CN108557815B - Preparation method of nanocrystalline micron graphite spheres - Google Patents

Preparation method of nanocrystalline micron graphite spheres Download PDF

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CN108557815B
CN108557815B CN201810504425.4A CN201810504425A CN108557815B CN 108557815 B CN108557815 B CN 108557815B CN 201810504425 A CN201810504425 A CN 201810504425A CN 108557815 B CN108557815 B CN 108557815B
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pressure
graphite
nanocrystalline
carbon microspheres
sodium chloride
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CN108557815A (en
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姚明光
董家君
杨振兴
张华�
刘冰冰
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Jilin University
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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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

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Abstract

The invention discloses a preparation method of nanocrystalline micron graphite nodules, and belongs to the technical field of preparation of nano materials. The invention takes glass carbon microspheres as an initiator, graphitizes the glass carbon microspheres under the conditions of temperature of 1500-1800K and pressure of 5GPa, and heat preservation and pressure maintenance for 20 minutes, and retains the spherical structure of the initiator by adopting a soft pressure transfer medium sodium chloride which is easy to separate. The method realizes the retention of the original appearance of the initial sample under the conditions of high temperature and high pressure, and synthesizes the nanocrystalline micron graphite spheres with complete structure and high graphitization. The spherical nano-crystalline micro graphite has wide application prospect in the fields of traditional electronic information kinescopes, sensors, mechanical lubrication, special graphite coatings, lithium battery electrodes and the like. The method also has potential application value in certain fields requiring graphite materials with special shapes and sizes.

Description

Preparation method of nanocrystalline micron graphite spheres
Technical Field
The invention belongs to the technical field of nano material preparation. In particular to a method for synthesizing high-quality nanocrystalline micron graphite nodules by a high-temperature high-pressure technology.
Background
As is well known, graphite is an allotrope of elemental carbon, and is one of the most common carbon materials, and has high chemical stability, corrosion resistance, high temperature resistance, good electrical and thermal conductivity, and the two-dimensional layered structure of graphite also makes it have excellent lubricating properties and low price, so that graphite becomes an important material in our production and life. In recent years, with the rapid development of nanotechnology, the nano graphite has a great number of excellent properties in the fields of electronic information display tubes, sensors, mechanical lubrication, special graphite coatings, lithium battery electrodes and the like, so that the nano graphite has wide application prospects in the aspects of novel functional materials, electronic devices and the like.
The spherical graphite material is a spherical or ellipsoidal graphite material with special morphology, and plays an important role in the fields of electrodes, electronic devices and the like at present. The method also has potential application value in certain application fields requiring graphite materials with special shapes and sizes. The conventional spherical graphite material is prepared by crushing, trimming, magnetically separating and purifying graphite. However, the spherical graphite material obtained by this method has a non-uniform spherical structure, is often subspherical and is often broken, and the performance thereof is affected thereby. There is a need for a method of producing high quality spheroidal graphite materials.
The existing graphitized glassy carbon material is characterized in that the shape of the glassy carbon particles is distorted and aggregated into block graphite due to mutual extrusion among the glassy carbon particles under the technical condition of high temperature and high pressure.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method capable of preserving the morphological morphology of a graphitized glassy carbon original sample under the condition of high temperature and high pressure; in particular to a method for preparing nanocrystalline micron graphite spheres for storing the morphological morphology of an original sample by using glass carbon micron spheres under the conditions of high temperature and high pressure, which solves the problem that the graphitized glass carbon material is distorted in morphology and aggregated into blocks under the conditions of high temperature and high pressure.
The technical scheme of the invention for preserving the graphitized glassy carbon with the original sample morphology is that in the process of graphitizing the glassy carbon at high temperature and high pressure, a soft pressure transmission medium is adopted to protect the morphology of the original glassy carbon. Specifically, in the process of graphitizing 20-50 um glass carbon microspheres at high temperature and high pressure, soft and easily cleaned sodium chloride (NaCl) is used as a pressure transmission medium to protect the spherical structure of the initial glass carbon microspheres.
The technical scheme of the specific preparation method of the nanocrystalline micron graphite nodule is as follows.
A method for preparing nano-crystalline micron graphite nodules, which comprises the following steps,
the method comprises the following steps: drying the sodium chloride; weighing glass carbon microspheres and dry sodium chloride according to the mass ratio of 1: 1.5-4; grinding the dried sodium chloride into white powder, adding the glass carbon microspheres into the sodium chloride powder, and uniformly mixing;
step two: filling the glass carbon microspheres and the sodium chloride powder in the step one into a high-pressure assembly, putting the assembly into a high-pressure device, and keeping the temperature and pressure for 20 minutes at the temperature of 1500-1800K and under the pressure of 5 GPa;
step three: washing the product obtained by pressure relief with distilled water, and drying to obtain the nanocrystalline micron graphite spheres.
The obtained nanocrystalline micron graphite spheres can preserve the original morphological spherical morphology of the glass carbon micron spheres.
In the first step, the mass purity of the sodium chloride is preferably more than or equal to 99.9%; the drying is carried out for 12 hours at the temperature of 80-95 ℃, for example, the drying is carried out for 12 hours in a vacuum drying oven at the temperature of 90 ℃; the diameter of the glass carbon microsphere can be selected from 20-50 um.
In step three, the distilled water is washed, and the washing can be repeated for 3 times to remove sodium chloride components.
The original highly disordered glassy carbon can be effectively graphitized at high temperature and high pressure, and the spherical structure of the glassy carbon microspheres can be well preserved as a proper amount of soft sodium chloride is added as a pressure transmission medium in the preparation process. After the treatment of water washing, centrifugation, drying and the like, the highly graphitized nanocrystalline micron graphite spheres with complete spherical structures can be obtained. The method realizes the retention of the original morphology of the initial glassy carbon under the conditions of high temperature and high pressure, and synthesizes the nanocrystalline micron graphite spheres with complete structure and high graphitization. The micron-sized spherical graphite material not only has wide application prospect in the fields of traditional electronic information display tubes, sensors, mechanical lubrication, special graphite paint, lithium battery electrodes and the like, but also has potential application value in certain application fields requiring graphite materials with special shapes and sizes.
Drawings
FIG. 1 is a scanning electron micrograph of the initial glassy carbon microspheres used in the present invention.
FIG. 2 is a high resolution electron micrograph of the initial glassy carbon microspheres used in the present invention.
FIG. 3 is a Raman spectrum of the initial glassy carbon microspheres used in the present invention.
FIG. 4 is the SEM photograph of the nano-crystalline micro-graphite spheres synthesized by the glass carbon microspheres in example 1.
FIG. 5 is a transmission electron micrograph of nanocrystalline micron graphite nodules synthesized from glassy carbon microspheres in example 1.
FIG. 6 is a high resolution electron micrograph of nanocrystalline micron graphite spheres synthesized from glassy carbon microspheres in example 1.
FIG. 7 is a Raman spectrum of nanocrystalline micron graphite nodules synthesized from glassy carbon microspheres in example 1.
FIG. 8 is the SEM photo of the nano-crystalline micro-graphite spheres synthesized by the glass carbon microspheres in example 2.
FIG. 9 is a transmission electron micrograph of nanocrystalline micron graphite nodules synthesized from glassy carbon microspheres in example 2.
FIG. 10 is a high resolution electron micrograph of nanocrystalline micron graphite nodules synthesized from glassy carbon microspheres in example 2.
FIG. 11 is a Raman spectrum of nanocrystalline micron graphite nodules synthesized from glassy carbon microspheres in example 2.
FIG. 12 is the SEM image of the nano-crystalline micro-graphite spheres synthesized by the glass carbon microspheres in example 3.
FIG. 13 is a scanning electron micrograph of nanocrystalline micron graphite spheres synthesized from glassy carbon microspheres in example 4.
FIG. 14 is a scanning electron micrograph of graphitized glassy carbon synthesized by glass carbon microspheres in example 5 without a pressure-transmitting medium.
FIG. 15 is a Raman spectrum of graphitized glassy carbon synthesized by glass carbon microspheres in example 5 without a pressure-transmitting medium.
FIG. 16 is a photograph of a Max Voggenzeitez model LPR1000-400/50 high-voltage device used for synthesis.
FIG. 17 is a longitudinal sectional view of 14/8 type high pressure assembly.
Detailed Description
The invention will be further illustrated with reference to specific examples.
In embodiments 1 to 5, the high voltage device is a Max Voggenzeitez, LPR1000-400/50 type six-eight large high voltage device, and the appearance structure of the high voltage device is shown in fig. 16. In examples 1 to 5, the 14/8-type high-pressure assembly is shown in FIG. 17. In fig. 17, 1 is magnesium oxide a; 2 is a graphite tube; 3 is a boron nitride tube; 4 is a lanthanum chromate tube; 5 is four-hole alumina; 6 is a thermocouple; 7 is an aluminum oxide sheet; 8 is a sample; 9 is zirconium dioxide; 10 is magnesium oxide B. Sample 8 was a mixture of glassy carbon microspheres and sodium chloride powder in examples 1 and 2, and only glassy carbon microspheres in example 3. The sample 8 is filled into the high-pressure assembly by a conventional assembly method, and specifically, the method comprises the following steps: the lanthanum chromate tube 4 and the graphite tube 2 are sleeved in the magnesium oxide A1 in sequence, the magnesium oxide B10, the zirconium dioxide 9 and the boron nitride tube 3 are sequentially placed in the graphite tube 2 from bottom to top, then the sample 8 is filled in the boron nitride tube 3, the upper part of the boron nitride tube is covered with the four-hole aluminum oxide 5, and finally the four-hole aluminum oxide 5 with the thermocouple 6 is placed in the graphite tube 2.
Example 1:
100mg of the dried high purity NaCl particles were ground in a mortar for 10min to give a fine white powder. Then 50mg of glass carbon microspheres are poured into the ground NaCl, and the mixture is fully mixed and stirred for 10 min. And filling the uniformly mixed glass carbon microspheres and NaCl into 14/8 type high-pressure assembly, putting the assembly into a high-pressure device, pressurizing to 5GPa after 10 hours, heating to 1500K by using a graphite tube, keeping the temperature and the pressure for 20 minutes, and unloading to normal pressure after 10 hours. Taking out, assembling under high pressure, disassembling, taking out the sample, washing with deionized water, centrifuging, removing supernatant, repeating the above washing operations for 3 times to ensure that a pressure transfer medium NaCl is removed, and finally drying in a drying oven at 80 ℃ to obtain the nanocrystalline micron graphite nodule.
Comparing the scanning electron micrographs of the glassy carbon microspheres before and after high temperature and high pressure (as shown in fig. 1 and fig. 4), it is found that the spherical structure of the glassy carbon microspheres after high temperature and high pressure (1500K, 5GPa) is well preserved, and the surface has an obvious graphitized lamellar structure. The transmission and high-resolution electron micrographs (such as fig. 5 and 6) after high temperature and high pressure show that the sample has an obvious graphite layered structure, and the evidence shows that the initial highly disordered glassy carbon structure has obvious graphitization after high temperature and high pressure treatment. The Raman spectrum characterization is carried out on the sample after high temperature and high pressure, and as shown in figure 7, two characteristic peaks 1350cm of the nanocrystalline graphite can be obviously observed-1And 1580cm-1The obtained nanocrystalline micron graphite nodule D band has reduced strength, the G band is enhanced, and obvious graphitization is shown by comparing the original glassy carbon micron sphere Raman (as shown in figure 3). It can be seen that the sample obtained by the above synthesis method is proved to be nanocrystalline micron graphite nodules by the above characterization.
Example 2:
the samples, pressure medium and their amounts and treatment were as in example 1. And filling the uniformly mixed glass carbon microspheres and NaCl into 14/8 type high-pressure assembly, putting the assembly into a high-pressure device, pressurizing to 5GPa after 10 hours, heating to 1800K by using a graphite tube, keeping the temperature and the pressure for 20 minutes, and unloading to normal pressure after 10 hours. Taking out, assembling under high pressure, disassembling, taking out the sample, washing with deionized water, centrifuging, removing supernatant, repeating the above washing operations for 3 times to ensure that a pressure transfer medium NaCl is removed, and finally drying in a drying oven at 80 ℃ to obtain the nanocrystalline micron graphite nodule.
Comparing the scanning electron micrographs of the glassy carbon microspheres before and after high temperature and high pressure (as shown in fig. 1 and fig. 8), it can be found that the spherical structure of the glassy carbon microspheres after high temperature and high pressure (1800K, 5GPa) is also well preserved, and the surface has an obvious graphitized lamellar structure. Transmission and high resolution electron micrographs (such as fig. 9 and 10) after high temperature and high pressure show that the sample has a distinct graphite layered structure, and similar to example 1, the glass carbon microspheres treated by 1800K and 5GPa show distinct graphitization. The Raman spectrum characterization of the sample after high temperature and high pressure is carried out, as shown in FIG. 11, two characteristic peaks 1350cm of the nanocrystalline graphite can be obviously observed-1And 1580cm-1The obtained nanocrystalline micron graphite nodule D band strength is obviously weakened, the G band is enhanced, and obvious graphitization is shown by comparing with the initial glassy carbon micron nodule Raman (as shown in figure 3), and compared with the embodiment 1, the temperature is increased to 1800K, the weakening degree of the D band is more obvious, the graphitization effect is more obvious, and the nanocrystalline micron graphite nodule with higher graphitization degree can be obtained.
Example 3
Uniformly mixing 90mg of dried NaCl and 60mg of glass carbon microspheres, filling the mixture into 14/8 type high-pressure assembly, putting the assembly into a high-pressure device, pressurizing the assembly to 5GPa for 10h, heating the assembly to 1800K by using a graphite tube, keeping the temperature and the pressure for 20min, and unloading the assembly to normal pressure for 10 h. And taking out the sample, washing with deionized water, centrifuging, removing supernatant, repeating the washing operation for 3 times to ensure that a pressure transfer medium NaCl is removed, and drying to obtain the nanocrystalline micron graphite nodule.
Comparing the scanning electron micrographs of the glassy carbon microspheres before and after high temperature and high pressure (as shown in fig. 1 and fig. 12), it can be found that the glassy carbon microspheres after high temperature and high pressure (1800K, 5GPa) have obvious graphitization, the spherical structure is preserved to a certain extent, but the addition of a pressure transfer medium NaCl is reduced, so that the protection effect of NaCl on the spherical morphology of the initial glassy carbon microspheres is reduced, and the synthesized nanocrystalline micron graphite spheres are damaged to a certain extent.
Example 4
And uniformly mixing 120mg of dried NaCl and 30mg of glass carbon microspheres, filling the mixture into 14/8 type high-pressure assembly, putting the assembly into a high-pressure device, pressurizing the assembly to 5GPa for 10 hours, heating the assembly to 1800K by using a graphite tube, keeping the temperature and the pressure for 20min, and unloading the assembly to normal pressure for 10 hours. And taking out the sample, washing with deionized water, centrifuging, removing supernatant, repeating the washing operation for 3 times to ensure that a pressure transfer medium NaCl is removed, and drying to obtain the nanocrystalline micron graphite nodule.
Comparing the scanning electron micrographs of the glassy carbon microspheres before and after high temperature and high pressure (as shown in fig. 1 and 13), it can be found that the glassy carbon microspheres after high temperature and high pressure (1800K, 5GPa) have obvious graphitization, and similar to example 2, the spherical structure is also well preserved. Compared with the example 3 (namely, the ratio of 1.5/1), it can be seen that in the synthesis process, the proportion of the pressure transmission medium and the glassy carbon microspheres has certain influence on the preservation of the spherical morphology of the glassy carbon microspheres, and the protective effect of the pressure transmission medium on the spherical morphology of the initial glassy carbon microspheres can be reduced if the pressure transmission medium is too little.
Example 5:
this example is a counter example where sodium chloride was not added as a soft pressure medium and thus the spherical structure thereof could not be retained.
150mg of glass carbon microspheres are taken, pressure transmission media are not added, the glass carbon microspheres are loaded into 14/8 type high-pressure assembly, then the glass carbon microspheres are placed into a high-pressure device, pressurized for 10 hours to 5GPa, heated to 1500K by using a graphite tube, kept at the temperature and pressure for 20min, and then unloaded to the normal pressure for 10 hours. And taking out the glass fiber to be assembled under high pressure, and taking out the sample to obtain the graphitized glassy carbon.
Comparing the scanning electron micrographs of the glassy carbon microspheres before and after high temperature and high pressure (as shown in fig. 1 and fig. 14), since NaCl is not added as a pressure transmission medium, the spherical structure of the glassy carbon microspheres after high temperature and high pressure (1500K, 5GPa) is completely destroyed, and a graphitized lamellar stacking block structure is presented. The sample after high temperature and high pressure is subjected to Raman spectrum characterization, as shown in FIG. 15, similar to example 1, the obtained graphitized glassy carbon D band has weakened strength, the G band is strengthened, and obvious graphitization is shown, but since no pressure transmission medium is added, glassy carbon microspheres are extruded mutually, and the spherical structure is damaged.
In conclusion, according to the data results, it can be found that the spherical structure of the glass carbon microspheres can be retained in the process of graphitizing the glass carbon microspheres at high temperature and high pressure by adding a proper amount of the soft pressure-transmitting medium NaCl, so as to synthesize the nanocrystalline micron graphite spheres. In addition, the graphitization degree of the nanocrystalline micron graphite nodules can be further improved by increasing the temperature.

Claims (3)

1. A method for preparing nano-crystalline micron graphite nodules, which comprises the following steps,
the method comprises the following steps: drying the sodium chloride; weighing glass carbon microspheres and dry sodium chloride according to the mass ratio of 1: 1.5-4; grinding the dried sodium chloride into white powder, adding the glass carbon microspheres into the sodium chloride powder, and uniformly mixing;
step two: filling the glass carbon microspheres and the sodium chloride powder in the step one into a high-pressure assembly, putting the assembly into a high-pressure device, and keeping the temperature and pressure for 20 minutes at the temperature of 1500-1800K and under the pressure of 5 GPa;
step three: washing the product obtained by pressure relief with distilled water, and drying to obtain the nanocrystalline micron graphite spheres.
2. The method for preparing nanocrystalline micron graphite nodules according to claim 1, wherein in the step one, the mass purity of the sodium chloride is greater than or equal to 99.9%; the drying is carried out for 12 hours at the temperature of 80-95 ℃; the diameter of the glass carbon microsphere is 20-50 um.
3. The method for preparing nano-crystalline micro graphite nodules according to claim 1 or 2, wherein in step three, the distilled water is washed, and the washing is repeated 3 times.
CN201810504425.4A 2018-05-24 2018-05-24 Preparation method of nanocrystalline micron graphite spheres Expired - Fee Related CN108557815B (en)

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CN101323446B (en) * 2008-06-27 2010-08-18 湖北大学 Preparation of carbon nanosphere
WO2011106685A1 (en) * 2010-02-26 2011-09-01 Brigham Young University Gas phase approach to in-situ/ex-situ functionalization of porous graphitic carbon via radical-generated molecules
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