CN105540575A - Method for preparing graphene by using high-pressure homogenizer delamination - Google Patents
Method for preparing graphene by using high-pressure homogenizer delamination Download PDFInfo
- Publication number
- CN105540575A CN105540575A CN201610057734.2A CN201610057734A CN105540575A CN 105540575 A CN105540575 A CN 105540575A CN 201610057734 A CN201610057734 A CN 201610057734A CN 105540575 A CN105540575 A CN 105540575A
- Authority
- CN
- China
- Prior art keywords
- graphite
- graphene
- pressure homogenizer
- dispersion
- high pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of graphene and particularly relates to a method for preparing the graphene by using high-pressure homogenizer delamination. According to the method, a graphite raw material is subjected to intercalation modifying treatment and is mixed with a dispersant so as to form dispersed slurry, the dispersed slurry is fed to a high-pressure homogenizer, the graphite is rapidly delaminated by using a large shearing force generated by high-pressure fluid during high-velocity flowing and impact pressure resulting from fluid collision, meanwhile, the layer-by-layer delamination of the graphite is realized by using the high-velocity flowing of the fluid, the damage to the structure of a graphene crystal caused by a mechanical shearing force is prevented, the prepared graphene can be low in crystal lattice defect and high in product quality, and the large-scale production of high-quality and small-layer-number graphene under high-shear mechanical conditions is achieved. According to the method provided by the invention, the yield of the prepared graphene is high, the number of layers is smaller than 10, the structural defect is low, the dispersity is good, the rapid and efficient preparation of the high-quality graphene is achieved, the production cost of the high-quality graphene is reduced substantially, and the preparation process is green and environment-friendly, so that the method has a remarkable market value.
Description
Technical field
The invention belongs to technical field of graphene, relate to a kind of method that mechanically peel prepares Graphene, particularly a kind of high pressure homogenizer that utilizes peels off the method preparing Graphene.
Background technology
Graphene is a kind of monolayer carbon atomic plane material separated from graphite material, is the two-dimensional material of the cellular hexaplanar structure formed with sp2 hydridization by carbon atom.Graphene is the thinnest at present is also the hardest nano material; there is good electricity and optical property, mechanical property, heat-conductive characteristic and high charge carrier mobility; also has the performance that numerous common material such as stronger physical strength and snappiness does not possess simultaneously; have potential application prospect at numerous areas such as the energy, electronic material, biomedicine and environment protection, therefore the basis of Graphene and applied research have become the focus that various countries scientist studies.
Since Graphene finds, the preparation of Graphene is the focus that people study always.The preparation method of Graphene comprises mechanically peel method, graphite oxide reduction method, epitaxial growth method, chemical Vapor deposition process etc.Oxidation reduction process is the method that application is more at present, but the method can introduce a large amount of defect in preparation process, can not repair completely, having had a strong impact on the performances such as the electricity of Graphene when reducing; Epitaxial growth method and chemical Vapor deposition process can obtain the Graphene monolithic of high-quality bulk, but these two kinds of method preparation conditions are harsh, and output is not high, requires high to substrate, and transfer exists difficulty greatly, and preparation cost is very high.By contrast, mechanically peel more easily obtains the Graphene of low cost.The method of mechanically peel is successively peeled off from the surface of graphite flake and is obtained graphene film, can prepare the Graphene closest to perfect condition, is a kind of simple method preparing high-quality graphene with low cost.The method that current mechanically peel method is commonly used comprises adhesive tape method, ultrasonic method, ball milled etc.
China Patent Publication No. CN104925799A discloses Graphene industrial production device, repeatedly adhesive tape is extruded by graphite wafer roller and rubber roll, manufacture the graphite adhesive tape of uniform adhesion graphite linings, the graphite adhesive tape and blank adhesive tape that relatively pass through to be separated again is repeatedly extruded by relative rubber roll, demultiplication graphite linings thickness, until produce the graphite adhesive tape of continuous uniform arrangement monolayer carbon atom, separate Graphene by Graphene stripping machine.The method has that Production Flow Chart is short, cost is low, continuous mechanized can produce the advantage of Graphene.But this method production efficiency is low, and due to the cohesive action of graphite layers, in the process of extruding, cause graphite to bond between layers, graphite linings can not be peeled off completely, and the graphene product obtained is in uneven thickness, affects quality product.
China Patent Publication No. CN103253659A discloses a kind of method that ultrasonic wave peels off preparing graphite alkene, by powdered graphite and intercalator Homogeneous phase mixing in organic solvent by a certain percentage, recycling ultrasound bath carries out stripping certain hour, centrifugation, namely obtains grapheme material after filtration.This invented technology is simple and easy to do, and product preparation cost is low, and the graphene dispersing solution concentration of synthesis is high and not easily assemble.But utilize the method to prepare Graphene and need a large amount of organic solvents, contaminate environment, the intercalator simultaneously in solution can remain in graphene product, is difficult to purifying, affects the quality of graphene product.
China Patent Publication No. CN103466608A discloses a kind of ball milling preparation method of Graphene, hexa-atomic to graphite carbon and alkyl aromatic ring or condensed ring polyether nonionic surfactant are mixed with water and is loaded on ball grinder, with the rotating speed ball milling 5-30 hour of 200-500rpm, centrifugation, obtained different concns graphene aqueous solution, employing ball-grinding machine is simple, easy to operate, operating safety, and ball milling does not introduce new surface oxygen functional group defect.But the Graphene adopting this method to produce very easily causes lattice imperfection, and the Graphene size obtained is less, hinders the large-scale application of Graphene.
In sum, current mechanically peel is prepared Graphene and is peeled off based on ultrasonic stripping and ball milling, and ultrasonic stripping method needs to use a large amount of organic solvents, contaminate environment, and there is the shortcoming that Graphene is difficult to purifies and separates, causes graphene product quality to reduce; Ball milled utilizes grinding to apply pressure to graphite, graphite is made to peel off into Graphene, but this surging force very easily causes the lattice imperfection of Graphene, reduce the crystalline size of graphene product, the crunch of simultaneous grinding medium can cause graphite linings structure to become more closely peeling effect being caused on the contrary to reduce, cause milling time long, with high costs, be therefore difficult to carry out large-scale industrialized production.
Summary of the invention
The present invention is directed to the defects such as the Graphene lattice imperfection that graphene product prepared by current ultrasonic stripping method is of low quality, prepared by ball milled is large, size is little, length consuming time, propose a kind of high pressure homogenizer that utilizes and peel off the method preparing Graphene.The method is by carrying out intercalation modifying process to graphite raw material; dispersed paste is formed with dispersant; dispersed paste is sent into high pressure homogenizer; the significant shear power utilizing high pressure fluid to produce in flow at high speed and and liquid collision produce surge pressure peel off graphite fast; utilize the flow at high speed of fluid simultaneously; achieve the successively stripping of graphite; prevent mechanical shear stress to the destruction of Graphene crystalline structure; make that the Graphene lattice imperfection of preparation is little, quality product is high, achieve the few layer graphene of large-scale production high quality under high-shear mechanical conditions.
For achieving the above object, the present invention adopts following technical scheme:
Utilize high pressure homogenizer to peel off the method preparing Graphene, it is characterized in that utilizing the pairing nozzle of high pressure homogenizer to make the graphite slurry head-on collision shearing-crushing of injection, obtain the graphene powder be evenly distributed that the number of plies is 1 ~ 10 layer, concrete grammar is as follows:
(1) be that 3 ~ 5:2 ~ 3:1 is mixed with intercalation modifying agent by vulkacit H, Tetra hydro Phthalic anhydride, polyvinyl alcohol with mass ratio, then by graphite raw material homogenous disperse in intercalation modifying agent, homogeneous 1 ~ 2h, filtration deionized water repetitive scrubbing is also filtered dry and obtains Graphite Cake;
(2) Graphite Cake in step (1) and dispersant are disperseed in organic solvent, the mass ratio of Graphite Cake and dispersion agent is 100:1 ~ 10, blending dispersion in high-speed stirring mixer, obtains the graphite dispersion slurry that mass concentration is 10 ~ 30%;
The graphite dispersion slurry that step (2) obtains is added in high pressure homogenizer, by high-pressure pump, graphite dispersion slurry is sucked, dispersion liquid fluid enters pump chamber with the high speed of 150 ~ 300m/s, make fluid by baffling road by plunger motion, the graphite dispersion of current downflow is starched and becomes left and right flowing, graphite is mixed and reaches the preliminary object pulverized, the nozzle of the pairing through being arranged on folding runner exit makes preliminary graphite slurry head-on collision of pulverizing, shearing effect when flow at high speed, effect of impact during high-velocity jet, graphite laminated is made under hole effect triple role when moment, crunch was fallen, then send in homogenizing valve, between spool and spool, narrow plane closed surface clamp-ons discharging chamber, carry out shearing again to the graphite after layering to peel off, graphite is made to peel off the few layer graphene being formed and be evenly distributed,
(4) the pulp centrifuged filtration of Graphene in step (3) is collected, with acetone cleaning 2 ~ 3 times, then centrifuging, namely vacuum-drying obtain the graphene powder be evenly distributed that the number of plies is 1 ~ 10 layer.
Described graphite raw material is at least one in crystalline flake graphite, expanded graphite, thermo-cracking graphite, graphite oxide.
Described dispersion agent is one or more in Morpan BB, benzalkonium chloride, polyprotonic acid sucrose ester, polyvinyl chloride-poiyoxypropylene copolymer.
Described organic solvent be N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, NOP, NVP, N-dodecylpyrrolidone one or more.
Described high pressure homogenizer is made up of homogenizing valve and high-pressure pump, described high-pressure pump comprises at least one pair of plunger, preferred employing two pairs of plungers, each plunger is arranged in a pump chamber, liquid material in corresponding two pump chambers is injected into head-on collision chamber by the nozzle in baffling road to plunger simultaneously and clashes by each, by the strong shock of fluid, transient burst of energy produces huge Pressure Drop and shearing force, makes graphite peel off the graphene powder be evenly distributed forming few layer.Wherein, described baffling road adopts arc-shaped transition, and make the material of current downflow become left and right flowing, the baffling of material not only can make material tentatively pulverize, and makes mixing of materials even; Described nozzle is relatively arranged on the both sides in head-on collision chamber, and the material simultaneously ejected from a pair nozzle occurs mutually to clash into, thus shears material.
A kind of high pressure homogenizer that utilizes of the present invention peels off the method preparing Graphene, after graphite is carried out intercalation modifying process, add dispersion agent and form dispersed paste, graphite dispersion slurry enters homogenizing valve by high-pressure pump pressurization, by the strong shock of fluid body, transient burst of energy produces huge Pressure Drop and shearing force, graphite slurry is made to be subject to strong machinery and aquashear, HF oscillation, liquid layer rubs, shock is torn and the comprehensive action such as cavitation erosion, thus make graphite produce crystal face horizontal displacement and sliding motion between layers, and then graphite is peeled off fast, moving in circles through high frequency, finally obtain stable few layer graphene.Simultaneously due to the high-speed motion of fluid, graphite is successively peeled off in different steps, can effectively prevent mechanical shear stress to the destruction of graphene-structured, keep the structural integrity of Graphene, improve the performance of Graphene.When utilizing high pressure homogenizer to peel off graphite, graphite and dispersant are disperseed to form graphite dispersion slurry, the electrostatic repulsion of the nanoparticle surface of fully dispersion can be relied on to avoid reuniting, and the integrity of self chemical structure can be kept, there is good dispersiveness.
A kind of high pressure homogenizer that utilizes of the present invention peels off the method preparing Graphene, and compared with prior art outstanding feature and useful effect are:
1, the comprehensive actions such as transient pressure falls, highly pressurised liquid shearing, high-speed impact effect, HF oscillation and cavitation erosion are produced by high pressure homogenizer, make graphite produce crystal face horizontal displacement and sliding motion between layers, and then fast graphite stripping is obtained stable few layer graphene.
2, by the high-speed motion of fluid, achieve the successively stripping of graphite, effectively prevent the destruction of traditional mechanically peel to graphene layer crystalline structure, save the perfection of lattice of Graphene preferably.
3, the present invention adds dispersion agent and makes graphite form dispersed paste, relies on the electrostatic repulsion of nanoparticle surface of dispersion to avoid reuniting, and can keep the integrity of Graphene chemical structure, make the Graphene of preparation have good dispersiveness.
4, invention preparation method drop into little, cost is low, non-environmental-pollution, can prepare few layer graphene fast and efficiently, is conducive to the large-scale production realizing high-quality graphene.
Accompanying drawing explanation
Utilizing high pressure homogenizer to peel off the method preparing Graphene for further illustrating, being described by accompanying drawing.
Accompanying drawing 1: be the structural representation of the preferred high pressure homogenizer of the present invention.1-high-pressure pump; The 2-pump housing; 3-pump chamber; 4-plunger; 5-baffling road; 6-nozzle; 7-clashes chamber.
Embodiment
Below in conjunction with embodiment, the present invention is explained in detail, is not restricted to the present invention.When not departing from aforesaid method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or improvement, all should be included within protection scope of the present invention.
embodiment 1
(1) be that 3:2:1 is mixed with intercalation modifying agent with mass ratio by vulkacit H, Tetra hydro Phthalic anhydride, polyvinyl alcohol, then by crystalline flake graphite homogenous disperse in intercalation modifying agent, homogeneous 1 ~ 2h, filtration deionized water repetitive scrubbing is also filtered dry and obtains Graphite Cake;
(2) by the Graphite Cake in step (1) and Morpan BB blending dispersion in N-Methyl pyrrolidone solvent, the mass ratio of Graphite Cake and dispersion agent is 100:1, blending dispersion in high-speed stirring mixer, stirring velocity is 1000r/min, churning time is 20min, obtains the graphite dispersion slurry that mass concentration is 10%;
The graphite dispersion slurry that step (2) obtains is added in high pressure homogenizer, by high-pressure pump, graphite dispersion slurry is sucked, dispersion liquid fluid enters pump chamber with the high speed of 150 ~ 300m/s, make fluid by baffling road by plunger motion, the graphite dispersion of current downflow is starched and becomes left and right flowing, graphite is mixed and reaches the preliminary object pulverized, the nozzle of the pairing through being arranged on folding runner exit makes preliminary graphite slurry head-on collision of pulverizing, shearing effect when flow at high speed, effect of impact during high-velocity jet, graphite laminated is made under hole effect triple role when moment, crunch was fallen, then send in homogenizing valve, between spool and spool, narrow plane closed surface clamp-ons discharging chamber, carry out shearing again to the graphite after layering to peel off, graphite is made to peel off the few layer graphene being formed and be evenly distributed,
(4) the pulp centrifuged filtration of Graphene in step (3) is collected, with acetone cleaning 2 ~ 3 times, then centrifuging, namely vacuum-drying obtain the graphene powder be evenly distributed that the number of plies is 1 ~ 10 layer.
Show through morphology analysis and structural analysis, in the present embodiment, the graphene film number of plies of 95% is at 1 ~ 10 layer, and the number of plies is evenly distributed, and textural defect is little, conducts electricity very well.
embodiment 2
(1) be that 5:2:1 is mixed with intercalation modifying agent with mass ratio by vulkacit H, Tetra hydro Phthalic anhydride, polyvinyl alcohol, then by expanded graphite homogenous disperse in intercalation modifying agent, homogeneous 1 ~ 2h, filtration deionized water repetitive scrubbing is also filtered dry and obtains Graphite Cake;
(2) by the Graphite Cake in step (1) and benzalkonium chloride blending dispersion in N-cyclohexyl pyrrolidone solvent, the mass ratio of Graphite Cake and dispersion agent is 100:5 blending dispersion in high-speed stirring mixer, stirring velocity is 1000r/min, churning time is 20min, obtains the graphite dispersion slurry that mass concentration is 15%;
The graphite dispersion slurry that step (2) obtains is added in high pressure homogenizer, by high-pressure pump, graphite dispersion slurry is sucked, dispersion liquid fluid enters pump chamber with the high speed of 150 ~ 300m/s, make fluid by baffling road by plunger motion, the graphite dispersion of current downflow is starched and becomes left and right flowing, graphite is mixed and reaches the preliminary object pulverized, the nozzle of the pairing through being arranged on folding runner exit makes preliminary graphite slurry head-on collision of pulverizing, shearing effect when flow at high speed, effect of impact during high-velocity jet, graphite laminated is made under hole effect triple role when moment, crunch was fallen, then send in homogenizing valve, between spool and spool, narrow plane closed surface clamp-ons discharging chamber, carry out shearing again to the graphite after layering to peel off, graphite is made to peel off the few layer graphene being formed and be evenly distributed,
(4) the pulp centrifuged filtration of Graphene in step (3) is collected, with acetone cleaning 2 ~ 3 times, then centrifuging, namely vacuum-drying obtain the graphene powder be evenly distributed that the number of plies is 1 ~ 10 layer.
Show through morphology analysis and structural analysis, in the present embodiment, the graphene film number of plies of 92% is at 1 ~ 10 layer, and the number of plies is evenly distributed, and textural defect is little, conducts electricity very well.
embodiment 3
(1) be that 5:3:1 is mixed with intercalation modifying agent with mass ratio by vulkacit H, Tetra hydro Phthalic anhydride, polyvinyl alcohol, then by thermo-cracking graphite homogenous disperse in intercalation modifying agent, homogeneous 1 ~ 2h, filtration deionized water repetitive scrubbing is also filtered dry and obtains Graphite Cake;
(2) by the Graphite Cake in step (1) and polyprotonic acid sucrose ester blending dispersion in NOP solvent, the mass ratio of Graphite Cake and dispersion agent is 100:3 blending dispersion in high-speed stirring mixer, stirring velocity is 800r/min, churning time is 30min, obtains the graphite dispersion slurry that mass concentration is 30%;
The graphite dispersion slurry that step (2) obtains is added in high pressure homogenizer, by high-pressure pump, graphite dispersion slurry is sucked, dispersion liquid fluid enters pump chamber with the high speed of 150 ~ 300m/s, make fluid by baffling road by plunger motion, the graphite dispersion of current downflow is starched and becomes left and right flowing, graphite is mixed and reaches the preliminary object pulverized, the nozzle of the pairing through being arranged on folding runner exit makes preliminary graphite slurry head-on collision of pulverizing, shearing effect when flow at high speed, effect of impact during high-velocity jet, graphite laminated is made under hole effect triple role when moment, crunch was fallen, then send in homogenizing valve, between spool and spool, narrow plane closed surface clamp-ons discharging chamber, carry out shearing again to the graphite after layering to peel off, graphite is made to peel off the few layer graphene being formed and be evenly distributed,
(4) the pulp centrifuged filtration of Graphene in step (3) is collected, with acetone cleaning 2 ~ 3 times, then centrifuging, namely vacuum-drying obtain the graphene powder be evenly distributed that the number of plies is 1 ~ 10 layer.
Show through morphology analysis and structural analysis, in the present embodiment, the graphene film number of plies of 89% is at 1 ~ 10 layer, and the number of plies is evenly distributed, and textural defect is little, conducts electricity very well.
embodiment 4
(1) be that 5:2:1 is mixed with intercalation modifying agent with mass ratio by vulkacit H, Tetra hydro Phthalic anhydride, polyvinyl alcohol, then by graphite oxide homogenous disperse in intercalation modifying agent, homogeneous 1 ~ 2h, filtration deionized water repetitive scrubbing is also filtered dry and obtains Graphite Cake;
(2) by the Graphite Cake in step (1) and polyvinyl chloride-poiyoxypropylene copolymer blending dispersion in NVP solvent, the mass ratio of Graphite Cake and dispersion agent is 100:10, blending dispersion in high-speed stirring mixer, stirring velocity is 50r/min, churning time is 40min, obtains the graphite dispersion slurry that mass concentration is 20%;
The graphite dispersion slurry that step (2) obtains is added in high pressure homogenizer, by high-pressure pump, graphite dispersion slurry is sucked, dispersion liquid fluid enters pump chamber with the high speed of 150 ~ 300m/s, make fluid by baffling road by plunger motion, the graphite dispersion of current downflow is starched and becomes left and right flowing, graphite is mixed and reaches the preliminary object pulverized, the nozzle of the pairing through being arranged on folding runner exit makes preliminary graphite slurry head-on collision of pulverizing, shearing effect when flow at high speed, effect of impact during high-velocity jet, graphite laminated is made under hole effect triple role when moment, crunch was fallen, then send in homogenizing valve, between spool and spool, narrow plane closed surface clamp-ons discharging chamber, carry out shearing again to the graphite after layering to peel off, graphite is made to peel off the few layer graphene being formed and be evenly distributed,
(4) the pulp centrifuged filtration of Graphene in step (3) is collected, with acetone cleaning 2 ~ 3 times, then centrifuging, namely vacuum-drying obtain the graphene powder be evenly distributed that the number of plies is 1 ~ 10 layer.
Show through morphology analysis and structural analysis, in the present embodiment, the graphene film number of plies of 95% is at 1 ~ 10 layer, and the number of plies is evenly distributed, and textural defect is little, conducts electricity very well.
embodiment 5
(1) be that 5:2:1 is mixed with intercalation modifying agent with mass ratio by vulkacit H, Tetra hydro Phthalic anhydride, polyvinyl alcohol, then by graphite oxide homogenous disperse in intercalation modifying agent, homogeneous 1 ~ 2h, filtration deionized water repetitive scrubbing is also filtered dry and obtains Graphite Cake;
(2) by the Graphite Cake in step (1) and Morpan BB blending dispersion in N-dodecylpyrrolidone solvent, the mass ratio of Graphite Cake and dispersion agent is 100:10, blending dispersion in high-speed stirring mixer, stirring velocity is 1000r/min, churning time is 20min, obtains the graphite dispersion slurry that mass concentration is 30%;
The graphite dispersion slurry that step (2) obtains is added in high pressure homogenizer, by high-pressure pump, graphite dispersion slurry is sucked, dispersion liquid fluid enters pump chamber with the high speed of 150 ~ 300m/s, make fluid by baffling road by plunger motion, the graphite dispersion of current downflow is starched and becomes left and right flowing, graphite is mixed and reaches the preliminary object pulverized, the nozzle of the pairing through being arranged on folding runner exit makes preliminary graphite slurry head-on collision of pulverizing, shearing effect when flow at high speed, effect of impact during high-velocity jet, graphite laminated is made under hole effect triple role when moment, crunch was fallen, then send in homogenizing valve, between spool and spool, narrow plane closed surface clamp-ons discharging chamber, carry out shearing again to the graphite after layering to peel off, graphite is made to peel off the few layer graphene being formed and be evenly distributed,
(4) the pulp centrifuged filtration of Graphene in step (3) is collected, with acetone cleaning 2 ~ 3 times, then centrifuging, namely vacuum-drying obtain the graphene powder be evenly distributed that the number of plies is 1 ~ 10 layer.
Show through morphology analysis and structural analysis, in the present embodiment, the graphene film number of plies of 90% is at 1 ~ 10 layer, and the number of plies is evenly distributed, and textural defect is little, conducts electricity very well.
Claims (7)
1. utilize high pressure homogenizer to peel off the method preparing Graphene, it is characterized in that utilizing the pairing nozzle of high pressure homogenizer to make the graphite slurry head-on collision shearing-crushing of injection, obtain the graphene powder be evenly distributed that the number of plies is 1 ~ 10 layer, concrete grammar is as follows:
(1) be that 3 ~ 5:2 ~ 3:1 is mixed with intercalation modifying agent by vulkacit H, Tetra hydro Phthalic anhydride, polyvinyl alcohol with mass ratio, then by graphite raw material homogenous disperse in intercalation modifying agent, homogeneous 1 ~ 2h, filtration deionized water repetitive scrubbing is also filtered dry and obtains Graphite Cake;
(2) Graphite Cake in step (1) and dispersant are disperseed in organic solvent, the mass ratio of Graphite Cake and dispersion agent is 100:1 ~ 10, blending dispersion in high-speed stirring mixer, obtains the graphite dispersion slurry that mass concentration is 10 ~ 30%;
(3) the graphite dispersion slurry that step (2) obtains is added in high pressure homogenizer, by high-pressure pump, graphite dispersion slurry is sucked, dispersion liquid fluid enters pump chamber with the high speed of 150 ~ 300m/s, make fluid by baffling road by plunger motion, the graphite dispersion of current downflow is starched and becomes left and right flowing, graphite is mixed and reaches the preliminary object pulverized, the nozzle of the pairing through being arranged on folding runner exit makes preliminary graphite slurry head-on collision of pulverizing, shearing effect when flow at high speed, effect of impact during high-velocity jet, graphite laminated is made under hole effect triple role when moment, crunch was fallen, then send in homogenizing valve, between spool and spool, narrow plane closed surface clamp-ons discharging chamber, carry out shearing again to the graphite after layering to peel off, graphite is made to peel off the few layer graphene being formed and be evenly distributed,
(4) the pulp centrifuged filtration of Graphene in step (3) is collected, with acetone cleaning 2 ~ 3 times, then centrifuging, namely vacuum-drying obtain the graphene powder be evenly distributed that the number of plies is 1 ~ 10 layer;
Described high pressure homogenizer is made up of homogenizing valve and high-pressure pump, described high-pressure pump comprises at least one pair of plunger, each plunger is arranged in a pump chamber, liquid material in corresponding two pump chambers is injected into head-on collision chamber by the nozzle in baffling road to plunger simultaneously and clashes by each, by the strong shock of fluid, transient burst of energy produces huge Pressure Drop and shearing force, makes graphite peel off the graphene powder be evenly distributed forming few layer.
2. a kind of high pressure homogenizer that utilizes according to claim 1 peels off the method preparing Graphene, it is characterized in that described baffling road adopts arc-shaped transition, make the material of current downflow become left and right flowing, the baffling of material not only can make material tentatively pulverize, and makes mixing of materials even.
3. according to claim 1ly a kind ofly utilize high pressure homogenizer to peel off to prepare the method for Graphene, it is characterized in that described nozzle is relatively arranged on the both sides in head-on collision chamber, the material simultaneously ejected from a pair nozzle occurs mutually to clash into, thus shears material.
4. a kind of high pressure homogenizer that utilizes according to claim 1 peels off the method preparing Graphene, it is characterized in that described graphite raw material is at least one in crystalline flake graphite, expanded graphite, thermo-cracking graphite, graphite oxide.
5. according to claim 1ly a kind ofly utilize high pressure homogenizer to peel off to prepare the method for Graphene, it is characterized in that described dispersion agent is one or more in Morpan BB, benzalkonium chloride, polyprotonic acid sucrose ester, polyvinyl chloride-poiyoxypropylene copolymer.
6. according to claim 1ly a kind ofly utilize high pressure homogenizer to peel off to prepare the method for Graphene, it is characterized in that described organic solvent be N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, NOP, NVP, N-dodecylpyrrolidone one or more.
7. a kind of high pressure homogenizer that utilizes according to claim 1 peels off the method preparing Graphene, it is characterized in that the stirring velocity of the homogenizer described in step (2) is 500 ~ 1000r/min, churning time is 20 ~ 40min, and graphite dispersion slurry remains on 20 ~ 30 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610057734.2A CN105540575A (en) | 2016-01-28 | 2016-01-28 | Method for preparing graphene by using high-pressure homogenizer delamination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610057734.2A CN105540575A (en) | 2016-01-28 | 2016-01-28 | Method for preparing graphene by using high-pressure homogenizer delamination |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105540575A true CN105540575A (en) | 2016-05-04 |
Family
ID=55820212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610057734.2A Pending CN105540575A (en) | 2016-01-28 | 2016-01-28 | Method for preparing graphene by using high-pressure homogenizer delamination |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105540575A (en) |
Cited By (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105819438A (en) * | 2016-05-06 | 2016-08-03 | 成都新柯力化工科技有限公司 | Method for preparing nanometer graphene materials in large scale mode through hydraulic shearing |
| CN105948028A (en) * | 2016-05-06 | 2016-09-21 | 成都新柯力化工科技有限公司 | Method for preparation of graphene precursor by internal mixer peeling and graphene precursor |
| CN106219536A (en) * | 2016-08-29 | 2016-12-14 | 青岛华高墨烯科技股份有限公司 | A kind of Graphene intellectuality preparation method |
| CN106241790A (en) * | 2016-08-29 | 2016-12-21 | 青岛华高墨烯科技股份有限公司 | The complete intelligent preparation facilities of a kind of Graphene |
| CN106542526A (en) * | 2016-11-08 | 2017-03-29 | 成都新柯力化工科技有限公司 | A kind of utilization fluid accelerates the apparatus and method that Graphene slurry is peeled off in stirring |
| CN106542527A (en) * | 2017-01-06 | 2017-03-29 | 成都新柯力化工科技有限公司 | A kind of method of mechanical stripping grading system for graphene microchip dispersion liquid |
| CN106587031A (en) * | 2016-11-02 | 2017-04-26 | 成都新柯力化工科技有限公司 | Device for continuously preparing graphene and method for producing graphene |
| CN106976870A (en) * | 2017-03-29 | 2017-07-25 | 天津工业大学 | Efficiently peel off the method that graphite powder prepares big size graphene |
| CN107055496A (en) * | 2017-01-12 | 2017-08-18 | 昆明理工大学 | A kind of magnanimity preparation method of phosphorus alkene |
| CN107317034A (en) * | 2017-07-06 | 2017-11-03 | 深圳市国创珈伟石墨烯科技有限公司 | A kind of preparation, process for dispersing and the equipment of graphene/carbon nano-tube composite conducting slurry |
| CN107674197A (en) * | 2017-10-11 | 2018-02-09 | 三门县鸿远塑业有限公司 | The polymerization of high-pressure injection legal system graphene dispersing solution and its graphene nylon processed |
| CN107827102A (en) * | 2017-11-27 | 2018-03-23 | 内蒙古碳烯石墨新材料有限公司 | A kind of method for preparing graphene |
| CN107971155A (en) * | 2016-10-24 | 2018-05-01 | 林逸樵 | A kind of nozzle and its manufacture method for tearing layer open for material |
| CN108178150A (en) * | 2018-03-08 | 2018-06-19 | 常州大学 | A kind of method for preparing graphene |
| CN109071230A (en) * | 2016-05-11 | 2018-12-21 | 株式会社Lg化学 | High-pressure homogenizer and the method for manufacturing graphene using it |
| CN109095462A (en) * | 2018-07-26 | 2018-12-28 | 北京旭碳新材料科技有限公司 | A kind of graphene and its preparation method and application |
| CN109368623A (en) * | 2018-09-20 | 2019-02-22 | 苏州博努奇纺织有限公司 | A kind of nano metal intercalated graphite alkene preparation method |
| CN109534330A (en) * | 2017-09-22 | 2019-03-29 | 天津大学 | A kind of large area lacks layer graphene and preparation method thereof |
| CN109652014A (en) * | 2018-12-26 | 2019-04-19 | 宁波杉元石墨烯科技有限公司 | A kind of graphene dispersion grinding aid and preparation method thereof |
| CN110072809A (en) * | 2016-10-13 | 2019-07-30 | 托马仕有限责任公司 | Device and method for producing the thin two-dimensional material of the atom level including graphene in batches |
| CN110152587A (en) * | 2018-02-13 | 2019-08-23 | 华瑞墨石丹阳有限公司 | High-speed jet percussion device and the method for preparing two-dimension nano materials using the device |
| CN110562967A (en) * | 2019-10-15 | 2019-12-13 | 上海纳米技术及应用国家工程研究中心有限公司 | preparation method of functional graphene |
| CN110694778A (en) * | 2019-10-29 | 2020-01-17 | 深圳市群卜鸿科技有限公司 | A water-saving high pressure homogenizer for preparation of graphite alkene |
| CN110980703A (en) * | 2019-12-30 | 2020-04-10 | 深圳市深瑞墨烯科技有限公司 | Graphene film batch production method and graphene film prepared by using same |
| CN111055552A (en) * | 2019-06-08 | 2020-04-24 | 王雅静 | Batch preparation method of high-performance graphene film, graphene film and antenna |
| CN112047311A (en) * | 2020-09-09 | 2020-12-08 | 天津工业大学 | Stripping method of graphite phase carbon nitride |
| CN112142019A (en) * | 2020-09-28 | 2020-12-29 | 山东晶亿新材料有限公司 | Preparation method of hexagonal boron nitride nanosheet |
| CN112408374A (en) * | 2020-11-27 | 2021-02-26 | 浙江工业大学 | Method for reducing graphene agglomeration |
| CN112823137A (en) * | 2018-10-12 | 2021-05-18 | 先进材料发展有限公司 | Liquid phase exfoliation of nanomaterials |
| CN112919841A (en) * | 2021-03-12 | 2021-06-08 | 青岛华高墨烯科技股份有限公司 | Graphene additive solution preparation device for cement material |
| CN113264510A (en) * | 2021-04-14 | 2021-08-17 | 佛山市晟鹏科技有限公司 | Two-dimensional layered material and preparation method and application thereof |
| WO2021212774A1 (en) * | 2020-04-24 | 2021-10-28 | 南京同诚节能环保装备研究院有限公司 | Preparation method for nickel-coated graphene |
| CN113563773A (en) * | 2021-07-26 | 2021-10-29 | 宝泰隆新材料股份有限公司北京技术研发中心 | Preparation method of graphene heat dissipation coating |
| CN113713943A (en) * | 2021-07-27 | 2021-11-30 | 上海莱布星科技有限公司 | Preparation method of water wax powder |
| US11453595B2 (en) * | 2016-07-27 | 2022-09-27 | Talga Advanced Materials GmbH | Pre-treatment coating composition and a method for producing the same |
| CN115196624A (en) * | 2016-09-30 | 2022-10-18 | 加利福尼亚大学董事会 | Continuous production of exfoliated 2D layered materials by compressed flow |
| WO2022222380A1 (en) | 2021-04-22 | 2022-10-27 | 中国石油化工股份有限公司 | Graphene powder, and preparation method therefor and application thereof |
| CN115465860A (en) * | 2022-07-06 | 2022-12-13 | 山东海科创新研究院有限公司 | Preparation method of low-oxygen high-stripping graphene oxide and application of obtained product |
| CN116081608A (en) * | 2022-12-12 | 2023-05-09 | 中国铝业股份有限公司 | Graphene stripping system and graphene stripping method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120039799A (en) * | 2010-10-18 | 2012-04-26 | 한국전기연구원 | Stable dispersion of reduced graphene oxide and its reduced graphene oxide solution |
| CN103521330A (en) * | 2013-10-17 | 2014-01-22 | 广州派勒机械设备有限公司 | High-pressure nano homogenizer |
| CN104528706A (en) * | 2015-01-21 | 2015-04-22 | 上海轻丰新材料科技有限公司 | Method for preparing graphene non-oxidation interlayer |
| TW201538422A (en) * | 2013-12-26 | 2015-10-16 | Lg Chemical Ltd | Preparation method of graphene |
-
2016
- 2016-01-28 CN CN201610057734.2A patent/CN105540575A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120039799A (en) * | 2010-10-18 | 2012-04-26 | 한국전기연구원 | Stable dispersion of reduced graphene oxide and its reduced graphene oxide solution |
| CN103521330A (en) * | 2013-10-17 | 2014-01-22 | 广州派勒机械设备有限公司 | High-pressure nano homogenizer |
| TW201538422A (en) * | 2013-12-26 | 2015-10-16 | Lg Chemical Ltd | Preparation method of graphene |
| CN104528706A (en) * | 2015-01-21 | 2015-04-22 | 上海轻丰新材料科技有限公司 | Method for preparing graphene non-oxidation interlayer |
Cited By (52)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948028A (en) * | 2016-05-06 | 2016-09-21 | 成都新柯力化工科技有限公司 | Method for preparation of graphene precursor by internal mixer peeling and graphene precursor |
| CN105819438A (en) * | 2016-05-06 | 2016-08-03 | 成都新柯力化工科技有限公司 | Method for preparing nanometer graphene materials in large scale mode through hydraulic shearing |
| CN109071230B (en) * | 2016-05-11 | 2022-02-01 | 株式会社Lg化学 | High pressure homogenizer and method for manufacturing graphene using the same |
| CN109071230A (en) * | 2016-05-11 | 2018-12-21 | 株式会社Lg化学 | High-pressure homogenizer and the method for manufacturing graphene using it |
| US11453595B2 (en) * | 2016-07-27 | 2022-09-27 | Talga Advanced Materials GmbH | Pre-treatment coating composition and a method for producing the same |
| CN106219536B (en) * | 2016-08-29 | 2018-08-17 | 青岛华高墨烯科技股份有限公司 | A kind of graphene intelligence preparation method |
| CN106219536A (en) * | 2016-08-29 | 2016-12-14 | 青岛华高墨烯科技股份有限公司 | A kind of Graphene intellectuality preparation method |
| CN106241790A (en) * | 2016-08-29 | 2016-12-21 | 青岛华高墨烯科技股份有限公司 | The complete intelligent preparation facilities of a kind of Graphene |
| CN115196624A (en) * | 2016-09-30 | 2022-10-18 | 加利福尼亚大学董事会 | Continuous production of exfoliated 2D layered materials by compressed flow |
| CN110072809B (en) * | 2016-10-13 | 2022-08-19 | 托马仕有限责任公司 | Apparatus and method for mass production of atomically thin two-dimensional materials including graphene |
| CN110072809A (en) * | 2016-10-13 | 2019-07-30 | 托马仕有限责任公司 | Device and method for producing the thin two-dimensional material of the atom level including graphene in batches |
| CN107971155B (en) * | 2016-10-24 | 2019-11-22 | 林逸樵 | A kind of nozzle and its manufacturing method for tearing layer open for material |
| CN107971155A (en) * | 2016-10-24 | 2018-05-01 | 林逸樵 | A kind of nozzle and its manufacture method for tearing layer open for material |
| CN106587031A (en) * | 2016-11-02 | 2017-04-26 | 成都新柯力化工科技有限公司 | Device for continuously preparing graphene and method for producing graphene |
| CN106542526A (en) * | 2016-11-08 | 2017-03-29 | 成都新柯力化工科技有限公司 | A kind of utilization fluid accelerates the apparatus and method that Graphene slurry is peeled off in stirring |
| CN106542526B (en) * | 2016-11-08 | 2018-08-24 | 成都新柯力化工科技有限公司 | A kind of device and method accelerating stirring stripping graphene slurry using fluid |
| CN106542527A (en) * | 2017-01-06 | 2017-03-29 | 成都新柯力化工科技有限公司 | A kind of method of mechanical stripping grading system for graphene microchip dispersion liquid |
| CN107055496A (en) * | 2017-01-12 | 2017-08-18 | 昆明理工大学 | A kind of magnanimity preparation method of phosphorus alkene |
| CN106976870B (en) * | 2017-03-29 | 2018-12-25 | 天津工业大学 | The efficiently method that removing graphite powder prepares big size graphene |
| CN106976870A (en) * | 2017-03-29 | 2017-07-25 | 天津工业大学 | Efficiently peel off the method that graphite powder prepares big size graphene |
| CN107317034A (en) * | 2017-07-06 | 2017-11-03 | 深圳市国创珈伟石墨烯科技有限公司 | A kind of preparation, process for dispersing and the equipment of graphene/carbon nano-tube composite conducting slurry |
| CN109534330A (en) * | 2017-09-22 | 2019-03-29 | 天津大学 | A kind of large area lacks layer graphene and preparation method thereof |
| CN109534330B (en) * | 2017-09-22 | 2022-04-05 | 天津大学 | Large-area few-layer graphene and preparation method thereof |
| CN107674197A (en) * | 2017-10-11 | 2018-02-09 | 三门县鸿远塑业有限公司 | The polymerization of high-pressure injection legal system graphene dispersing solution and its graphene nylon processed |
| CN107674197B (en) * | 2017-10-11 | 2020-08-11 | 三门县鸿远塑业有限公司 | Graphene dispersion liquid prepared by high-pressure injection method and polymerization method for preparing graphene nylon by using graphene dispersion liquid |
| CN107827102A (en) * | 2017-11-27 | 2018-03-23 | 内蒙古碳烯石墨新材料有限公司 | A kind of method for preparing graphene |
| CN110152587A (en) * | 2018-02-13 | 2019-08-23 | 华瑞墨石丹阳有限公司 | High-speed jet percussion device and the method for preparing two-dimension nano materials using the device |
| CN108178150B (en) * | 2018-03-08 | 2020-02-14 | 常州大学 | Method for preparing graphene |
| CN108178150A (en) * | 2018-03-08 | 2018-06-19 | 常州大学 | A kind of method for preparing graphene |
| CN109095462A (en) * | 2018-07-26 | 2018-12-28 | 北京旭碳新材料科技有限公司 | A kind of graphene and its preparation method and application |
| CN109368623A (en) * | 2018-09-20 | 2019-02-22 | 苏州博努奇纺织有限公司 | A kind of nano metal intercalated graphite alkene preparation method |
| CN112823137B (en) * | 2018-10-12 | 2023-10-27 | 先进材料发展有限公司 | Liquid phase exfoliated nanomaterial |
| CN112823137A (en) * | 2018-10-12 | 2021-05-18 | 先进材料发展有限公司 | Liquid phase exfoliation of nanomaterials |
| CN109652014A (en) * | 2018-12-26 | 2019-04-19 | 宁波杉元石墨烯科技有限公司 | A kind of graphene dispersion grinding aid and preparation method thereof |
| CN111055552A (en) * | 2019-06-08 | 2020-04-24 | 王雅静 | Batch preparation method of high-performance graphene film, graphene film and antenna |
| CN110562967A (en) * | 2019-10-15 | 2019-12-13 | 上海纳米技术及应用国家工程研究中心有限公司 | preparation method of functional graphene |
| CN110694778A (en) * | 2019-10-29 | 2020-01-17 | 深圳市群卜鸿科技有限公司 | A water-saving high pressure homogenizer for preparation of graphite alkene |
| CN110694778B (en) * | 2019-10-29 | 2022-02-01 | 陈荣才 | A water-saving high pressure homogenizer for preparation of graphite alkene |
| CN110980703A (en) * | 2019-12-30 | 2020-04-10 | 深圳市深瑞墨烯科技有限公司 | Graphene film batch production method and graphene film prepared by using same |
| WO2021212774A1 (en) * | 2020-04-24 | 2021-10-28 | 南京同诚节能环保装备研究院有限公司 | Preparation method for nickel-coated graphene |
| CN112047311A (en) * | 2020-09-09 | 2020-12-08 | 天津工业大学 | Stripping method of graphite phase carbon nitride |
| CN112142019A (en) * | 2020-09-28 | 2020-12-29 | 山东晶亿新材料有限公司 | Preparation method of hexagonal boron nitride nanosheet |
| CN112408374A (en) * | 2020-11-27 | 2021-02-26 | 浙江工业大学 | Method for reducing graphene agglomeration |
| CN112919841A (en) * | 2021-03-12 | 2021-06-08 | 青岛华高墨烯科技股份有限公司 | Graphene additive solution preparation device for cement material |
| CN112919841B (en) * | 2021-03-12 | 2024-02-09 | 青岛华高墨烯科技股份有限公司 | Preparation device of graphene additive liquid for cement material |
| CN113264510A (en) * | 2021-04-14 | 2021-08-17 | 佛山市晟鹏科技有限公司 | Two-dimensional layered material and preparation method and application thereof |
| WO2022222380A1 (en) | 2021-04-22 | 2022-10-27 | 中国石油化工股份有限公司 | Graphene powder, and preparation method therefor and application thereof |
| CN113563773A (en) * | 2021-07-26 | 2021-10-29 | 宝泰隆新材料股份有限公司北京技术研发中心 | Preparation method of graphene heat dissipation coating |
| CN113713943A (en) * | 2021-07-27 | 2021-11-30 | 上海莱布星科技有限公司 | Preparation method of water wax powder |
| CN115465860A (en) * | 2022-07-06 | 2022-12-13 | 山东海科创新研究院有限公司 | Preparation method of low-oxygen high-stripping graphene oxide and application of obtained product |
| CN115465860B (en) * | 2022-07-06 | 2023-06-16 | 山东海科创新研究院有限公司 | Preparation method of low-oxygen and high-stripping graphene oxide and application of obtained product |
| CN116081608A (en) * | 2022-12-12 | 2023-05-09 | 中国铝业股份有限公司 | Graphene stripping system and graphene stripping method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105540575A (en) | Method for preparing graphene by using high-pressure homogenizer delamination | |
| CN106582994B (en) | A kind of device and production method continuously preparing graphene slurry | |
| CN106587031B (en) | A kind of device and graphene production method continuously preparing graphene | |
| CN105819438B (en) | A kind of method using aquashear prepare with scale nano-graphene material | |
| CN104445158B (en) | Graphene stripping off device, Graphene production system and the method for producing Graphene | |
| CN110143586B (en) | Preparation method of single-layer or few-layer graphene | |
| CN106185895A (en) | A kind of graphene dispersion liquid and preparation method thereof | |
| CN105271206B (en) | Method for continuously preparing graphene material in cut mode through screw machine | |
| CN104085888B (en) | The preparation method of detonation nanodiamond liquid dispersion | |
| CN105819437B (en) | A kind of method that scale cleaning prepares graphene | |
| CN107298440B (en) | A kind of method for continuously preparing graphene in screw machine using supercritical fluid | |
| CN106976870B (en) | The efficiently method that removing graphite powder prepares big size graphene | |
| CN106882795B (en) | A kind of scale ultrasound stripping prepares the method for graphene and the application of graphene | |
| CN105329886A (en) | Method for preparing graphene through composite shear stress stripping of vibrating screw extruder | |
| CN105905888B (en) | A kind of compound microplate of graphene peeled off using turbine sand mill and preparation method thereof | |
| CN105645394A (en) | Method for preparing graphene continuously by using rotary homogenizer | |
| CN107117603B (en) | It is a kind of to peel off method of the grading system for graphene using pulse ultrasonic wave | |
| CN105776193A (en) | Method for preparing graphene nanoplatelets with pulsed high pressure water jet mill | |
| CN105776190A (en) | Method for preparing graphene micro-sheets through foaming expansion and stretching of screw machine | |
| CN107055518B (en) | A kind of application for the method and graphene powder preparing graphene powder by crushing | |
| EP3699214B1 (en) | Method for preparing graphene using a block copolymer | |
| CN106744876A (en) | A kind of method that utilization multi-level cone type kneading machine prepares grapheme material | |
| CN107265444A (en) | A kind of utilization jet prepares the complexes and method of graphene | |
| CN106607125A (en) | High-speed stirring machine for graphene stripping and graphene stripping method | |
| CN106672953A (en) | Internal mixer for preparing graphene through tensile peeling and method for preparing graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160504 |