CN104370283B - A kind of Graphene peels off still, Graphene production system and the method producing Graphene - Google Patents
A kind of Graphene peels off still, Graphene production system and the method producing Graphene Download PDFInfo
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Abstract
The invention discloses a kind of Graphene and peel off still.This Graphene stripping still includes periphery and is provided with the kettle of heating jacket, and kettle is provided with for detecting the temperature measuring equipment of the Pressure gauge of pressure and detection temperature in the kettle in still；The top of kettle is provided with charging aperture, and the middle and lower part of kettle is provided with discharging opening, is provided with rotation axle in kettle, rotates axle and is connected to stirrer paddle, rotates axle and is connected with the drive motor at the outer top being located at kettle；Tighten solid matter to be furnished with and determine shear-blade in inner wall of kettle face for exfoliated graphite, determine the blade of shear-blade inwardly beyond the internal face of described kettle, adjacent determine to be formed between shear-blade groove.Graphene of the present invention is peeled off still and is determined shear-blade by arranging on inner wall of kettle face, and determining shear-blade can when without abrading-ball, without the successful stripping realizing Graphene when directly pressing.The invention still further relates to the Graphene production system containing this Graphene stripping still and the method producing Graphene by this production system.
Description
Technical field
The present invention relates to Graphene production technical field, be specifically related to a kind of stripping still for being Graphene by graphite stripping and Graphene production system, further relate to the production method of a kind of Graphene.
Background technology
Graphene is a kind of lamellar two-dimensional material, and carbon atom therein is with sp2Hybrid orbital composition hexagonal honeycomb lattice structure.This special two-dimensional structure causes that Graphene presents various special performance, such as high intensity, high rigidity, high-termal conductivity and electric conductivity；Due to these construction featuress and performance characteristics, Graphene is described as the potential material for manufacturing protection coating, transparent bent electronic component, capacitor with super capacity etc..You need to add is that, stricti jurise is said, Graphene is the lamellar of a kind of monolayer；But due to the preparation difficulty of single-layer graphene, generally also the form the few-layer graphene alkene with similar performance is also ranged in the category of Graphene.
At present, the method that prepared by Graphene mainly has: chemically grown method and physics stripping method.Low compared to efficiency, be not suitable for the chemically grown method of industrialized mass production; it is raw material that physics stripping method mainly adopts cheap graphite; make graphite layers peeling-off by graphite crystal is applied mechanical force; break the Van der Waals force of graphite layers; forming monolithic graphite alkene or form the few-layer graphene alkene, this physical separation methods has more industrial prospect and applicable large-scale production.
In order to make graphite layers peeling-off, stripping means conventional in physics stripping method have conventional grinding, ball milling, stirring ball-milling etc..
Wherein, routine grinding refers to grinds graphite in mortar formula beveller, and its shortcoming is: first, the frictional force that shearing force source pressure causes, and pressure is crossed conference and caused that motor is difficult to drive pestle body to rotate, and limits shearing force, and too small being difficult to of pressure shears stripping；Secondly, shear efficiency is low, increases and can be caused that part powder body shearing force is not enough on the contrary by powder compact amount；Again, graphite is applied pressure inequality by pestle body, it is easy to produce overground, and graphite is applied pressure by pestle body can make Graphene produce fault of construction, and after even making stripping, Graphene is pulverized so that the product edge prepared has " burr " more, and crystalline size is little.
Ball milling refers to and by abrading-ball, graphite composite powder is ground in ball mill, this method overcomes conventional powder and grinds the shortcoming that pressurized is uneven, local applying pressure is big, but powder body can be provided and impacts and shear two kinds of active force by abrading-ball in mechanical milling process, abrading-ball not only againsts the inwall of ball grinder and graphite is applied shear action, and abrading-ball can the inwall of impact bead grinding jar back and forth, the Graphene peeled off is produced huge impulsive force；Pressure in conventional lapping mode, this impulsive force coming from abrading-ball also can make Graphene produce fault of construction, reduces the size of Graphene after peeling off so that prepared product edge has " burr " more, and crystalline size is little.
Stirring spheroidal graphite is the machinery mill mode that a kind of stirring combines with spheroidal graphite, and agitator drives abrading-ball collision friction in cavity, and powder body is ground；The percussion of its abrading-ball relatively ball milling method is gentle, but due to the existence of abrading-ball, still unavoidably the Graphene peeled off is produced impulsive force, Graphene is made to produce fault of construction, reduce the size of Graphene after peeling off so that prepared product edge has " burr " more, and crystalline size is little.
It in contrast to above-mentioned physics stripping method, have the solution of powdered graphite to peel off Graphene by simple dispersed with stirring, due to the deficiency of shearing force, it is common to there is the shortcoming that productivity is low, and need by some external auxiliary media and householder method often.More reported media and method have: as introduced other groups on graphite linings surface to increase interlamellar spacing, publication number for making graphite layers expand and publication number is for ul-trasonic irradiation disclosed in the Chinese patent of CN103910354A etc. by supercritical at the pressure of abrupt release disclosed in the Chinese patent of CN102765717A by redox reaction disclosed in Chinese patent that publication number is CN102502611A.Wherein increase interlamellar spacing by oxidation-reduction method and can introduce defect to graphene-structured, affect the performances such as conductivity, although can pass through to reduce to remove the group introduced, but process is complicated, it is unfavorable for industrialized production, and cannot realize graphene-structured 100% reduction, and the treatment fluid used can to environment produce pollute；And the splitting that the impulsive force that supercritical and ultrasound wave produce is not only graphite provides driving force, and due to the astaticism of impulsive force, Graphene also can be made to produce explosion, thus reducing its size.
Summary of the invention
The Graphene size obtained for Graphene mechanical stripping method is little, edge has " burr ", fault of construction many more and method is difficult to industrialized shortcoming, it is an object of the invention to design a kind of applicable industrialized production, the stripping still obtaining large area zero defect Graphene on the basis of graphite flake layer natural structure can not destroyed.
Another object of the present invention also resides in, it is provided that the production system of a kind of applicable industrialized production high-quality Graphene.
Another purpose of the present invention also resides in, it is provided that a kind of method of industrialized production Graphene.
For realizing above-mentioned first purpose, the present invention is achieved through the following technical solutions: a kind of Graphene peels off still, is provided with the kettle of heating jacket including periphery, and kettle is provided with for detecting the temperature measuring equipment of the Pressure gauge of pressure and detection temperature in the kettle in still；The top of kettle is provided with charging aperture, and the middle and lower part of kettle is provided with discharging opening, is provided with rotation axle in kettle, rotates axle and is connected to stirrer paddle, rotates axle and is connected with the drive motor at the outer top being located at kettle；Tighten solid matter to be furnished with and determine shear-blade in inner wall of kettle face for exfoliated graphite, determine the blade of shear-blade inwardly beyond the internal face of described kettle, adjacent determine to be formed between shear-blade groove.
Compared with existing Graphene stripping off device, the Graphene of the present invention is peeled off still and is determined shear-blade by arranging on inner wall of kettle face, and determining shear-blade can produce good shear action to the graphite slipping over shear-blade surface when without abrading-ball, nothing directly pressure；The groove determining to be formed between shear-blade can be treated the graphite of shearing and produce frictional force, further increases shear effect；High rotating speed is coordinated again by the groove between shear-blade and shear-blade, it is achieved thereby that the successful stripping of Graphene.Graphene of the present invention peels off still without equally graphite or Graphene directly being applied immense pressure to pestle body, and without adding membership, graphite or Graphene are produced the abrading-ball of impulsive force, graphite is produced mainly shear action by whole device, so that the graphite size of preparation is big, fault of construction is few, burrs on edges is few.Owing to graphite can be produced high shear forces by this stripping still, therefore conventional in stirring stripping mode auxiliary media and householder method can also be saved when producing Graphene with this device, only add disperse medium and dispersant protects the Graphene after peeling off.In addition by the control of temperature and pressure, it is ensured that the controllability of each condition and repeatability in preparation process, the product repeatability of preparation is high.
Separate Graphene to make to determine shear-blade, reduce to the utmost simultaneously and determine the shear-blade destruction to graphene-structured, it is preferable that described determine that shear-blade is tapered or zigzag or both combinations；Taper or zigzag corner angle are 10-160 °.
The inventors have also found that, it is be sheared in unoriented direction that the reason that after the stripping of existing Graphene, size is little, shear effect is poor also resides in graphite, wherein when graphite linings is sheared in the way of non-parallel to described shear surface, it is not be sheared and separate Graphene that the result caused tends to graphite, but graphite or Graphene are ground into less size.
In order to improve shear effect, increase the effective active area of shear action, it is preferable that described stirrer paddle is axial flow type agitating valve leaf；Described determine shear-blade and be arranged on described region, inner wall of kettle face and this areas adjacent that described stirrer paddle slips over；Described determine shear-blade and arrange along the rotation direction spiral of described rotation axle at the internal face of described kettle.
The fragmentation because of non-parallel shearing in order to avoid graphite or graphene planes size, it is further preferred that described, to determine shear-blade be zigzag, and is plastic cutter；Each both sides end face determining shear-blade is perpendicular to its place helix, and crown, slightly towards deviating from the described spiral direction bending determining shear-blade, forms the warpage portion of plastic cutter.Determine the crown of shear-blade slightly towards deviating from the described spiral direction bending determining shear-blade, form the warpage portion of plastic cutter.In order to improve peeling effect, it is further preferred that the described crown determining shear-blade is 5-15 ° slightly towards the angle deviating from the described spiral direction bending determining shear-blade.
In order to improve shear effect, increase the effective active area of shear action, or preferably, described stirrer paddle is radial-flow type stirrer paddle, described determine shear-blade and be arranged on above and below the region, described inner wall of kettle face that described stirrer paddle slips over, respectively upper determine shear-blade and lower determine shear-blade；Described upper determine shear-blade and arrange along the rotation direction spiral of described rotation axle at the internal face of described kettle；Described lower determine shear-blade described kettle internal face along described rotation axle rotation direction spiral decline arrangement.The fragmentation because of non-parallel shearing in order to avoid graphite or graphene planes size, it is further preferred that described, to determine shear-blade be zigzag, and is plastic cutter；Each both sides end face determining shear-blade is respectively perpendicular to its place helix, and the upper crown determining shear-blade bends slightly towards deviating from the described upper spiral direction determining shear-blade, forms the warpage portion of plastic cutter；The described lower crown determining shear-blade bends slightly towards deviating from the described lower spiral descent direction determining shear-blade, forms the warpage portion of plastic cutter.In order to improve peeling effect, still more preferably, the described upper crown determining shear-blade is 5-15 ° slightly towards the angle deviating from the described upper spiral direction bending determining shear-blade, and the described lower crown determining shear-blade is 5-15 ° slightly towards the angle deviating from the described lower spiral descent direction bending determining shear-blade.
When adopting radial-flow type stirrer paddle, in order to improve shear action near stirrer paddle and peeling effect, preferably, stating the radial extremity of stirrer paddle and be also distributed and have the dynamic shear-blade for exfoliated graphite, dynamic shear-blade is arranged from the radial extremity of stirrer paddle towards the internal face of described kettle；Described dynamic shear-blade is zigzag, and is plastic cutter；The crown of the dynamic shear-blade being positioned at the radial extremity top of described stirrer paddle is bent upwards slightly, and forms the warpage portion of plastic cutter；The crown of the dynamic shear-blade being positioned at the radial extremity bottom of described stirrer paddle is slightly bent downwardly, and forms the warpage portion of plastic cutter.In order to improve shear action and the peeling effect of dynamic shear-blade, it is preferable that the crown of described dynamic shear-blade is slightly 75-85 ° to the angle of vertical direction bending.
For realizing above-mentioned second purpose, the present invention is achieved through the following technical solutions: a kind of Graphene production system peeling off still containing above-mentioned Graphene, except described Graphene peels off still, this Graphene production system also includes the storage tank going out product for collecting and stand described Graphene stripping still process heel row successively along process sequence, for being centrifuged upper strata suspension in storage tank separating the centrifuge peeling off Graphene and unstripped graphite, for the supernatant obtained after centrifuge is filtered, the vacuum apparatus of washing, and for drying the freeze drying plant of Graphene after vacuum filters.Here, the discharging opening of described stripping still is connected with the charging aperture of described storage tank, and the discharging opening of described storage tank is connected with the charging aperture of described centrifuge, and the supernatant discharging opening of described centrifuge is connected with described vacuum apparatus.
For realizing above-mentioned 3rd purpose, the present invention is achieved through the following technical solutions: a kind of method using above-mentioned Graphene production system to produce Graphene, comprises the following steps:
Step one, graphite flakes and solvent are injected Graphene peel off in still, add dispersant, start motor and be stirred, make mixing of materials uniform, after stirring, close kettle；
Step 2, heated graphite alkene peel off the kettle of still, keep still body temperature to be 80-150 DEG C, and pressure is 0.1-5Mpa, and agitator shaft speed is 1000-20000rpm, stir and at least close motor after 3h；
Step 3, by the discharging opening of kettle, upper strata graphene suspension is expelled in storage tank, stands 12-24h；
Step 4, being delivered in centrifuge by the graphene suspension in storage tank in step 3, centrifuge speed is 1000-6000rpm, and centrifugation time 10min-2h takes the supernatant, and in vacuum apparatus, vacuum is filtrated to get filter cake；
Step 5, the filter cake that step 4 is obtained with appropriate distilled water wash, filter cake more than lyophilization 3h in freeze drying plant, namely obtain graphene product.
Compared with prior art, advantages of the present invention and having the beneficial effects that:
1, the present invention holds on in Graphene stripping preparation process, most important shear action, logical excessive speeds, determine the mode such as arrange of shear-blade and groove, give full play to the shearing between material and material at high speed with " collision " of groove, it is achieved that the successful stripping of Graphene.
2, peel off, by Graphene of the present invention, the Graphene quality that still and production system mechanical stripping prepare good, save the lamellar structure of Graphene preferably, the Graphene distribution prepared is homogeneous, fault of construction is few, edge is rounded, it is applied in " the four big characteristics " that play Graphene that the fields such as Material cladding can be maximum, expands practical value and the range of application of Graphene.
3, adopt Graphene of the present invention to peel off still and graphite is carried out stripping and prepares Graphene by production dress system; owing to adopting the method that physics is peeled off to produce Graphene; prime cost is graphite; labour cost, charges for water and electricity and administration fee; graphite raw material is cheap; there is great cost advantage, and the commercial production of scale can be realized；Preparation process does not use strong acid and strong base or other noxious substances, and additive is few, the auxiliary media peeled off without common mechanical and supplementary means so that prepare Graphene more environmental protection, technique simple.
Accompanying drawing explanation
Fig. 1 is the structural representation of Graphene production system of the present invention；
Fig. 2 is the structural representation that in embodiment 1, Graphene peels off still；
Fig. 3 is the partial schematic diagram in Fig. 2 after the inner wall of kettle face expansion of Graphene stripping still；
Fig. 4 is the partial schematic diagram in embodiment 2 after the inner wall of kettle face expansion of middle Graphene stripping still；
Fig. 5 be along Fig. 4 from P to vertical direction, namely A to observe inner wall of kettle face time partial structurtes schematic diagram；
Fig. 6 is the structural representation that in embodiment 3, Graphene peels off still；
Fig. 7 is the partial schematic diagram in Fig. 6 after the inner wall of kettle face expansion of Graphene stripping still；
Fig. 8 be along Fig. 7 from P to vertical direction, namely A to observe inner wall of kettle face time partial structurtes schematic diagram；
Fig. 9 be along Fig. 7 from Q to vertical direction, namely B to observe inner wall of kettle face time partial structurtes schematic diagram；
Figure 10 is the structural representation that in embodiment 4, Graphene of the present invention peels off still；
Figure 11 is the close-up schematic view at D place in Figure 10.
In figure: 1, Graphene peels off still；2, storage tank；3, centrifuge；4, vacuum apparatus；5, freeze drying plant；11, kettle；12, heating jacket；13, axle is rotated；14, stirrer paddle；15, drive motor；16, shear-blade is determined；16-1, upper determine shear-blade；16-2, lower determine shear-blade；17, groove；18, dynamic shear-blade；18-1, upper dynamic shear-blade；18-2, lower dynamic shear-blade；19, temperature measuring equipment；20, Pressure gauge；111, charging aperture；112, discharging opening；160 and 180, warpage portion.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the specific embodiment of the present invention is further described.Following example are only for clearly illustrating technical scheme, and can not limit the scope of the invention with this.
Embodiment 1
The present invention relates to a kind of Graphene and peel off still and Graphene production system and Graphene production method.
This Graphene production system, as it is shown in figure 1, include Graphene successively to peel off still 1, storage tank 2, centrifuge 3, vacuum apparatus 4 and freeze drying plant 5 along process sequence；Storage tank 2 is used for collecting and stand Graphene and peels off still 1 and process heel row and go out product, centrifuge 3 is for being centrifuged upper strata suspension in storage tank 2 separating stripping Graphene and unstripped graphite, vacuum apparatus 4 is filtered for the supernatant obtained after being centrifuged by centrifuge 3, washs, and freeze drying plant 5 is used for drying Graphene after vacuum filters.Here, the discharging opening 112 peeling off still 1 is connected with the charging aperture of storage tank 2, and the discharging opening of storage tank 2 is connected with the charging aperture of centrifuge 3, and the supernatant discharging opening of centrifuge 3 is connected with vacuum apparatus 4.
As in figure 2 it is shown, it is the kettle 11 that a periphery is provided with heating jacket 12 that Graphene peels off still, kettle 11 is provided with the Pressure gauge 20 for detecting pressure in still and the temperature measuring equipment 19 of detection temperature in the kettle；The top of kettle 11 is provided with the charging aperture 111 for charging, the middle and lower part of kettle 11 is provided with for the discharging opening 112 by peeling off rear suspension liquid, rotation axle 13 it is provided with in kettle 11, rotate axle 13 and be connected to stirrer paddle 14, rotate axle 13 to be connected with the drive motor 15 at the outer top being located at kettle 11, drive stirrer paddle 14 to rotate.Tightening solid matter at kettle 11 internal face to be furnished with and determine shear-blade 16 for exfoliated graphite, determining shear-blade 16 can be fixed on kettle 11 inwall by the mode of such as directly welding, it is also possible to by kettle 11 inwall is directly processed to form.Preferably first groove is set at kettle 11 inwall, is being fixed on having processed the arc determining shear-blade 16 in advance on the inwall of kettle 11.Regardless of mode, the blade determining shear-blade 16 inwardly to exceed the internal face of kettle 11, thus forming the stirrer paddle 14 that graphite can produce shear action.Additionally, each groove 17 determining to form the graphite generation good friction power that can treat shearing between shear-blade 16, thus further increasing the shear effect to graphite.
Determine shear-blade 16 and stirrer paddle 14 is the two of wherein of paramount importance two structure members.
Here, determining shear-blade 16 can be tapered, and its cone rib can be disposed as blade, and the graphite slipping over its surface can be produced shear action by each blade boring rib and the vertex of a cone.Determine shear-blade 16 and can also is that zigzag, as in figure 2 it is shown, the graphite slipping over its surface is produced shear action by the flank of tooth particularly between cog of sawtooth.When arranging without special construction, the former shearing effect is better, although the latter's shearing force is slightly weak, but is more beneficial for reducing the destruction determining shear-blade 16 to graphene-structured, and the Graphene average-size obtained is bigger again.Certainly can also be designed to taper and zigzag combination by determining shear-blade 16, each determine between shear-blade 16 or groove 17 can be formed, repeat no more here.What no matter select which kind of structure mentioned here determines shear-blade 16, it is preferred that embodiment is, taper or zigzag corner angle are 10-160 °.
Shear effect except relevant with the shape determining shear-blade 16, also has the area forming shear action relevant with peeling effect.What area here was directed not only to determine shear-blade 16 arranges quantity and density, more concerns in graphite in which way through shear-blade 16 region.If the graphite linings in graphite with determine the approximately perpendicular direction of shear-blade 16 through overdetermined shear-blade, as shown in Figure 2, then determine shear-blade 16 can to greatest extent to graphite apply shear action, thus improving shear effect and peeling effect.In Graphene mechanical stripping device before, Graphene substantially all right and wrong are directionally stripped, and cause that shear effect is poor, it is therefore desirable to additional medium；And cause that peels off is concurrently milled or destructurized.
Inventor have found that have the graphite of lamellar structure when moving with disperse medium in disperse medium, graphite linings is tended to parallel with the flow direction of disperse medium.Inventor utilizes this point to study intensively how to arrange and determine shear-blade 16 and stirrer paddle 14, so that graphite linings in graphite by the way of near normal determines shear-blade 16 through overdetermined shear-blade 16 region, sheared abreast in the way of being parallel to kettle 11 internal face, so that Graphene is stripped out, reduce graphite or the pulverized probability of Graphene.
In the present embodiment, stirrer paddle 14 is the stirrer paddle 14 of a kind of axial-flow type, it is characterized in main discharge opeing direction and rotates the axially in parallel of axle 13, so that the Flow of Goods and Materials direction in kettle 11 is as shown in Figure 2, migrate to and rise along kettle 11 spiral inner wall near along the dispersion liquid at kettle 11 inwall place, so that graphite linings contained by graphite is to be parallel to kettle 11 internal face, approximately perpendicular to determining in the way of shear-blade 16 through overdetermined shear-blade 16 region in dispersion liquid, thus being sheared to greatest extent, reduce impulsive force, and then reduce by the probability of impact comminution.In the layout area determining shear-blade 16, determine shear-blade 16 and be preferably disposed on kettle 11 internal face region and this areas adjacent that stirrer paddle 14 slips over.Internal face in the upper and lower of kettle 11 is preferably not provided with determining shear-blade 16, because the dispersion liquid near the internal face of the upper and lower of kettle 11 is not flow along being parallel to the direction along kettle 11 inwall, if here arrange determine shear-blade 16 to improve shear effect there is no big help, can reduce on the contrary peel off Graphene size.On the arrangement mode determining shear-blade 16, determine shear-blade 16 and preferably rotate the rotation direction spiral arrangement of axle 13 at the internal face of kettle 11, as shown in Figure 3.The adjacent shear-blade 16 that is ranked can be arranged in parallel and can also be crisscross arranged, and is crisscross arranged by contrast, as it is shown on figure 3, be a kind of can improve determine shear-blade 16 arrangement density, increase groove 17 rubbing action, strengthen shear effect mode.In Fig. 3, P direction represents the fluid flow direction near kettle 11 internal face, namely determines the spiral direction of shear-blade 16.
Embodiment 2
It has been observed that profile of tooth to determine shear-blade 16 less to the Structural Disintegration of Graphene than taper shear-blade 16.On the basis of embodiment 1, the present embodiment has made improvement.One of difference of the present embodiment and embodiment 1 is in that to determine the structure of shear-blade 16.
In the present embodiment, selecting zigzag shear-blade 16 of determining, each both sides end face determining shear-blade 16 is perpendicular to its place helix, thus greatly adding shearing effective area possibly；Simultaneously, in order to reduce the crown determining shear-blade 16 to the damage of graphene-structured, as shown in Figure 4 and Figure 5, it is designed to a kind of plastic cutter by determining shear-blade 16, not only each both sides end face determining shear-blade 16 is perpendicular to its place helix (P direction), bend slightly towards deviating from the spiral direction determining shear-blade 16 from the crown determining shear-blade 16, form the warpage portion 160 of plastic cutter.The crown that can preferably determine shear-blade 16 is 5-15 ° slightly towards the angle [alpha] deviating from the spiral direction bending determining shear-blade 16.In Fig. 4 and Fig. 5, P direction represents the fluid flow direction near kettle 11 internal face, namely determines the spiral direction of shear-blade 16；A direction is the vertical direction in P direction.
By arranging warpage portion 160, make when realizing approximately parallel shearing graphite linings, reduce the crown determining shear-blade 16 destruction to graphite linings or graphene-structured, so that the Graphene defect prepared is less, size better, burr minimizing around.
Embodiment 3
For making graphite linings be sheared abreast, it is different in that with embodiment 1, as shown in Figure 6, in the present embodiment, select radial flow type stirrer paddle 14, be characterized in main discharge opeing direction and rotate the axially vertical of axle 13, i.e. stirrer paddle 14 primarily radially discharge opeing, discharge liquid fit again inner wall of kettle face, respectively with spiral mode flowing above and in spiral decline mode to the flowing underneath in kettle 11 internal face region to kettle 11 internal face region, as shown in Figure 6.In order to graphite linings is sheared to greatest extent, reduce impulsive force, and then reduce by the probability of impact comminution, be respectively provided with and determine shear-blade 16-1 and lower determine shear-blade 16-2；Upper determine shear-blade 16-1 and be arranged on the top in the kettle 11 internal face region that stirrer paddle 14 slips over, lower determine that shear-blade 16-2 determines shear-blade 16-1 and be arranged on the lower section in the kettle 11 internal face region that stirrer paddle 14 slips over；Above determine shear-blade 16-1 to arrange along the rotation direction spiral rotating axle 13 at the internal face of kettle 11；Determine down the shear-blade 16-2 internal face at kettle 11 along the rotation direction spiral decline arrangement rotating axle 13, as shown in Figure 7.
In the present embodiment, it is upper and lower that to determine shear-blade 16-1,16-2 be zigzag, and be plastic cutter, each upper both sides end face determining shear-blade 16-1 is perpendicular to its place helix (P direction), each lower both sides end face determining shear-blade 16-2 is perpendicular to its place helix (Q direction), thus to increase the effective area sheared；The upper crown determining shear-blade 16-1 bends slightly towards deviating from the upper spiral direction determining shear-blade 16-1, forms the warpage portion 160 of plastic cutter, as shown in Figure 8；Determine down the crown of shear-blade 16-2 slightly towards deviating from the lower spiral descent direction bending determining shear-blade 16-2, form the warpage portion 160 of plastic cutter, as shown in Figure 9.Described in the effect in plastic cutter warpage portion 160 and embodiment 2 identical, be different in that, in the present embodiment, owing to the flow direction of dispersion liquid is different, the bending direction difference in the upper and lower warpage portion 160 determine shear-blade 16-1,16-2.Preferably can being 5-15 ° slightly towards the angle beta deviating from the upper spiral direction bending determining shear-blade 16-1 by the upper crown determining shear-blade 16-1, the lower crown determining shear-blade 16-2 is 5-15 ° slightly towards the angle γ deviating from the lower spiral descent direction bending determining shear-blade 16-2.In Fig. 7 to Fig. 9, P direction represents the fluid flow direction determined in correspondence near kettle 11 internal face of shear-blade 16-1 namely the upper spiral direction determining shear-blade 16-1；A direction is the vertical direction in P direction；Q direction represents the fluid flow direction determined under correspondence near kettle 11 internal face of shear-blade 16-3, namely drops direction on the lower spiral determining shear-blade 16-2；B direction is the vertical direction in Q direction.
Embodiment 4
In embodiment 3, the shear action near stirrer paddle 14 is weak.For this, in order to improve shear action and peeling effect, on the basis of embodiment 3, the present embodiment is the feature of Radial Flow for dispersion liquid near stirrer paddle 14 and graphite linings, and stirrer paddle has been improved.
As shown in Figure 10 and Figure 11, the radial extremity of stirrer paddle 14 is also distributed the dynamic shear-blade 18 for exfoliated graphite, and dynamic shear-blade 18 is arranged from the radial extremity of stirrer paddle 14 towards the internal face of kettle 11；Dynamic shear-blade 18 is also zigzag, and is plastic cutter；The crown of the upper dynamic shear-blade 18-1 being positioned at the radial extremity top of stirrer paddle 14 is bent upwards slightly, and forms the warpage portion 180 of plastic cutter；The crown of the lower dynamic shear-blade 18-2 being positioned at the radial extremity bottom of stirrer paddle 14 is slightly bent downwardly, and forms the warpage portion 180 of plastic cutter.Can be 75-85 ° by the angle, φ that bends to vertical direction of the crown of preferred upper and lower dynamic shear-blade 18-1,18-2.
Utilize above-mentioned Graphene to peel off still and Graphene process units to prepare the basic step of Graphene and be:
Step one, graphite flakes and solvent are injected Graphene peel off in still 1, add dispersant, start motor and be stirred, make mixing of materials uniform, after stirring, close kettle 11, wherein, solvent is selected from water, acetonitrile, n-butyl alcohol, ethanol, acetone, DMF, one or more the mixture in N-Methyl pyrrolidone, dispersant selects cetyl trimethylammonium bromide, sodium lauryl sulphate, dodecylbenzene sodium sulfonate, sodium cholate, polyvinyl alcohol, one or more composite in polyvinylpyrrolidone；
Step 2, heated graphite alkene peel off the kettle 11 of still 1, keep temperature in kettle 11 to be 80-150 DEG C, and pressure is 0.1-5Mpa, and agitator shaft speed is 1000-20000rpm, stir and at least close motor after 3h；
Step 3, by the discharging opening of kettle 11, upper strata graphene suspension is expelled in storage tank 2, stands 12-24h；
Step 4, being delivered in centrifuge 3 by the graphene suspension in storage tank in step 32, centrifuge 3 rotating speed is 1000-6000rpm, and centrifugation time 10min-2h takes the supernatant, and in vacuum apparatus 4, vacuum is filtrated to get filter cake；
Step 5, filter cake step 4 obtained are with appropriate distilled water wash, and filter cake is more than lyophilization 3h in freeze drying plant 5, namely obtains graphene product.
The following is the several embodiments utilizing above-mentioned Graphene stripping still and Graphene process units to prepare Graphene:
Such as, it is possible to 50kg graphite flakes, 350kg distilled water are injected Graphene and peel off in still 1, adds 1kg sodium cholate dispersant, start motor stirring mixed liquor, make mixing of materials uniform.After stirring, close kettle 11.By steam mode of heating, keep kettle 11 inner suspension liquid temp to be 80 DEG C and pressure is 0.1-5Mpa, increasing stirrer paddle 14 rotating speed is 3000rpm, now due to high rotating speed in reactor, shearing between material self and even determine the interaction of shear-blade 18 with inwall shear-blade 16, groove 17 so that graphite is successively peeled off.Keep steady temperature, rotating speed, stopped reaction after 5h, by discharging opening, upper strata suspension is expelled in storage tank 2, stand 24h.Being delivered in centrifuge 3 by the graphene suspension in storage tank 2, centrifuge 3 rotating speed is 6000rpm, centrifugal action 10min, and by centrifugal, the graphite being not peeled off and multi-layer graphene are deposited in bottom, take the supernatant, filter through vacuum apparatus 4 vacuum.The filter cake obtained is with appropriate distilled water wash 3 times, and filter cake is transferred in freezer dryer 5, and namely more than lyophilization 3h obtains graphene product.
For another example, it is possible to 20kg graphite flakes, 400kgN-methyl pyrrolidone are injected Graphene and peel off in still 1, adds 1kg sodium lauryl sulphate dispersant, start motor stirring, make mixing of materials uniform.After stirring, close kettle 11.Steam is passed in chuck, keep Graphene to peel off the temperature in still 1 and be 90 DEG C and pressure is 0.1-5Mpa, increasing stirrer paddle 14 rotating speed is 1000rpm, due to higher rotating speed, shearing between material self and even determine the interaction of shear-blade 18 with inwall shear-blade 16, groove 17 so that graphite is successively peeled off.Keep steady temperature, rotating speed, stopped reaction after 3h, by discharging opening, upper strata suspension is expelled in storage tank 2, stand 15h.Being delivered in centrifuge 3 by the graphene suspension in storage tank 2, centrifuge 3 rotating speed is 5000rpm, centrifugal action 1h, and by centrifugal, the graphite being not peeled off and multi-layer graphene are deposited in bottom, take the supernatant, filter through vacuum apparatus 4 vacuum.The filter cake obtained is with appropriate absolute ethanol washing 3 times, and filter cake is transferred in freezer dryer 5, and namely more than lyophilization 3h obtains graphene product.
Again such as, it is possible to by 30kg graphite flakes, 500kgN, dinethylformamide injects Graphene and peels off in still 1, adds 1kg polyvinyl alcohol dispersant, starts motor stirring, makes mixing of materials uniform.After stirring, close Graphene and peel off still 1.By heat-conducting oil heating mode, keep temperature to be 150 DEG C and pressure is 0.1-5Mpa, increasing stirrer paddle 14 rotating speed is 20000rpm, due to higher rotating speed, shearing between material self and even determine the interaction of shear-blade 18 with inwall shear-blade 16, groove 17 so that graphite is successively peeled off.Keep steady temperature, rotating speed, stopped reaction after 7h, by discharging opening, upper strata suspension is expelled in storage tank 2, stand 12h.Being delivered in centrifuge 3 by the graphene suspension in storage tank 2, centrifuge 3 rotating speed is 1000rpm, centrifugal action 2h, and by centrifugal, the graphite being not peeled off and multi-layer graphene are deposited in bottom, take the supernatant, filter through vacuum apparatus 4 vacuum.The filter cake obtained is with appropriate absolute ethanol washing 3 times, and filter cake is transferred in freezer dryer 5, and namely more than lyophilization 3h obtains graphene product.
The above is only the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the technology of the present invention principle; can also making some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. a Graphene peels off still, it is characterised in that includes periphery and is provided with the kettle of heating jacket, and kettle is provided with for detecting the temperature measuring equipment of the Pressure gauge of pressure and detection temperature in the kettle in still；The top of kettle is provided with charging aperture, and the middle and lower part of kettle is provided with discharging opening, is provided with rotation axle in kettle, rotates axle and is connected to stirrer paddle, rotates axle and is connected with the drive motor at the outer top being located at kettle；Tighten solid matter to be furnished with and determine shear-blade in inner wall of kettle face for exfoliated graphite, determine the blade of shear-blade inwardly beyond the internal face of described kettle, adjacent determine to be formed between shear-blade groove；Described determine that shear-blade is tapered or zigzag or both combinations；Taper or zigzag corner angle are 10-160 °.
2. Graphene as claimed in claim 1 peels off still, it is characterised in that described stirrer paddle is axial flow type agitating valve leaf；Described determine shear-blade and be arranged on described region, inner wall of kettle face and this areas adjacent that described stirrer paddle slips over；Described determine shear-blade and arrange along the rotation direction spiral of described rotation axle at the internal face of described kettle.
3. Graphene as claimed in claim 2 peels off still, it is characterised in that described to determine shear-blade be zigzag, and is plastic cutter；Each both sides end face determining shear-blade is perpendicular to its place helix, and crown, slightly towards deviating from the described spiral direction bending determining shear-blade, forms the warpage portion of plastic cutter；The described crown determining shear-blade is 5-15 ° slightly towards the angle deviating from the described spiral direction bending determining shear-blade.
4. Graphene as claimed in claim 1 peels off still, it is characterized in that, described stirrer paddle is radial-flow type stirrer paddle, described determine shear-blade and is arranged on above and below the region, described inner wall of kettle face that described stirrer paddle slips over, and respectively upper determine shear-blade and lower determines shear-blade；Described upper determine shear-blade and arrange along the rotation direction spiral of described rotation axle at the internal face of described kettle；Described lower determine shear-blade described kettle internal face along described rotation axle rotation direction spiral decline arrangement.
5. Graphene as claimed in claim 4 peels off still, it is characterised in that described to determine shear-blade be zigzag, and is plastic cutter；Each both sides end face determining shear-blade is respectively perpendicular to its place helix, and the upper crown determining shear-blade bends slightly towards deviating from the described upper spiral direction determining shear-blade, forms the warpage portion of plastic cutter；The described lower crown determining shear-blade bends slightly towards deviating from the described lower spiral descent direction determining shear-blade, forms the warpage portion of plastic cutter.
6. Graphene as claimed in claim 5 peels off still, it is characterised in that the radial extremity of described stirrer paddle is also distributed the dynamic shear-blade for exfoliated graphite, and dynamic shear-blade is arranged from the radial extremity of stirrer paddle towards the internal face of described kettle；Described dynamic shear-blade is zigzag, and is plastic cutter；The crown of the dynamic shear-blade being positioned at the radial extremity top of described stirrer paddle is bent upwards slightly, and forms the warpage portion of plastic cutter；The crown of the dynamic shear-blade being positioned at the radial extremity bottom of described stirrer paddle is slightly bent downwardly, and forms the warpage portion of plastic cutter.
7. Graphene as claimed in claim 6 peels off still, it is characterized in that, the described upper crown determining shear-blade is 5-15 ° slightly towards the angle deviating from the described upper spiral direction bending determining shear-blade, and the described lower crown determining shear-blade is 5-15 ° slightly towards the angle deviating from the described lower spiral descent direction bending determining shear-blade；The crown of described dynamic shear-blade is slightly 75-85 ° to the angle of vertical direction bending.
8. the Graphene production system peeling off still containing Graphene described in claim 1 to 7 any one, it is characterized in that, except described Graphene peels off still, this Graphene production system also includes the storage tank going out product for collecting and stand described Graphene stripping still process heel row successively along process sequence, for being centrifuged upper strata suspension in storage tank separating the centrifuge peeling off Graphene and unstripped graphite, for the supernatant obtained after centrifuge is filtered, the vacuum apparatus of washing, and for drying the freeze drying plant of Graphene after vacuum filters.
9. one kind uses the method producing Graphene containing the Graphene production system described in claim 8, it is characterised in that comprise the following steps:
Step one, graphite flakes and solvent are injected Graphene peel off in still, add dispersant, start motor and be stirred, make mixing of materials uniform, after stirring, close kettle；
Step 2, heated graphite alkene peel off the kettle of still, keep still body temperature to be 80-150 DEG C, and pressure is 0.1-5Mpa, and agitator shaft speed is 1000-20000rpm, stir and at least close motor after 3h；
Step 3, by the discharging opening of kettle, upper strata graphene suspension is expelled in storage tank, stands 12-24h；
Step 4, being delivered in centrifuge by the graphene suspension in storage tank in step 3, centrifuge speed is 1000-6000rpm, and centrifugation time 10min-2h takes the supernatant, and in vacuum apparatus, vacuum is filtrated to get filter cake；
Step 5, the filter cake that step 4 is obtained with appropriate distilled water wash, filter cake more than lyophilization 3h in freeze drying plant, namely obtain graphene product.
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