阅读说明：本技术 摊铺沉降法制取石墨烯前的超声波破拆石墨团粉方法 (Method for breaking and dismantling graphite powder by ultrasonic wave before preparing graphene by paving sedimentation method ) 是由 董兰田 王智 董恬纲 于 2019-11-20 设计创作，主要内容包括：本发明提供一种摊铺沉降法制取石墨烯前的超声波破拆石墨团粉方法,包括超声波发生器和反应釜,其特征是使用可调频和功率的超声波发生器,以与石墨相同的振动频率破拆石墨团粉为游离碳原子,为后序在液态CO<Sub>2</Sub>中沉降摊铺形成石墨烯提供必须的前提预备,本发明与现有技术相比,较机械动力直接破拆更均衡周至全覆盖,局部能量更集中强大,破拆速率更高、省时节能,为应用中与摊铺装置一对一还是一对多套甚至异地使用等提供更多选择方案,因而,本发明具有很好的推广应用价值。(The invention provides a method for breaking and removing graphite powder by ultrasonic wave before preparing graphene by a paving sedimentation method, which comprises an ultrasonic generator and a reaction kettle and is characterized in that the ultrasonic generator with adjustable frequency and power is used, the graphite powder is broken and removed by the ultrasonic generator with the same vibration frequency as graphite as free carbon atoms and is subsequently subjected to liquid CO 2 Compared with the prior art, the invention has the advantages of more uniform cycle to full coverage compared with the mechanical power direct breaking and dismantling, more concentrated and strong local energy, higher breaking and dismantling speed, time saving and energy saving, and provides more selection schemes for one-to-one or one-to-many sets of spreading devices and even different-place use in application, thereby having good popularization and application values.)

1. A method for breaking and dismantling graphite group powder by ultrasonic wave before preparing graphene by a paving sedimentation method comprises an ultrasonic generator and a reaction kettle, wherein the ultrasonic generator has frequency modulation and power modulation performances, the reaction kettle is a special customized container which is provided with a stirring device and is sealed, heat-insulating, pressure-bearing and free of dead angles, the reaction kettle is further provided with a pressure safety valve, a charging opening and a pressure reduction discharge opening, and the method is characterized in that an ultrasonic generator probe is arranged on the inner side wall of the middle lower part of the reaction kettle, and when the ultrasonic generator probe is used, high-mesh graphite powder and liquid CO which are accurately metered and are filled into the reaction kettle at₂Closing the seal, starting the ultrasonic generator during stirring, and adjusting the ultrasonic generator to be in contact with the graphite and the liquid CO₂After the mixed liquid is kept in the same vibration frequency for a preset time, the mixed liquid is closed, the pressure reduction discharge port is still opened in stirring, and free carbon atoms and liquid CO with rated quantity are slowly and quickly poured into the settling tray₂With a nominal flow rate of the suspension or being released into the continuously-operating settling apparatusFree carbon atoms and liquid CO₂And (3) suspension.

2. The method for breaking and detaching the graphite particles by ultrasonic waves before preparing the graphene by the paving sedimentation method as claimed in claim 1, wherein a plurality of and a plurality of layers of ultrasonic generator probes are arranged at the middle part and the lower part of the side wall of the reaction kettle, and the liquid CO with continuous and uninterrupted uniform flow rate and quantity is respectively or uniformly arranged at the top of the reaction kettle₂And a graphite powder feeding port, wherein the bottom of the graphite powder feeding port is provided with an uninterrupted uniform-speed flow discharge port, and free carbon atoms and liquid CO with fixed ratio concentration and flow are continuously supplied to the settling device in continuous feeding, continuous stirring and ultrasonic oscillation₂And (3) suspension.

3. The method for preparing the graphite powder by the paving sedimentation method as claimed in claim 1, wherein the method comprises the steps of arranging an independent reaction kettle which takes the graphite powder as a basic function, and mixing the strictly-measured graphite powder with a large ratio and liquid CO₂Putting into the reactor to produce liquid CO with high concentration of free carbon atoms₂The suspension is used as a preorder raw material for dilution and uniform mixing of a plurality of stirred tank reactors.

4. The method for breaking graphite powder by ultrasonic wave before preparing graphene by paving and settling method as claimed in claim 1, wherein a dry dead-angle-free stirring reaction kettle is arranged, and the graphite powder is directly broken into free carbon atom powder in stirring by using the resonance frequency of an ultrasonic generator and graphite, and the free carbon atom powder is used as raw material for the stirring reaction kettle and liquid CO₂The suspension is mixed uniformly to be used as rated concentration.

5. The method for preparing graphene by using the paving sedimentation method as claimed in claim 1, wherein the method is characterized in that the dry or water-wet graphite powder is broken by electromagnetic microwave to form free carbon atom powder, and carbon liquid CO for preparing graphene by using the sedimentation method is further prepared₂And (3) suspension.

6. According to the claimsThe method for breaking and detaching graphite particles by ultrasonic wave before preparing graphene by using the paving and settling method disclosed by claim 1 is characterized in that carbon liquid CO released into a settling tray₂The suspension is released directly into the settler tray in a state of uniform stirring.

7. The method for breaking and detaching graphite agglomerate powder by using ultrasonic waves before preparing graphene by using a paving and settling method as claimed in claim 1, wherein a settling tray or a continuous settling device is subjected to precooling and cooling treatment in the production process.

The technical field is as follows:

the invention relates to the manufacture of new materials, in particular to a method for breaking and removing graphite cluster powder by ultrasonic waves before preparing graphene by a paving and settling method.

Secondly, background art:

graphene is a new material which subverts the world, because of its outstanding advantageous properties, performances and qualities in the aspects of electricity, heat, mechanics and the like, it is recognized that its existence is concerned and valued by countries in the world. However, since graphene is formed and exists in the structural form of a single-carbon two-dimensional planar crystal, natural graphene does not exist in nature. There are also significant difficulties and challenges with manual manufacturing.

The current industrialized production of graphene mainly adopts a physical micro-mechanical stripping method, a seal cutting transfer printing method, a template method, a chemical oxidation-reduction method, a solution stripping method, a heating Si-c method, a chemical vapor deposition method and 2 minutes of oxidationThe bulk 2 reduction method is realized by low production efficiency or excessively fine single-chip area, which hardly reflects the complete essential attribute of graphene, and has limited application range and use effect, thereby having defects and great discount, and newly appearing liquid CO₂Although the graphite suspension sedimentation and spreading method has certain advantages, the thoroughness of breaking and dismantling the graphite group powder before the method is implemented, namely the thoroughness or ratio of breaking and dismantling the graphite group powder particles into free carbon atoms still determines whether the method can produce graphene or not, and the core and the key of influencing the subsequent integrity of the formed graphene are the same.

Thirdly, the invention content:

the object of the present invention is to address the above-mentioned situations and problems, in particular with regard to liquid CO of graphite₂The key technical core in the preparation of graphene by a suspension sedimentation paving method provides a method for breaking and detaching graphite cluster powder by ultrasonic waves before preparing graphene by a sedimentation paving method.

The purpose of the invention is realized by the following technical scheme:

a method for breaking and dismantling graphite group powder by ultrasonic wave before preparing graphene by a paving sedimentation method comprises an ultrasonic generator and a reaction kettle, wherein the ultrasonic generator has frequency modulation and power modulation performances, the reaction kettle is a special customized container which is provided with a stirring device and is sealed, heat-insulating, pressure-bearing and free of dead angles, the reaction kettle is further provided with a pressure safety valve, a charging opening and a pressure reduction discharge opening, and the method is characterized in that an ultrasonic generator probe is arranged on the inner side wall of the middle lower part of the reaction kettle, and when the ultrasonic generator probe is used, high-mesh graphite powder and liquid CO which are accurately metered and are filled into the reaction kettle at₂Closing the seal, starting the ultrasonic generator during stirring, and adjusting the ultrasonic generator to be in contact with the graphite and the liquid CO₂After the mixed liquid is kept in the same vibration frequency for a preset time, the mixed liquid is closed, the pressure reduction discharge port is still opened in stirring, and free carbon atoms and liquid CO with rated quantity are slowly and quickly poured into the settling tray₂The suspension or the continuously operated settling device is quickly filled with free carbon atoms and liquid CO at rated flow rate₂And (3) suspension.

The method for breaking and dismantling the graphite powder by ultrasonic wave before preparing the graphene by the paving sedimentation method is characterized in that the method is used for reactingMultiple and multilayer ultrasonic generator probes are arranged at the middle part and the lower part of the side wall of the reaction kettle, and continuous and uninterrupted liquid CO with uniform flow and quantity is respectively or uniformly arranged at the top of the reaction kettle₂And a graphite powder feeding port, wherein the bottom of the graphite powder feeding port is provided with an uninterrupted uniform-speed flow discharge port, and free carbon atoms and liquid CO with fixed ratio concentration and flow are continuously supplied to the settling device in continuous feeding, continuous stirring and ultrasonic oscillation₂And (3) suspension.

The ultrasonic break-in graphite cluster powder method before preparing graphene by the paving sedimentation method is characterized in that an independent reaction kettle is arranged, break-in graphite clusters are used as basic functions, and strictly metered large-ratio graphite powder and liquid CO are mixed₂Putting into the reactor to produce liquid CO with high concentration of free carbon atoms₂The suspension liquid is used as a preorder raw material for dilution and uniform mixing of a plurality of stirred tank reactors.

The method for breaking and removing the graphite group powder by ultrasonic wave before preparing the graphene by the paving sedimentation method is characterized in that a dry stirring reaction kettle without dead angles is arranged, the graphite group powder is directly broken and removed in stirring to be free carbon atom powder by using the resonance frequency of an ultrasonic generator and graphite, and the free carbon atom powder is used as a raw material to be supplied to the stirring reaction kettle and liquid CO₂The suspension is mixed uniformly to be used as rated concentration.

The method for preparing the graphene by the paving sedimentation method before the ultrasonic breaking-in of the graphite group powder is characterized in that the dry or water-wet graphite powder is broken-in by electromagnetic microwaves to form free carbon atom powder, and carbon liquid CO for preparing the graphene by the paving sedimentation method is further prepared₂And (3) suspension.

The method for breaking and dismantling the graphite group powder by ultrasonic wave before preparing the graphene by the paving sedimentation method is characterized in that carbon liquid CO released into a sedimentation tray₂The suspension is released directly into the settler tray in a state of uniform stirring.

Compared with the prior art, the method for breaking and dismantling the graphite group powder by ultrasonic wave before preparing the graphene by the paving sedimentation method has the remarkable characteristics of mature application technology, simple equipment structure, easy manufacture and assembly, reliable effect and high efficiency, and also has the following advantages:

1. the ultrasonic wave acts on the graphite molecular group, the energy is easy to concentrate, the local power is strong, and particularly when the ultrasonic wave resonates with the internal frequency of the graphite, the molecular group is easy to break, and free carbon atoms are formed.

2. High penetration of ultrasonic waves through liquid CO₂The kinetic energy loss is very little, the coverage is wide, and all space corners in the reaction kettle can have the uniform breaking and dismantling function.

3. The ultrasonic wave breaks and tears open graphite group powder, and is efficient save time and electricity, effectual, the thoroughness is high.

4. The graphite powder is broken and disassembled by ultrasonic waves, and the processing content and the mode and the method are various. The alternative range is wide, the dry graphite powder can be directly used as a raw material for paving after being broken and dismantled, also can be used for breaking and dismantling high-concentration raw materials, can be used after being paved, stirred and diluted by a plurality of machines, or can be used for providing raw materials for paving and paving.

5. Direct and indirect diversified raw material handling and feeding modes can meet the production requirements of independent continuous strip-shaped sheet graphene, and more convenient preconditions are created for producing graphene with various shapes, thicknesses and different functions and purposes.

6. The quantity of the graphite powder processed by indirect breaking and dismantling is large, the total quantity is easy to measure, the graphite powder is measured by the percentage of the total quantity when in use, and is not measured by concentration, and concentration errors caused by the loss of the suspending agent in the breaking and dismantling process can be avoided.

The fifth embodiment is as follows:

the invention is described in further detail below in connection with the preparation and assembly and use of the apparatus:

the ultrasonic generator with adjustable frequency and power is selected and purchased to be suitable for planning production scale, the ultrasonic generator probe which is matched with the reaction kettle and is convenient to install and fix is customized, and the reaction kettle which is sealed, insulated, pressure-bearing, has no internal dead angle and is provided with a stirring device is customized. The top cover of the reaction kettle is provided with a pressure safety valve, the inner wall of the middle lower part of the reaction kettle is provided with a plurality of homologous ultrasonic generator probes, the bottom of the reaction kettle is provided with a discharge hole, and a conveying pipe connected with the discharge hole is provided with a pressure reducing device.

When in use, one-time injection is strictMetered liquid CO₂And graphite powder, starting the stirring device and the ultrasonic generator after the functional state of each part is checked in the reaction kettle, adjusting the frequency of the ultrasonic generator to be the same as the resonance state of the graphite and continue, stopping the ultrasonic generator after the graphite powder is completely broken into free carbon atoms, and discharging liquid CO at the dead angle in the discharge port₂. Quantitative liquid CO releasing normal pressure carbon to settling tray system device₂And (3) suspension.

The above embodiment is limited to the same set of devices for breaking and removing the graphite powder and outputting the carbon liquid CO one-to-one₂And (3) preparing the graphene by a spreading sedimentation method through the suspension liquid. The graphite is broken and disassembled by an ultrasonic generator or a microwave way to form dry powder of free carbon atoms or wet free carbon atom suspension liquid with various concentrations, and independent single set or multiple sets of paving and settling devices are supplied on site or in other places to produce flaky or continuous strip-shaped, single-layer or multi-layer graphene.

In addition to the technical features described in the specification, the methods are known to those skilled in the art.