CN105271206B - Method for continuously preparing graphene material in cut mode through screw machine - Google Patents
Method for continuously preparing graphene material in cut mode through screw machine Download PDFInfo
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Abstract
The invention provides a method for continuously preparing a graphene material in a cut mode through a screw machine. The method includes the steps that a graphite premixture is evenly dispersed in the screw rotating direction through the continuous-rotating same-direction engaging screw machine to form slice-shaped orientation, and cutting and stripping are carried out through the orientation direction of engaged screw elements, wherein stripping is carried out through a same-direction-engaging double-screw machine or a same-direction-engaging three-screw machine or a same-direction-engaging four-screw machine or a same-direction-engaging screw machine with more screws, high shearing stress is generated on interfaces between screws and the engaged screw elements in the same-direction rotating process of the screws, and therefore the large size area graphene is formed. The graphene is prepared in a stripped mode through the screw machine, the surge pressure on graphite layers is small, and cutting and striping are carried out in the direction parallel to the graphite layer faces. Further, continuous carbonizing, reduction, cutting and stripping of carbon raw materials can be achieved in the continuous screw machine, the layer face structure of the graphene is reserved to the maximum degree, the graphene can be continuously and stably prepared, the large-scale mass production of the graphene is further promoted, and remarkable market application value is achieved.
Description
Technical field
It is more particularly to a kind of the present invention relates to grapheme material field, and in particular to prepare Graphene by Mechanical Method
The method for continuously preparing grapheme material using screw machine shearing.
Background technology
2004, two scientists of Univ Manchester UK were found that Graphene using the method that micromechanics is peeled off,
And obtained Nobel Prize in physics in 2010.Graphene is a kind of single atomic thickness and the carbon original with sp2 bonds
The slab construction of son, in theory, with perfect hexagonal reticulated structure, present excellent electronic stability, thermal conductivity, optical property,
Mechanical property etc..After Graphene is found, because its excellent performance and huge market application foreground have caused thing
The research boom in the field such as reason and material science.Graphene be it is at present most thin be also most hard nano material, be provided simultaneously with
The performance that numerous common materials do not possess such as photosensitiveness is good, thermal conductivity factor is high, electron mobility is high, resistivity is low, mechanical strength is high,
Future is expected to numerous in electrode, battery, transistor, touch-screen, solar energy, sensor, super light material, medical treatment, desalinization etc.
Field is extensively applied, and is one of most promising advanced material.But, there is presently no effective method can volume production high-quality stone
Black alkene.
The preparation method of Graphene mainly includes that chemical vapour deposition technique, oxidation intercalation restore method, liquid phase stripping method, machine
Tool stripping method.Wherein chemical vapour deposition technique can obtain high-quality Graphene, however low yield, substrate is had high demands, turn
Move and there is greatly difficulty；Oxidation intercalation restores method and can realize producing Graphene in batches, but due to stone in oxidizing process
The structure of black alkene is destroyed, it is difficult to obtain high-quality graphene product；Liquid phase stripping method is in a suitable solvent, to utilize
Ultrasonic energy dissociates to graphite flake layer, however, solvent stripping method prepares Graphene presence to be difficult to remove asking for residual solvent
Topic, and solvent stripping yield is general very low.By contrast, mechanical stripping method is that one kind can prepare high-quality stone with low cost
The simple method of black alkene.
Chinese invention patent application number 201410286173.4 discloses a kind of preparation method of Graphene, by graphite oxide
Fractionlet is broken into the mode of mechanical shearing or ball milling, stripping is ground by airflow collision and is obtained Graphene.The invention is based on
Fractionlet graphite oxide under low hydrogen concentration and low temperature reduction and stripping, there is provided it is prepared by a kind of safety, inexpensive hydrogen reduction
The method of Graphene.But the collsion damage of this strength Rotating fields of Graphene, and the Graphene dimensioned area for obtaining is little.
Chinese invention patent application number 201280019582.7 discloses a kind of method for preparing Graphene, by grinding,
Ball milling, airflow milling etc. are ground 4 hours and obtain Graphene by ionic liquid.The stripping of graphite is promoted by ionic liquid, but
The Graphene crystalline size obtained using prolonged grinding is little, and by ionic liquid graphene layer lattice can be made to be subject to shadow
Ring.
Chinese invention patent application number 201310411516.0 discloses a kind of ball-milling preparation method of grapheme material,
The mass volume ratio of graphitic carbon and the hexa-atomic aromatic ring of alkyl or condensed ring polyether nonionic surfactant is 1 by the invention：2～1：
15 and deionized water mixing be loaded on ball grinder, be fixed on ball mill with the rotating speed ball milling 5-30 hours of 200-500rpm, be obtained not
With concentration graphene aqueous solution.
Chinese invention patent application number 201510073825.0 discloses the class mechanical stripping of a kind of tonne of production Graphene
Device and its production method, it passes through rotor as a mill, when rotor is rotated, the outer surface of rotor and the interior table of material bin
Face is ground, so that graphite is stripped thinning acquisition Graphene.
According to above-mentioned, although mechanically repeatedly grinding obtains Graphene, due to being answered by grinding pressure
The effect of power, grinding is clashed into and causes certain destruction to graphite lattice, because grinding applies pressure to graphite, to the graphite peeled off
Huge impulsive force is produced, this impulsive force can make graphene layer produce fault of construction, easily cause graphene layer structural lattice
Defect, the size of Graphene after reducing peeling off so that obtained graphene product crystalline size is little, it is difficult to obtain large-size high-quality
Amount Graphene, either mechanical ball milling or mechanical Gas grinding are to sacrifice Graphene size and lattice is complete
Whole property；In addition, the crunch of abrasive media can cause graphite Rotating fields to become even closer peeling effect can be caused on the contrary to drop
It is low, cause milling time length, cost very high；Furthermore, the Graphene of grinding production at present belongs to batch (-type), and graphite is being carried out
While stripping, the Graphene to having peeled off cannot be filtered out in time, thus be difficult to the volume production of continuous-stable, it is difficult to be carried out
Large-scale industrialized production.
The content of the invention
Graphene is prepared for mechanical strippings such as current ball milling, Gas grindings easily cause graphite lattice damage, two-dimensional
Area is little, time-consuming, high cost, cannot continuous-stable large-scale production defect, the present invention propose one kind is cut using screw machine
The method for continuously preparing grapheme material is cut, so as to realize that continuous-stable prepares large scale area graphite alkene, is further promoted
The mass production production of Graphene.
To solve the above problems, the present invention is employed the following technical solutions：
A kind of method that utilization screw machine shearing continuously prepares grapheme material, it is characterised in that using engagement screws in the same direction
Machine prepares Graphene by the stripping of shearing force, and concrete grammar is as follows：
（1）By graphite raw material and starch, polyvinyl alcohol, polyalcohol, dispersant in high-speed mixer with 600-1200rpm
Rotating speed mix dispersion 10-25min, obtain pre-composition；The quality sum of pre-composition in terms of 100% mass fraction, wherein stone
Black material quality fraction be 80 ~ 90%, starch quality fraction be 5-10%, polyvinyl alcohol mass fraction be 3-8%, polyol quality
Fraction is 1.5-3%, and dispersant mass fraction is 0.5-1%；
（2）By step（1）The pre-composition that obtains is added in engagement screws machine in the same direction, screw machine from feed end to discharge end according to
Secondary setting disperses orientation section, shearing carbonization section, shearing stripping section, when screw rod is rotated with the rotating speed of 100-1200rpm, takes in dispersion
To section, pre-composition is opened along screw rod direction of rotation is dispersed, forms the orientation of piece shape, and is gradually fed forward；
（3）Step（2）Material continue through shearing carbonization section, shearing carbonization section arrange reducing agent charge door, pass through
Charge door pumps into reducing agent, and starch, polyvinyl alcohol, polyalcohol are sheared carbonization in reducing atmosphere；
（4）Step（3）Shearing is continued through by the material of shearing carbonization section and peels off section, using shearing section engagement spiral shell is peeled off
The shear stress that texel part border rotation direction is produced on the contrary, in this shearing stripping process, makes graphite peel off to form individual layer
Or the Graphene of multilayer large scale area；
Described engagement screws machine in the same direction is meshed double screw machine in the same direction, in the same direction three screw machines of engagement, in the same direction four spiral shells of engagement
The engagement screws machine in the same direction of bar machine or more multiscrew；
Described engagement screws machine in the same direction is combined on mandrel by screwing element, by arranging different screw thread units
Part, makes graphite continuously be orientated, be carbonized along vertical and horizontal direction when screw rod rotates, shears stripping so as to obtain large scale area
Graphene；
Described dispersion orientation section conveys screwing element, two groups of teeth shape disk, four groups of oblique angles and is 60 ° by two group 56/56 nibbles
Close screwing element, four groups of reverse 56/56 conveying screwing element compositions；
Described shearing carbonization Duan Yousi groups oblique angle is 45 ° and engages the engagement screw thread that screwing element, four groups of oblique angles are 60 °
Element, four groups reverse 45 ° of engagement screwing element composition；
Described shearing is peeled off Duan Yousi groups oblique angle and is 30 ° and engages the engagement screw thread that screwing element, four groups of oblique angles are 45 °
Element, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups of reverse 60 ° of engagements
Screwing element is constituted；
It is 100-200 DEG C that the mixing section arranges temperature, and it is 300-500 DEG C that shearing carbon section arranges temperature, and section is peeled off in shearing
It is 100-300 DEG C to arrange temperature.
In the same direction engagement screws machine is a kind of conventional equipment used in material processing field, by different screwing elements with product
Wood block type combine on screw rod, material from charge door enter screw rod after, screwing element fricting shearing pull under, along screw rod to
Front conveying material, will be subject to the shear action of strength, due to engaging screw machine in the same direction in engagement screwing element setting area material
Screw rod is in opposite direction region of engagement gap location, and it causes have more excellent tangent plane orientation in region of engagement gap location, engages spiral shell in the same direction
Bar region of engagement is because border rotation direction is conversely, the sub-fraction material on boundary of only keeping to the side can pass through radial clearance.Hence with
In the same direction orientation of the engagement screws machine in its region of engagement is sheared, and is realized by the different screwing elements combination of setting graphite is continuous
Stripping obtains Graphene.Its project the characteristics of be screw rod between any two rotating Vortex when produce tangent plane shearing, reduce to graphite linings
Surge.
Preferably, described engagement screws machine in the same direction is that draw ratio is more than 25/1, screw diameter for the in the same direction of 20-180mm
Meshed double screw machine, in the same direction three screw machines of engagement, in the same direction four screw machines of engagement or in the same direction four screw rod above screw machines of engagement
In one kind.
Preferably, the engagement screws machine in the same direction is triangular form six screw machines of engagement in the same direction.
Preferably, three screw machines of the engagement in the same direction are yi word pattern three screw machines of engagement in the same direction.
Preferably, three screw machines of the engagement in the same direction are three screw machines of Chinese character pin-shaped engagement in the same direction.
Preferably, described graphite raw material is graphite powder, crystalline flake graphite, expanded graphite, highly oriented graphite, thermal cracking stone
At least one in ink, graphite oxide.
Preferably, described starch is etherification starch, esterification starch, pre-gelatinized starch, crosslinking of the particle diameter less than 10 microns
At least one in starch, oxidized starch, acidified starch.
Preferably, described polyalcohol is at least one in ethylene glycol, pentaerythrite, sorbierite, glycerine.
Preferably, described dispersant be lauryl sodium sulfate, neopelex, polyvinylpyrrolidone,
At least one in 1- pyridine acids.
Preferably, the reducing agent is at least one in ethanol, citric acid, tartaric acid, oxalic acid, urea.
Although the reason for existing Graphene size for being by mechanically pulling off acquisition is little is produced during ball milling, Gas grinding
Shearing obtains Graphene, or even single-layer graphene, but this stripping is to be ground into less size by graphite and obtain
, process of lapping produces huge impulsive force to graphite linings, and the dimensioned area for not only making Graphene diminishes, and the layer of Graphene
Lattice is also affected.In consideration of it, the method that a kind of utilization screw machine shearing of the invention continuously prepares grapheme material, using even
The engagement screws machine in the same direction of continuous rotation, graphite preformed objects are opened along screw rod direction of rotation is dispersed, form the orientation of piece shape, are led to
The direction shearing for crossing engagement screwing element orientation is peeled off, and this stripping is dual-screw-stem machine, three screw machines, four screw rods of engagement in the same direction
Interface is high between screw rod engagement screwing element during screw rod rotating Vortex for the meshed double screw machine in the same direction of machine, even more multiscrew
Shear stress, so as to define the Graphene of large scale area.It is this that Graphene is prepared by screw rod stripping, not only to graphite linings
Surge it is minimum, and by setting shearing threaded block, stripping is sheared with the direction parallel to graphite aspect.Enter one
Step, continuous carbonization, reduction and the shearing that carbon raw material can be realized in continuous screw is peeled off, and stone is not only remained to greatest extent
The deck structure of black alkene, and Graphene can be prepared with continuous-stable, the mass production for further having promoted Graphene is produced.
The present invention is sheared using engagement screws machine in the same direction and is peeled off the Graphene of preparation and is ground using ball milling, mill
Mill, Gas grinding, the Graphene for preparing are compared, and are had a clear superiority at aspects such as Graphene quality, yield, cost, inputs, such as
Shown in table 1.
Table 1：
The method that a kind of utilization screw machine shearing of the present invention continuously prepares grapheme material, compared with prior art, it is dashed forward
The characteristics of going out and excellent effect are：
1st, the method that Graphene is prepared by high shear stripping using engagement screws machine in the same direction is proposed.
2nd, stripping is sheared by engagement screws machine in the same direction and prepares Graphene, during screw rod is continued through, graphite is formed
The orientation of piece shape, and the gear block screwing element peeled off by shearing is sheared stripping in the direction of orientation, so as to define footpath
To the high-quality graphene of large scale area, the mechanical strippings such as traditional ball milling, Gas grinding are overcome to Graphene layer crystal
The impact of lattice, it is ensured that the complete lattice structure of Graphene.
3rd, continuous, stable, prepare with scale is realized as the reactor for preparing Graphene by engagement screws machine in the same direction
Graphene, will further promote the extensive industrialized development of Graphene.
4th, the inventive method prepares Graphene, little, low cost, non-environmental-pollution, yield height is put into, with significant market
Using value.
Description of the drawings
Method further to explicitly use screw machine shearing continuously to prepare grapheme material, is illustrated by accompanying drawing.
Accompanying drawing 1：In-line type engages in the same direction three screw machine appearance schematic diagrams.1- screw drive machines；The main charge doors of 2-；3- is also
Former agent charge door；4- dispersion orientation sections；5- shearing carbonization sections；Section is peeled off in 6- shearings.
Accompanying drawing 2：In-line type engages in the same direction three screw machine screw rod schematic diagrames.4- dispersion orientation sections；5- shearing carbonization sections；6-
Section is peeled off in shearing；7- engages screwing element.
Accompanying drawing 3：In-line type engages in the same direction three screw machine cross-sectional shear schematic diagrames.7- engages screwing element.
Accompanying drawing 4：In the same direction engagement screws machine oblique angle is to shear schematic diagram between 45 ° of engagement screwing element.It is homodromal to nibble
Screwing element is closed, in opposite direction in shearing contact position, graphite engages the side of screwing element orientation by by the shear action of strength
Peel off to shearing, so as to obtain the Graphene of high-quality large scale area.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as into the present invention
Scope be only limitted to Examples below.In the case of without departing from said method thought of the present invention, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）By the graphite powder that mass fraction is 85%, mass fraction is 8% etherification starch, measures the polyethylene that fraction is 4%
Alcohol, mass fraction is 2.5% glycerine, mass fraction be 0.5% lauryl sodium sulfate in high-speed mixer with 800rpm
Rotating speed mix dispersion 10min, obtain pre-composition；
（2）By step（1）The pre-composition that obtains adds the main charge door of yi word pattern three screw machines of engagement in the same direction, screw machine by
Feed end to discharge end sets gradually dispersion orientation section, shearing carbonization section, shears and peel off section, and it is 100- that mixing section arranges temperature
200 DEG C, it is 300-500 DEG C that shearing carbon section arranges temperature, and it is 100-300 DEG C that shearing is peeled off section and arranges temperature, and screw rod is with 500rpm
Rotating speed when rotating, convey screwing element, two groups of teeth shape disk, four groups of oblique angles by two group 56/56 and be 60 ° in dispersion orientation section and nibble
Screwing element, four groups of reverse 56/56 conveying screwing elements compositions are closed, pre-composition is opened along screw rod direction of rotation is dispersed, formed
The orientation of piece shape, and be gradually fed forward；
（3）Step（2）Material continue through shearing carbonization section, shearing carbonization Duan Yousi groups oblique angle is 45 ° of engagement spiral shell
Texel part, four groups of oblique angles are 60 ° of engagement screwing element, four groups reverse 45 ° of engagement screwing element composition, in shearing carbonization section
Reducing agent charge door is set, reducing agent tartaric acid is pumped into by charge door, the etherification starch, polyvinyl alcohol, sweet in reducing atmosphere
Oil is sheared carbonization；
（4）Step（3）Shearing is continued through by the material of shearing carbonization section and peels off section, Duan Yousi groups oblique angle is peeled off in shearing
For 30 ° of engagement screwing element, the engagement screwing element that four groups of oblique angles are 45 °, four groups reverse 45 ° of engagement screwing element group,
Four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement screwing element composition, using shearing section engagement spiral shell is peeled off
The shearing section that texel part border rotation direction is produced on the contrary, makes graphite peel off to form thickness in 0.3-5nm in dynamic response
, 90% radial dimension is 10-15 μm of large scale area graphite alkene.
Embodiment 2
（1）By the crystalline flake graphite that mass fraction is 40%, mass fraction is 40% highly oriented graphite, and mass fraction is 10%
Esterification starch, mass fraction is 7.5% polyvinyl alcohol, and mass fraction is 1.5% ethylene glycol, and mass fraction is the ten of 1%
Dialkyl benzene sulfonic acids sodium mixes dispersion 15min in high-speed mixer with the rotating speed of 1000rpm, obtains pre-composition；
（2）By step（1）The pre-composition that obtains adds the main charge door of three screw machines of Chinese character pin-shaped engagement in the same direction, screw machine by
Feed end to discharge end sets gradually dispersion orientation section, shearing carbonization section, shears and peel off section, and screw machine is that draw ratio is more than 30/
1st, screw diameter is 65mm, and it is 100-200 DEG C that mixing section arranges temperature, and it is 300-500 DEG C that shearing carbon section arranges temperature, shearing stripping
It is 100-300 DEG C to arrange temperature from section, when screw rod is rotated with the rotating speed of 800rpm, is conveyed by two group 56/56 in dispersion orientation section
Screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° of engagement screwing element, convey screwing element groups for four groups reverse 56/56
Open along screw rod direction of rotation is dispersed into, pre-composition, form the orientation of piece shape, and be gradually fed forward；
（3）Step（2）Material continue through shearing carbonization section, shearing carbonization Duan Yousi groups oblique angle is 45 ° of engagement spiral shell
Texel part, four groups of oblique angles are 60 ° of engagement screwing element, four groups reverse 45 ° of engagement screwing element composition, in shearing carbonization section
Reducing agent charge door is set, reducing agent citric acid is pumped into by charge door, esterification starch, polyvinyl alcohol, second in reducing atmosphere
Glycol is sheared carbonization；
（4）Step（3）Shearing is continued through by the material of shearing carbonization section and peels off section, Duan Yousi groups oblique angle is peeled off in shearing
For 30 ° of engagement screwing element, the engagement screwing element that four groups of oblique angles are 45 °, four groups reverse 45 ° of engagement screwing element group,
Four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement screwing element composition, using shearing section engagement spiral shell is peeled off
The shearing section that texel part border rotation direction is produced on the contrary, makes graphite peel off to form thickness in 0.3-5nm in dynamic response
, 90% radial dimension is 10-15 μm of large scale area graphite alkene.
By test, yield reaches 80kg/ hours.
Embodiment 3
（1）By the expanded graphite that mass fraction is 90%, mass fraction is 3% pre-gelatinized starch, and mass fraction is 2%
Etherification starch, mass fraction is 3% polyvinyl alcohol, and mass fraction is 1.5% pentaerythrite, and mass fraction is 0.5% poly- second
Alkene pyrrolidone mixes dispersion 25min in high-speed mixer with the rotating speed of 1200rpm, obtains pre-composition；
（2）By step（1）The pre-composition for obtaining adds the main charge door of meshed double screw machine in the same direction, and screw machine is by feed end
Dispersion orientation section, shearing carbonization section are set gradually, is sheared and is peeled off section to discharge end, it is 100-200 DEG C that mixing section arranges temperature, is cut
It is 300-500 DEG C to cut carbon section and arrange temperature, and it is 100-300 DEG C that shearing is peeled off section and arranges temperature, and screw rod is revolved with the rotating speed of 1000rpm
When turning, the engagement screw thread unit that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° is conveyed by two group 56/56 in dispersion orientation section
Part, four groups of reverse 56/56 conveying screwing elements compositions, pre-composition is opened along screw rod direction of rotation is dispersed, forms taking for piece shape
To, and be gradually fed forward；
（3）Step（2）Material continue through shearing carbonization section, shearing carbonization Duan Yousi groups oblique angle is 45 ° of engagement spiral shell
Texel part, four groups of oblique angles are 60 ° of engagement screwing element, four groups reverse 45 ° of engagement screwing element composition, in shearing carbonization section
Reducing agent charge door is set, reducing agent urea is pumped into by charge door, pre-gelatinized starch, polyvinyl alcohol, season in reducing atmosphere
Penta tetrol is sheared carbonization；
（4）Step（3）Shearing is continued through by the material of shearing carbonization section and peels off section, Duan Yousi groups oblique angle is peeled off in shearing
For 30 ° of engagement screwing element, the engagement screwing element that four groups of oblique angles are 45 °, four groups reverse 45 ° of engagement screwing element group,
Four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement screwing element composition, using shearing section engagement spiral shell is peeled off
The shearing section that texel part border rotation direction is produced on the contrary, makes graphite peel off to form thickness in 0.3-5nm in dynamic response
, 90% radial dimension is 10-15 μm of large scale area graphite alkene.
Embodiment 4
（1）By the graphite oxide that mass fraction is 82%, mass fraction is 7% crosslinked starch, measures the poly- second that fraction is 8%
Enol, mass fraction is 2% sorbierite, mass fraction be 1% 1- pyridine acids in high-speed mixer with the rotating speed of 800rpm
Dispersion 15min is mixed, pre-composition is obtained；
（2）By step（1）The pre-composition for obtaining adds the main charge door of four screw machines of engagement in the same direction, and screw machine is by feed end
Dispersion orientation section, shearing carbonization section are set gradually, is sheared and is peeled off section to discharge end, it is 100-200 DEG C that mixing section arranges temperature, is cut
It is 300-500 DEG C to cut carbon section and arrange temperature, and it is 100-300 DEG C that shearing is peeled off section and arranges temperature, and screw rod is revolved with the rotating speed of 500rpm
When turning, the engagement screw thread unit that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° is conveyed by two group 56/56 in dispersion orientation section
Part, four groups of reverse 56/56 conveying screwing elements compositions, pre-composition is opened along screw rod direction of rotation is dispersed, forms taking for piece shape
To, and be gradually fed forward；
（3）Step（2）Material continue through shearing carbonization section, shearing carbonization Duan Yousi groups oblique angle is 45 ° of engagement spiral shell
Texel part, four groups of oblique angles are 60 ° of engagement screwing element, four groups reverse 45 ° of engagement screwing element composition, in shearing carbonization section
Reducing agent charge door is set, reducing agent oxalic acid is pumped into by charge door, crosslinked starch, polyvinyl alcohol, sorb in reducing atmosphere
Alcohol is sheared carbonization；
（4）Step（3）Shearing is continued through by the material of shearing carbonization section and peels off section, Duan Yousi groups oblique angle is peeled off in shearing
For 30 ° of engagement screwing element, the engagement screwing element that four groups of oblique angles are 45 °, four groups reverse 45 ° of engagement screwing element group,
Four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement screwing element composition, using shearing section engagement spiral shell is peeled off
The shearing section that texel part border rotation direction is produced on the contrary, makes graphite peel off to form thickness in 0.3-5nm in dynamic response
, 90% radial dimension is 10-15 μm of large scale area graphite alkene.
Embodiment 5
（1）It is 5% acidified starch by the thermal cracking graphite that mass fraction is 90%, mass fraction, mass fraction is 3%
Polyvinyl alcohol, mass fraction is 1.5% glycerine, mass fraction be 0.5% lauryl sodium sulfate in high-speed mixer with
The rotating speed of 1000rpm mixes dispersion 25min, obtains pre-composition；
（2）By step（1）The pre-composition for obtaining adds the main charge door of six screw machines of engagement triangular form arrangement in the same direction, spiral shell
Bar machine is set gradually dispersion orientation section, shearing carbonization section, is sheared and peel off section from feed end to discharge end, and screw machine is that draw ratio is big
It is 120mm in 20/1, screw diameter, it is 100-200 DEG C that mixing section arranges temperature, and it is 300-500 DEG C that shearing carbon section arranges temperature,
It is 100-300 DEG C that shearing is peeled off section and arranges temperature, when screw rod is rotated with the rotating speed of 1200rpm, in dispersion orientation section by two group 56/
56 conveying screwing elements, two groups of teeth shape disk, four groups of oblique angles are 60 ° of engagement screwing element, convey screw threads unit for four groups reverse 56/56
Part is constituted, and pre-composition is opened along screw rod direction of rotation is dispersed, forms the orientation of piece shape, and is gradually fed forward；
（3）Step（2）Material continue through shearing carbonization section, shearing carbonization Duan Yousi groups oblique angle is 45 ° of engagement spiral shell
Texel part, four groups of oblique angles are 60 ° of engagement screwing element, four groups reverse 45 ° of engagement screwing element composition, in shearing carbonization section
Reducing agent charge door is set, reducing agent ethanol is pumped into by charge door, acidified starch, polyvinyl alcohol, glycerine in reducing atmosphere
It is sheared carbonization；
（4）Step（3）Shearing is continued through by the material of shearing carbonization section and peels off section, Duan Yousi groups oblique angle is peeled off in shearing
For 30 ° of engagement screwing element, the engagement screwing element that four groups of oblique angles are 45 °, four groups reverse 45 ° of engagement screwing element group,
Four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement screwing element composition, using shearing section engagement spiral shell is peeled off
The shearing section that texel part border rotation direction is produced on the contrary, makes graphite peel off to form thickness in 0.3-5nm in dynamic response
, 90% radial dimension is 10-15 μm of large scale area graphite alkene.
Claims (10)
1. a kind of method that utilization screw machine shearing continuously prepares grapheme material, it is characterised in that using engagement screws machine in the same direction
Graphene is prepared by the stripping of shearing force, concrete grammar is as follows：
（1）By graphite raw material and starch, polyvinyl alcohol, polyalcohol, dispersant in high-speed mixer turning with 600-1200rpm
Speed mixes dispersion 10-25min, obtains pre-composition；In terms of 100% mass fraction, wherein graphite is former for the quality sum of pre-composition
Material mass fraction be 80 ~ 90%, starch quality fraction be 5-10%, polyvinyl alcohol mass fraction be 3-8%, polyol quality fraction
For 1.5-3%, dispersant mass fraction is 0.5-1%；
（2）By step（1）The pre-composition for obtaining is added in engagement screws machine in the same direction, and screw machine is set successively from feed end to discharge end
Dispersion orientation section, shearing carbonization section are put, is sheared and is peeled off section, when screw rod is rotated with the rotating speed of 100-1200rpm, in dispersion orientation
Section, pre-composition is opened along screw rod direction of rotation is dispersed, forms the orientation of piece shape, and is gradually fed forward；
（3）Step（2）Material continue through shearing carbonization section, shearing carbonization section arrange reducing agent charge door, by charging
Mouth pumps into reducing agent, and starch, polyvinyl alcohol, polyalcohol are sheared carbonization in reducing atmosphere；
（4）Step（3）Shearing is continued through by the material of shearing carbonization section and peels off section, using shearing section engagement screw thread unit is peeled off
The shear stress that part border rotation direction is produced on the contrary, in this shearing stripping process, makes graphite peel off to form individual layer or many
The Graphene of layer large scale area；
Described engagement screws machine in the same direction is meshed double screw machine in the same direction, in the same direction three screw machines of engagement, in the same direction four screw machines of engagement
Or the engagement screws machine in the same direction of more multiscrew；
Described engagement screws machine in the same direction is combined on mandrel by screwing element, by arranging different screwing elements,
Graphite is continuously orientated, is carbonized along vertical and horizontal direction when screw rod rotates, shear stripping so as to obtain large scale area
Graphene；
Described dispersion orientation section conveys the engagement spiral shell that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° by two group 56/56
Texel part, four groups of reverse 56/56 conveying screwing element compositions；
Described shearing carbonization Duan Yousi groups oblique angle be 45 ° engagement screwing element, engagement screw thread that four groups of oblique angles are 60 ° it is first
Part, four groups reverse 45 ° of engagement screwing element composition；
It is first that the engagement screw thread that the engagement screwing element that Duan Yousi groups oblique angle is 30 °, four groups of oblique angles are 45 ° is peeled off in described shearing
Part, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement spiral shell
Texel part is constituted；
It is 100-200 DEG C that the mixing section arranges temperature, and it is 300-500 DEG C that shearing carbonization section arranges temperature, and shearing is peeled off section and set
Temperature is put for 100-300 DEG C.
2. a kind of method that according to claim 1 utilization screw machine shearing continuously prepares grapheme material, it is characterised in that：
Described engagement screws machine in the same direction be draw ratio more than 25/1, screw diameter for 20-180mm meshed double screw machine in the same direction, same
To three screw machines of engagement, the one kind engaged in the same direction in four screw machines.
3. a kind of method that according to claim 1 utilization screw machine shearing continuously prepares grapheme material, it is characterised in that：
The engagement screws machine in the same direction is triangular form six screw machines of engagement in the same direction.
4. a kind of method that according to claim 2 utilization screw machine shearing continuously prepares grapheme material, it is characterised in that：
Three screw machines of the engagement in the same direction are yi word pattern three screw machines of engagement in the same direction.
5. a kind of method that according to claim 2 utilization screw machine shearing continuously prepares grapheme material, it is characterised in that：
Three screw machines of the engagement in the same direction are three screw machines of Chinese character pin-shaped engagement in the same direction.
6. a kind of method that according to claim 1 utilization screw machine shearing continuously prepares grapheme material, it is characterised in that：
Described graphite raw material be graphite powder, crystalline flake graphite, expanded graphite, highly oriented graphite, thermal cracking graphite, graphite oxide in extremely
Few one kind.
7. a kind of method that according to claim 1 utilization screw machine shearing continuously prepares grapheme material, it is characterised in that：
Described starch is etherification starch, esterification starch, pre-gelatinized starch, crosslinked starch, oxidized starch, acid of the particle diameter less than 10 microns
Change at least one in starch.
8. a kind of method that according to claim 1 utilization screw machine shearing continuously prepares grapheme material, it is characterised in that：
Described polyalcohol is at least one in ethylene glycol, pentaerythrite, sorbierite, glycerine.
9. a kind of method that according to claim 1 utilization screw machine shearing continuously prepares grapheme material, it is characterised in that：
Described dispersant be lauryl sodium sulfate, neopelex, polyvinylpyrrolidone, 1- pyridine acids at least
It is a kind of.
10. a kind of method that according to claim 1 utilization screw machine shearing continuously prepares grapheme material, its feature exists
In：The reducing agent is at least one in ethanol, citric acid, tartaric acid, oxalic acid, urea.
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| CN107055519A (en) * | 2016-12-28 | 2017-08-18 | 成都新柯力化工科技有限公司 | A kind of method peeled off and prepare graphene microchip that rubbed using three-roll grinder in the same direction |
| CN106672953A (en) * | 2016-12-29 | 2017-05-17 | 成都新柯力化工科技有限公司 | Internal mixer for preparing graphene through tensile peeling and method for preparing graphene |
| CN107459035A (en) * | 2017-05-25 | 2017-12-12 | 拜永孝 | A kind of large-scale preparation method of the controllable high-quality graphene of lamellar spacing |
| CN107298440B (en) * | 2017-06-14 | 2018-05-04 | 成都新柯力化工科技有限公司 | A kind of method for continuously preparing graphene in screw machine using supercritical fluid |
| CN107265446A (en) * | 2017-07-07 | 2017-10-20 | 哈尔滨摆渡新材料有限公司 | A kind of preparation method of graphene |
| CN107324320A (en) * | 2017-07-10 | 2017-11-07 | 安徽理工大学 | A kind of method that mechanical shearing prepares two-dimension nano materials |
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