CN115650210B - 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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- 239000002109 single walled nanotube Substances 0.000 title claims abstract description 74
- 239000002079 double walled nanotube Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 230000007704 transition Effects 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 229940087654 iron carbonyl Drugs 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 1
- 238000005087 graphitization Methods 0.000 abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 39
- 239000002245 particle Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 21
- 239000012159 carrier gas Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 8
- 230000004323 axial length Effects 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000000443 aerosol Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000033001 locomotion Effects 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012685 metal catalyst precursor Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
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Classifications
-
- 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
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: passing the mixture of the catalyst precursor and the carbon source through the inlet of the plasma reactor, the plasma flame zone and the growth zone in sequence; 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 length of 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 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 a single wall carbon nanotube or a double wall carbon nanotube, and has a larger length-diameter ratio and a higher graphitization degree (I G /I D More than 10), has more excellent conductivity and flexibility, and can form developed conductive network in the anode and cathode materials under the condition of low addition (the minimum amount can be 0.05%) when used for the secondary battery conductive agent, thereby remarkably prolonging the cycle life and the rate capability of the lithium battery. In particular, silicon carbon negative electrode is subject to high volume expansion rate (more than 200 percent) of silicon in the charge and discharge process, silicon carbon negative electrode particles are easy to pulverize, and finally the battery is rapidly exhausted, while single/double-wall carbon nano tube has high flexibility and excellent conductivity by virtue of the silicon carbon negative electrode particles,the above problems faced by silicon carbon anodes can be solved.
In order to better meet the application requirements of silicon-based cathodes, it is desirable that the single/double walled carbon nanotubes have a high degree of graphitization (I G /I D > 80), in order to improve the graphitization degree, an effective method is to adopt nano iron aerosol (particle size is less than 5 nm) to catalyze the decomposition of carbon source to grow the required product under the temperature condition of more than 1000 ℃. In order to prepare nano-iron aerosol, the technology discloses that a dilute solution of organic metal compounds such as ferrocene is used as a catalyst precursor to be injected into a reactor at 1100-1500 ℃, the catalyst precursor solution enters the reactor to generate nano-iron aerosol in situ, and then a carbon source (toluene and ethylene) is catalyzed to decompose and grow single-walled carbon nanotubes. In order to prevent the formation of nano-iron with oversized dimensions (particle size > 5 nm), the amount of catalyst precursor to be introduced is limited, and thus the growth efficiency of single-walled tubes is limited. Also disclosed is a single-walled carbon nanotube reactor comprising a catalyst pretreatment and acceleration unit, which accelerates a mixed gas comprising a catalyst and a carbon source to 5-50 m/s, and a large amount of catalyst particles having a narrow particle size distribution (main particle size range of 1-8 nm) rapidly enter a reaction zone, thereby obtaining a growth efficiency of 2.3kg/h at a reaction volume of 3000L while avoiding catalyst agglomeration. But the production efficiency per unit reaction volume is only 0.77 g/(L.h), and the catalyst prepared by the method still has partial particles with the particle diameter of more than 5nm, thus the product I obtained by the method G /I D Up to only 78.
In summary, the single/double wall carbon nanotubes prepared by the conventional preparation method have low graphitization degree and low growth efficiency per unit reaction volume.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in 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 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 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, there is provided a method for preparing a single/double-walled carbon nanotube, the method comprising:
passing the mixture of the catalyst precursor and the carbon source through the inlet of the plasma reactor, the plasma flame zone and the growth zone in sequence;
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 length of 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 has the following mechanism:
the mixture is converted into a high-activity plasma state in a plasma flame zone, and in the process of transferring the high-activity plasma state to a growth zone, the plasma state of a catalyst precursor is converted into a corresponding catalyst with small particle size (1-5 nm), and the plasma state of a carbon source is converted into carbon atoms;
and then the carbon atoms and the catalyst are quickly transferred to a growth area, and the carbon atoms are arranged to form the single/double-wall carbon nano tube under the action of the catalyst.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects:
(1) The invention discovers that the density of small-particle-size (less than or equal to 5 nm) catalysts in a growth area needs to be improved if the growth efficiency of single/double-wall carbon nanotubes is to be improved.
In the conventional technology, the pyrolysis temperature is usually about 1000 ℃, the energy density is low, and a large amount of catalyst precursor is not enough to be decomposed into single atoms, so that an aerosol catalyst with high concentration and narrow particle diameter (1 nm-5 nm) is difficult to form, and the growth efficiency (the ratio of the mass of the carbon nano tube collected in unit time to the volume of a growth zone) of the single/double-wall carbon nano tube is limited. If the particle size of the catalyst is larger (i.e., the catalyst is agglomerated, the particle size is more than 5 nm), the carbon nanotubes formed are mostly multi-walled carbon nanotubes or carbon impurities, which at least affect the graphitization degree of the obtained carbon nanotubes. Therefore, to increase the growth efficiency of single/double walled carbon nanotubes, the density of small particle size (5 nm) catalysts in the growth zone is increased.
The invention adopts the plasma flame as pyrolysis energy, the center temperature of which is more than or equal to 5000 ℃ and provides enough energy density, so that the catalyst precursor can be rapidly decomposed to form high-concentration aerosol catalyst, the density of the catalyst with small particle size (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 suppresses the agglomeration (short time, and short time) of the catalyst generated in the plasma flame zone by limiting the time required for the mixture to reach the growth zone from the center of the plasma flame zone, thereby suppressing 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 when the temperature is greater than or equal to 5000 ℃.
According to some embodiments of the invention, the carbon source comprises at least one of an alkane, alkene, 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 metal-organic is at least one of ferrocene, nickel-dicyclopentadienyl, cobalt-dicyclopentadienyl, iron carbonyl, and cobalt carbonyl.
According to some preferred embodiments of the invention, the metal-organic compound is ferrocene.
According to some embodiments of the invention, a sulfur aid is also included in the mixture. The sulfur promoter may promote the growth of the single/double walled carbon nanotubes.
According to some embodiments of the invention, the sulfur promoter is at least one of elemental sulfur and sulfur-containing small organic molecules.
According to some embodiments of the invention, the molecular weight of the small sulfur-containing organic molecules is less than or equal to 500.
According to some preferred embodiments of the invention, the small sulfur-containing organic molecule is selected from thiophenes.
According to some embodiments of the invention, the ratio of the amount of metal atoms in the catalyst precursor to the amount of sulfur atoms in the sulfur promoter is from 2 to 70:1.
according to some preferred embodiments of the invention, the ratio of the amount of metal atoms in the catalyst precursor to the amount of sulfur atoms in the sulfur promoter is from 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, a carrier gas is also included in the mixture.
The carrier gas may assist the catalyst precursor and the carbon source in passing smoothly 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 ratio of the flow rates of the carbon source and the carrier gas in the mixture is (10 to 50): 30. for example, may be 1:2.
According to some preferred embodiments of the 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, it may be 7:5 or 5:3.
According to some embodiments of the invention, the mass of the catalyst precursor and the flow ratio of the carrier gas in the mixture is 77g (100-1000) L.
According to some preferred embodiments of the invention, the mass of the catalyst precursor and the flow ratio of the carrier gas in the mixture is 77g (370-930) L. For example, 7g:75L, 1g:6L, 11g:54L, 1g: 8.7-8.8L, 1g: 11-12L or 1g: 10.3-10.4L.
The carrier gas may also adjust the concentrations of the carbon source and the catalyst precursor in the mixture, thereby enhancing the growth efficiency and graphitization degree of the single/double wall carbon nanotubes 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 electromagnetic waves.
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 description of the process, the flow 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 resulting mixture in the plasma flame zone is the sum of the flow rate through the inlet of the plasma reactor and the flow rate of the inert gas.
According to some embodiments of the invention, the time period 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.
This time is affected by the flow rate of the mixture and the cross-sectional area of the plasma flame zone, which can be adjusted by adjusting the ratio of the two during the actual test.
According to some embodiments of the invention, the temperature of the growth zone near the edge of the plasma flame zone is about 2000 ℃.
According to some embodiments of the invention, the time required for the mixture generated by the plasma flame zone to reach the edge of the growth zone, which is close to one side of the plasma flame zone, is less than or equal to 0.2s from the center 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 area is short, and the catalyst precursor is prevented from generating side reaction in the transition area (from the plasma flame area to the growth area) to generate large-particle catalyst, so that the generation of multi-wall carbon nano tubes and miscellaneous carbon is prevented.
This time is affected by the flow rate of the mixture generated by the plasma flame zone (the sum of the inert gas, carbon source, carrier gas, metal catalyst precursor flow rates), 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 controlled, and the required time can be regulated.
According to some embodiments of the invention, a cross-sectional area of the growth zone near a side edge of the plasma flame zone is greater than a cross-sectional area of the plasma flame zone.
Thus, in this process, the density of the resultant mixture (the number of particles per unit volume) is reduced corresponding to the plasma flame zone, whereby the particle size of the catalyst is small and uniform, and the graphitization degree of the obtained single/double walled carbon nanotubes 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 invention, the residence time of the resulting mixture in the plasma flame zone in the growth zone is between 1s and 2s.
According to some preferred embodiments of the invention, the residence time of the resulting mixture in the plasma flame zone in the growth zone is between 2s and 3s.
According to some embodiments of the invention, the temperature of the side edge of the growth zone remote from the plasma flame zone is about 1200 ℃.
In the present invention, the residence time (t n ) The calculation method of (2) is shown as follows:
t n ＝273·S n ·L n /(V n ·(T n +273))；
wherein:
S n : in the calculation region, the average cross-sectional area of the plasma reactor perpendicular to the axial direction is expressed as m 2 The method comprises the steps of carrying out a first treatment on the surface of the If the shape of the calculated area is irregular, the average sectional area is the ratio of the volume of the calculated area to the axial length;
V n : total gas flow in Nm 3 /s；
T n : temperature in degrees celsius; 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 further comprises collecting the single/double walled carbon nanotubes produced by the growth region.
According to some embodiments of the invention, the growth efficiency of the preparation method is equal to or greater than 3 g/(L.h). For example, 3.6 g/(L.h) or 4.8 g/(L.h) may be mentioned.
The growth efficiency (M tV ) The calculation method of (2) 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 given in m.
S 3 : average cross-sectional area of growth zone in m 2 ；
M tV The unit is g/(L.h).
According to the preparation method provided by the invention, the gas flow fields formed by various gases are controlled, the residence time of each stage is controlled, and the growth efficiency and graphitization degree of the obtained single/double-wall carbon nano tube are improved by controlling the relationship between the temperature field and the residence time.
According to a second aspect of the present invention, there is provided a single/double walled carbon nanotube produced by the production method, the single/double walled carbon nanotubeI of the tube G /I D The value is more than or equal to 80.
The single/double-wall carbon nanotubes adopt all the technical schemes of the preparation method in the embodiment, so that the preparation method at least has all the beneficial effects brought by the technical schemes of the embodiment, namely high growth efficiency and high graphitization degree.
According to some embodiments of the invention, I G /I D I in value G The Raman spectrum of the obtained single/double-walled carbon nano-tube is 1570-1610 c -11 Peak intensity in range, I D Is of 1320-1360 cm in Raman spectrum -1 Peak intensity in the range, and the ratio of the peak intensity to the peak intensity is in positive correlation with the graphitization degree of the obtained single/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 invention, I of the single/double walled carbon nanotubes G /I D The value is more than or equal to 100.
According to some embodiments of the invention, the ash content of the single/double walled carbon nanotubes is less than or equal to 30wt%.
Namely, the mass ratio of the residue after the calcination of the single/double-walled carbon nano-tube to the single/double-walled carbon nano-tube before the calcination is less than or equal to 30 percent.
The single/double wall carbon nanotubes are known to have high carbon purity.
According to some embodiments of the invention, the ash content of the single/double walled carbon nanotubes 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 tube diameter of the single/double walled carbon nanotubes is 1-5 nm.
According to an embodiment of the third aspect of the present invention, there is provided the use of the single/double walled carbon nanotubes in the manufacture of a secondary battery.
The application according to 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 for a secondary battery conductive agent, the addition amount of the conductive agent can be reduced, namely the dosage proportion of positive and negative electrode 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 negative electrode, the structural advantage of the single/double-wall carbon nano tube can accommodate the volume change of the silicon negative electrode in the charging and discharging process of the silicon negative electrode, 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 walled carbon nanotubes are 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 positive electrode dressing or the negative electrode 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 nanotubes, and a binder.
According to a fourth aspect embodiment of the present invention, there is provided a plasma reactor for carrying out the preparation method, the plasma reactor comprising a plasma reactor inlet, a plasma flame zone and a growth zone in conductive connection in sequence.
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 zone is flared; in the transition zone, one side of the small opening is communicated with the plasma flame zone, and the other side of the small opening is communicated with the growth zone.
The term "about" in the present invention means that the allowable error is within + -2% unless otherwise specified.
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 foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic view showing 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 single/double walled carbon nanotubes obtained in example 1 of the present invention;
FIG. 4 is an SEM image of a single/double walled carbon nanotube obtained in example 1 of the present invention;
FIG. 5 is an SEM image of a single/double walled carbon nanotube 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 image of a sample obtained in comparative example 1 of the present invention;
FIG. 8 is an SEM image 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 210 of the plasma flame zone, a transition zone 300, a growth zone 400.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
In the description of the present invention, the description of first, second, etc. is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present invention, it should be understood that the direction or positional relationship indicated with respect to the description of the orientation, such as up, down, etc., is based on the direction or positional relationship shown in the drawings, is merely for convenience of describing the present invention and simplifying the description, and does not indicate or imply that the apparatus or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention.
In the description of the present invention, unless explicitly defined otherwise, terms such as arrangement, installation, connection, etc. should be construed broadly and the specific meaning of the terms in the present invention can be determined reasonably by a person skilled in the art in combination with the specific content of the technical solution.
Example 1
In this embodiment, a single/double wall carbon nanotube is prepared by using the plasma reactor shown in fig. 1, and the specific steps are as follows:
s1, argon is excited by electromagnetic waves to form a plasma flame zone 200 (the flow of inactive gas argon is V 1 =80L/min), the temperature of the center 210 of the plasma flame zone is equal to or greater than 5000 ℃;
s2, taking gaseous ferrocene and thiophene as catalyst precursors (the flow rate of the catalyst precursors is 60g/h, the atomic number ratio of Fe to S is 60:1), natural gas (namely a carbon source, the component is methane, the flow rate is 9L/min) and argon (carrier gas, the flow rate is 6L/min) as a mixture, and entering a plasma flame zone 200 through a plasma reactor inlet 100;
the above mixture (total flow V 2 =15L/min) the movement time t from the 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 motion 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 The median temperature is about 3000 ℃;
s3, mixing the mixture in the step S2 with inactive gas argon for providing plasma high temperature in the step S1 when the mixture passes through the plasma flame zone 200, so as to obtain a new mixture with the flow of 95L/min;
the new mixture enters the growth zone 400 from the center 210 of the plasma flame zone, via the remainder of the plasma flame zone 200 and the transition zone 300; the movement time length is t 2 =0.124 s; the length of the motion path is L 2 ＝0.3m；
Wherein the average sectional area of the plasma reactor is S within the L2 path distance 2 ＝0.00784，T 2 The median temperature is about 3000 ℃;
s4, the temperature of the side, close to the transition region 300, of the growth region 400 is about 2000 ℃, and the temperature of the side, far from the transition region 300, is about 1200 ℃;
the mixture obtained in step S3 remains in the growth zone 400 for a period of time t 3 ＝2.31s；
The growth zone 400 is cylindrical and has an axial length L 3 =0.8m, cross-sectional area S 3 ＝0.0314m 2 ，T 3 The median temperature is about 1600 ℃;
s5, collecting the product generated in the step S4, wherein the total collection time is 3 hours, the product weight is 226.2g, the single-wall tube growth efficiency is 75.4g/h, and the growth efficiency per unit reaction volume is M t V＝3g/(L·h)。
In this embodiment, the method for calculating the residence time in each step includes:
t n ＝273·S n ·L n /(V n ·(T n +273))；
wherein:
S n : in the calculation region, the average cross-sectional area of the plasma reactor perpendicular to the axial direction is expressed as m 2 ；
V n : total gas flow in Nm 3 /s；
T n : temperature in degrees celsius;
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))=0.0105 s is calculated.
In this example, the growth efficiency per unit volume is the ratio of the product weight collected per unit length of time to the volume of the growth zone 400, which in this example is: 226.2 g/(3 h) (0.0314 x 0.8 x 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 and example 1 were different in that:
some of the parameters are different and the specific parameters are shown in table 1.
Table 1 parameters of examples 1 to 3
Comparative example 2
This comparative example produced a single/double walled carbon nanotube, differing 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 Calculated at 1500℃and residence time t 1 ＝0.019s。
(3) In step S3, T 2 Calculated at 2200℃and residence time t 2 ＝0.164s。
(4) In step S4, T 3 Calculated at 1600℃and residence time t 3 ＝2.31s。
(5) In step S5, growth efficiency M tv ＝1.4g/(L·h)。
Test case
The present test examples tested the morphology, ash content and graphitization degree of the products obtained in examples 1 to 3 and comparative examples 1 to 2, and the specific test methods and results were as follows:
the morphology of the product was tested using Scanning Electron Microscopy (SEM) and high resolution transmission electron microscopy (HR-TEM), respectively. The results show that the single/double walled carbon nanotubes obtained in example 1 do have a single or double walled structure, combined with the Raman RMB peak wavenumber range, which tubesThe diameter is between 1 and 5nm, and the length-diameter ratio 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 1-3, comparative example 1 shows a lot of particulate matter (heterocarbon) which illustrates the length of 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 particle size is 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 because the temperature in the center of the plasma flame zone is low, the residence time of the corresponding mixture at each stage is changed, and at the same time, the plasma temperature is low, it is difficult to decompose the catalyst precursor effectively, resulting in a low catalyst density with narrow particle size distribution, and part of the non-decomposed catalyst precursor will decompose in the transition zone or the growth zone, resulting in an increase in the particle size of part of the catalyst, so that the amount of single/double walled carbon nanotubes formed is small, and more impurities are produced. 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 tested by the calcination method, which comprises the following steps: about 1g (accurate to 0.1 mg) of the sample was weighed, calcined in a muffle furnace at 900 ℃ in an air atmosphere for 4 hours, the calcined ash was weighed by a ten-thousandth balance, the mass percent of the ash was 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 according to the invention is less than 30%, if t 2 The ash content of the obtained product is significantly increased if the temperature of the center 210 of the plasma flame zone is lower than 5000 c (comparative example 1) or if the temperature is not within the scope of the present invention (comparative example 2), because the change of conditions may result in an increase of impurity (impurity carbon) content, and the purity of the obtained single/double walled carbon nanotubes may be significantly increased within the scope of the present invention.
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 I in range G And at 1320-1360 cm -1 Peak intensity I in range D And calculate I G /I D The larger the value, the higher the graphitization degree. 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 I G /I D The values are greater than or equal to 100, indicating a higher degree of graphitization, whereas the products obtained in comparative examples 1-2, either because the catalyst particle size is difficult to control (comparative example 1) or because a high density catalyst aerogel cannot be formed (comparative example 2), have significantly reduced graphitization, and it is expected that the degree of conductivity will also be significantly reduced. 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 not only improve the performance of the obtained single/double-walled carbon nanotubes, but also improve the growth efficiency thereof by controlling the condition parameters.
In summary, in embodiments 1-3 of the present invention, the high energy density plasma flame zone 200 (center temperature is greater than or equal to 5000 ℃) can not only rapidly decompose the catalyst precursor to form a large amount of iron atoms, but also decompose the carbon source into highly active carbon atoms; the mixture rapidly (less than or equal to 0.2 s) enters a growth area, ensures that the proportion of catalyst particles with the particle diameter of more than 5nm is low, and further rapidly reacts with high-activity carbon atoms to generate a large number of highly graphitized single-wall carbon nanotubes.
In comparative example 1, however, the iron atoms were produced in a high concentration, but the iron atoms were produced for a long period of time (t 2 =0.22 > 0.2 s) into the growth zone, resulting in an increase in the proportion of particles having a size > 5nm, and thus in the proportion of impurity carbon in the product (as shown in fig. 7), leading to I G /I D Decrease and ash increase. In comparative example 2, the plasma flame zone 200 was at a lower temperature and insufficient energy density, and the concentration of iron atoms generated in the plasma flame zone 200 was lower, resulting in a single wallThe tube production efficiency is lowered.
Further, the single/double-walled carbon nanotubes prepared by the method have higher length-diameter ratio, graphitization degree and lower ash content, so that the single/double-walled carbon nanotubes are expected to have excellent conductive performance and have wide application prospects in 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 one of ordinary skill in the art without departing from the spirit of the present invention.
Claims (10)
1. The preparation method of the single/double-wall carbon nano tube is characterized by adopting a plasma reactor to implement the preparation method, wherein the plasma reactor consists of a plasma reactor inlet, a plasma flame zone, a transition zone and a growth zone which are connected in turn in a conducting manner;
the transition zone is horn-shaped; in the transition zone, one side of the small opening is communicated with the plasma flame zone, and the other side is communicated with the growth zone;
the preparation method comprises the following steps:
passing a mixture of catalyst precursor and carbon source from the plasma reactor inlet through the plasma reactor;
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 length of the mixture from the center of the plasma flame zone to the growth zone is less than or equal to 0.2s;
the residence time of the mixture in the growth zone is 1 s-60 s.
2. The method of claim 1, wherein the temperature at the inlet of the plasma reactor is about 200 ℃; "about" means that the allowable error is within + -2%.
3. The method of claim 1, wherein the mixture is at least 0.03 seconds long from the entrance of the plasma reactor to the center of the plasma flame zone.
4. The method according to any one of claims 1 to 3, wherein the carbon source is decomposed to form gaseous carbon atoms when the temperature is at least 5000 ℃.
5. The method of claim 4, wherein the carbon source comprises at least one of an alkane, alkene, alkyne, and carbon powder.
6. A method of preparing a catalyst according to any one of claims 1 to 3, wherein the catalyst precursor comprises a metal organic.
7. The method according to claim 6, wherein the metal organic is at least one of ferrocene, nickel dicyclopentadienyl, cobalt dicyclopentadienyl, iron carbonyl and cobalt carbonyl.
8. A method of preparing a composition according to any one of claims 1 to 3, wherein the mixture further comprises a sulfur aid.
9. The method of claim 8, wherein the sulfur promoter is at least one of elemental sulfur and small sulfur-containing organic molecules.
10. The method according to any one of claims 1 to 3, wherein the growth efficiency of the method is not less than 3 g/(l.h).
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