CN115650210A - Preparation method and application of single/double-wall carbon nano tube - Google Patents
Preparation method and application of single/double-wall carbon nano tube Download PDFInfo
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- 239000002079 double walled nanotube Substances 0.000 title claims abstract description 77
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
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- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 2
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method and application of a single/double-wall carbon nano tube, wherein the preparation method of the single/double-wall carbon nano tube comprises the following steps: the method comprises the following steps of (1) enabling a mixture of a catalyst precursor and a carbon source to sequentially pass through an inlet of a plasma reactor, a plasma flame zone and a growth zone; the temperature of the center of the plasma flame zone is more than or equal to 5000 ℃; the temperature of the growth area is 1200-2000 ℃; the time required by the mixture from the center of the plasma flame zone to the growth zone is less than or equal to 0.2s. The preparation method provided by the invention can effectively improve the growth efficiency and the graphitization degree of the obtained single/double-wall carbon nano tube. The invention also provides the single/double-wall carbon nano tube prepared by the preparation method and a plasma reactor for implementing the preparation method.
Description
Technical Field
The invention relates to the technical field of micro-nano synthesis, in particular to a preparation method and application of a single/double-wall carbon nano tube.
Background
The single/double-wall carbon nanotube refers to Shan Bi carbon nanotube or double-wall carbon nanotube, and compared with the multi-wall carbon nanotube, the single/double-wall carbon nanotube has larger length-diameter ratio and higher graphitization degree (I) G /I D More than 10), has more excellent conductivity and flexibility, and can be used as a conductive agent of a secondary battery at low addition amount (as low as 0.05 percent) in positive and negative electrodesA developed conductive network is formed inside the material, so that the cycle life and the rate capability of the lithium battery are obviously prolonged. Particularly, the silicon-carbon negative electrode is subject to a high volume expansion rate (more than 200%) of silicon during charging and discharging processes, silicon-carbon negative electrode particles are easy to pulverize, and finally, the battery is rapidly exhausted, and the single/double-wall carbon nano tube can effectively solve the problems faced by the silicon-carbon negative electrode due to high flexibility and excellent conductivity of the single/double-wall carbon nano tube.
In order to better meet the application requirements of the silicon-based negative electrode, the single/double-wall carbon nano-tube is required to have higher graphitization degree (I) G /I D More than 80), in the traditional technology, in order to improve the graphitization degree, an effective method is to adopt nano iron aerosol (the grain diameter is less than 5 nm) to catalyze a carbon source to decompose and grow the required product at the temperature of more than 1000 ℃. In order to prepare the nano-iron aerosol, the technology discloses that dilute solution of organic metal compounds such as ferrocene and the like is used as a catalyst precursor and injected into a reactor at 1100-1500 ℃, the catalyst precursor solution enters the reactor to generate the nano-iron aerosol in situ, and then a catalytic carbon source (toluene and ethylene) is decomposed to grow a single-walled carbon nanotube. In order to prevent the formation of nano-iron with an excessively large size (particle size > 5 nm), the amount of catalyst precursor introduced is limited, and the growth efficiency of the single-walled tube is limited. Also, a single-walled carbon nanotube reactor containing a catalyst pretreatment and acceleration unit is disclosed, which accelerates a mixed gas containing a catalyst and a carbon source to 5m/s to 50m/s, and a large number of catalyst particles having a narrow particle size distribution (a main particle size range of 1nm to 8 nm) rapidly enter a reaction zone, thereby preventing catalyst agglomeration and achieving a growth efficiency of 2.3kg/h at a reaction volume of 3000L. But the production efficiency per reaction volume is only 0.77 g/(L.h) and the I of the product obtained therefrom is that a proportion of particles with a particle size > 5nm is still present in the catalyst prepared therefrom G /I D Up to only 78.
In conclusion, the single/double-wall carbon nano tube prepared by the traditional preparation method has lower graphitization degree and lower growth efficiency per unit reaction volume.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of the single/double-wall carbon nano tube, which can effectively improve the growth efficiency and the graphitization degree of the obtained single/double-wall carbon nano tube.
The invention also provides the single/double-wall carbon nano tube prepared by the preparation method.
The invention also provides the application of the single/double-wall carbon nano tube.
The invention also provides a plasma reactor for implementing the preparation method.
According to an embodiment of the first aspect of the present invention, a method for preparing a single/double-wall carbon nanotube is provided, the method comprising:
the method comprises the following steps of (1) enabling a mixture of a catalyst precursor and a carbon source to sequentially pass through an inlet of a plasma reactor, a plasma flame zone and a growth zone;
the temperature of the center of the plasma flame zone is more than or equal to 5000 ℃;
the temperature of the growth area is 1200-2000 ℃;
the time required by the mixture from the center of the plasma flame zone to the growth zone is less than or equal to 0.2s.
The mechanism of the preparation method is as follows:
the mixture is converted into a high-activity plasma state in a plasma flame zone, and in the process of transferring the mixture to a growth zone, the plasma state of a catalyst precursor is converted into a corresponding small-particle-size catalyst (1-5 nm), and the plasma state of a carbon source is converted into carbon atoms;
then the carbon atoms and the catalyst are quickly transferred to a growth area, and under the action of the catalyst, the carbon atoms are arranged to form the single/double-wall carbon nano tube.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects:
(1) The invention discovers that if the growth efficiency of the single/double-wall carbon nano tube is improved, the density of the catalyst with small grain diameter (less than or equal to 5 nm) in a growth area needs to be improved.
In the conventional technology, the pyrolysis temperature is usually about 1000 ℃, the energy density is low, a large amount of catalyst precursor is not enough to be decomposed into single atoms, and an aerosol catalyst with high concentration and narrow particle size (1 nm-5 nm) is difficult to form, so that the growth efficiency (the ratio of the mass of the collected carbon nanotube to the volume of a growth area in unit time) of the single/double-wall carbon nanotube is limited. If the catalyst has a large particle size (i.e., the catalyst is agglomerated and the particle size is greater than 5 nm), then the formed carbon nanotubes are mostly multi-walled carbon nanotubes, or are mixed carbon, and at least the graphitization degree of the obtained carbon nanotubes is affected. Therefore, in order to improve the growth efficiency of the single/double-wall carbon nano-tube, the density of the catalyst with small particle size (less than or equal to 5 nm) in the growth area needs to be improved.
The invention adopts plasma flame as pyrolysis energy, the central temperature of the plasma flame is more than or equal to 5000 ℃, and enough energy density is provided, so that the catalyst precursor can be rapidly decomposed to form a high-concentration aerosol catalyst, the density of the catalyst with small grain diameter (less than or equal to 5 nm) in a growth area is ensured, and a foundation is provided for improving the growth efficiency of the single/double-wall carbon nano tube.
(2) The invention inhibits the catalyst generated in the plasma flame zone from agglomerating (the time is short and the agglomeration is not time to) by limiting the time required by the mixture from the center of the plasma flame zone to the growth zone, thereby inhibiting the generation of multi-wall carbon nanotubes and miscellaneous carbon and improving the graphitization degree of the obtained single/double-wall carbon nanotubes.
According to some embodiments of the invention, the carbon source decomposes to form gaseous carbon atoms at a temperature ≧ 5000 ℃.
According to some embodiments of the invention, the carbon source comprises at least one of an alkane, an alkene, an alkyne, and carbon powder.
According to some embodiments of the invention, the alkane comprises at least one of methane and ethane.
According to some embodiments of the invention, the catalyst precursor comprises a metal organic.
According to some embodiments of the invention, the metallorganic is at least one of ferrocene, nickelocene, cobaltocene, iron carbonyl, and cobalt carbonyl.
According to some preferred embodiments of the invention, the metallorganic is ferrocene.
According to some embodiments of the invention, the mixture further comprises a sulfur adjuvant. The sulfur adjuvant can promote the growth of the single/double-wall carbon nano-tube.
According to some embodiments of the invention, the sulfur adjuvant is at least one of elemental sulfur and a small sulfur-containing organic molecule.
According to some embodiments of the invention, the sulfur-containing small organic molecule has a molecular weight of 500 or less.
According to some preferred embodiments of the invention, the sulfur-containing small organic molecule is selected from thiophene.
According to some embodiments of the invention, the ratio of the amount of metal atoms in the catalyst precursor to the amount of species of sulfur atoms in the sulfur promoter is from 2 to 70:1.
according to some preferred embodiments of the present invention, the ratio of the amount of metal atoms in the catalyst precursor to the amount of sulfur atoms in the sulfur promoter is 60 to 70:1.
according to some embodiments of the invention, the catalyst precursor may be added in solid form or in gaseous form.
According to some embodiments of the invention, the mixture further comprises a carrier gas.
The carrier gas may help the catalyst precursor and the carbon source smoothly pass through the plasma flame zone and the growth zone.
According to some embodiments of the invention, the carrier gas comprises at least one of nitrogen and an inert gas.
According to some embodiments of the invention, the mixture has a ratio of the flow rates of the carbon source and the carrier gas of (10 to 50): 30. for example, 1:2.
According to some preferred embodiments of the present invention, the ratio of the flow rates of the carbon source and the carrier gas in the mixture is (42 to 50): 30. for example, 7:5 or 5:3.
According to some embodiments of the invention, the mixture has a ratio of the mass of the catalyst precursor to the flow rate of the carrier gas of 77g (100 to 1000) L.
According to some preferred embodiments of the present invention, the ratio of the mass of the catalyst precursor to the flow rate of the carrier gas in the mixture is 77g (370-930) L. For example, it may be 7g: 6L, 11g:54L, 1g: 8.7-8.8L, 1g:10.3 to 10.4L.
The carrier gas can also adjust the concentration of the carbon source and the catalyst precursor in the mixture, thereby improving the growth efficiency and the graphitization degree of the single/double-wall carbon nanotube as much as possible.
According to some embodiments of the invention, the temperature of the plasma reactor inlet is about 200 ℃.
According to some embodiments of the invention, the plasma flame zone is formed by exciting an inert gas with an electromagnetic wave.
According to some embodiments of the invention, the inert gas comprises at least one of nitrogen and an inert gas.
Preferably, when the inactive gas includes the inert gas, the inert gas includes at least one of argon and neon.
From the above process description, the flow rate of the mixture through the inlet of the plasma reactor is: the sum of the flow rates of the catalyst precursor, the carbon source and the carrier gas;
the flow rate of the mixture obtained in the plasma flame zone is the sum of the flow rate of the mixture passing through the inlet of the plasma reactor and the flow rate of the inactive gas.
According to some embodiments of the invention, the mixture takes a time period of ≦ 0.03s from the plasma reactor inlet to the center of the plasma flame zone.
The time is influenced by the flow rate of the mixture and the cross-sectional area of the plasma flame zone, and the time can be adjusted by adjusting the proportion of the mixture and the cross-sectional area of the plasma flame zone in the actual test process.
According to some embodiments of the invention, the temperature of the growth zone near one side edge of the plasma flame zone is about 2000 ℃.
According to some embodiments of the invention, the mixture generated by the plasma flame zone takes 0.2s or less from the center of the plasma flame zone to the edge of the growth zone near one side of the plasma flame zone; for example, it may be 0.124s, 0.0676s, or 0.025s.
Therefore, the time for the mixture to reach the growth region is short, the catalyst precursor is inhibited from generating side reaction in the transition region (from the plasma flame region to the growth region) to generate large-particle catalyst, and further the generation of multi-wall carbon nanotubes and miscellaneous carbon is inhibited.
This time is influenced by the flow rate of the mixture generated in the plasma flame zone (the sum of the flow rates of the inert gas, the carbon source, the carrier gas, and the metal catalyst precursor), the cross-sectional area of the plasma flame zone, the cross-sectional area of the growth zone, and the distance from the center of the plasma flame zone to the growth zone near the plasma flame zone. In actual production, the parameters can be regulated and the time required can be regulated.
According to some embodiments of the invention, a cross-sectional area of the growth region near an edge of the plasma flame region is greater than a cross-sectional area of the plasma flame region.
Thus, in this process, the density of the resultant mixture (number of particles per unit volume) corresponding to the plasma flame zone is decreased, whereby the particle size of the catalyst is small and uniform, and the graphitization degree of the resulting single/double wall carbon nanotube is improved.
According to some embodiments of the invention, the residence time of the mixture in the growth zone is between 1s and 60s.
Similarly, the residence time of the inactive gas in the growth zone is also 1 to 60s.
According to some preferred embodiments of the present invention, the residence time of the mixture obtained in the plasma flame zone in the growth zone is 1s to 2s.
According to some preferred embodiments of the present invention, the residence time of the mixture obtained in the plasma flame zone in the growth zone is 2s to 3s.
According to some embodiments of the invention, a temperature of an edge of the growth zone remote from an edge of the plasma flame zone is about 1200 ℃.
In the present invention, the residence time (t) is not particularly limited n ) The calculation method of (a) is shown as follows:
t n ＝273·S n ·L n /(V n ·(T n +273))；
wherein:
S n : calculating the average cross-sectional area perpendicular to the axial direction of the plasma reactor in m 2 (ii) a If the calculation region is irregular in shape, the average sectional area is the ratio of the volume of the calculation region to the axial length;
V n : total gas flow in Nm 3 /s；
T n : temperature in units of; if the temperature is not uniform, taking a median thermometer, namely the temperature at the midpoint of the axial length;
L n : the axial length of the region is calculated in m.
According to some embodiments of the invention, the method of preparing further comprises collecting single/double-walled carbon nanotubes produced by the growth zone.
According to some embodiments of the invention, the growth efficiency of the preparation method is 3 g/(L.h) or more. Specifically, it may be, for example, 3.6 g/(L.h) or 4.8 g/(L.h).
The growth efficiency (M) tV ) The calculation method of (a) is shown as follows:
M tV ＝M t /(L 3 ·S 3 ×1000)；
wherein:
M t the mass of the single/double-wall carbon nano tube collected in unit time is g/h;
L 3 : the axial length of the growth zone is in m.
S 3 : average cross-sectional area of growth region in m 2 ；
M tV The unit is g/(L · h).
According to the preparation method provided by the invention, the gas flow field formed by various gases is controlled, the residence time of each stage is controlled, and the growth efficiency and the graphitization degree of the obtained single/double-wall carbon nano tube are improved by controlling the relation between the temperature field and the residence time.
According to the embodiment of the second aspect of the invention, the single/double-wall carbon nanotube prepared by the preparation method is provided, and the I of the single/double-wall carbon nanotube G /I D The value is greater than or equal to 80.
Because the single/double-wall carbon nanotube adopts all the technical schemes of the preparation methods in the above embodiments, the single/double-wall carbon nanotube has at least all the beneficial effects brought by the technical schemes of the above embodiments, namely, high growth efficiency and high graphitization degree.
According to some embodiments of the invention, I G /I D Value of I G The Raman spectrum of the obtained single/double-wall carbon nano tube is 1570-1610 c -11 Peak intensity in the range, I D Raman spectrum is 1320-1360 cm -1 The peak intensity in the range and the proportion of the peak intensity are in positive correlation with the graphitization degree of the obtained single-wall/double-wall carbon nano tube. Therefore, the single/double-wall carbon nano tube obtained by the invention has higher graphitization degree.
According to some preferred embodiments of the present invention, I of the single/double-walled carbon nanotube G /I D The value is greater than or equal to 100.
According to some embodiments of the invention, the single/double walled carbon nanotubes have an ash content of 30wt%.
Namely, the mass ratio of the calcined residues of the single/double-wall carbon nano tubes to the calcined single/double-wall carbon nano tubes is less than or equal to 30 percent.
Therefore, the single/double-wall carbon nano tube has higher carbon purity.
According to some embodiments of the invention, the ash content of the single/double walled carbon nanotube is 24% to 27.5%.
According to some embodiments of the invention, the single/double-walled carbon nanotubes are at least one of single-walled carbon nanotubes or double-walled carbon nanotubes.
According to some embodiments of the invention, the single/double-walled carbon nanotube has a tube diameter of 1 to 5nm.
According to the third aspect embodiment of the invention, the application of the single/double-wall carbon nanotube in preparing a secondary battery is provided.
The application of the embodiment of the invention has at least the following beneficial effects:
the single/double-wall carbon nano tube provided by the invention has higher graphitization degree, thinner tube diameter, larger length-diameter ratio and excellent conductivity and flexibility, so that when the single/double-wall carbon nano tube is used as a conductive agent of a secondary battery, the addition amount of the conductive agent can be reduced, namely, the dosage proportion of positive and negative active materials is improved, and finally, the energy density of the obtained secondary battery is improved.
When the single/double-wall carbon nano tube is matched with the silicon cathode, the structural advantage can accommodate the volume change of the silicon cathode in the charging and discharging process, and finally the cycle performance and the safety performance of the obtained secondary battery are improved.
According to some embodiments of the invention, the single/double wall carbon nanotube is added in an amount of 0.05% to 1%.
The addition amount refers to the mass percentage of the single/double-wall carbon nano tube in the anode dressing or the cathode dressing.
The positive electrode dressing includes a positive electrode active material, the single/double-walled carbon nanotubes, and a binder.
The negative electrode dressing includes a negative electrode active material, the single/double-walled carbon nanotube, and a binder.
According to a fourth aspect of the embodiment of the invention, a plasma reactor for implementing the preparation method is provided, and the plasma reactor comprises a plasma reactor inlet, a plasma flame zone and a growth zone which are sequentially connected in a conducting manner.
According to some embodiments of the invention, the plasma flame zone is cylindrical.
According to some embodiments of the invention, the growth region is cylindrical.
According to some embodiments of the invention, the plasma reactor further comprises a transition zone disposed between the plasma flame zone and the growth zone.
According to some embodiments of the invention, the transition region is flared; and in the transition region, one side of the small opening is communicated with the plasma flame region, and the other side of the small opening is communicated with the growth region.
Unless otherwise specified, "about" in the present invention means within ± 2% of the allowable error.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic view of the structure of a plasma reactor used in examples 1 to 3 of the present invention;
FIG. 2 is a Raman spectrum of a single/double-walled carbon nanotube obtained in example 1 of the present invention;
FIG. 3 is an HR-TEM image of the single/double wall carbon nanotube obtained in example 1 of the present invention;
FIG. 4 is an SEM image of single/double-walled carbon nanotubes obtained in example 1 of the present invention;
FIG. 5 is an SEM image of single/double-walled carbon nanotubes obtained in example 2 of the present invention;
FIG. 6 is an SEM image of single/double-walled carbon nanotubes obtained in example 3 of the present invention;
FIG. 7 is an SEM photograph of a sample obtained in comparative example 1 of the present invention;
FIG. 8 is an SEM photograph of a sample obtained in comparative example 2 of the present invention.
Reference numerals:
a plasma reactor inlet 100, a plasma flame zone 200, a center of the plasma flame zone 210, a transition zone 300, a growth zone 400.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the present invention, if there are first, second, etc. described, it is only for the purpose of distinguishing technical features, and it is not understood that relative importance is indicated or implied or that the number of indicated technical features is implicitly indicated or that the precedence of the indicated technical features is implicitly indicated.
In the description of the present invention, it should be understood that the orientation descriptions, such as the orientation or positional relationship indicated by upper, lower, etc., are based on the orientation or positional relationship shown in the drawings, and are only for convenience of description and simplification of the description, but do not indicate or imply that the device or element referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that unless otherwise explicitly defined, terms such as arrangement, installation, connection and the like should be broadly understood, and those skilled in the art can reasonably determine the specific meanings of the above terms in the present invention in combination with the specific contents of the technical solutions.
Example 1
In this embodiment, a single/double-walled carbon nanotube is prepared by using the plasma reactor shown in fig. 1, and the specific steps are as follows:
s1, exciting argon gas through electromagnetic waves to form a plasma flame zone 200 (the flow of inert gas argon gas is V) 1 = 80L/min), the temperature of the center 210 of the plasma flame zone is greater than or equal to 5000 ℃;
s2, taking gaseous ferrocene and thiophene as a catalyst precursor (the flow of the catalyst precursor is 60g/h, the atomic number ratio of Fe to S is 60;
the above mixture (total flow rate is V) 2 = 15L/min) movement time t from plasma reactor inlet 100, at a temperature of 200 ℃, to the center 210 of the plasma flame zone 1 ＝0.0105s；
The length of the movement path is L 1 =0.1m, the plasma flame zone 200 is cylindrical and has an average cross-sectional area S 1 ＝0.000314m 2 ，T 1 Median temperature about 3000 ℃;
s3, when the mixture in the step S2 passes through the plasma flame zone 200, mixing the mixture with the inert gas argon for providing high temperature plasma in the step S1 to obtain a new mixture with the flow rate of 95L/min;
the new mixture enters the growth zone 400 from the center 210 of the plasma flame zone, through the remainder of the plasma flame zone 200 and the transition zone 300; the movement duration is t 2 =0.124s; length of motion path L 2 ＝0.3m；
Wherein the average cross-sectional area of the plasma reactor over the distance of the L2 path is S 2 ＝0.00784，T 2 Median temperature about 3000 ℃;
s4, the temperature of one side, close to the transition area 300, of the growth area 400 is about 2000 ℃, and the temperature of one side, far away from the transition area 300, of the growth area is about 1200 ℃;
the residence time of the mixture obtained in step S3 in the growth area 400 is t 3 ＝2.31s；
The growth zone 400 is cylindrical with an axial length L 3 =0.8m, cross-sectional area S 3 ＝0.0314m 2 ，T 3 A median temperature of about 1600 ℃;
s5, collecting the product generated in the step S4 for 3 hours, wherein the weight of the product is 226.2g, the growth efficiency of a single-wall tube is 75.4g/h, and the growth efficiency of the unit reaction volume is M t V＝3g/(L·h)。
In this embodiment, the method for calculating the residence time in each step is as follows:
t n ＝273·S n ·L n /(V n ·(T n +273))；
wherein:
S n : calculating the average cross-sectional area perpendicular to the axial direction of the plasma reactor in m 2 ；
V n : total gas flow in Nm 3 /s；
T n : temperature in units of;
L n : the axial length of the region is calculated in m.
For example, in step S2 of example 1, L 1 ＝0.1m，S 1 ＝0.000314m 2 ，T1＝3000℃，V1＝6+9＝15L/min＝15/(60*1000)m 3 /s。
From this, t1= (273 × 0.1 × 0.000314) = (60 × 1000)/(15 = (3000 + 273)) =0.0105s is calculated.
In this embodiment, the growth efficiency per unit volume is the ratio of the weight of the product collected per unit time to the volume of the growth region 400, which in this embodiment is: 226.2 g/(3 h (0.0314 0.8 10) 3 ))L≈3g/(L·h)。
Examples 2 to 3 and comparative example 1 each prepared a single/double-walled carbon nanotube, and the specific preparation method was different from example 1 in that:
some parameters are different, and specific parameters are shown in table 1.
TABLE 1 parameters of examples 1 to 3
Comparative example 2
This comparative example prepared a single/double-walled carbon nanotube, which was different from example 1 in that:
(1) The temperature of the center 210 of the plasma flame zone is 2500-3500 ℃;
(2) In step S2, T 1 The residence time t is calculated according to 1500 DEG C 1 ＝0.019s。
(3) In step S3, T 2 The residence time t is calculated according to 2200 DEG C 2 ＝0.164s。
(4) In step S4, T 3 The residence time t is calculated according to 1600 DEG C 3 ＝2.31s。
(5) In step S5, growth efficiency M tv ＝1.4g/(L·h)。
Test example
The test examples tested the morphology, ash content and graphitization degree of the products obtained in examples 1-3 and comparative examples 1-2, and the specific test methods and results were as follows:
the appearance of the product was tested by Scanning Electron Microscopy (SEM) and high resolution transmission electron microscopy (HR-TEM), respectively. The results show that the single/double-wall carbon nano tube obtained in the example 1 has a single-wall or double-wall structure, the RMB peak wave number range of the combined Raman is that the tube diameter is between 1nm and 5nm, and the major diameter is higher. Specific results are shown in FIGS. 3 to 4. The morphology of the single/double-walled carbon nanotubes obtained in examples 2 to 3 was similar to that of example 1, and the specific results are shown in FIGS. 5 to 6. In comparison with the morphology of the single/double-walled carbon nanotubes obtained in examples 1 to 3, comparative example 1 exhibited a lot of particulate matter (hetero-carbon), which illustrates the time t required for the mixture to travel from the center 210 of the plasma flame zone to the growth zone 400 2 If the catalyst is used for more than 0.2s, the particle size of the catalyst is difficult to control, and the performance of the product is finally reduced. The morphology of the product obtained in comparative example 1 is shown in FIG. 7; comparative example 2 since the temperature of the center of the plasma flame zone was low, the residence time of the corresponding mixture was changed at each stage, and simultaneously the plasma temperature was low, it was difficult to effectively decompose the catalyst precursor, resulting in a low catalyst density with a narrow particle size distribution, and a part of the undecomposed catalyst precursor was decomposed in the transition zone or the growth zone to cause an increase in particle size of a part of the catalyst, so that the amount of the single/double walled carbon nanotubes formed was small and more impurities were generated. The morphology of the product obtained in comparative example 2 is shown in fig. 8.
The ash content of the products obtained in examples 1 to 3 and comparative examples 1 to 2 was measured by a calcination method, which specifically comprises the following steps: about 1g (accurate to 0.1 mg) of the sample is weighed, the sample is calcined in a muffle furnace for 4h at 900 ℃ in the air atmosphere, the calcined ash is weighed by a ten-thousandth balance, the mass percentage of the ash in the product before calcination is calculated, and the test results are shown in Table 2. The results show that the ash content of the products obtained in examples 1 to 3 of the present invention is less than 30%, if t 2 If the range of (b) is not within the range claimed in the present invention (comparative example 1) or if the temperature of the center 210 of the plasma flame zone is less than 5000 c (comparative example 2), the ash content of the resulting product is significantly increased, since the change of conditions leads to an increase of the impurity (heterocarbon) content, within the range provided in the present invention,the purity of the obtained single/double-wall carbon nano tube can be obviously improved.
Raman spectra of the products obtained in examples 1 to 3 and comparative examples 1 to 2 were obtained, and 1570 to 1610cm was read -1 Peak intensity in the range I G And at 1320-1360 cm -1 Peak intensity in the range I D And calculate I G /I D A larger value indicates a higher degree of graphitization. The test results are shown in table 2. The results show that the single/double-wall carbon nanotubes obtained in the examples of the present invention have the same structure G /I D A value of 100 or more indicates a higher degree of graphitization, whereas the products of comparative examples 1-2 show a significant decrease in the degree of graphitization and, as expected, a significant decrease in the degree of conductivity, either due to difficulty in controlling the catalyst particle size (comparative example 1) or due to the inability to form a high density catalyst aerogel (comparative example 2). The raman spectrum of the product obtained in example 1 is shown in fig. 2.
TABLE 2 Properties of the products obtained in examples 1 to 3 and comparative examples 1 to 2
The results in table 2 also show that the growth efficiency of the single/double-walled carbon nanotubes obtained in examples 1 to 3 of the present invention is significantly higher than that of comparative examples 1 to 2, and thus it can be shown that the preparation method provided by the present invention can improve not only the performance of the obtained single/double-walled carbon nanotubes, but also the growth efficiency thereof by controlling the condition parameters.
In summary, in the embodiments 1 to 3 of the present invention, the high energy density plasma flame region 200 (the center temperature is not less than 5000 ℃) can not only rapidly decompose the catalyst precursor to form a large amount of iron atoms, but also decompose the carbon source to highly active carbon atoms; the mixture quickly (less than or equal to 0.2 s) enters a growth zone, so that the catalyst particles with the particle size of more than 5nm are ensured to have lower proportion, and further the catalyst particles and high-activity carbon atoms quickly react to generate a large amount of highly graphitized single-walled carbon nanotubes.
In comparative example 1, however, iron atoms were generated in a high concentration but for a long period of time (t) 2 =0.22 > 0.2 s) into the growth zone, leading to an increase in the proportion of particles with a particle size > 5nm and, in turn, an increase in the proportion of heterocarbon in the product (as shown in fig. 7), causing I G /I D Decrease and ash increase. In comparative example 2, the plasma flame zone 200 was at a lower temperature and insufficient in energy density, and the concentration of iron atoms generated in the plasma flame zone 200 was lower, resulting in a decrease in the production efficiency of the single-walled tube.
Furthermore, the single/double-wall carbon nano tube prepared by the invention has higher length-diameter ratio and graphitization degree and lower ash content, so that the single/double-wall carbon nano tube has more excellent conductive performance and wide application prospect in the preparation of secondary batteries.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (10)
1. A method for preparing single/double-walled carbon nanotubes, the method comprising:
the method comprises the following steps of (1) enabling a mixture of a catalyst precursor and a carbon source to sequentially pass through an inlet of a plasma reactor, a plasma flame zone and a growth zone;
the temperature of the center of the plasma flame zone is more than or equal to 5000 ℃;
the temperature of the growth area is 1200-2000 ℃;
the time required by the mixture from the center of the plasma flame zone to the growth zone is less than or equal to 0.2s.
2. The method of claim 1, wherein the temperature of the plasma reactor inlet is about 200 ℃; preferably, the time required for the mixture to reach the center of the plasma flame zone from the plasma reactor inlet is less than or equal to 0.03s.
3. The method of claim 1, wherein the residence time of the mixture in the growth zone is 1s to 60s.
4. The production method according to any one of claims 1 to 3, wherein the carbon source is decomposed to form gaseous carbon atoms at a temperature of 5000 ℃ or more; preferably, the carbon source comprises at least one of an alkane, an alkene, an alkyne, and carbon powder.
5. The production method according to any one of claims 1 to 3, characterized in that the catalyst precursor comprises a metal organic; preferably, the metal organic matter is at least one of ferrocene, nickelocene, cobaltocene, carbonyl iron and carbonyl cobalt.
6. The method according to any one of claims 1 to 3, wherein a sulfur auxiliary is further included in the mixture; preferably, the sulfur auxiliary agent is at least one of elemental sulfur and sulfur-containing organic small molecules.
7. The production method according to any one of claims 1 to 3, wherein the growth efficiency of the production method is not less than 3 g/(L-h).
8. The single/double-walled carbon nanotube according to any one of claims 1 to 7, wherein I of the single/double-walled carbon nanotube G /I D The value is greater than or equal to 80.
9. Use of the single/double-walled carbon nanotube of claim 8 for the preparation of a secondary battery.
10. A plasma reactor for carrying out the production method according to any one of claims 1 to 7, wherein the plasma reactor comprises a plasma reactor inlet, a plasma flame zone and a growth zone which are in turn connected in flow communication.
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