CN1522955A - Method for preparing single wall nanometer carbon tube using mesophase asphalt as raw material - Google Patents
Method for preparing single wall nanometer carbon tube using mesophase asphalt as raw material Download PDFInfo
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- CN1522955A CN1522955A CNA031339727A CN03133972A CN1522955A CN 1522955 A CN1522955 A CN 1522955A CN A031339727 A CNA031339727 A CN A031339727A CN 03133972 A CN03133972 A CN 03133972A CN 1522955 A CN1522955 A CN 1522955A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002994 raw material Substances 0.000 title claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 11
- 239000010426 asphalt Substances 0.000 title abstract description 10
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 53
- 239000003245 coal Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000011302 mesophase pitch Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 239000011295 pitch Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 238000010891 electric arc Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 abstract description 13
- 230000008020 evaporation Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000011232 storage material Substances 0.000 abstract description 3
- 230000016507 interphase Effects 0.000 abstract 2
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000011208 reinforced composite material Substances 0.000 abstract 1
- 239000003610 charcoal Substances 0.000 description 19
- 239000002041 carbon nanotube Substances 0.000 description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 16
- 239000010439 graphite Substances 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 238000002309 gasification Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 239000002826 coolant Substances 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
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- 230000005540 biological transmission Effects 0.000 description 3
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- 238000010926 purge Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
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- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000004621 scanning probe microscopy Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 230000010415 tropism Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
The present invention relates to a method for preparing single-wall carbon nano tube by using petroleum base interphase bitumen as raw material. It is characterized by that said method includes the following steps: mixing the interphase bitumen and catalyst, filling them into a coal base carbon tube, then using the composite carbon tube which is filled with bitumen as anode and placing it into an arc plasma equipment to make DC discharge and evaporation, after the discharge is completed, opening the reactor so as to obtain large-flake film high-purity single wall carbon nano tube with uniformly-distributed tube diameter which is 1-2 nm. It can be used in several fields of electronic device, field emission, hydrogen storage material, chemical sensor and reinforced composite material.
Description
Technical field
The invention belongs to petrochemical complex, Coal Chemical Industry and carbon material technical field, relating to a kind of is the method for feedstock production Single Walled Carbon Nanotube with the mesophase pitch.
Background technology
CNT (carbon nano-tube) (Carbon nanotube) is a kind of raw material of wood-charcoal material with novel structure of finding in 1991.The ideal carbon nanotube is the seamless hollow tube that is curled and formed by the graphite flake layer that carbon atom forms, wherein have only the carbon nanotube of one deck graphite flake layer to be called as Single Walled Carbon Nanotube (Single walled carbonnanotubes, brief note is SWCNT), the diameter of SWCNT is generally 1～6nm, and the nearest diameter minimum of discovering carbon nanotube can reach 0.4nm.SWCNT is a kind of ultimate limit state of carbon nanotube, be characterized in that length-to-diameter ratio is big, textural defect is little and end curvature little etc.Existing to studies show that in a large number of SWCNT, SWCNT has wide application prospect in all many-sides such as electron device, an emission, Scanning Probe Microscopy technology, hydrogen storage material, chemical sensor and reinforced composites.In recent years, the preparation research of relevant Single Walled Carbon Nanotube has become a worldwide focus.Single Walled Carbon Nanotube can prepare with arc process, laser method or chemical Vapor deposition process (CVD).
It is reported that SWCNT almost finds simultaneously the researchist by Japanese scholar S.Iijima and IBM Corporation in 1993.But early stage technology of preparing mainly is to be raw material with the high purity graphite electrode, adopts arc process to prepare SWCNT, and the productive rate of product is very low, and impurity is more; Afterwards, people such as professor RichardSmalley of U.S. rice university discovered with the laser evaporation graphite material and can obtain the very high SWCNT of purity, and this technological method is referred to as the laser evaporation method, but productive rate is lower; Afterwards, about the research of the preparation method of SWCNT and physical property enjoys scientific and technical personnel's concern always, wherein technology of preparing is a key link and the challenging difficult problem in the SWCNT research always.
The preparation method of SWCNT has arc process, laser evaporation method and pyrolysis method (brief note is the CVD method) at present, wherein arc process is similar with the Wolfgang-Kr tschmer method of preparation soccerballene, its specific practice is: add catalyzer in the raw material graphite rod, as transition-metal Fe, Co, Ni etc. or lanthanide series metal Ld, Nd, Y etc., and under inert atmosphere, make graphite rod evaporation gasification finally obtain SWCNT on the wall of reactor and in the cathode deposit at reactor through arc-over; Using more catalyzer at present is iron and nickel, and the charcoal pipe mechanical property of preparation is better, but productive rate is not high.Pyrolysis method or CVD method be a kind of with the metal be catalyzer under 700-1600K, by pyrolyze hydrocarbon, as methane, acetylene, ethene etc., the preparation carbon nanotube technological method.Japan scholar professor Endo is take the lead in the world preparing with the CVD method pioneer of carbon nanotube, subsequently, the academic team that the leader such as becomes to understand that penetrating judgment is awarded of the Fan Shoushan of the Xie Sishen of Inst. of Physics, CAS professor, Tsing-Hua University professor and Shenyang metal institute of the Chinese Academy of Sciences has also obtained gratifying achievement in this field.Compare with arc process, the technology of CVD method is simple relatively, can obtain the carbon nano pipe array product, but the degree of graphitization of the SWCNT that obtains mechanical property low, the charcoal pipe is relatively poor.The SWCNT of laser evaporation method preparation is purer, the degree of graphitization height, but need expensive plant and instrument, this causes the cost of SWCNT high, is difficult to realize the scale operation of SWCNT.
In sum, from the quality of cost and SWCNT product, the technology of existing preparation carbon nanotube can't realize cheapness and prepare the SWCNT of purity height and good physical performance with high yield.At above problem, it is raw material is equipped with high-purity SWCNT with the electric arc legal system method that the present invention proposes with mesophase pitch cheap and easy to get.Up to the present, be reported in both at home and abroad and also do not have about to be raw material with the mesophase pitch be equipped with disclosing of SWCNT with the electric arc legal system, only limit to document (Fuel 81 (2002) 5-14) seldom at present, and just mention in the preparation nanotube process and use pitch, do not provide the result at last.
Summary of the invention
The purpose of this invention is to provide a kind of is the method for feedstock production Single Walled Carbon Nanotube with the mesophase pitch, and preparation process is by realizing with the charcoal pipe of arc discharge method evaporation filled bitumen and catalyzer.
Technical scheme of the present invention is at first the raw material mesophase pitch to be mixed with catalyzer (iron, cobalt and nickel), and the granularity of catalyst system therefor is 100～200 μ m; Then mixture is filled in a kind of coal-based carbon pipe (external diameter is 10mm, and internal diameter is 6mm), two ends are sealed with graphite plugs; The charcoal pipe of filled bitumen is heated to 290 ℃, and keep 10min in this temperature, make the pitch fusion and with the catalyzer thorough mixing after, the cooling back is as the electrode evaporation of discharging, working gas is a helium, cools off with the wall and the negative electrode of water coolant to reactor in discharge process.In the arc evaporation gasification, the control electrode spacing makes arc light be in a kind of steady state, can make like this as the coal-based compound charcoal pipe of anodic evenly to evaporate gasification, and Single Walled Carbon Nanotube forms in this process.Discharge is opened reactor after finishing, obtain large stretch of high-purity Single Walled Carbon Nanotube material that exists with membranoid substance on the cage shape wire frames in placing reactor, its productive rate can reach the gram magnitude/hour, the caliber of gained Single Walled Carbon Nanotube is evenly distributed, and is 1～2nm.
The preparation process of Single Walled Carbon Nanotube is as follows:
1. the preparation of hollow charcoal pipe: with raw coal pulverize, screening, dry and mix with coal tar, make hollow coal rod through compression molding, 900 ℃ of charings, finally obtain external diameter 10mm then, the charcoal pipe of internal diameter 6mm.
2. raw material mesophase pitch (about granularity 200 μ m) and catalyzer (iron, cobalt and nickel) were pressed mass ratio 1: 5, equal proportion mixed in 1: 10; Fill the tube chamber of hollow charcoal pipe then with this mixture, after the compacting end of tube chamber is sealed with graphite block.
3. will be through step 1, obtain charcoal pipe behind the filled bitumen after 2 at charring furnace internal heating to 290 ℃, and at this constant temperature 10min, cool to room temperature subsequently, purpose is to make pitch fusion and even with catalyst mix.
4. will put into plasma arc reactor through the composite anode charcoal pipe that step 1,2 and 3 makes, carry out arc-over evaporation gasification, sparking voltage is 40～50V, electric current is 50～70A, interelectrode distance remains on 2～3mm, regulate control arc discharge state, anode is gasified equably, be about 20min whole discharge time.
5. open reactor after discharge finishes, obtain large stretch of high-purity Single Walled Carbon Nanotube material that exists with membranoid substance on the cage shape wire frames in placing reactor.
Effect of the present invention and benefit are as follows:
1. be raw material with mesophase pitch cheap and easy to get, and use transition metal (as iron powder, nickel powder) to make Preparation of Catalyst SWCNT that the purity height of resultant SWCNT, cost are low.
2. mesophase pitch is a kind of mixture that is keeping the silk fabric Polycyclic aromatic hydrocarbons of nematic structure arrangement, molecular weight distribution evenly molecule has bent tropism highly, help the formation of nanotube during arc evaporation, preparation SWCNT also can open up a route that is equipped with the high added value nano material with pitch.
3. directly collect the SWCNT product with cage shape wired frame, SWCNT is with on the membranoid substance settling wire cage, avoided mixing with impurity such as soccerballene cigarette ash, helps the collection of product and improves the purity of SWCNT product.
4. adopt the SWCNT output of present method preparation higher, productive rate can reach 0.5～3g/h, and device is expected to reach a kilogram magnitude after amplifying improvement.
5. the content of agraphitic carbon is seldom among Zhi Bei the SWCNT.
6. few and mechanics of Zhi Bei SWCNT textural defect and Electronic Performance are good, can be used as hydrogen storage material, electronic device material, matrix material and catalyst support material and use.
Description of drawings
Fig. 1 is low power transmission electron microscope (TEM) photo of the SWCNT that made by mesophase pitch.
Fig. 2 is the high power electromicroscopic photograph of the SWCNT that makes with present technique, and electromicroscopic photograph can clearly show the tube wall of carbon nanotube, and a spot of metallic cover thing is only arranged, and does not have impurity such as decolorizing carbon to exist.
Embodiment
Be described in detail specific embodiments of the invention below.
Embodiment 1
With mesophase pitch (softening temperature is between 220 ℃～290 ℃) is that raw material is sent out legal system with electric arc and is equipped with SWCNT.At first prepare the used coal-based carbon pipe of filled bitumen, the basic character of used coal is as follows: M
Ad=2.34%, A
d=3.13%, V
Daf=15.70%; C
Daf=87.21%, H
Daf=3.53%, N
Daf=1.06%. gets raw material coal sample 500g, and in crusher for crushing and be sized to granularity less than 150 μ m, dry back is standby.Get above-mentioned dry coal sample 200g and mix, put into agitator and stir, obtain having viscous mixture, then this mixture is put into mould and be squeezed into tubulose coal rod with hydropress with 100g coal tar.Forming pressure is 10MPa, and shaping speed is 0.5cm/s, and obtaining external diameter is that 10mm, internal diameter are the tubulose coal rod of 6mm.Above-mentioned hollow coal rod is blocked, and the stub of making length (10cm) homogeneous is put into mode that electric furnace takes temperature programming then 900 ℃ of carbonizations 3 hours, and whole carbonization process carries out under protection of nitrogen gas.The charcoal pipe for preparing takes out standby.
Next take by weighing asphalt sample 100g and mix (purity of iron powder is 99.9%, and granularity is less than 200 μ m) with the 10g iron powder evenly, be filled in the coal-based carbon pipe, compacting, two ends are sealed with the graphite plug.Then with populated charcoal pipe at charring furnace internal heating to 290 ℃, and constant temperature 10min, cool to room temperature then.Can guarantee pitch fusion and even like this with catalyst mix.The charcoal pipe of the filled bitumen that obtains is like this put into arcing device as anode and is carried out arc-over evaporation gasification.
To collect the iron wire frame of carbon nanotube product before the reaction beginning and put into reactor, reactor is at first used nitrogen purging 3 times, and usefulness helium purge 1 time is with the air in the eliminating reactor then.Feeding helium to pressure at last is 0.065MPa (absolute pressure), logical water coolant, and power-on is regulated distance between electrodes, and the discharge condition that makes electric arc be in a kind of " stablizing " finishes until the gasification of charcoal pipe, continues about 20min whole discharge time; After discharge finished, powered-down stopped water coolant.Open reactor and can find that a large amount of membranaceous or rope form materials is deposited on the wire cage.Collect weighing products and calculated yield, under these conditions, the yield of carbon nanotube is 1.5g/h.(see accompanying drawing 1 with high resolution scanning electron microscope (SEM) and transmission electron microscope (TEM), 2) and laser Raman spectroscopy (Raman Spectroscopy) technology prepared carbon nanotube product is carried out phenetic analysis, the carbon nanotube that confirmation is made by pitch is the very high SWCNT of purity, and its content is about 65%.
Embodiment 2
With nickel is catalyzer, and pitch is feedstock production SWCNT.Get mesophase pitch sample 200g, pulverize and be sized to granularity, with 40g nickel powder (purity of nickel powder is 99.9%, and granularity is less than 150 μ m) thorough mixing less than 150 μ m; This mixture is filled in the hollow charcoal pipe and compacting, is that 2mm, diameter are that the graphite block of 6mm is sealed with length then.The preparation of hollow charcoal pipe is identical with embodiment 1.Populated composite anode charcoal pipe is put into arcing device carry out arc-over evaporation gasification.To collect the iron wire frame of carbon nanotube product before the reaction beginning and put into reactor, reactor respectively usefulness nitrogen and helium purge 3 times and 1 time with the air in the eliminating reactor.Feeding helium to pressure at last is 0.065MPa (absolute pressure), logical water coolant, and power-on is regulated distance between electrodes, and the discharge condition that makes electric arc be in a kind of " stablizing " finishes until the gasification of charcoal pipe, continues about 25min whole discharge time; After discharge finished, powered-down stopped water coolant.Open reactor and can find that a large amount of membranaceous or rope form materials is deposited on the wire cage.Collect weighing products and calculated yield, under these conditions, the yield of carbon nanotube is 1.2g/h.With high resolution scanning electron microscope (SEM) and transmission electron microscope (TEM) and laser Raman spectroscopy (Raman Spectroscopy) technology prepared carbon nanotube product is carried out phenetic analysis, the highly purified SWCNT that electromicroscopic photograph that obtains and Raman spectrum confirmation can be made by mesophase pitch, content is about 60%.
Claims (3)
1. one kind is the method for feedstock production Single Walled Carbon Nanotube with the mesophase pitch, it is characterized in that with the mesophase pitch being that raw material adds iron, cobalt, nickel and lanthanide series metal catalyzer high yield in direct current arc discharge respectively and prepares Single Walled Carbon Nanotube.
2. one kind is the method for feedstock production Single Walled Carbon Nanotube with the mesophase pitch; it is characterized in that preparing the addition manner of mesophase pitch in the electrode process; at first external diameter 10mm will be filled into after pitch and the catalyst mix; in the coal-based carbon pipe of internal diameter 6mm; then 290 ℃ of heating 10 minutes; pitch is dissolved fully and catalyst mix, cool to room temperature then, whole heat-processed has nitrogen protection.
3. one kind is the method for feedstock production Single Walled Carbon Nanotube with the mesophase pitch, the ratio the when kind that it is characterized in that catalyzer is mixed with pitch, and catalyzer comprises iron, cobalt, nickel and lanthanide series metal, metal catalyst and bituminous mass ratio are 1: 5,1: 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031339727A CN1522955A (en) | 2003-09-12 | 2003-09-12 | Method for preparing single wall nanometer carbon tube using mesophase asphalt as raw material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031339727A CN1522955A (en) | 2003-09-12 | 2003-09-12 | Method for preparing single wall nanometer carbon tube using mesophase asphalt as raw material |
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| Publication Number | Publication Date |
|---|---|
| CN1522955A true CN1522955A (en) | 2004-08-25 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457947C (en) * | 2006-08-14 | 2009-02-04 | 山东科技大学 | Carbon nano-crystal hydrogen-storage material and preparation method |
| CN101941691A (en) * | 2010-09-21 | 2011-01-12 | 上海大学 | Preparation method of single-walled carbon nanotube |
| CN101992104A (en) * | 2010-09-21 | 2011-03-30 | 上海大学 | Method of preparing single-wall carbon nanotube loaded with noble metal nanoparticle |
| CN102020266A (en) * | 2010-12-30 | 2011-04-20 | 上海大学 | Method for preparing and purifying massive single-wall carbon nanotubes |
| CN102438937A (en) * | 2009-03-27 | 2012-05-02 | 俄亥俄州立大学 | Pretreatment method for the synthesis of carbon nanotubes and carbon nanostructures from coal and carbon chars |
| CN103241725A (en) * | 2013-05-09 | 2013-08-14 | 中国石油大学(北京) | Method for preparing carbon nano tube by taking coke as raw material and prepared carbon nano tube |
| CN107994229A (en) * | 2017-10-31 | 2018-05-04 | 常州富思通管道有限公司 | A kind of preparation method of novel lithium iron phosphate anode |
| CN114369475A (en) * | 2021-11-29 | 2022-04-19 | 清华大学 | Method for preparing carbonized mesophase pitch |
-
2003
- 2003-09-12 CN CNA031339727A patent/CN1522955A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457947C (en) * | 2006-08-14 | 2009-02-04 | 山东科技大学 | Carbon nano-crystal hydrogen-storage material and preparation method |
| CN102438937A (en) * | 2009-03-27 | 2012-05-02 | 俄亥俄州立大学 | Pretreatment method for the synthesis of carbon nanotubes and carbon nanostructures from coal and carbon chars |
| CN102438937B (en) * | 2009-03-27 | 2015-03-04 | 俄亥俄州立大学 | Pretreatment method for the synthesis of carbon nanotubes and carbon nanostructures from coal and carbon chars |
| CN101941691A (en) * | 2010-09-21 | 2011-01-12 | 上海大学 | Preparation method of single-walled carbon nanotube |
| CN101992104A (en) * | 2010-09-21 | 2011-03-30 | 上海大学 | Method of preparing single-wall carbon nanotube loaded with noble metal nanoparticle |
| CN101992104B (en) * | 2010-09-21 | 2012-07-04 | 上海大学 | Method of preparing single-wall carbon nanotube loaded with noble metal nanoparticle |
| CN102020266A (en) * | 2010-12-30 | 2011-04-20 | 上海大学 | Method for preparing and purifying massive single-wall carbon nanotubes |
| CN103241725A (en) * | 2013-05-09 | 2013-08-14 | 中国石油大学(北京) | Method for preparing carbon nano tube by taking coke as raw material and prepared carbon nano tube |
| CN107994229A (en) * | 2017-10-31 | 2018-05-04 | 常州富思通管道有限公司 | A kind of preparation method of novel lithium iron phosphate anode |
| CN114369475A (en) * | 2021-11-29 | 2022-04-19 | 清华大学 | Method for preparing carbonized mesophase pitch |
| CN114369475B (en) * | 2021-11-29 | 2023-02-03 | 清华大学 | Method for preparing carbonized mesophase pitch |
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