be more easy to peel off the graphene oxide for individual layer；And graphite oxy radical one after oxidation
As at the edge of graphite oxide, the natural scale piece footpath of preferable particle size is small, and the oxy radical in unit piece footpath is more, in water
Dispersiveness it is more preferable, be not easy to reunite after peeling off into graphene oxide.If the particle diameter of the natural flake graphite is excessive, graphite
Piece footpath is too big after oxidation, is not easily stripped into the graphene oxide of individual layer, it is difficult to ensure that the graphite subsequently prepared from technique
Alkene powder is individual layer.
Further, the natural flake graphite is subjected to oxidation processes, prepares graphite oxide slurry.It is specific preferable,
It is described prepare graphite oxide slurry method be：By the 30-100 μm of natural flake graphite of 1-5 parts and the sodium nitrate of 0.5-2.5 parts
It is dispersed in the concentrated sulfuric acid of 50-200 parts, the potassium permanganate of 3-15 parts is added under ice bath, after reacting 0.5-4h, oil bath heating
Continue to react 2-24h to 20-40 DEG C, add the deionized water of 200-500 parts, and keep oil bath temperature to react 2- at 70-100 DEG C
24h, hydrogen peroxide is eventually adding until reaction solution no longer produces bubble, stopping reaction；1000-2000 is added into mixed solution
5% hydrochloric acid solution of part, is centrifuged using filter cloth formula centrifuge, is washed, until slurry pH >=6, obtain graphite oxide slurry
Material.In the embodiment of the present invention, sulfuric acid is allowed to carry out abundant intercalation in graphite layers under cryogenic conditions (ice bath) first, then in
Oxidant carries out deep oxidation to graphite under the conditions of temperature, finally allows the compound of graphite layers to be hydrolyzed under the high temperature conditions.
The method provided in an embodiment of the present invention for preparing graphite oxide slurry, low temperature intercalation is abundant, and medium temperature reaction depth has aoxidized
Entirely, pyroreaction hydrolysis is thorough, is the effective way for ensureing to be formed larger spacing graphite oxide.The larger oxidation of this interlamellar spacing
Graphite is not only easy to other atom and molecules and inserted, and is easily peeled off into single-layer graphene, further to prepare individual layer stone
Black alkene lays the first stone.Further, the filter cloth mesh number of the filter cloth formula centrifuge is 8000-12000 mesh, and centrifugal speed is
3000-12000rpm.The graphene oxide sheet footpath that the filter cloth mesh number of the filter cloth formula centrifuge obtains according to embodiments of the present invention
Size is selected, and centrifugal speed is too low, is dehydrated not thoroughly, too high, is easily caused graphite oxide and is stacked too closely.
In above-mentioned steps S02, deionized water is added in the graphite oxide slurry, it is therefore intended that scattered graphite oxide
Alkene, it is easy to peel off.Preferably, the graphite oxide slurry and the mass ratio of the deionized water are 1-2:20-40, so as to ensure
Viscosity is not too large after lift-off for graphene oxide, to prevent from blocking high pressure homogenizer.Further, high pressure homogenizer is passed through
It is broken to peel off, it is repeated several times, until graphite oxide is completely exfoliated out.Specifically, until obtain average thickness for 0.4-0.7nm,
The graphene oxide that average piece footpath is 0.8-10 μm.To graphene oxide sheet footpath, the detection of thickness, atomic force microscopy can be passed through
Microscopy is surveyed.The embodiment of the present invention can be effectively peeled off graphite oxide using high pressure homogenizer, graphite oxide is broken for satisfaction one
The graphene oxide of stator footpath scope individual layer, thereby guaranteeing that the single-layer graphene of preparation still has good thermal conductivity
Energy.Because the particle diameter of graphite oxide of the embodiment of the present invention is very small, if the insufficient pressure of high pressure homogenizer, then act on list
Impulsive force above one graphite oxide particle is inadequate, is not enough to by graphite oxide peel off to crush, does not reach the effect of stripping.
In view of this, it is preferred that the pressure of the high pressure homogenizer is 20000-70000psi, and sufficiently oxidation stone is peeled off so as to obtain
Black alkene.
Then, to the graphene oxide carry out freeze-drying process, by way of direct subliming solvent to stripping after
Graphene oxide be dried, effectively prevent tradition filter or drying mode present in graphene oxide heap combinate form again
The problem of into graphite oxide structure, it ensure that the individual layer laminated structure of graphene oxide.Further, by the oxygen after freeze-drying
Graphite alkene is passed through nitrogen and hydrogen mixture at high temperature, carries out heating treatment.Specifically, the method for described program heating treatment is：
The graphene oxide after freeze-drying is warming up to 150-300 DEG C, keeps 0.5-12h；600-800 DEG C is warming up to again, is protected
Hold 0.5-12h；1000-1200 DEG C is continuously heating to, keeps 0.5-12h.The embodiment of the present invention uses the journey of segmented high-temperature reduction
Sequence heating treatment mode, makes graphene oxide progressively slough oxy radical in a gaseous form in Temperature Programmed Processes.By institute
It is gaseous state that oxy radical, which is stated, in the process sloughed, and therefore, will not cause the reunion of graphene oxide, and can further strut individual layer
Spacing between graphene powder.In addition, temperature programming processing mode can avoid disposably causing to heat-treat by temperature rise
Reaction it is too fast, in turn result in graphene powder fly away everywhere and the oxy radical of graphene oxide removing it is insufficient the problem of.
Meanwhile the embodiment of the present invention is passed through nitrogen and hydrogen mixture at high temperature, can will likely undecomposed oxy radical reduced simultaneously
Its defect is repaired, so that the single-layer graphene powder prepared has excellent electrical and thermal conductivity performance.
It is further preferred that being counted using the cumulative volume of the nitrogen and hydrogen mixture as 100%, the volume fraction content of hydrogen is 1-
8%；And/or the flow velocity of the nitrogen and hydrogen mixture is 10-100sccm.The volume fraction content of preferable hydrogen, nitrogen and hydrogen mixture
Flow velocity, the oxy radical of remaining under the premise that security is guaranteed, can be effectively reduced, repairs graphene defect.If the hydrogen
Volume fraction content is too low, then the recovery time is long, and reaction is insufficient, it is difficult to realizes the effect above；If the volume integral of the hydrogen
Number too high levels, easily trigger potential safety hazard, particularly in the case of high temperature furnace seal is imperfect.If the nitrogen hydrogen mixes
It is too small to close the flow velocity of gas, then it is excessive in the flow velocity of nitrogen and hydrogen mixture described in unit, hydrogen, in the time with graphite oxide alkene reaction
Hydrogen total amount can reduce, it will extend duration of ventilation；If the flow velocity of the nitrogen and hydrogen mixture is too fast, contacted with graphene oxide
Time is too short, and reaction is not abundant enough.
In step S03, the single-layer graphene powder is placed in spray mixer, made with the ethanol solution containing dispersant
For spray, it is spray-dried under conditions of rotating speed is 300-1000rpm, temperature is 70-100 DEG C.The embodiment of the present invention
By single-layer graphene powder in the case where heating high-speed stirred, atomizing adds dispersant, and dispersant can be made uniformly attached
In single-layer graphene powder surface, so as to ensure that final step graphene will not also cause to reunite.Carried in the embodiment of the present invention
Under the speed conditions of confession, dispersant contacts fully with the single-layer graphene powder, does not easily cause reunion；It is simultaneously as described
Ethyl alcohol boiling point is about 78 DEG C, therefore single-layer graphene powder own temperature is not lower than 70 DEG C, otherwise can form local reunion.
Preferably, the weight ratio of the single-layer graphene powder, dispersant and ethanol is 100-200:1-5:10-20.Should
Preferable ratio, it is ensured that the partially wetted graphene powder of dispersant, prevent dispersant from coating single-layer graphene powder completely
When, cause graphene thermal conductivity to decline.
It is further preferred that the dispersant is phthalic acid ester, octadecanoid acid, γ-methacryloxypropyl
Trimethoxy silane, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanium
At least one of acid esters, the oleic acid acyloxy of isopropyl two (dioctyl phosphoric acid acyloxy) titanate esters.Preferable above-mentioned dispersant
It is stronger with the affinity of the graphene, and be easier to disperse in organic solvent, single-layer graphene is easier in a solvent
It is wetted, it is not easy to reunite, so as to form uniform and stable disperse.After to be spray dried, continue to be uniformly mixed, the time
Preferably 10-60min.Stop spraying homogenizer, the single-layer graphene powder after being modified (is handled by dispersant
Single-layer graphene).
Further, the single-layer graphene powder of the modification is dissolved in organic solvent, ultrasonic disperse processing, the time is excellent
Elect 5~30min as, obtain the dispersion liquid of single-layer graphene.Preferably, the organic solvent be ethanol, acetone, tetrahydrofuran,
At least one of dimethylbenzene, ether, cyclohexanol, ethyl acetate.The preferable organic solvent, can effective dispersed graphite alkene powder
Body, obtain uniform and stable dispersion liquid.
The preparation method of single-layer graphene dispersion liquid provided in an embodiment of the present invention, ensure that preparation from process route
Graphene powder is single-layer graphene, and adds dispersant in single-layer graphene powder in a manner of spraying, is avoided directly
The problem of graphene and dispersant are added in solvent so as to cause to reunite.The embodiment of the present invention is by reasonably controlling stone simultaneously
Black alkene piece footpath size and optimization high temperature reduction process, make the graphene dispersing solution electrical and thermal conductivity performance of preparation more excellent.Specifically
,
First, the natural flake graphite in present invention selection smaller pieces footpath is raw material, is cut into by redox mode
The oxidized graphite flake of more small flake diameter, it is set subsequently to be more easy to peel off the graphene oxide for individual layer.Because graphite contains after oxidation
Oxygen groups are at the edge of graphite oxide, and therefore, the natural scale in smaller pieces footpath, the oxy radical in unit piece footpath is more, in water
It is dispersed more preferable, it is not easy to reunite after peeling off into graphene oxide, after oxidized stripping, unit piece footpath oxygen-containing group can be obtained
The more graphene oxide of group, so as to improve the dispersiveness in water.
Secondly, on the basis of natural flake graphite is used as raw material, the embodiment of the present invention uses high pressure homogenizer by oxygen
Graphite is peeled off, and is broken for the graphene oxide of individual layer, and controls the graphene oxide of individual layer in the range of a stator footpath,
It is possible thereby to the single-layer graphene for ensureing to prepare still has good thermal conductivity.
Again, the graphene oxide after stripping is dried using freeze-drying mode for the embodiment of the present invention, by straight
Graphene oxide after stripping is dried the mode for connecing subliming solvent, it is possible to prevente effectively from tradition suction filtration or drying mode
Existing graphene oxide piles up the problem of forming graphite oxide structure again.The embodiment of the present invention is using segmented high-temperature reduction
Temperature programming processing mode, graphene oxide is set progressively to slough oxy radical in a gaseous form in Temperature Programmed Processes.Due to
The oxy radical is gaseous state in the process sloughed, and therefore, will not cause the reunion of graphene oxide, and can further strut list
Spacing between layer graphene powder.In addition, temperature programming processing mode can avoid that temperature rise disposably is caused into heat also
Original reaction is too fast, in turn results in that graphene powder is flown away everywhere and the removing of the oxy radical of graphene oxide insufficient is asked
Topic.Simultaneously be passed through nitrogen and hydrogen mixture at high temperature, can will likely undecomposed oxy radical reduced and repair its defect,
So that the single-layer graphene powder prepared has excellent electrical and thermal conductivity performance.
In addition, the embodiment of the present invention by single-layer graphene powder in the case where heating high-speed stirred, atomizing add point
Powder, dispersant can be made to be uniformly adhered to single-layer graphene powder surface, so as to ensure that final step graphene also will not
Cause to reunite.
Single-layer graphene dispersion liquid prepared by the embodiment of the present invention, ensure that the graphene powder of preparation from process route
For single-layer graphene, and dispersant is added in single-layer graphene powder in a manner of spraying, avoid directly by graphene with
The problem of dispersant is added in solvent so as to cause to reunite, while the embodiment of the present invention is by reasonably controlling graphene film footpath big
Small and optimization high temperature reduction process, makes the graphene dispersing solution electrical and thermal conductivity performance of preparation more excellent, the present invention is implemented in addition
Example enables the graphene of individual layer scattered more stable in a solvent by preferred suitable dispersant.
And the embodiment of the present invention additionally provides a kind of single-layer graphene dispersion liquid, the single-layer graphene dispersion liquid by
The above method prepares.
Single-layer graphene dispersion liquid individual layer rate prepared by the embodiment of the present invention is high, and electrical and thermal conductivity performance is excellent, can high concentration
Stable dispersion, with polymer-polymer miscibility it is good the advantages that, can be widely applied to e-inks, film, electronic radiation and composite wood
The fields such as material, effective path is provided for the commercial application of graphene.
Illustrated with reference to specific embodiment.
Embodiment 1
A kind of preparation method of single-layer graphene powder dispersion, comprises the following steps:
S11. the preparation of graphite oxide
The sodium nitrate of 1g 30 μm of natural flake graphites and 0.5g is dispersed in the 50g concentrated sulfuric acid, added under ice bath
3g potassium permanganate, after reacting 0.5h, bath of changing oil is warming up to 20 DEG C and continues to react 2h, adds 200g deionized water, and protect
Hold oil bath temperature and react 2h at 70 DEG C, be eventually adding 20% hydrogen peroxide until reaction solution no longer produces bubble, stop reaction,
1000g 5% hydrochloric acid solution is added into mixed solution, filter cloth formula centrifuge is reused and is dried, filter cloth formula centrifuge
Filter cloth mesh number be 8000 mesh, centrifugal speed 3000rpm, then the slurry of drying is washed using 1000g deionized water,
Dry again, washing repeatedly is dried until slurry pH >=6, obtain graphite oxide slurry.
S12. the preparation of single-layer graphene
By 10g graphite oxide slurry and 200g deionized water, peeled off by high-pressure homogeneous crusher machine, high pressure homogenizer
Pressure be 20000psi, be repeated several times, until graphite oxide is completely exfoliated out, exist through AFM detection average thickness
Then the graphene oxide peeled off is freeze-dried by 0.4~0.7nm, average piece footpath untill 0.8~10 μm, then will freezing
Dried graphene oxide is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture, the volume integral of the hydrogen content of nitrogen and hydrogen mixture
Number is 1%, and the flow velocity of nitrogen and hydrogen mixture is 10sccm, is warming up to 150 DEG C, keeps 0.5h, then is warming up to 600 DEG C, keeps 0.5h,
1000 DEG C are continuously heating to, 0.5h is kept, naturally cools to room temperature, obtain single-layer graphene powder.
S13. single-layer graphene dispersion liquid is prepared
100g single-layer graphene powder is placed in spraying homogenizer, 1g phthalic acid ester is dissolved in 10g's
In ethanol, the sprayer unit of spraying homogenizer is placed in, starts spraying homogenizer, adjustment of rotational speed to 300rpm, temperature
Degree rises to 70 DEG C, is then turned on sprayer unit, after the solution spraying for treating dispersant, continues to stir 10min, stops spraying at a high speed
Mixer, the single-layer graphene powder after being modified, then modified single-layer graphene powder is dissolved in ethanol, ultrasound
Scattered 5min, obtains the dispersion liquid of single-layer graphene.
Embodiment 2
A kind of preparation method of single-layer graphene powder dispersion, comprises the following steps:
S21. the preparation of graphite oxide
The sodium nitrate of 2.5g 50 μm of natural flake graphites and 1.5g is dispersed in the 125g concentrated sulfuric acid, added under ice bath
Enter 9g potassium permanganate, after reacting 2h, bath of changing oil is warming up to 30 DEG C and continues to react 14h, adds 350g deionized water, and protect
Hold oil bath temperature and react 14h at 85 DEG C, be eventually adding 20% hydrogen peroxide until reaction solution no longer produces bubble, stop anti-
Should, 1500g 5% hydrochloric acid solution is added into mixed solution, filter cloth formula centrifuge is reused and is dried, the centrifugation of filter cloth formula
The filter cloth mesh number of machine is 10000 mesh, centrifugal speed 8000rpm, is then washed the slurry of drying using 1500g deionization
Wash, dry again, washing repeatedly is dried until slurry pH >=6, obtain graphite oxide slurry.
S22. the preparation of single-layer graphene
By 15g graphite oxide slurry and 300g deionized water, peeled off by high-pressure homogeneous crusher machine, high pressure homogenizer
Pressure be 50000psi, be repeated several times, until graphite oxide is completely exfoliated out, exist through AFM detection average thickness
Then the graphene oxide peeled off is freeze-dried by 0.4~0.7nm, average piece footpath untill 0.8~10 μm, then will freezing
Dried graphene oxide is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture, the volume integral of the hydrogen content of nitrogen and hydrogen mixture
Number is 5%, and the flow velocity of nitrogen and hydrogen mixture is 50sccm, is warming up to 200 DEG C, keeps 6h, then is warming up to 700 DEG C, keeps 6h, is continued
1100 DEG C are warming up to, 6h is kept, naturally cools to room temperature, obtain single-layer graphene powder.
S23. single-layer graphene dispersion liquid is prepared
150g single-layer graphene powder is placed in spraying homogenizer, 3g phthalic acid ester is dissolved in 15g's
In ethanol, the sprayer unit of spraying homogenizer is placed in, starts spraying homogenizer, adjustment of rotational speed to 600rpm, temperature
Degree rises to 80 DEG C, is then turned on sprayer unit, after the solution spraying for treating dispersant, continues to stir 40min, stops spraying at a high speed
Mixer, the single-layer graphene powder after being modified, then modified single-layer graphene powder is dissolved in acetone, ultrasound
Scattered 15min, obtains the dispersion liquid of single-layer graphene.
Embodiment 3
A kind of preparation method of single-layer graphene powder dispersion, comprises the following steps:
S31. the preparation of graphite oxide
The sodium nitrate of 5g 100 μm of natural flake graphites and 2.5g is dispersed in the 200g concentrated sulfuric acid, added under ice bath
Enter 15g potassium permanganate, after reacting 4h, bath of changing oil is warming up to 40 DEG C and continues to react 24h, adds 500g deionized water, and
Keep oil bath temperature 100 DEG C react 24h, be eventually adding 20% hydrogen peroxide until reaction solution no longer produce bubble, stop
Reaction, into mixed solution addition 2000g 5% hydrochloric acid solution, reuse filter cloth formula centrifuge and dried, filter cloth formula from
The filter cloth mesh number of scheming is 12000 mesh, centrifugal speed 12000rpm, then the slurry of drying is used to 2000g deionization
Water washing, dry again, washing repeatedly is dried until slurry pH >=6, obtain graphite oxide slurry.
S32. the preparation of single-layer graphene
By 20g graphite oxide slurry and 400g deionized water, peeled off by high-pressure homogeneous crusher machine, high pressure homogenizer
Pressure be 70000psi, be repeated several times, until graphite oxide is completely exfoliated out, exist through AFM detection average thickness
Then the graphene oxide peeled off is freeze-dried by 0.4~0.7nm, average piece footpath untill 0.8~10 μm, then will freezing
Dried graphene oxide is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture, the volume integral of the hydrogen content of nitrogen and hydrogen mixture
Number is 8%, and the flow velocity of nitrogen and hydrogen mixture is 100sccm, is warming up to 300 DEG C, keeps 12h, then is warming up to 800 DEG C, keeps 12h,
1200 DEG C are continuously heating to, 12h is kept, naturally cools to room temperature, obtain single-layer graphene powder.
S33. single-layer graphene dispersion liquid is prepared
200g single-layer graphene powder is placed in spraying homogenizer, 5g octadecanoid acid is dissolved in 20g ethanol
In, the sprayer unit of spraying homogenizer is placed in, starts spraying homogenizer, adjustment of rotational speed to 1000rpm, temperature liter
To 100 DEG C, sprayer unit is then turned on, after the solution spraying for treating dispersant, continues to stir 60min, stops spraying high-speed stirring
Machine is mixed, the single-layer graphene powder after being modified, then modified single-layer graphene powder is dissolved in tetrahydrofuran, is surpassed
Sound disperses 30min, obtains the dispersion liquid of single-layer graphene.
Embodiment 4
A kind of preparation method of single-layer graphene powder dispersion, comprises the following steps:
S41. the preparation of graphite oxide
The sodium nitrate of 1g 30 μm of natural flake graphites and 0.5g is dispersed in the 50g concentrated sulfuric acid, added under ice bath
3g potassium permanganate, after reacting 0.5h, bath of changing oil is warming up to 20 DEG C and continues to react 2h, adds 200g deionized water, and protect
Hold oil bath temperature and react 2h at 70 DEG C, be eventually adding 20% hydrogen peroxide until reaction solution no longer produces bubble, stop reaction,
1000g 5% hydrochloric acid solution is added into mixed solution, filter cloth formula centrifuge is reused and is dried, filter cloth formula centrifuge
Filter cloth mesh number be 8000 mesh, centrifugal speed 3000rpm, then the slurry of drying is washed using 1000g deionized water,
Dry again, washing repeatedly is dried until slurry pH >=6, obtain graphite oxide slurry.
S42. the preparation of single-layer graphene
By 10g graphite oxide slurry and 200g deionized water, peeled off by high-pressure homogeneous crusher machine, high pressure homogenizer
Pressure be 20000psi, be repeated several times, until graphite oxide is completely exfoliated out, exist through AFM detection average thickness
Then the graphene oxide peeled off is freeze-dried by 0.4~0.7nm, average piece footpath untill 0.8~10 μm, then will freezing
Dried graphene oxide is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture, the volume integral of the hydrogen content of nitrogen and hydrogen mixture
Number is 1%, and the flow velocity of nitrogen and hydrogen mixture is 10sccm, is warming up to 150 DEG C, keeps 0.5h, then is warming up to 600 DEG C, keeps 0.5h,
1000 DEG C are continuously heating to, 0.5h is kept, naturally cools to room temperature, obtain single-layer graphene powder.
S43. single-layer graphene dispersion liquid is prepared
100g single-layer graphene powder is placed in spraying homogenizer, 1g octadecanoid acid is dissolved in 10g ethanol
In, the sprayer unit of spraying homogenizer is placed in, starts spraying homogenizer, adjustment of rotational speed to 300rpm, temperature liter
To 70 DEG C, sprayer unit is then turned on, after the solution spraying for treating dispersant, continues to stir 10min, stops spraying high-speed stirred
Machine, the single-layer graphene powder after being modified, then modified single-layer graphene powder is dissolved in tetrahydrofuran, ultrasound
Scattered 5min, obtains the dispersion liquid of single-layer graphene.
Embodiment 5
A kind of preparation method of single-layer graphene powder dispersion, comprises the following steps:
S51. the preparation of graphite oxide
The sodium nitrate of 2.5g 50 μm of natural flake graphites and 1.5g is dispersed in the 125g concentrated sulfuric acid, added under ice bath
Enter 9g potassium permanganate, after reacting 2h, bath of changing oil is warming up to 30 DEG C and continues to react 14h, adds 350g deionized water, and protect
Hold oil bath temperature and react 14h at 85 DEG C, be eventually adding 20% hydrogen peroxide until reaction solution no longer produces bubble, stop anti-
Should, 1500g 5% hydrochloric acid solution is added into mixed solution, filter cloth formula centrifuge is reused and is dried, the centrifugation of filter cloth formula
The filter cloth mesh number of machine is 10000 mesh, centrifugal speed 8000rpm, is then washed the slurry of drying using 1500g deionization
Wash, dry again, washing repeatedly is dried until slurry pH >=6, obtain graphite oxide slurry.
S52. the preparation of single-layer graphene
By 15g graphite oxide slurry and 300g deionized water, peeled off by high-pressure homogeneous crusher machine, high pressure homogenizer
Pressure be 50000psi, be repeated several times, until graphite oxide is completely exfoliated out, exist through AFM detection average thickness
Then the graphene oxide peeled off is freeze-dried by 0.4~0.7nm, average piece footpath untill 0.8~10 μm, then will freezing
Dried graphene oxide is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture, the volume integral of the hydrogen content of nitrogen and hydrogen mixture
Number is 5%, and the flow velocity of nitrogen and hydrogen mixture is 50sccm, is warming up to 200 DEG C, keeps 6h, then is warming up to 700 DEG C, keeps 6h, is continued
1100 DEG C are warming up to, 6h is kept, naturally cools to room temperature, obtain single-layer graphene powder.
S53. single-layer graphene dispersion liquid is prepared
150g single-layer graphene powder is placed in spraying homogenizer, by 3g γ-methacryloxypropyl
Trimethoxy silane is dissolved in 15g ethanol, is placed in the sprayer unit of spraying homogenizer, starts spraying high-speed stirred
Machine, adjustment of rotational speed to 600rpm, temperature rise to 80 DEG C, are then turned on sprayer unit, after the solution spraying for treating dispersant, continue
40min is stirred, stops spraying homogenizer, the single-layer graphene powder after being modified, then by modified individual layer stone
Black alkene powder is dissolved in dimethylbenzene, ultrasonic disperse 15min, obtains the dispersion liquid of single-layer graphene.
Embodiment 6
A kind of preparation method of single-layer graphene powder dispersion, comprises the following steps:
S61. the preparation of graphite oxide
The sodium nitrate of 5g 100 μm of natural flake graphites and 2.5g is dispersed in the 200g concentrated sulfuric acid, added under ice bath
Enter 15g potassium permanganate, after reacting 4h, bath of changing oil is warming up to 40 DEG C and continues to react 24h, adds 500g deionized water, and
Keep oil bath temperature 100 DEG C react 24h, be eventually adding 20% hydrogen peroxide until reaction solution no longer produce bubble, stop
Reaction, into mixed solution addition 2000g 5% hydrochloric acid solution, reuse filter cloth formula centrifuge and dried, filter cloth formula from
The filter cloth mesh number of scheming is 12000 mesh, centrifugal speed 12000rpm, then the slurry of drying is used to 2000g deionization
Water washing, dry again, washing repeatedly is dried until slurry pH >=6, obtain graphite oxide slurry.
S62. the preparation of single-layer graphene
By 20g graphite oxide slurry and 400g deionized water, peeled off by high-pressure homogeneous crusher machine, high pressure homogenizer
Pressure be 70000psi, be repeated several times, until graphite oxide is completely exfoliated out, exist through AFM detection average thickness
Then the graphene oxide peeled off is freeze-dried by 0.4~0.7nm, average piece footpath untill 0.8~10 μm, then will freezing
Dried graphene oxide is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture, the volume integral of the hydrogen content of nitrogen and hydrogen mixture
Number is 8%, and the flow velocity of nitrogen and hydrogen mixture is 100sccm, is warming up to 300 DEG C, keeps 12h, then is warming up to 800 DEG C, keeps 12h,
1200 DEG C are continuously heating to, 12h is kept, naturally cools to room temperature, obtain single-layer graphene powder.
S63. single-layer graphene dispersion liquid is prepared
200g single-layer graphene powder is placed in spraying homogenizer, by 5g γ-methacryloxypropyl
Trimethoxy silane is dissolved in 20g ethanol, is placed in the sprayer unit of spraying homogenizer, starts spraying high-speed stirred
Machine, adjustment of rotational speed to 1000rpm, temperature rise to 100 DEG C, are then turned on sprayer unit, after the solution spraying for treating dispersant, after
Continuous stirring 60min, stops spraying homogenizer, the single-layer graphene powder after being modified, then by modified individual layer
Graphene powder is dissolved in dimethylbenzene, ultrasonic disperse 30min, obtains the dispersion liquid of single-layer graphene.
Embodiment 7
A kind of preparation method of single-layer graphene powder dispersion, comprises the following steps:
S71. the preparation of graphite oxide
The sodium nitrate of 1g 30 μm of natural flake graphites and 0.5g is dispersed in the 50g concentrated sulfuric acid, added under ice bath
3g potassium permanganate, after reacting 0.5h, bath of changing oil is warming up to 20 DEG C and continues to react 2h, adds 200g deionized water, and protect
Hold oil bath temperature and react 2h at 70 DEG C, be eventually adding 20% hydrogen peroxide until reaction solution no longer produces bubble, stop reaction,
1000g 5% hydrochloric acid solution is added into mixed solution, filter cloth formula centrifuge is reused and is dried, filter cloth formula centrifuge
Filter cloth mesh number be 8000 mesh, centrifugal speed 3000rpm, then the slurry of drying is washed using 1000g deionized water,
Dry again, washing repeatedly is dried until slurry pH >=6, obtain graphite oxide slurry.
S72. the preparation of single-layer graphene
By 10g graphite oxide slurry and 200g deionized water, peeled off by high-pressure homogeneous crusher machine, high pressure homogenizer
Pressure be 20000psi, be repeated several times, until graphite oxide is completely exfoliated out, exist through AFM detection average thickness
Then the graphene oxide peeled off is freeze-dried by 0.4~0.7nm, average piece footpath untill 0.8~10 μm, then will freezing
Dried graphene oxide is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture, the volume integral of the hydrogen content of nitrogen and hydrogen mixture
Number is 1%, and the flow velocity of nitrogen and hydrogen mixture is 10sccm, is warming up to 150 DEG C, keeps 0.5h, then is warming up to 600 DEG C, keeps 0.5h,
1000 DEG C are continuously heating to, 0.5h is kept, naturally cools to room temperature, obtain single-layer graphene powder.
S73. single-layer graphene dispersion liquid is prepared
100g single-layer graphene powder is placed in spraying homogenizer, by the 1g (dioctylphyrophosphoric acid of isopropyl three
Acyloxy) titanate esters are dissolved in 10g ethanol, the sprayer unit for the homogenizer that is placed in spraying, start spraying high-speed stirred
Machine, adjustment of rotational speed to 300rpm, temperature rise to 70 DEG C, are then turned on sprayer unit, after the solution spraying for treating dispersant, continue
10min is stirred, stops spraying homogenizer, the single-layer graphene powder after being modified, then by modified individual layer stone
Black alkene powder is dissolved in ether, ultrasonic disperse 5min, obtains the dispersion liquid of single-layer graphene.
Embodiment 8
A kind of preparation method of single-layer graphene powder dispersion, comprises the following steps:
S81. the preparation of graphite oxide
The sodium nitrate of 2.5g 50 μm of natural flake graphites and 1.5g is dispersed in the 125g concentrated sulfuric acid, added under ice bath
Enter 9g potassium permanganate, after reacting 2h, bath of changing oil is warming up to 30 DEG C and continues to react 14h, adds 350g deionized water, and protect
Hold oil bath temperature and react 14h at 85 DEG C, be eventually adding 20% hydrogen peroxide until reaction solution no longer produces bubble, stop anti-
Should, 1500g 5% hydrochloric acid solution is added into mixed solution, filter cloth formula centrifuge is reused and is dried, the centrifugation of filter cloth formula
The filter cloth mesh number of machine is 10000 mesh, centrifugal speed 8000rpm, is then washed the slurry of drying using 1500g deionization
Wash, dry again, washing repeatedly is dried until slurry pH >=6, obtain graphite oxide slurry.
S82. the preparation of single-layer graphene
By 15g graphite oxide slurry and 300g deionized water, peeled off by high-pressure homogeneous crusher machine, high pressure homogenizer
Pressure be 50000psi, be repeated several times, until graphite oxide is completely exfoliated out, exist through AFM detection average thickness
Then the graphene oxide peeled off is freeze-dried by 0.4~0.7nm, average piece footpath untill 0.8~10 μm, then will freezing
Dried graphene oxide is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture, the volume integral of the hydrogen content of nitrogen and hydrogen mixture
Number is 5%, and the flow velocity of nitrogen and hydrogen mixture is 50sccm, is warming up to 200 DEG C, keeps 6h, then is warming up to 700 DEG C, keeps 6h, is continued
1100 DEG C are warming up to, 6h is kept, naturally cools to room temperature, obtain single-layer graphene powder.
S83. single-layer graphene dispersion liquid is prepared
150g single-layer graphene powder is placed in spraying homogenizer, by the 3g (dioctylphyrophosphoric acid of isopropyl three
Acyloxy) titanate esters are dissolved in 15g ethanol, the sprayer unit for the homogenizer that is placed in spraying, start spraying high-speed stirred
Machine, adjustment of rotational speed to 600rpm, temperature rise to 80 DEG C, are then turned on sprayer unit, after the solution spraying for treating dispersant, continue
40min is stirred, stops spraying homogenizer, the single-layer graphene powder after being modified, then by modified individual layer stone
Black alkene powder is dissolved in ether, ultrasonic disperse 15min, obtains the dispersion liquid of single-layer graphene.
Embodiment 9
A kind of preparation method of single-layer graphene powder dispersion, comprises the following steps:
S91. the preparation of graphite oxide
The sodium nitrate of 5g 100 μm of natural flake graphites and 2.5g is dispersed in the 200g concentrated sulfuric acid, added under ice bath
Enter 15g potassium permanganate, after reacting 4h, bath of changing oil is warming up to 40 DEG C and continues to react 24h, adds 500g deionized water, and
Keep oil bath temperature 100 DEG C react 24h, be eventually adding 20% hydrogen peroxide until reaction solution no longer produce bubble, stop
Reaction, into mixed solution addition 2000g 5% hydrochloric acid solution, reuse filter cloth formula centrifuge and dried, filter cloth formula from
The filter cloth mesh number of scheming is 12000 mesh, centrifugal speed 12000rpm, then the slurry of drying is used to 2000g deionization
Water washing, dry again, washing repeatedly is dried until slurry pH >=6, obtain graphite oxide slurry.
S92. the preparation of single-layer graphene
By 20g graphite oxide slurry and 400g deionized water, peeled off by high-pressure homogeneous crusher machine, high pressure homogenizer
Pressure be 70000psi, be repeated several times, until graphite oxide is completely exfoliated out, exist through AFM detection average thickness
Then the graphene oxide peeled off is freeze-dried by 0.4~0.7nm, average piece footpath untill 0.8~10 μm, then will freezing
Dried graphene oxide is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture, the volume integral of the hydrogen content of nitrogen and hydrogen mixture
Number is 8%, and the flow velocity of nitrogen and hydrogen mixture is 100sccm, is warming up to 300 DEG C, keeps 12h, then is warming up to 800 DEG C, keeps 12h,
1200 DEG C are continuously heating to, 12h is kept, naturally cools to room temperature, obtain single-layer graphene powder.
S93. single-layer graphene dispersion liquid is prepared
200g single-layer graphene powder is placed in spraying homogenizer, by 5g (the dioctyl phosphoric acid acyl of isopropyl three
Epoxide) titanate esters are dissolved in 20g ethanol, the sprayer unit for the homogenizer that is placed in spraying, start spraying homogenizer,
For adjustment of rotational speed to 1000rpm, temperature rises to 100 DEG C, is then turned on sprayer unit, after the solution spraying for treating dispersant, continues
60min is stirred, stops spraying homogenizer, the single-layer graphene powder after being modified, then by modified individual layer stone
Black alkene powder is dissolved in cyclohexanol, ultrasonic disperse 30min, obtains the dispersion liquid of single-layer graphene.
Embodiment 10
A kind of preparation method of single-layer graphene powder dispersion, comprises the following steps:
S101. the preparation of graphite oxide
The sodium nitrate of 1g 30 μm of natural flake graphites and 0.5g is dispersed in the 50g concentrated sulfuric acid, added under ice bath
3g potassium permanganate, after reacting 0.5h, bath of changing oil is warming up to 20 DEG C and continues to react 2h, adds 200g deionized water, and protect
Hold oil bath temperature and react 2h at 70 DEG C, be eventually adding 20% hydrogen peroxide until reaction solution no longer produces bubble, stop reaction,
1000g 5% hydrochloric acid solution is added into mixed solution, filter cloth formula centrifuge is reused and is dried, filter cloth formula centrifuge
Filter cloth mesh number be 8000 mesh, centrifugal speed 3000rpm, then the slurry of drying is washed using 1000g deionized water,
Dry again, washing repeatedly is dried until slurry pH >=6, obtain graphite oxide slurry.
S102. the preparation of single-layer graphene
By 10g graphite oxide slurry and 200g deionized water, peeled off by high-pressure homogeneous crusher machine, high pressure homogenizer
Pressure be 20000psi, be repeated several times, until graphite oxide is completely exfoliated out, exist through AFM detection average thickness
Then the graphene oxide peeled off is freeze-dried by 0.4~0.7nm, average piece footpath untill 0.8~10 μm, then will freezing
Dried graphene oxide is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture, the volume integral of the hydrogen content of nitrogen and hydrogen mixture
Number is 1%, and the flow velocity of nitrogen and hydrogen mixture is 10sccm, is warming up to 150 DEG C, keeps 0.5h, then is warming up to 600 DEG C, keeps 0.5h,
1000 DEG C are continuously heating to, 0.5h is kept, naturally cools to room temperature, obtain single-layer graphene powder.
S103. single-layer graphene dispersion liquid is prepared
100g single-layer graphene powder is placed in spraying homogenizer, by 1g (the dioctyl phosphoric acid acyl of isopropyl three
Epoxide) titanate esters are dissolved in 10g ethanol, the sprayer unit for the homogenizer that is placed in spraying, start spraying homogenizer,
For adjustment of rotational speed to 300rpm, temperature rises to 70 DEG C, is then turned on sprayer unit, after the solution spraying for treating dispersant, continues to stir
10min is mixed, stops spraying homogenizer, the single-layer graphene powder after being modified, then by modified mono-layer graphite
Alkene powder is dissolved in cyclohexanol, ultrasonic disperse 5min, obtains the dispersion liquid of single-layer graphene.
Embodiment 11
A kind of preparation method of single-layer graphene powder dispersion, comprises the following steps:
S111. the preparation of graphite oxide
The sodium nitrate of 2.5g 50 μm of natural flake graphites and 1.5g is dispersed in the 125g concentrated sulfuric acid, added under ice bath
Enter 9g potassium permanganate, after reacting 2h, bath of changing oil is warming up to 30 DEG C and continues to react 14h, adds 350g deionized water, and protect
Hold oil bath temperature and react 14h at 85 DEG C, be eventually adding 20% hydrogen peroxide until reaction solution no longer produces bubble, stop anti-
Should, 1500g 5% hydrochloric acid solution is added into mixed solution, filter cloth formula centrifuge is reused and is dried, the centrifugation of filter cloth formula
The filter cloth mesh number of machine is 10000 mesh, centrifugal speed 8000rpm, is then washed the slurry of drying using 1500g deionization
Wash, dry again, washing repeatedly is dried until slurry pH >=6, obtain graphite oxide slurry.
S112. the preparation of single-layer graphene
By 15g graphite oxide slurry and 300g deionized water, peeled off by high-pressure homogeneous crusher machine, high pressure homogenizer
Pressure be 50000psi, be repeated several times, until graphite oxide is completely exfoliated out, exist through AFM detection average thickness
Then the graphene oxide peeled off is freeze-dried by 0.4~0.7nm, average piece footpath untill 0.8~10 μm, then will freezing
Dried graphene oxide is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture, the volume integral of the hydrogen content of nitrogen and hydrogen mixture
Number is 5%, and the flow velocity of nitrogen and hydrogen mixture is 50sccm, is warming up to 200 DEG C, keeps 6h, then is warming up to 700 DEG C, keeps 6h, is continued
1100 DEG C are warming up to, 6h is kept, naturally cools to room temperature, obtain single-layer graphene powder.
S113. single-layer graphene dispersion liquid is prepared
150g single-layer graphene powder is placed in spraying homogenizer, by the 3g oleic acid acyloxy (two of isopropyl two
Octylphosphonic acid acyloxy) titanate esters are dissolved in 15g ethanol, the sprayer unit for the homogenizer that is placed in spraying, start spraying
Homogenizer, adjustment of rotational speed to 600rpm, temperature rise to 80 DEG C, are then turned on sprayer unit, treat that the solution of dispersant has been sprayed
Bi Hou, continue to stir 40min, stop spraying homogenizer, the single-layer graphene powder after being modified then will be modified
Single-layer graphene powder be dissolved in ethyl acetate, ultrasonic disperse 15min, obtain the dispersion liquid of single-layer graphene.
Embodiment 12
A kind of preparation method of single-layer graphene powder dispersion, comprises the following steps:
S121. the preparation of graphite oxide
The sodium nitrate of 5g 100 μm of natural flake graphites and 2.5g is dispersed in the 200g concentrated sulfuric acid, added under ice bath
Enter 15g potassium permanganate, after reacting 4h, bath of changing oil is warming up to 40 DEG C and continues to react 24h, adds 500g deionized water, and
Keep oil bath temperature 100 DEG C react 24h, be eventually adding 20% hydrogen peroxide until reaction solution no longer produce bubble, stop
Reaction, into mixed solution addition 2000g 5% hydrochloric acid solution, reuse filter cloth formula centrifuge and dried, filter cloth formula from
The filter cloth mesh number of scheming is 12000 mesh, centrifugal speed 12000rpm, then the slurry of drying is used to 2000g deionization
Water washing, dry again, washing repeatedly is dried until slurry pH >=6, obtain graphite oxide slurry.
S122. the preparation of single-layer graphene
By 20g graphite oxide slurry and 400g deionized water, peeled off by high-pressure homogeneous crusher machine, high pressure homogenizer
Pressure be 70000psi, be repeated several times, until graphite oxide is completely exfoliated out, exist through AFM detection average thickness
Then the graphene oxide peeled off is freeze-dried by 0.4~0.7nm, average piece footpath untill 0.8~10 μm, then will freezing
Dried graphene oxide is placed in atmosphere high temperature furnace, is passed through nitrogen and hydrogen mixture, the volume integral of the hydrogen content of nitrogen and hydrogen mixture
Number is 8%, and the flow velocity of nitrogen and hydrogen mixture is 100sccm, is warming up to 300 DEG C, keeps 12h, then is warming up to 800 DEG C, keeps 12h,
1200 DEG C are continuously heating to, 12h is kept, naturally cools to room temperature, obtain single-layer graphene powder.
S123. single-layer graphene dispersion liquid is prepared
200g single-layer graphene powder is placed in spraying homogenizer, by the 5g oleic acid acyloxy (two of isopropyl two
Octylphosphonic acid acyloxy) titanate esters are dissolved in 20g ethanol, the sprayer unit for the homogenizer that is placed in spraying, start spraying
Homogenizer, adjustment of rotational speed to 1000rpm, temperature rise to 100 DEG C, are then turned on sprayer unit, treat the solution spraying of dispersant
After, continue to stir 60min, stop spraying homogenizer, the single-layer graphene powder after being modified, then will change
The single-layer graphene powder of property is dissolved in ethyl acetate, ultrasonic disperse 30min, obtains the dispersion liquid of single-layer graphene.
Single-layer graphene powder dispersion prepared by the embodiment of the present invention carries out performance test, as a result shows, using this
Individual layer rate >=95% of single-layer graphene dispersion liquid single-layer graphene prepared by inventive embodiments method, concentration >=3mg/mL,
And it can stablize and preserve more than 3 months.
The preferred embodiment of the embodiment of the present invention is the foregoing is only, is not intended to limit the invention embodiment, it is all
All any modification, equivalent and improvement made within the spirit and principle of the embodiment of the present invention etc., should be included in this hair
Within the protection domain of bright embodiment.
Claims (10)
1. a kind of preparation method of single-layer graphene dispersion liquid, it is characterised in that comprise the following steps：
Natural flake graphite is provided, oxidation processes is carried out, prepares graphite oxide slurry；
Deionized water is added in the graphite oxide slurry, is peeled off by high-pressure homogeneous crusher machine, until obtaining average thickness
The graphene oxide for being 0.8-10 μm for 0.4-0.7nm, average piece footpath；After the graphene oxide is freeze-dried, put
In atmosphere high temperature furnace, it is passed through nitrogen and hydrogen mixture and carries out temperature programming processing, be cooled to room temperature, obtain single-layer graphene powder；
The single-layer graphene powder is placed in spray mixer, the ethanol solution to contain dispersant is turning as spray
Speed is 300-1000rpm, temperature is spray-dried under conditions of being 70-100 DEG C, after treating the spray drying, is continued
It is uniformly mixed, obtains modified single-layer graphene powder；Then the single-layer graphene powder of the modification is dissolved in organic
In solvent, ultrasonic disperse processing, single-layer graphene dispersion liquid is obtained；
Wherein, the method for described program heating treatment is：The graphene oxide after freeze-drying is warming up to 150-300
DEG C, keep 0.5-12h；600-800 DEG C is warming up to again, keeps 0.5-12h；1000-1200 DEG C is continuously heating to, keeps 0.5-
12h。
2. the preparation method of single-layer graphene dispersion liquid as claimed in claim 1, it is characterised in that the natural flake graphite
Particle diameter be 30-100 μm.
3. the preparation method of single-layer graphene dispersion liquid as claimed in claim 1, it is characterised in that with the nitrogen and hydrogen mixture
Cumulative volume for 100% meter, the volume fraction content of hydrogen is 1-8%；And/or
The flow velocity of the nitrogen and hydrogen mixture is 10-100sccm.
4. the preparation method of the single-layer graphene dispersion liquid as described in claim 1-3 is any, it is characterised in that the high pressure is equal
The pressure of matter machine is 20000-70000psi.
5. the preparation method of the single-layer graphene dispersion liquid as described in claim 1-3 is any, it is characterised in that the individual layer stone
The weight ratio of black alkene powder, dispersant and ethanol is 100-200:1-5:10-20.
6. the preparation method of the single-layer graphene dispersion liquid as described in claim 1-3 is any, it is characterised in that the spraying is dry
In dry, the dispersant is phthalic acid ester, octadecanoid acid, γ-methacryloxypropyl trimethoxy silane, isopropyl
Base three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, the oleic acid of isopropyl two
At least one of acyloxy (dioctyl phosphoric acid acyloxy) titanate esters.
7. the preparation method of the single-layer graphene dispersion liquid as described in claim 1-3 is any, it is characterised in that described organic molten
Agent is at least one of ethanol, acetone, tetrahydrofuran, dimethylbenzene, ether, cyclohexanol, ethyl acetate.
8. the preparation method of the single-layer graphene dispersion liquid as described in claim 1-3 is any, it is characterised in that described to prepare oxygen
The method of graphite slurry is：The sodium nitrate of the 30-100 μm of natural flake graphite of 1-5 parts and 0.5-2.5 parts is dispersed to 50-
In 200 parts of the concentrated sulfuric acid, the potassium permanganate of 3-15 parts is added under ice bath, after reacting 0.5-4h, oil bath is warming up to 20-40 DEG C
Continue to react 2-24h, add the deionized water of 200-500 parts, and keep oil bath temperature to react 2-24h at 70-100 DEG C, finally
Hydrogen peroxide is added until reaction solution no longer produces bubble, stopping reaction；The 5% of 1000-2000 parts is added into mixed solution
Hydrochloric acid solution, centrifuged, washed using filter cloth formula centrifuge, until slurry pH >=6, obtain graphite oxide slurry.
9. the preparation method of single-layer graphene dispersion liquid as claimed in claim 8, it is characterised in that the filter cloth formula centrifuge
Filter cloth mesh number be 8000-12000 mesh, centrifugal speed 3000-12000rpm.
10. a kind of single-layer graphene dispersion liquid, it is characterised in that the single-layer graphene dispersion liquid is any by claim 1-9
Methods described prepares.
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| CN112408374A (en) * | 2020-11-27 | 2021-02-26 | 浙江工业大学 | Method for reducing graphene agglomeration |
| CN112408385A (en) * | 2019-08-22 | 2021-02-26 | 常州富烯科技股份有限公司 | Graphene oxide slurry with low viscosity and preparation method thereof, graphene oxide film and preparation method thereof |
| CN112479196A (en) * | 2020-06-11 | 2021-03-12 | 中科远方(北京)科技有限公司 | Graphene oxide and preparation method thereof |
| CN112850699A (en) * | 2019-11-28 | 2021-05-28 | 广东墨睿科技有限公司 | Preparation method of graphene oxide |
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| CN109553094A (en) * | 2019-01-03 | 2019-04-02 | 深圳天元羲王材料科技有限公司 | A kind of grapheme platelet liquid phase ultrasonic dispersing method |
| CN112408385A (en) * | 2019-08-22 | 2021-02-26 | 常州富烯科技股份有限公司 | Graphene oxide slurry with low viscosity and preparation method thereof, graphene oxide film and preparation method thereof |
| CN112408385B (en) * | 2019-08-22 | 2021-08-27 | 常州富烯科技股份有限公司 | Graphene oxide slurry with low viscosity and preparation method thereof, graphene oxide film and preparation method thereof |
| US11673808B2 (en) | 2019-08-22 | 2023-06-13 | Changzhou Fuxi Technology Co., Ltd | Low-viscosity graphene oxide slurry and preparation method thereof, and graphene oxide film and preparation method thereof |
| CN112850699A (en) * | 2019-11-28 | 2021-05-28 | 广东墨睿科技有限公司 | Preparation method of graphene oxide |
| CN112479196A (en) * | 2020-06-11 | 2021-03-12 | 中科远方(北京)科技有限公司 | Graphene oxide and preparation method thereof |
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| CN115448299A (en) * | 2022-08-30 | 2022-12-09 | 深圳市米韵科技有限公司 | High-conductivity graphene film and preparation method thereof |
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