CN107716002A - The apparatus and method that a kind of pure shear ball milling prepares hexagonal boron nitride nanosheet with supersonic synergic - Google Patents
The apparatus and method that a kind of pure shear ball milling prepares hexagonal boron nitride nanosheet with supersonic synergic Download PDFInfo
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- CN107716002A CN107716002A CN201711075597.6A CN201711075597A CN107716002A CN 107716002 A CN107716002 A CN 107716002A CN 201711075597 A CN201711075597 A CN 201711075597A CN 107716002 A CN107716002 A CN 107716002A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/14—Mills in which the charge to be ground is turned over by movements of the container other than by rotating, e.g. by swinging, vibrating, tilting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/16—Mills in which a fixed container houses stirring means tumbling the charge
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/18—Details
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0648—After-treatment, e.g. grinding, purification
Abstract
The present invention relates to the apparatus and method that a kind of pure shear ball milling and supersonic synergic prepare hexagonal boron nitride nanosheet.Described device includes：Dividing plate is provided with concussion groove, concussion groove is divided into working chamber and power cavity；It is provided with the ball grinding cylinder with agitating device in the working chamber, the cavity outside ball grinding cylinder is sonification medium liquid containing chamber；There is the abrading-ball layer that abrading-ball is accumulated in the ball grinding cylinder, pressing plate, briquetting are disposed with above the abrading-ball layer；Puddler is stretched into abrading-ball layer；Supersonic generator and ultrasonic transducer are provided with power cavity.The present invention also provides the method that hexagonal boron nitride nanosheet is prepared using described device.Apparatus and method of the present invention has the advantages of equipment and technology is simple, easy to operate, cost is cheap, green, and hexagonal boron nitride nanosheet preparative-scale can be achieved.
Description
Technical field
The present invention relates to the apparatus and method that a kind of pure shear ball milling and supersonic synergic prepare hexagonal boron nitride nanosheet, category
In the technical field of inorganic nano material.
Background technology
Hexagonal boron nitride (h-BN) is because with the title that " white graphite " is known as with layer structure as graphite-phase, accordingly
Ground, h-BN nanometer sheets are commonly referred to as " white graphite alkene " and " boron nitride alkene " because of the two-dimensional structure with similar graphene.Phase
It is steady with unique performance, including high band gap (insulator), high chemical stability and heat for graphene, h-BN nanometer sheets
Qualitative, UV luminescent characteristics.In addition, it is had many kinds of substance good for high surface area and the N-B bond polarity of h-BN nanometer sheets
Good absorption property.Therefore, h-BN nanometer sheets are in composite, catalyst carrier, gas absorption and nano electron device field
With important application prospect.For majority is applied, h-BN nanometer sheets of good performance should have larger piece footpath size
(more than 100nm), less lamellar spacing (below 10nm) and good crystal structure (no lattice defect).Realize h-BN nanometers
The good performance of piece, low cost, scale, ecological, environmental protective, continuous controllable production prepare significant.
At present, the preparation method of h-BN nanometer sheets can be divided into the stripping method of " from top to bottom " and the synthetic method of " from bottom to top "
Two major classes.The former is mainly mechanical stripping method and chemical stripping method, and the latter is mainly chemical synthesis and chemical gas phase synthetic method.
Chemical stripping method is peeled off using Van der Waals force between the effect confrontation h-BN atomic layers of chemical reagent and h-BN material powders,
With efficient, inexpensive advantage, but in this method preparation process, substantial amounts of strong oxidizer, reducing agent, strong acid and strong are used
Alkali, environmental pollution is caused, and the crystal structure of h-BN nanometer sheets is damaged, formed defect, influence its combination property.Chemistry
Synthetic method boride and ammonium salt generate h-BN nanometer sheets, operating environment peace in the reactor situ nitridation reaction of HTHP
Full property is poor, and product is difficult to control.Chemical vapour deposition technique is that the raw material containing nitrogen and boron is become into gaseous state in a manner of heating etc.,
Conveyed, be deposited at a higher temperature on Lattice Matching and very clean substrate by inert gas.This method it is main excellent
Gesture is to prepare the h-BN nanometer sheets of large area, but its costly, complex process, is difficult to large-scale development.By contrast,
Mechanical stripping method is green, preparation method efficiently, inexpensive.
Mechanical stripping method, which prepares h-BN nanometer sheets, includes ball milling stripping method, ultrasonic stripping method, water jet stripping method and gas
Flow pulverizer stripping method etc..Ball milling stripping method has that technique is simple, cost is cheap, be produced on a large scale the excellent of h-BN nanometer sheets
Gesture, but the abrading-ball in this method has the shearing force of release effect to h-BN powders except applying, also as the collision between abrading-ball
And huge impulsive force is produced, impulsive force not only makes the piece footpath size of h-BN nanometer sheets diminish, and the layer crystal of h-BN nanometer sheets
Lattice are also affected, thus the piece footpath size of h-BN nanometer sheets for preparing of this method compared with it is small, lattice defect is big, it is difficult to prepare large stretch of
Footpath size, the h-BN nanometer sheets of high-quality.Therefore should try to reduce impulsive force, increase shearing when ball-milling method prepares h-BN nanometer sheets
Power.Water jet stripping method and airslide disintegrating mill stripping method are to powder by the collision friction between impulsive force, cavitation force and powder
Crushed and peeled off, not only equipment is complicated, cumbersome, and there can be the disadvantages mentioned above of ball milling stripping method.Ultrasound stripping
It is to be dispersed in h-BN material powders to peel off in solvent from method, the huge energy discharged using cavitation effect caused by ultrasonic wave will
The method that h-BN lamellas are peeled off and prepare h-BN nanometer sheets.This method technique is simple, cost is cheap, to h-BN nanometer sheets
The influence of layer crystal lattice is smaller, can prepare the h-BN nanometer sheets of higher quality.But because the electricity of B atoms and N atoms in h-BN structures is born
Sex differernce causes the active force between atomic layer also to carry the active force of part ion key matter in addition to Van der Waals force, causes h-BN
It is more difficult to peel off than graphite.Therefore, yield (the h-BN nanometer sheets prepared and the h-BN material powders of addition of ultrasonic stripping method
Mass percent) it is very low, it is impossible to meet the needs of large-scale production h-BN nanometer sheets, and with the increase of ultrasonic time, obtain
To the piece footpath sizes of h-BN nanometer sheets correspondingly reduce.Chinese patent document CN103130236A provides a kind of ball milling and liquid
The method for being combined and preparing BN alkene dispersion liquids is mutually peeled off, this method successively carries out ball-milling treatment and supersound process, at two kinds
Reason process is carried out respectively, the shortcomings that failing to overcome ball milling stripping method and ultrasonic stripping method each.
The content of the invention
In view of the shortcomings of the prior art, a kind of pure shear ball milling of present invention offer prepares hexagonal boron nitride with supersonic synergic and received
The device of rice piece.
The present invention also provides a kind of method that hexagonal boron nitride nanosheet is prepared using said apparatus.
The technical scheme is that：
A kind of pure shear ball milling prepares the device of hexagonal boron nitride nanosheet with supersonic synergic, including：
The concussion groove of one fixed installation, described shake in groove are provided with dividing plate, and the concussion groove is divided into working chamber
And power cavity；It is provided with the ball grinding cylinder with agitating device in the working chamber, the cavity outside ball grinding cylinder is that sonification medium liquid is contained
Put chamber；
There is the abrading-ball layer that abrading-ball is accumulated in the ball grinding cylinder, pressing plate, briquetting are disposed with above the abrading-ball layer；Institute
The puddler for stating agitating device is stretched into abrading-ball layer；
Supersonic generator and ultrasonic transducer are provided with the power cavity.
According to currently preferred, the abrading-ball layer height is the 1/2~2/3 of ball grinding cylinder height.
According to currently preferred, some a diameter of 0.5~1mm through hole is provided with the pressing plate.Further preferably,
The through hole is uniformly distributed on the pressing plate.H-BN suspension can be flowed down by the through hole on pressing plate in mechanical milling process
It is logical.
According to currently preferred, the pressing plate diameter is adapted with ball grinding cylinder internal diameter.The abrading-ball layer can be covered substantially
Lid, makes abrading-ball be crushed on below.
According to currently preferred, the diameter of the briquetting is less than the pressing plate diameter.The weight of briquetting is can push down
Plate and abrading-ball are advisable, and make to move in the space that abrading-ball is limited in mechanical milling process below pressing plate.
According to currently preferred, the agitating device includes buncher, puddler；The bottom of the puddler is set
It is equipped with the paddle of single or multiple lift；The pressing plate and briquetting are respectively equipped with center hole, make puddler from pressing plate and briquetting
Center hole passes through.Briquetting and pressing plate can move up and down along the puddler.Further preferably, the center hole of the pressing plate with
The center hole of briquetting is concentric axis hole.
It is further preferred that the paddle of the puddler bottom is paddle paddle, anchor formula paddle, push type stir
Mix leaf or helical-ribbon type paddle.
According to currently preferred, the concussion groove is fixedly mounted on the base of belt supporting frame；The support includes vertical
Support bar, horizontally disposed retainer and horizontally disposed crossbeam；
The buncher of the ball grinding cylinder and agitating device is fixedly installed on described vertical by retainer and crossbeam respectively
On support bar；The crossbeam and retainer are arranged in the vertical support bar by puller bolt.The crossbeam and retainer
Position in vertical support bar can adjust up and down, be fixed with puller bolt.
It is further preferred that the buncher is connected by shaft coupling with puddler；The buncher passes through suspension
Bolt is fixedly installed on the crossbeam；The ball grinding cylinder is fixedly connected by locking nut with retainer.The ball grinding cylinder by
The shaft shoulder and locking nut on retainer are fixed, and avoid it from moving or topple in mechanical milling process.
It is further preferred that concussion groove, ball grinding cylinder, pressing plate, briquetting and the puddler are stainless steel.
According to currently preferred, the ball grinding cylinder is cylinder；The open top of ball grinding cylinder is simultaneously provided with ball milling cover.
According to currently preferred, the abrading-ball layer is made up of or by two or more specifications a kind of abrading-ball accumulation of specification
Abrading-ball accumulates composition in any proportion；The specification of the abrading-ball is the stainless steel ball of 1~5mm of diameter G10 grades.
According to currently preferred, the quality of the briquetting is 0.5~2kg；The power of the buncher be 200~
500W, speed adjustable range are 0~3000r/min, stepless speed regulation.
According to currently preferred, the power of the supersonic generator is 100~300W, and frequency is 20~40kHz.
According to currently preferred, the supersonic generator and ultrasonic transducer are electrically connected by cable.
A kind of method that hexagonal boron nitride nanosheet is prepared using said apparatus, including step：
(1) ball grinding cylinder is positioned in the working chamber of concussion groove, adjusts the beam height of support, make puddler bottom and ball
The distance of mill tube bottom is 5~10mm；
(2) abrading-ball is added in ball grinding cylinder, the height of abrading-ball layer accumulation is the 1/2~2/3 of ball grinding cylinder height, lays stirring
Device, puddler is set to stretch into abrading-ball layer；
(3) ball-milling medium liquid is added into ball grinding cylinder, the liquid level of ball-milling medium liquid is higher than the 20~50mm of pressing plate；
(4) h-BN material powders are added according to the volume of the ball-milling medium liquid of addition, h-BN material powders are situated between in ball milling
Concentration in matter liquid is 3~10g/L；
(5) sonification medium liquid is added into the sonification medium liquid containing chamber outside ball grinding cylinder；Ball grinding cylinder is passed through
The retainer of support is fixed, and ball milling cover is penetrated by center hole from the top of puddler, covered on ball milling nozzle, then will
Puddler is coupled with buncher with shaft coupling；
(6) buncher is opened, adjusts rotating speed, carries out ball milling；Meanwhile supersonic generator is opened, carry out ultrasonic vibration；
(7) after the completion of step (6) ball milling and ultrasonic vibration, abrading-ball is isolated, gained ball milling liquid is with 2500~3000r/
Min rotating speed centrifugation, is taken upper strata suspension and is centrifuged again with 3500~4000r/min rotating speed, taking precipitate, by gained sediment
It is dried in vacuo to obtain h-BN nanometer sheets.
According to currently preferred, in the step (1), the step of adjusting beam height, is：Puddler is put into ball milling
In cylinder, then it is coupled with buncher with shaft coupling, then along vertical support bar moving beam, make puddler bottom and ball milling
The distance of cylinder bottom is 5~10mm, fixes crossbeam with puller bolt, finally unloads puddler from shaft coupling, and from ball
Taken out in mill tube.
According to currently preferred, in the step (2), the step of laying agitating device, is：Puddler is put into vertically
Ball grinding cylinder, paddle is set to be placed in abrading-ball layer；Pressing plate and briquetting are passed through from the top of puddler successively by center hole, put
Enter ball grinding cylinder.
According to currently preferred, the ball-milling medium liquid in the step (3) is isopropanol or N, N- dimethyl formyl
Amine.
According to currently preferred, the average grain diameter of the h-BN material powders in the step (4) is 10~50 μm.It is preferred that
Purity is more than 99.9%.
According to currently preferred, the sonification medium liquid in the step (5) is water.It is further preferred that ultrasound is situated between
The liquid level of ball-milling medium liquid in matter liquid containing chamber in the liquid level and ball grinding cylinder of sonification medium liquid maintains an equal level.
According to currently preferred, in the step (6), the rotating speed of the buncher is 200~2500r/min；Institute
The power for stating supersonic generator is 100~300W, and frequency is 20~40kHz；Ball milling and ultrasonic vibration processing time be 3~
10h.Further preferably, the rotating speed of the buncher is 500~2500r/min；The power of the supersonic generator is 200
~300W, frequency are 30~40kHz；Ball milling and ultrasonic vibration processing time are 5~8h.
According to currently preferred, in the step (7), the separation abrading-ball is that sieving filters out abrading-ball；Concretely comprise the following steps：
Ball milling operation and ultrasonic vibration operation close buncher and supersonic generator after terminating, and puddler is unloaded from shaft coupling；
Ball milling cover is removed, and puddler is taken out together with pressing plate and briquetting from ball grinding cylinder；By abrading-ball and ball milling liquid from ball grinding cylinder
Pour out and sieve and filter out abrading-ball, obtain ball milling liquid.
According to currently preferred, in the step (7), ball milling liquid with 2500~3000r/min rotating speed centrifugation 30~
45min；The upper strata suspension centrifuges 20~30min with 3500~4000r/min rotating speed；By sediment at 40~50 DEG C
15~20h is dried under vacuum condition, obtains h-BN nanometer sheets.
The working mechanism of device of the present invention is：On the one hand, buncher drives puddler to abrading-ball by shaft coupling
It is stirred, the gravity of itself is applied on abrading-ball by briquetting by pressing plate, abrading-ball is mutually drawn close in motion and is adjacent to, both disappeared
, again can be by the size for the quality adjustment shearing force for changing briquetting except the collision impact effect between abrading-ball, and then realize to h-
BN material powders carry out pure shear ball milling stripping.On the other hand, supersonic generator and ultrasonic transducer are to ball-milling medium liquid
Body carries out ultrasonic vibration, and then realizes and carry out ultrasonic stripping to h-BN material powders.In a word, h-BN material powders are applied simultaneously
The pure shear power effect of ball milling and the cavitation of ultrasonic wave, h-BN nanometer sheets are prepared so as to high-efficiency high-quality.
Beneficial effects of the present invention are：
1. apparatus and method of the present invention, by ball milling stripping method and ultrasonic stripping method simultaneously applied to preparation h-BN nanometers
Piece, the advantages of combining the two, the shortcomings that avoiding the two.Compared with existing ball milling stripping method, first, by briquetting to mill
Ball, which presses, can eliminate the mutual collision of abrading-ball, and then provides pure shear shear force and h-BN powders are peeled off, and avoid because abrading-ball collides
The piece footpath size of h-BN nanometer sheets caused by impact reduces and lattice damage, can prepare the h- of larger piece footpath size and higher quality
BN nanometer sheets；Second, existing ball milling stripping method also needs to be ultrasonically treated after ball milling, the present invention peels off h-BN in ball milling
Ultrasound is introduced while powder to peel off, that is, is simplified technological process, can be improved the peeling effect to h-BN powders again；With it is existing
Ultrasonic stripping method is compared, and the pure shear power effect of ball milling is added while the cavitation of ultrasonic wave, can more overcome h-BN
The active force of Van der Waals force and ionic bond property between atomic layer, and then the yield of h-BN nanometer sheets is improved, realize that h-BN receives
Rice piece preparative-scale；
2. apparatus and method of the present invention are compared with existing chemical stripping method, chemical synthesis and chemical deposition,
With the advantages of equipment and technology is simple, easy to operate, cost is cheap, green.
Brief description of the drawings
Fig. 1 is that the structure for the device that pure shear ball milling of the present invention prepares hexagonal boron nitride nanosheet with supersonic synergic is shown
It is intended to；
Wherein, 1, base；2nd, vertical support bar；3rd, groove is shaken；4th, retainer；5th, puller bolt；6th, crossbeam；7th, locking screw
It is female；8th, Hanging bolt；9th, buncher；10th, shaft coupling；11st, ball milling cover；12nd, puddler；13rd, briquetting；14th, pressing plate；15、
Ball grinding cylinder；16th, sonification medium liquid containing chamber；17th, abrading-ball；18th, dividing plate；19th, ultrasonic transducer；20th, ultrasonic wave occurs
Device.
Fig. 2 is SEM (SEM) photo for the h-BN material powders that embodiment 2 uses, and wherein scale is 2 μ
m；
Fig. 3 is the SEM photograph of h-BN nanometer sheets prepared by embodiment 2, and wherein scale is 200nm；
Fig. 4 is transmission electron microscope (TEM) photo of h-BN nanometer sheets prepared by embodiment 2, and wherein scale is
100nm；
Fig. 5 is high resolution transmission electron microscopy (HRTEM) photo of h-BN nanometer sheets prepared by embodiment 2, and it is got the bid
Chi is 5nm；
Fig. 6 is AFM (AFM) photo of h-BN nanometer sheets prepared by embodiment 2；
Fig. 7 is the height distribution map at A, B two in Fig. 6；
Fig. 8 is the height distribution map at C in Fig. 6；
Fig. 9 is the TEM photos of h-BN nanometer sheets prepared by comparative example 1, and wherein scale is 100nm；
Figure 10 is the HRTEM photos of h-BN nanometer sheets prepared by comparative example 1, and wherein scale is 5nm；
Figure 11 is the TEM photos of h-BN nanometer sheets prepared by comparative example 2, and wherein scale is 100nm.
Embodiment
With reference to embodiment and accompanying drawing, the present invention will be further described, but not limited to this.
Embodiment 1
A kind of pure shear ball milling prepares the device of hexagonal boron nitride nanosheet with supersonic synergic, and structure is as shown in figure 1, described
Device, including：Groove 3 is shaken to be arranged on the base 1 of belt supporting frame；Dividing plate 18 is provided with the concussion groove 3, dividing plate 18 is by described in
Concussion groove 3 is divided into working chamber and power cavity；Supersonic generator 20 and ultrasonic transducer 19 are provided with the power cavity.
The supersonic generator 20 and ultrasonic transducer 19 are electrically connected by cable.Band agitating device is provided with the working chamber
Ball grinding cylinder 15, the ball grinding cylinder 15 for cylinder；The open top of ball grinding cylinder 15 is simultaneously provided with ball milling cover 11.Ball grinding cylinder 15
Outer cavity is sonification medium liquid containing chamber 16；There are the abrading-ball layer that abrading-ball 17 is accumulated, the abrading-ball in the ball grinding cylinder 15
17 specification is the stainless steel ball of diameter 3mm G10 grades.Pressing plate 14, briquetting 13 are disposed with above the abrading-ball layer；
The agitating device includes buncher 9, puddler 12；The puddler 12 is stretched into abrading-ball layer；Set on the pressing plate 14
There are equally distributed some through holes, the through-hole diameter is 0.5mm.H-BN suspension can pass through the through hole in mechanical milling process
Circulated in pressing plate about 14.The bottom of the puddler 12 is provided with three layers of two leaf flat paddle formula paddles；The pressing plate 14
Center hole is respectively equipped with briquetting 13, passes through the center hole of puddler 12 from pressing plate 14 and briquetting 13.Briquetting 13 and pressure
Plate 14 can move up and down along the puddler 12.The diameter of pressing plate 14 is adapted with the internal diameter of ball grinding cylinder 15, can be by the abrading-ball
The basic covering of layer, makes abrading-ball 17 be crushed on below.The diameter of the briquetting 13 is less than the diameter of pressing plate 14.The matter of briquetting 13
Measure as 0.5kg, can make to move in the space that abrading-ball 17 is limited in mechanical milling process below pressing plate.The center of the pressing plate 14
The center hole of circular hole and briquetting 13 is concentric axis hole.
The support includes vertical support bar 2, horizontally disposed retainer 4 and horizontally disposed crossbeam 6；The ball grinding cylinder
15 and the buncher 9 of agitating device be fixedly installed on respectively by retainer 4 and crossbeam 6 in the vertical support bar 2；It is described
Crossbeam 6 and retainer 4 are arranged in the vertical support bar 2 by puller bolt 5.The crossbeam 6 and retainer 4 are vertically propping up
Position on strut 2 can adjust up and down, be fixed with puller bolt 5.
The buncher 9 is connected by shaft coupling 10 with puddler 12；The buncher 9 is solid by Hanging bolt 8
Surely it is arranged on the crossbeam 6；The ball grinding cylinder 15 is fixedly connected by locking nut 7 with retainer 4.Ball grinding cylinder 15 is by keeping
The shaft shoulder and locking nut 7 on frame 4 are fixed, and avoid it from moving or topple in mechanical milling process.
Concussion groove 3, ball grinding cylinder 15, pressing plate 14, briquetting 13 and the puddler 12 are stainless steel.
Embodiment 2
A kind of method that hexagonal boron nitride nanosheet is prepared using the described device of embodiment 1, including step：
(1) ball grinding cylinder 15 is positioned in the working chamber of concussion groove 3, adjusts the height of crossbeam 6 of support, make the bottom of puddler 12
The distance at end and the bottom of ball grinding cylinder 15 is 5mm；
(2) abrading-ball 17 is added in ball grinding cylinder 15, the height of abrading-ball layer accumulation is the 1/2 of the height of ball grinding cylinder 15, and placement is stirred
Device is mixed, puddler 12 is stretched into abrading-ball layer；
(3) ball-milling medium liquid is added into ball grinding cylinder 15, the liquid level of ball-milling medium liquid is higher than the 20mm of pressing plate 14；Ball
Grinding media liquid is isopropanol；
(4) h-BN material powders are added according to the volume of the ball-milling medium liquid of addition, h-BN material powders are situated between in ball milling
Concentration in matter liquid is 3g/L；The average grain diameter of h-BN material powders is 10 μm, and purity is more than 99.9%.
(5) sonification medium liquid is added in the sonification medium liquid containing chamber 16 to outside ball grinding cylinder 15；By ball grinding cylinder 15
Fixed by the retainer 4 of support, ball milling cover 11 is penetrated by center hole from the top of puddler 12, covered in ball grinding cylinder
On mouth, then puddler 12 coupled with buncher 9 with shaft coupling 10；Sonification medium liquid is water；Sonification medium liquid containing
The liquid level of the liquid level of sonification medium liquid and the ball-milling medium liquid in ball grinding cylinder 15 maintains an equal level in chamber 16.
(6) buncher 9 is opened, adjusts rotating speed, carries out ball milling；Meanwhile supersonic generator 20 is opened, carry out ultrasonic shake
Swing；The rotating speed of the buncher 9 is 1000r/min, power 300W, and speed adjustable range is 0~3000r/min, stepless speed regulation.
The power of the supersonic generator 20 is 200W, frequency 40kHz；Ball milling and ultrasonic vibration processing time are 5h.
(7) after the completion of step (6) ball milling and ultrasonic vibration, abrading-ball 17 is isolated, gained ball milling liquid is with 2500r/min's
Rotating speed centrifuges 45min, takes upper strata suspension and centrifuges 30min, taking precipitate, by sediment 40 again with 3500r/min rotating speed
DEG C vacuum condition under dry 20h, obtain h-BN nanometer sheets.
The h-BN material powders that the present embodiment uses structure in the form of sheets, as shown in Fig. 2 and piece thickness it is larger.The h- of preparation
BN nanometer sheet thickness very littles, thus flock together, as shown in figure 3, being dispersible by general supersound process, do not influence to use
Effect.The piece footpath size of h-BN nanometer sheets is 200~350nm as seen from Figure 4, and transparency is larger, and has crimp, shows
Its very thin thickness.The lattice fringe of h-BN nanometer sheets is straight as seen from Figure 5, spacing is consistent, shows prepared by h-BN nanometer sheets
Good crystal structure is maintained in journey.It is larger that the piece footpath of h-BN nanometer sheets is also shown by Fig. 6, is crimped.By Fig. 7 and figure
The lamellar spacing of 8 visible h-BN nanometer sheets is 3~6nm.The yield of the h-BN nanometer sheets of the present embodiment is 30%.
Comparative example 1
A kind of method for preparing hexagonal boron nitride nanosheet, the difference with embodiment 2 are preparation facilities using existing
Ball milling method；Pressing plate and briquetting are not provided with abrading-ball layer.The two leaf flat paddle formulas that the bottom of puddler used is provided with three layers are stirred
Mix leaf.After tested, the piece footpath size of h-BN nanometer sheets prepared by comparative example 1 is 50~200nm, as shown in Figure 9.Can by Figure 10
See, the lattice fringe of h-BN nanometer sheets has buckling phenomenon, spacing also inconsistent, shows prepared by the crystal structure of h-BN nanometer sheets
During receive destruction, generate lattice defect.The lamellar spacing of h-BN nanometer sheets prepared by comparative example 1 is 5~10nm, production
Rate is 25%.
Comparative example 2
A kind of method for preparing hexagonal boron nitride nanosheet, the difference with embodiment 2 are preparation facilities using existing
Ultrasonic stripping method, that is, be not provided with ball mill device.Concussion groove, ball grinding cylinder used are made of stainless steel.After tested, comparative example 2 is made
The piece footpath size of standby h-BN nanometer sheets is 100~300nm, as shown in figure 11.The lamella of h-BN nanometer sheets prepared by comparative example 2
Thickness is 4~8nm, yield 9%.
Embodiment 3
A kind of method that hexagonal boron nitride nanosheet is prepared using the described device of embodiment 1, as described in Example 2, institute is not
Be：The bottom of puddler used is provided with two layers of anchor formula paddle.Abrading-ball used is diameter 2mm G10 grades
Stainless steel ball.Some a diameter of 1mm through hole is provided with pressing plate used.The quality of briquetting used is 1kg.Buncher used
Power be 350W, the power of supersonic generator used is 300W.The average grain diameter of h-BN material powders used is 15 μm, pure
Degree is more than 99.9%.
In the step (1), the distance of puddler bottom and ball grinding cylinder bottom is 10mm；In the step (2), abrading-ball layer
The height of accumulation is the 2/3 of ball grinding cylinder height.In the step (3), the liquid level of isopropanol is higher than the pressing plate 30mm；The step
Suddenly in (4), concentration of the h-BN material powders in isopropanol is 4g/L；In the step (6), the rotating speed of buncher is
1200r/min, ball milling and ultrasonic vibration processing time are 6h；In the step (7), ball milling liquid is centrifuged with 3000r/min
30min, upper strata suspension centrifuge 20min with 4000r/min.Gained sediment is dried into 15h under 50 DEG C of vacuum condition, obtained
To h-BN nanometer sheets.
After tested, the piece footpath size of h-BN nanometer sheets manufactured in the present embodiment is 200~400nm, lamellar spacing is 3~
7nm, yield 28%.
Embodiment 4
A kind of method that hexagonal boron nitride nanosheet is prepared using the described device of embodiment 1, as described in Example 2, institute is not
Be：The bottom of puddler used is provided with the helical-ribbon type paddle of individual layer.Abrading-ball used is diameter 2mm and 4mm G10
The stainless steel ball of grade, in mass ratio 1:3 are used in mixed way.Some a diameter of 1mm through hole is provided with pressing plate used.Pressure used
The quality of block is 1.5kg.The power of buncher used is 400W.The power of supersonic generator used is 300W.Balls
Grinding media liquid is N,N-dimethylformamide.The average grain diameter of h-BN material powders used is 20 μm, and purity is more than 99.9%.
The liquid level of N,N-dimethylformamide in the step (3) is higher than the pressing plate 40mm；In the step (4),
Concentration of the h-BN material powders in isopropanol is 5g/L；In the step (6), the rotating speed of buncher is 1500r/min, ball
Mill and ultrasonic vibration processing time are 7h；In the step (7), ball milling liquid centrifuges 40min, upper strata suspension with 2700r/min
25min is centrifuged with 3800r/min.Gained sediment is dried into 17h under 47 DEG C of vacuum condition, obtains h-BN nanometer sheets.
After tested, the piece footpath size of h-BN nanometer sheets manufactured in the present embodiment is 250~500nm, lamellar spacing is 4~
7nm, yield 26%.
Embodiment 5
A kind of method that hexagonal boron nitride nanosheet is prepared using the described device of embodiment 1, as described in Example 2, enters one
Step, in the step (1), adjust beam height the step of be：Puddler is put into ball grinding cylinder, then by itself and buncher
Coupled with shaft coupling, then along vertical support bar moving beam, the distance for making puddler bottom and ball grinding cylinder bottom is 5mm, is used
Puller bolt fixes crossbeam, finally unloads puddler from shaft coupling, and taken out from ball grinding cylinder.
Embodiment 6
A kind of method that hexagonal boron nitride nanosheet is prepared using the described device of embodiment 1, as described in Example 2, enters one
Step, in the step (2), lay agitating device the step of be：Puddler is put into ball grinding cylinder vertically, paddle is stretched in mill
In layers of balls；Pressing plate and briquetting are passed through from the top of puddler successively by center hole, put ball grinding cylinder into.
Embodiment 7
A kind of method that hexagonal boron nitride nanosheet is prepared using the described device of embodiment 1, as described in Example 2, enters one
Step, in step (7), the separation abrading-ball is that sieving filters out abrading-ball；Concretely comprise the following steps：Ball milling operation and ultrasonic vibration operation knot
Buncher and supersonic generator are closed after beam, puddler is unloaded from shaft coupling；Ball milling cover is removed, and puddler is connected
Taken out with pressing plate and briquetting from ball grinding cylinder；Abrading-ball and ball milling liquid are poured out and sieved from ball grinding cylinder and filters out abrading-ball, obtains ball
Grinding fluid.
Claims (10)
1. a kind of device for preparing hexagonal boron nitride nanosheet, including：
The concussion groove of one fixed installation, described shake in groove are provided with dividing plate, and the concussion groove is divided into working chamber and moved
Power chamber；It is provided with the ball grinding cylinder with agitating device in the working chamber, the cavity outside ball grinding cylinder is sonification medium liquid containing chamber
Room；
There is the abrading-ball layer that abrading-ball is accumulated in the ball grinding cylinder, pressing plate, briquetting are disposed with above the abrading-ball layer；It is described to stir
The puddler for mixing device is stretched into abrading-ball layer；
Supersonic generator and ultrasonic transducer are provided with the power cavity.
2. the device of hexagonal boron nitride nanosheet is prepared as claimed in claim 1, it is characterised in that including appointing in following scheme
It is one or more：
a1:The abrading-ball layer height is the 1/2~2/3 of ball grinding cylinder height；
a2:Some a diameter of 0.5~1mm through hole is provided with the pressing plate；
a3:The pressing plate diameter is adapted with ball grinding cylinder internal diameter；
a4:The diameter of the briquetting is less than the pressing plate diameter.
3. the device of hexagonal boron nitride nanosheet is prepared as claimed in claim 1, it is characterised in that including appointing in following scheme
It is one or more：
b1：The agitating device includes buncher, puddler；The bottom of the puddler is provided with stirring for single or multiple lift
Mix leaf；
b2:The pressing plate and briquetting are respectively equipped with center hole, pass through the center hole of puddler from pressing plate and briquetting；
b3:The center hole of the pressing plate is concentric axis hole with the center hole of briquetting；
b4:The paddle of the puddler bottom is that paddle paddle, anchor formula paddle, pusher paddle or helical-ribbon type stir
Mix leaf.
4. the device of hexagonal boron nitride nanosheet is prepared as claimed in claim 3, it is characterised in that including appointing in following scheme
It is one or more：
c1:The concussion groove is fixedly mounted on the base of belt supporting frame；The support includes vertical support bar, horizontally disposed guarantor
Hold frame and horizontally disposed crossbeam；
c2:The buncher of the ball grinding cylinder and agitating device is fixedly installed on the vertical branch by retainer and crossbeam respectively
On strut；
c3:The abrading-ball layer is made up of a kind of abrading-ball accumulation of specification or accumulated in any proportion by the abrading-ball of two or more specifications
Form；
c4:The specification of the abrading-ball is the stainless steel ball of 1~5mm of diameter G10 grades.
5. the device of hexagonal boron nitride nanosheet is prepared as claimed in claim 3, it is characterised in that including appointing in following condition
It is one or more：
d1:The quality of the briquetting is 0.5~2kg；
d2:The power of the buncher is 200~500W, and speed adjustable range is 0~3000r/min, stepless speed regulation；
d3:The power of the supersonic generator is 100~300W, and frequency is 20~40kHz；
d4:The supersonic generator and ultrasonic transducer are electrically connected by cable.
A kind of 6. method for preparing hexagonal boron nitride nanosheet, including the use of the device described in any one of claim 1 to 5, bag
Include step：
(1) ball grinding cylinder is positioned in the working chamber of concussion groove, adjusts the beam height of support, make puddler bottom and ball grinding cylinder
The distance of bottom is 5~10mm；
(2) abrading-ball is added in ball grinding cylinder, the height of abrading-ball layer accumulation is the 1/2~2/3 of ball grinding cylinder height, lays stirring dress
Put, puddler is stretched into abrading-ball layer；
(3) ball-milling medium liquid is added into ball grinding cylinder, the liquid level of ball-milling medium liquid is higher than the 20~50mm of pressing plate；
(4) h-BN material powders are added according to the volume of the ball-milling medium liquid of addition, h-BN material powders are in ball-milling medium liquid
Concentration in body is 3~10g/L；
(5) sonification medium liquid is added into the sonification medium liquid containing chamber outside ball grinding cylinder；Ball grinding cylinder is passed through into support
Retainer fix, ball milling cover is penetrated by center hole from the top of puddler, covered on ball milling nozzle, then will stirring
Bar is coupled with buncher with shaft coupling；
(6) buncher is opened, adjusts rotating speed, carries out ball milling；Meanwhile supersonic generator is opened, carry out ultrasonic vibration；
(7) after the completion of step (6) ball milling and ultrasonic vibration, abrading-ball is isolated, gained ball milling liquid is with 2500~3000r/min's
Rotating speed centrifuges, and takes upper strata suspension and is centrifuged again with 3500~4000r/min rotating speed, taking precipitate, by gained sediment vacuum
Dry h-BN nanometer sheets.
7. the method for hexagonal boron nitride nanosheet is prepared as claimed in claim 6, it is characterised in that in the step (1), adjust
The step of whole beam height is：Puddler is put into ball grinding cylinder, then it is coupled with buncher with shaft coupling, then along vertical
Support bars moving beam, the distance for making puddler bottom and ball grinding cylinder bottom is 5~10mm, is consolidated crossbeam with puller bolt
It is fixed, finally puddler is unloaded from shaft coupling, and is taken out from ball grinding cylinder.
8. the method for hexagonal boron nitride nanosheet is prepared as claimed in claim 6, it is characterised in that in the step (2), peace
The step of putting agitating device be：Puddler is put into ball grinding cylinder vertically, paddle is stretched in abrading-ball layer；Pressing plate and briquetting are led to
Cross center hole to pass through from the top of puddler successively, put ball grinding cylinder into.
9. the method for hexagonal boron nitride nanosheet is prepared as claimed in claim 6, it is characterised in that including appointing in following condition
It is one or more：
e1:Ball-milling medium liquid in step (3) is isopropanol or N,N-dimethylformamide；
e2:The average grain diameter of h-BN material powders in step (4) is 10~50 μm；
e3:Sonification medium liquid in step (5) is water；
e4:In step (6), the rotating speed of the buncher is 200~2500r/min；The power of the supersonic generator is
100~300W, frequency are 20~40kHz；Ball milling and ultrasonic vibration processing time are 3~10h；Preferably, the buncher
Rotating speed be 500~2500r/min, the power of the supersonic generator is 200~300W, and frequency is 30~40kHz, ball milling
It is 5~8h with ultrasonic vibration processing time；
e5:In step (7), ball milling liquid centrifuges 30~45min with 2500~3000r/min rotating speed；The upper strata suspension with
3500~4000r/min rotating speed centrifuges 20~30min；
e6:In step (7), sediment is dried into 15~20h under 40~50 DEG C of vacuum condition.
10. the method for hexagonal boron nitride nanosheet is prepared as claimed in claim 6, it is characterised in that in the step (7),
The separation abrading-ball is that sieving filters out abrading-ball；Step is：Ball milling operation and ultrasonic vibration operation terminate after close buncher and
Supersonic generator, puddler is unloaded from shaft coupling；Remove ball milling cover, and by puddler together with pressing plate and briquetting from ball milling
Taken out in cylinder；Abrading-ball and ball milling liquid are poured out and sieved from ball grinding cylinder and filters out abrading-ball, obtains ball milling liquid.
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