CN105833797B - The high temperature and high pressure preparation process of nano-onions carbon - Google Patents
The high temperature and high pressure preparation process of nano-onions carbon Download PDFInfo
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Abstract
本发明的纳米洋葱碳的高温高压制备方法，属于纳米材料制备的技术领域。制备过程为将纳米金刚石粉按合成腔体大小压成圆柱状，将冷压得到的圆柱状原料装入加热容器，放入合成腔体中，在压力1.0～5.2GPa、温度1273～1773K下保温保压1～90分钟；最后冷却卸压，制得块状纳米洋葱碳材料。本发明工艺流程简单，制备周期短；产量和纯度高；产物粒度可以通过原料的尺寸大小调控；可以通过控制温度、保温时间和压力制备出不同形貌的纳米洋葱碳；该方法制备的纳米洋葱碳具有多孔结构提高其比表面积，并且制备的纳米洋葱碳含有含氧官能团提高了其亲水性。
The high temperature and high pressure preparation method of nano onion carbon of the invention belongs to the technical field of nano material preparation. The preparation process is to press the nano-diamond powder into a cylindrical shape according to the size of the synthesis cavity, put the cylindrical raw material obtained by cold pressing into a heating container, put it into the synthesis cavity, and keep the temperature at a pressure of 1.0-5.2GPa and a temperature of 1273-1773K. The pressure is maintained for 1 to 90 minutes; finally, the pressure is released by cooling to obtain a massive nano-onion carbon material. The invention has simple technological process, short preparation period, high yield and high purity; product particle size can be regulated by the size of raw materials; nano-onion carbons with different shapes can be prepared by controlling temperature, holding time and pressure; the nano-onion prepared by the method Carbon has a porous structure to improve its specific surface area, and the prepared nano-onion carbon contains oxygen-containing functional groups to improve its hydrophilicity.
Description
Technical field
The invention belongs to the technical fields of nano-onions carbon preparation, are related to the preparation method of nano-onions carbon high-temp high pressure.
Background technique
Nano-onions carbon is formed by concentric graphitic layers of balls nesting, is a member in fullerene family, and the homoatomic for belonging to carbon is different
Body.Nano-onions carbon has big specific surface area, high conductivity, good mechanical stability, thermal stability and and electrification
Learn stability.These excellent physicochemical properties make it all have a good application prospect in various fields, such as lithium battery, fuel electricity
The fields such as pond, dye-sensitized solar cells, supercapacitor, electrochemical hydrogen storage, microwave absorption, lubrication, catalysis.From 1992
Nano-onions carbon is found, and a variety of preparation methods, including arc discharge, electron beam irradiation, chemistry have been invented over more than 20 years
Annealing etc. in vapor deposition, ion beam mutation, ball milling, catalytic pyrolysis, Nano diamond vacuum or atmosphere of inert gases.But this
A little methods all have that energy consumption height, low output, purity is low and poor controllability in one or several disadvantages.
Summary of the invention
The technical problem to be solved by the present invention is to using nano-diamond powder as raw material, using high temperature and pressure synthetic method system
The nano-onions carbon of standby different-shape out, including core-shell structure, torispherical structure and hollow polyhedron structure.This method is directly logical
Overregulate the high-purity nano onion carbon that synthesis temperature, pressure and soaking time prepare different-shape.
The specific technical solution of the present invention is as described below.
A kind of high temperature and high pressure preparation process of nano-onions carbon, through briquetting, assembling, high temperature and pressure synthesis, cooling release work
Lumpy nanometer onion carbon material is made in skill process；The briquetting is to be pressed into raw material by synthetic cavity size using hydraulic press
It is cylindric；The assembling is that the cylindric raw material of block is packed into heating container, is put into synthetic cavity；The cooling is unloaded
Pressure, assembling block naturally cools to room temperature after being off electrified regulation, then release；It is characterized in that, the raw material is nanometer
Bortz powder；The high temperature and pressure synthesis, is the heat-insulation pressure keeping in the case where pressure is 1.0~5.2GPa, temperature is 1273~1773K
1~90 minute.
After obtained lumpy nanometer onion carbon material, nano-onions carbon dust is obtained by smashing and grinding.The powder
Broken is that the lumpy nanometer onion carbon dust that is synthesized high temperature and pressure by mechanical method is broken；The grinding be using mortar or
Ball mill is by smashed nano-onions carbon grind into powder.
The raw material is nano-diamond powder, and average particle size is 2~50 nanometers.
Experiment of the invention can be completed on domestic DS029B type cubic hinge press.The experimental results showed that reaction temperature,
Soaking time is an important factor for influencing the structure and pattern of the onion carbon of synthesis.It can be seen from Examples 1 to 4 in preparation
The optimum condition of the nano-onions carbon of hard rock covered with gold leaf is: synthesis pressure 1.0GPa, synthesis temperature 1273K, when heat-insulation pressure keeping
Between be 15 minutes, the nano-onions carbon of the described interior hard rock covered with gold leaf, core is Nano diamond, and shell is graphite layers of balls；It has prepared
The holomorphological preferred condition of torispherical nano-onions carbon is: synthesis pressure is about 1.0GPa, and synthesis temperature is about 1373K, is protected
Warm pressure maintaining 15 minutes；The preparation preferred condition of hollow polyhedron structure nano onion carbon is: synthesis pressure is about 1.0GPa, synthesis
Temperature is about 1673K, and heat-insulation pressure keeping 15 minutes；Preparing hollow polyhedron structure nano onion carbon can also be in lower synthesis temperature
The lower extension heat-insulation pressure keeping time will realize that specific condition is: synthesis pressure is about 1.0GPa, and synthesis temperature is about 1273K, heat preservation
Pressure maintaining 90 minutes.
The uniformity of synthetic cavity temperature during in order to guarantee synthetic sample, the heating method that this method uses is logical
The heating of electro-graphitic pipe heater-type；In order to guarantee that sample does not react with the graphite-pipe for generating heat, the cavity of synthetic sample is adopted
It is protected with hexagonal boron nitride.High temperature and high pressure method provides a closed system, Nano diamond can at high temperature under high pressure to
The transformation of onion carbon.The onion carbon granule size of such method preparation is controllable (can be lower than 10nm, mainly by raw material nano bortz powder
Size determine), and uniformly unified, purity is high.Its yield can press the size of chamber to adjust by changing press, up to gram quantity
Grade is horizontal.The nano-onions carbon of different-shape can be prepared by adjusting temperature, soaking time and pressure.Reaction temperature is improved,
Extend soaking time, reducing pressure helps to obtain the nano-onions carbon of hollow polyhedron structure, conversely, being easy to get with core
The nano-onions carbon (core is diamond, and shell is nested concentric graphitic layers of balls) or torispherical nano-onions carbon of shell structure.Due to
The certain oxygen-containing gas of nano-diamond powder adsorption, the onion carbon for preparing in this way have porous structure (by oxygen
Etching causes) and containing a certain number of oxygen-containing functional groups, this helps to improve its specific surface area and hydrophily.Specific surface area
Raising helps to improve its performance, and the specific capacity of lithium battery and the ratio electricity of supercapacitor such as can be improved as electrode material
Hold.The site of onion carbon with porous hollow polyhedron structure, hydrogen absorption is increased, and hydrogen storage ability can significantly improve.
It is well known that condition of high voltage can inhibit the graphitization of diamond, with the raising of pressure, the graphitization temperature of diamond
Degree improves, so high temperature and pressure prepares nano-onions carbon method and do not attempted and utilized by people.However, due to Nano diamond
The a small amount of oxygen-containing gas of raw material adsorption, can reduce the graphitization temperature of diamond.Nano diamond in 1GPa, 1373K,
The torispherical nano-onions carbon of Gestalt can be transformed under the conditions of heat preservation 15min.Than obtained by Nano diamond vacuum annealing
The torispherical nano-onions carbon temperature arrived reduces about 300K；15min is kept the temperature when 1GPa, 1673K can be transformed into hollow more
The nano-onions carbon of face body structure, compared with Nano diamond vacuum annealing method, synthesis temperature reduces about 500K.
In short, present invention process process is simple, nano-onions carbon is controlled by adjusting temperature, soaking time and pressure
Structure and pattern, and prepared the higher block nanometer onion carbon material of purity；It crushed, grind available powdered receive
Rice onion carbon.The present invention overcomes the low output of traditional preparation methods, energy consumption is high, purity is low, poor controllability the disadvantages of, i.e.,
Method of the invention has the characteristics that low energy consumption, yield is high, purity is high, granularity and morphology controllable are good, short preparation period, the party
Method preparation onion carbon have porous structure and contain a certain number of oxygen-containing functional groups, this help to improve its specific surface area and
Hydrophily promotes its industrial application to be of great significance for improving the performance of such material.
Detailed description of the invention
Fig. 1 is the nano-onions carbon of core-shell structure prepared by embodiment 1 (core is Nano diamond, and shell is graphite layers of balls)
High resolution electron microscope image.
Fig. 2 is the high resolution electron microscope image of the torispherical nano-onions carbon of Gestalt prepared by embodiment 2.
Fig. 3 is the high resolution electron microscope image of the polyhedron nano-onions carbon of hollow structure prepared by embodiment 3.
Fig. 4 is the high resolution electron microscope image of the polyhedron nano-onions carbon of hollow structure prepared by embodiment 4.
Fig. 5 is the high resolution electron microscope image of sample prepared by comparative example 1.
Fig. 6 is the high resolution electron microscope image of sample prepared by comparative example 2.
Fig. 7 is the high resolution electron microscope image of sample prepared by comparative example 3.
Fig. 8 is the high resolution electron microscope image of sample prepared by comparative example 4.
Specific embodiment
Embodiment 1
The nano-diamond powder that average particle size is 9nm is filled sample using hydraulic press by after bortz powder compression moulding
Enter in synthetic cavity.It assembles in cavity and is heated using graphite-pipe, do thermal insulation material with pyrophillite, protected using hexagonal boron nitride
Cavity, synthesis pressure 1.0GPa, synthesis temperature 1273K, heat-insulation pressure keeping time are 15 minutes, and sample is natural after stopping heating
It is cooled to room temperature rear release, this condition prepares the nano-onions carbon of interior hard rock covered with gold leaf, and (core is Nano diamond, and shell is graphite nodule
Layer), specific high resolution electron microscope picture is shown in Fig. 1.
Embodiment 2
Using raw material same as Example 1, assembling same as Example 1 is used after powder sample compression moulding, is closed
It is 1.0GPa, synthesis temperature 1373K at pressure, the pressure-maintaining and heat-preservation time 15 minutes, sample naturally cooled to room after stopping heating
Release after temperature, this condition prepare the torispherical nano-onions carbon of Gestalt.Specific high resolution electron microscope picture is shown in
Fig. 2.
Embodiment 3
Using raw material same as Example 1, assembling same as Example 1 is used after powder sample compression moulding, is closed
It is 1.0GPa, synthesis temperature 1673K at pressure, the pressure-maintaining and heat-preservation time 15 minutes, sample naturally cooled to room after stopping heating
Release after temperature.The nano-onions carbon of hollow polyhedron structure is synthesized under this condition.Specific high resolution electron microscope figure
Piece is shown in Fig. 3.By Examples 1 to 3 it is found that under certain pressure and soaking time, as the temperature rises, it may occur that nanogold
Hard rock → interior hard rock covered with gold leaf nano-onions carbon → Gestalt torispherical nano-onions carbon → hollow polyhedron structure is received
The transformation of rice onion carbon.
Embodiment 4
Using raw material same as Example 1, assembling same as Example 1 is used after powder sample compression moulding, is closed
It is 1.0GPa, synthesis temperature 1273K at pressure, the pressure-maintaining and heat-preservation time 90 minutes, sample naturally cooled to room after stopping heating
Release after temperature.The onion carbon of hollow polyhedron structure is prepared under this condition.Specific high resolution electron microscope picture is shown in figure
4.By embodiment 1 and 4 it is found that under certain pressure and temperature, with the extension of soaking time, it may occur that Nano diamond →
Nano-onions carbon → Gestalt torispherical nano-onions carbon → hollow polyhedron structure nano-onions of interior gold filled hard rock
The transformation of carbon.
Embodiment 5
In embodiment 3, the heat-insulation pressure keeping time is reduced, the heat-insulation pressure keeping time can obtain receiving for other patterns in 1~10min
Rice onion carbon, the interior gold filled nano-onions carbon of hard rock or the torispherical nano-onions carbon of Gestalt.It is certain in pressure
In the case of (1GPa), synthesis temperature certain (1673K), hollow polyhedron nanometer can be made within the relatively short heat-insulation pressure keeping time
Onion carbon changes to the torispherical nano-onions carbon of Gestalt or the nano-onions carbon of interior hard rock covered with gold leaf.
Embodiment 6
In embodiment 3, synthesis pressure is improved, makes it in 1~5.2GPa, the nano-onions carbon of other patterns can be obtained,
The interior gold filled nano-onions carbon of hard rock or the torispherical nano-onions carbon of Gestalt.In certain (1673K) feelings of synthesis temperature
Under condition, as pressure increase makes nano-onions carbon that hollow polyhedron → Gestalt torispherical nano-onions carbon → interior packet occur
The transformation of the nano-onions carbon of diamond.
Embodiment 7
Using raw material same as Example 1, assembling same as Example 1 is used after powder sample compression moulding, is closed
It is 1.0GPa, synthesis temperature 1773K at pressure, block nanometer onion carbon materials can be made in 1~10min in the heat-insulation pressure keeping time
Material.
Embodiment 8
In Examples 1 to 7, the average particle size of bortz powder increases to 50nm, or is reduced to 2nm, and block can be made
Body nano-onions carbon material only influences onion carbon granule size.The average particle size of nano-diamond powder is bigger, in identical synthesis
Under pressure, synthesis temperature needed for preparing the nano-onions carbon of corresponding pattern is higher accordingly (but being not higher than 1873K), Huo Zhesuo
The heat-insulation pressure keeping time needed is longer accordingly (but being not more than 90min).This is because granularity is bigger, the crystallization of nano-diamond powder
Property it is better, at identical temperature, granularity it is big nano-diamond powder graphitization speed it is low, improve synthesis temperature can accelerate its graphite
Change.
Embodiment 9
In Examples 1 to 5,7~8, lumpy nanometer onion carbon materials can be made between 1~5.2GPa in synthesis pressure
Material.When raw material average particle size is identical, synthesis pressure is higher, and it is longer to prepare the time required for the nano-onions carbon of corresponding pattern
Or synthesis temperature it is higher (with synthesis pressure be 1GPa when compared with).
Comparative example 1
Using raw material same as Example 1, assembling same as Example 1 is used after powder sample compression moulding, is closed
It is 1.0GPa, synthesis temperature 1873K at pressure, the pressure-maintaining and heat-preservation time 15 minutes, sample naturally cooled to room after stopping heating
Release after temperature.The onion carbon of graphite and hollow structure containing silk ribbon shape in the sample synthesized under this condition.Specific high-resolution
Electron microscope picture is shown in Fig. 5.
Comparative example 1 is to be conducive to the graphitization of onion carbon, synthetic sample since synthesis temperature is excessively high or soaking time is too long
In produce the graphite of silk ribbon shape.
Comparative example 2
Using raw material same as Example 1, assembling same as Example 1 is used after powder sample compression moulding, is closed
It is 5.2GPa, synthesis temperature 2273K at pressure, the pressure-maintaining and heat-preservation time 15 minutes, sample naturally cooled to room after stopping heating
Release after temperature.Occurs the graphite of stratiform under this condition.Specific high resolution electron microscope picture is shown in Fig. 6.
Comparative example 2 is conducive to Nano diamond and changes rapidly to onion carbon, but changing since synthesis temperature is excessively high
Cheng Hou, high synthesis temperature and synthesis pressure promote onion carbon to change to lamellar graphite again.
Comparative example 3
Using raw material same as Example 1, the assembling of embodiment 1 is used after powder is molded, synthesis pressure is
1.0GPa, temperature 1173K the pressure-maintaining and heat-preservation time 15 minutes, stop release after sample cooled to room temperature, this condition after heating
Amorphous graphite and interrupted graphite linings are produced in the sample prepared, around nano-diamond powder.Specific high-resolution
Electron microscope picture is shown in Fig. 7.
Comparative example 3 is since synthesis temperature is too low or the reaction time is too short, in product based on Nano diamond, around shape
At discontinuous graphite linings or amorphous graphite, but spherical shape is not connected into.
Comparative example 4
Using raw material same as Example 1, assembling same as Example 1 is used after powder sample compression moulding, is closed
It is 5.2GPa, synthesis temperature 1873K at pressure, the pressure-maintaining and heat-preservation time 15 minutes, sample naturally cooled to room after stopping heating
Release after temperature.Synthesize the graphite of spherical onion carbon and stratiform under this condition.Specific high resolution electron microscope picture is shown in figure
8。
Comparative example 4 is to cause the onion carbon generated to change to lamellar graphite since temperature and pressure is excessively high.
Claims (5)
1. a kind of high temperature and high pressure preparation process of nano-onions carbon, through briquetting, assembling, high temperature and pressure synthesis, cooling release technique
Lumpy nanometer onion carbon material is made in process；The briquetting is that raw material is pressed into circle by synthetic cavity size using hydraulic press
Column；The assembling is that the cylindric raw material of block is packed into heating container, is put into synthetic cavity；The cooling release,
Assembling block naturally cools to room temperature after being off electrified regulation, then release；The raw material is nano-diamond powder；Its feature
It is, the high temperature and pressure synthesis, is that interior packet is made in the case where pressure is 1.0GPa, temperature is 1273K heat-insulation pressure keeping 15 minutes
The nano-onions carbon of diamond；Or in the case where pressure is 1.0GPa, temperature is 1373K heat-insulation pressure keeping 15 minutes, complete shape is made
The torispherical nano-onions carbon of state；The hydraulic press is domestic DS029B type cubic hinge press.
2. the high temperature and high pressure preparation process of nano-onions carbon according to claim 1, characterized in that the raw material is
The bortz powder that average particle size is 2~50 nanometers.
3. the high temperature and high pressure preparation process of nano-onions carbon according to claim 1, characterized in that in obtained lumpy nanometer
After onion carbon material, nano-onions carbon dust is obtained by smashing and grinding.
4. the high temperature and high pressure preparation process of nano-onions carbon according to claim 1,2 or 3, characterized in that described is interior
The nano-onions carbon of hard rock covered with gold leaf, core are Nano diamond, and shell is graphite layers of balls.
5. a kind of high temperature and high pressure preparation process of nano-onions carbon, through briquetting, assembling, high temperature and pressure synthesis, cooling release technique
Lumpy nanometer onion carbon material is made in process；The briquetting is that raw material is pressed into circle by synthetic cavity size using hydraulic press
Column；The assembling is that the cylindric raw material of block is packed into heating container, is put into synthetic cavity；The cooling release,
Assembling block naturally cools to room temperature after being off electrified regulation, then release；The raw material is nano-diamond powder；Its feature
It is, the described high temperature and pressure synthesis, is in the case where pressure is 1.0GPa, temperature is 1673K heat-insulation pressure keeping 15 minutes, or in pressure
It is heat-insulation pressure keeping 90 minutes under 1273K for 1.0GPa, temperature, the nano-onions carbon of hollow polyhedron structure is made；The liquid
Press is domestic DS029B type cubic hinge press.
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| CN108530098B (en) * | 2017-03-06 | 2022-04-08 | 海南大学 | A kind of bulk carbon reinforcement/carbon composite material and preparation method thereof |
| US10920035B2 (en) | 2017-03-16 | 2021-02-16 | Lyten, Inc. | Tuning deformation hysteresis in tires using graphene |
| EP3596163A4 (en) | 2017-03-16 | 2021-01-13 | Lyten, Inc. | CARBON AND ELASTOMER INTEGRATION |
| US9862606B1 (en) | 2017-03-27 | 2018-01-09 | Lyten, Inc. | Carbon allotropes |
| CN107645065A (en) * | 2017-09-08 | 2018-01-30 | 西安工程大学 | A kind of preparation method of onion carbon/MXene stratiform Wave suction composite materials |
| CN109112330B (en) * | 2018-08-20 | 2020-10-16 | 东南大学 | Nano onion carbon reinforced titanium-based composite material and preparation method thereof |
| CN109701447B (en) * | 2019-03-07 | 2021-05-07 | 吉林大学 | A catalyst-free low-pressure method for preparing nano-polycrystalline diamond |
| CN111348628A (en) * | 2020-03-27 | 2020-06-30 | 燕山大学 | A cubic boron nitride-nano polycrystalline diamond composite material and preparation method thereof |
| CN114751748B (en) * | 2022-03-18 | 2023-06-16 | 燕山大学 | High-strength compact onion-like carbon block material and preparation method thereof |
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