CN101555007A - Method for preparing multi-walled carbon nanometer tube by polyacrylonitrile nanometer microsphere - Google Patents
Method for preparing multi-walled carbon nanometer tube by polyacrylonitrile nanometer microsphere Download PDFInfo
- Publication number
- CN101555007A CN101555007A CNA2009100511580A CN200910051158A CN101555007A CN 101555007 A CN101555007 A CN 101555007A CN A2009100511580 A CNA2009100511580 A CN A2009100511580A CN 200910051158 A CN200910051158 A CN 200910051158A CN 101555007 A CN101555007 A CN 101555007A
- Authority
- CN
- China
- Prior art keywords
- walled carbon
- polyacrylonitrile
- nano
- micro
- tubes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing a multi-walled carbon nanometer tube by polyacrylonitrile nanometer microsphere. Pure acrylonitrile or acrylonitrile and copolymer monomers thereof and deionized water are mixed according to a volume ratio of 1:20-1:5, are heated to a temperature between 50 and 80 DEG C after being stirred for 30 minutes at rotating speed between 300 and 800 revolutions/minute under protection of nitrogen, are added with 1-90mg/100ml of initiator to react for 1 to 12 hours, and are cooled to room temperature to directly prepare or, after being mixed with an additive, to prepare polyacrylonitrile nanometer microsphere emulsion; the polyacrylonitrile nanometer microsphere emulsion is prepared into the multi-walled carbon nanometer tube through cooling, drying, oxidizing and carbonizing. The method prepares the carbon nanometer tube with purity reaching 95 to 99 percent, even tube diameter and wall thickness by adopting the polymer nanometer microsphere as a raw material. The carbon nanometer tube prepared by the method has the advantages of high purity, purification omission, good dispersibility, large-scale production and the like.
Description
Technical field
The present invention relates to a kind of method for preparing carbon nanotube, be specifically related to a kind of method for preparing high-purity multi-wall carbon nano-tube with the polyacrylonitrile micro-nano ball.
Background technology
Carbon nanotube is as the orderly nanometer carbon 26S Proteasome Structure and Function material of a kind of one dimension, have characteristics such as specific tenacity height, thermal conductivity height, specific conductivity height, surfactivity height and resistance to chemical attack, can have potential and application prospects at aspects such as absorption, energy storage, gas storage, nano-device, support of the catalyst, high performance structures and functional composite materials.Multi-walled carbon nano-tubes is as composite additives; can effectively improve the performances such as intensity of matrix material; its preparation cost is again far below Single Walled Carbon Nanotube; be expected to obtain using more widely, this extensive degree depends on it in mass-producing, low cost, the technical further breakthrough of prepared in high purity.
Arc discharge method, laser evaporation method and chemical Vapor deposition process are maximum as the concern that three kinds of traditional preparation method of carbon nano-tube obtain.Wherein arc discharge method is under inert atmosphere protection, two root graphite electrode direct-current discharges, and anode graphite consumption, carbon distillation and condensation deposit by products such as carbon nanotube and other decolorizing carbon; The laser evaporation method is in High Temperature Furnaces Heating Apparatus, and with the laser evaporation carbon source, the carbon after the evaporation distils in carrier gas and condensation deposits by products such as carbon nanotube and other decolorizing carbon; Chemical Vapor deposition process then is under catalyst action, makes carbonaceous hydrocarbon polymer or hydrocarbon catalytic decomposition go out carbon source, then nucleating growth carbon nanotube in the presence of catalyzer.
Aspect scale preparation and cost control; arc discharge method and laser evaporation method institute energy requirement height; in the product often with by products such as soccerballene, decolorizing carbon; need to purify; make cost high; in addition; because preparation technology is limited by the graphite velocity of evaporation; large-scale production is brought difficulty; although obtained some progress in recent years; as preparation condition being studied to improve productive rate, with the coal be raw material to reduce cost, do not solve but cost height and large-scale production problem of difficult are still basic.Chemical Vapor deposition process has the advantage that is easy to accomplish scale production; obtaining very much progress aspect catalyst type, large-scale production and the array carbon nano tube growth in recent years; but because the decomposition of carbon compound and the growth of carbon nanotube all need catalyzer; and catalyzer often is present in carbon nanotube inside and needs to remove, and the technology cost is increased.
Additive method such as polymkeric substance spinning method, flame method, electrolytic process and microwave method etc. also are studied.Wherein polymkeric substance spinning method by Japanese A.Oya in calendar year 2001 (D.Hulicova; F.Sato; K.Okabe; M.Koishi; A.Oya.An attempt to preparecarbon nanotubes by the spinning of microcapsules.Carbon; 2001; 39:1421-1446) propose to prepare carbon nanotube from the high molecular micro nanometer ball capsule spinning of nucleocapsid structure; because all technological processs are easy to the multiplying gauge modelling, this method has the possibility of low-cost preparation multi-walled carbon nano-tubes in enormous quantities.Yet this method exists a lot of not enough, all obtains effective tensile deformation as not every nucleocapsid micro-nano ball in the spinning process, has phenomenon of phase separation in the spinning process, and carbon nano pipe purity that obtains and yield are very low etc.
Summary of the invention
The invention discloses and a kind ofly prepare the method for high-purity multi-wall carbon nano-tube with the polyacrylonitrile micro-nano ball, its purpose is to overcome prior art such as arc discharge method and laser evaporation method preparation process institute energy requirement height, and cost is high; Chemical Vapor deposition process need add metal catalyst, and the carbon nano pipe purity of preparation is not high, contains agraphitic carbon and granules of catalyst; Drawbacks such as carbon nano pipe purity that polymkeric substance spinning method obtains and yield are very low.Employing the present invention prepares the method for carbon nanotube, the characteristics that have purity height, good dispersity and can be mass-produced; Significantly be better than preparing the method for carbon nanotube from the spinning of nucleocapsid structure high molecular micro nanometer ball capsule.
A kind ofly prepare the method for multi-walled carbon nano-tubes, it is characterized in that comprising following process with the polyacrylonitrile micro-nano ball:
(1) pure vinyl cyanide or vinyl cyanide and polymer monomers thereof are mixed with 1: 20～1: 5 volume ratio with deionized water, rotating speed stirring with 300～800 rev/mins under nitrogen protection was warming up to 50～80 ℃ after 30 minutes, add initiator for reaction 1-12 hour of 1～90mg/100ml, be cooled to room temperature and directly make or add and make polyacrylonitrile micro-nano ball emulsion after additive mixes;
(2) the polyacrylonitrile micro-nano ball emulsion that step (1) is obtained places freeze drier, obtains polyacrylonitrile micro-nano ball powder after the lyophilize;
(3) the micro-nano ball powder that step (2) is obtained places oxidized still, temperature rise rate with 0.1～5 ℃/min in air is warming up to 200～300 ℃, and carries out oxide treatment in constant temperature 1-10 hour do not melted polyacrylonitrile micro-nano ball powder under this temperature;
(4) the micro-nano ball powder that do not melt that step (3) is obtained places charring furnace, temperature rise rate with 3～100 ℃/min under nitrogen protection is warmed up to 800～1500 ℃, and keeps carrying out in 0.1～10 hour charing handle and to obtain multi-walled carbon nano-tubes under this temperature;
(5) carbon nanotube that step (4) is obtained is warmed up to 2300～3000 ℃ with 10～50 ℃/min speed under argon shield, is incubated the multi-walled carbon nano-tubes that carried out obtaining after the greying high graphitization degree in 1～5 hour.
The described multipolymer of step (1) is methylene-succinic acid and derivative thereof, perhaps acrylamide and derivative thereof, and perhaps methyl acrylate and derivative thereof, the mol ratio of polymer monomers and vinyl cyanide is 1: 99～10: 90.
The described initiator of step (1) comprises thermolysis type initiators such as Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate.
The described additive of step (1) comprises metal-salts such as Potassium Persulphate, Potassium ethanoate, iron trichloride, Cobaltous diacetate, and addition is 0.1～10% of a polyacrylonitrile quality.
The invention has the advantages that: technology have flow process short, need not purifying, cost is low and the advantage that can be mass-produced, product has advantages such as purity height, good dispersity and length-to-diameter ratio are big.Such carbon nanotube is expected to be used widely in fields such as high performance structures and functional composite material, support of the catalyst, ultracapacitor, lithium ion battery, Chu Qing, environmental protection.
Embodiment
Below in conjunction with embodiment the technology of the present invention content is described in further detail, but present embodiment is not limited to the present invention, every employing similarity method of the present invention and similar variation thereof all should be listed protection scope of the present invention in.
[embodiment one]
Get in the monomer vinyl cyanide and 300ml deionized water of 30ml, the rotating speed with 300 rev/mins under nitrogen protection stirs, and is warming up to 60 ℃ simultaneously, adds the initiator potassium persulfate of 30mg, reacts to obtain polyacrylonitrile micro-nano ball emulsion in 6 hours.Above-mentioned emulsion adds the 3mg Potassium Persulphate after being cooled to room temperature, stirs, and puts into freeze drier, obtains polyacrylonitrile micro-nano ball powder after the lyophilize.This micro-nano ball powder is put into oxidized still, under air atmosphere, be warming up to 280 ℃, under this temperature, kept 3 hours, do not melted the micro-nano ball powder with 0.5 ℃/minute speed.Put into charring furnace not melting the micro-nano ball powder, under nitrogen protection, be warmed up to 1000 ℃, under this temperature, kept 1 hour, obtain multi-walled carbon nano-tubes with 30 ℃/minute speed.The gained multi-walled carbon nano-tubes is put into graphitizing furnace, and the speed with 20 ℃/minute under argon shield is warming up to 2800 ℃, and keeps 1 hour under this temperature, obtains the greying multi-walled carbon nano-tubes.The yield of multi-walled carbon nano-tubes is 20wt.% (based on not melting the micro-nano ball powder), and diameter is between 20～100nm, and purity is about 99%, and wherein, multi-walled carbon nano-tubes improves greatly with respect to 1000 ℃ of degree of graphitization after 2800 ℃ of processing.
[embodiment two]
Experimentation, method and condition and [embodiment one] are basic identical, but initiator is an ammonium persulphate, and the polymerization stirring velocity is 800 rev/mins, and the initiator add-on is 50mg/100ml, and polymerization temperature is 50 ℃, and polymerization time is 12 hours; The oxidation temperature rise rate of micro-nano ball powder is 0.1 ℃/min, and the whole temperature of oxidation is 200 ℃, and soaking time is 10 hours; Carbonization heating rate is 3 ℃/min, and the whole temperature of charing is 800 ℃, and soaking time is 0.1 hour; The greying temperature rise rate is 50 ℃/min, and the whole temperature of greying is 2300 ℃, is incubated 10 hours.The yield of multi-walled carbon nano-tubes is 20wt.% (based on not melting the micro-nano ball powder), purity is about 95%, the diameter of multi-walled carbon nano-tubes is between 50-100nm, and the degree of graphitization of multi-walled carbon nano-tubes all is lower than made multi-walled carbon nano-tubes in [embodiment one] after charing and the greying.
[embodiment three]
Experimentation, method and condition and [embodiment one] are basic identical, but polymerization single polymerization monomer is the mixture of vinyl cyanide and methylene-succinic acid, the mol ratio of methylene-succinic acid and vinyl cyanide is 1: 99, the volume ratio of polymerization single polymerization monomer and water is 1: 20, the initiator add-on is 1mg/100ml, reaction times is 12 hours, does not add any material after reaction finishes and directly emulsion is carried out lyophilize; The oxidation temperature rise rate is 5 ℃/min, and the whole temperature of oxidation is 300 ℃, is incubated 1 hour.The yield of multi-walled carbon nano-tubes is 22wt.% (based on not melting the micro-nano ball powder), and purity is about 97%, and diameter is between 60-100nm, and the degree of graphitization of many walls of carbon nanotube all is lower than made multi-walled carbon nano-tubes in [embodiment one] after charing and the greying.
[embodiment four]
Experimentation, method and condition and [embodiment one] are basic identical, but monomer is the mixture of vinyl cyanide and methylene-succinic acid dialkyl, the mol ratio of methylene-succinic acid dialkyl and vinyl cyanide is 2: 98, initiator is an ammonium persulphate, and the initiator add-on is 20mg/100ml, and the polymerization stirring velocity is 500 rev/mins, the Cobaltous diacetate that adds relative polyacrylonitrile quality 10% after the polymerization, carbonization heating rate is 20 ℃/min, and the whole temperature of charing is 1500 ℃, and soaking time is 10 hours.The yield of multi-walled carbon nano-tubes is 30wt.% (based on not melting the micro-nano ball powder), and purity is about 99%, and diameter is between 40-100nm, but the degree of graphitization of multi-walled carbon nano-tubes all is higher than made multi-walled carbon nano-tubes in [embodiment one] after charing and the greying.
[embodiment five]
Experimentation, method and condition and [embodiment one] are basic identical, but monomer is the mixture of vinyl cyanide and acrylamide, the mol ratio of acrylamide and vinyl cyanide is that mass ratio is 10: 90, initiator is a Diisopropyl azodicarboxylate, the initiator add-on is 30mg/100ml, and the polymerization stirring velocity is 800 rev/mins, and polymerization temperature is 80 ℃, polymerization time is 1 hour, adds the Potassium ethanoate of relative polyacrylonitrile quality 1% after the polymerization; Carbonization heating rate is 20 ℃/min, and the whole temperature of charing is 1200 ℃, and carbonization time is 5 hours; Graphitization temperature is 3000 ℃.The yield of multi-walled carbon nano-tubes is 28wt.% (based on not melting the micro-nano ball powder), and purity is about 99%, and diameter is between 20-70nm, but the degree of graphitization of multi-walled carbon nano-tubes all is higher than made multi-walled carbon nano-tubes in [embodiment four] after charing and the greying.
[embodiment six]
Experimentation, method and condition and [embodiment one] are basic identical, but monomer is the mixture of vinyl cyanide and Methacrylamide, the mol ratio of Methacrylamide and vinyl cyanide is that mass ratio is 5: 95, the volume ratio of polymerization single polymerization monomer and deionized water is 1: 15, and initiator is a Potassium Persulphate, and the initiator add-on is 90mg/100ml, the polymerization stirring velocity is 600 rev/mins, polymerization temperature is 50 ℃, and polymerization time is 10 hours, adds the iron trichloride of relative polyacrylonitrile quality 10% after the polymerization; The oxidation temperature rise rate is 0.1 ℃/min, and the whole temperature of oxidation is 300 ℃, and soaking time is 2 hours; Carbonization heating rate is 25 ℃/min, and the whole temperature of charing is 900 ℃, and carbonization time is 0.1 hour; The greying temperature rise rate is 30 ℃/min, is incubated 5 hours.The yield of multi-walled carbon nano-tubes is 30wt.% (based on not melting the micro-nano ball powder), and purity is about 99%, and diameter is between 20-80nm, but the degree of graphitization of carbon nanotube all is higher than made multi-walled carbon nano-tubes in [embodiment four] after charing and the greying.
[embodiment seven]
Experimentation, method and condition and [embodiment one] are basic identical, but monomer is the mixture of vinyl cyanide and methyl acrylate, the mol ratio of methyl acrylate and vinyl cyanide is that mass ratio is 5: 95, the volume ratio of polymerization single polymerization monomer and deionized water is 1: 15, and initiator is a Potassium Persulphate, and the initiator add-on is 40mg/100ml, the polymerization stirring velocity is 600 rev/mins, polymerization temperature is 50 ℃, and polymerization time is 10 hours, adds the iron trichloride of relative polyacrylonitrile quality 8% after the polymerization; The oxidation temperature rise rate is 0.1 ℃/min, and the whole temperature of oxidation is 300 ℃, and soaking time is 2 hours; Carbonization heating rate is 25 ℃/min, and the whole temperature of charing is 900 ℃, and carbonization time is 0.1 hour; The greying temperature rise rate is 30 ℃/min, is incubated 5 hours.The yield of multi-walled carbon nano-tubes is 28wt.% (based on not melting the micro-nano ball powder), and purity is about 99%, and diameter is between 20-80nm, but the degree of graphitization of multi-walled carbon nano-tubes all is higher than made multi-walled carbon nano-tubes in [embodiment four] after charing and the greying.
[embodiment eight]
Experimentation, method and condition and [embodiment one] are basic identical, but monomer is the mixture of vinyl cyanide and methyl methacrylate, the mol ratio of methyl methacrylate and vinyl cyanide is that mass ratio is 10: 90, the volume ratio of polymerization single polymerization monomer and deionized water is 1: 5, and initiator is an ammonium persulphate, and the initiator add-on is 80mg/100ml, the polymerization stirring velocity is 400 rev/mins, polymerization temperature is 75 ℃, and polymerization time is 8 hours, adds the Cobaltous diacetate of relative polyacrylonitrile quality 0.1% after the polymerization; The oxidation temperature rise rate is 3 ℃/min, and the whole temperature of oxidation is 220 ℃, and soaking time is 10 hours; Carbonization heating rate is 80 ℃/min, and the whole temperature of charing is 1500 ℃, and carbonization time is 2 hours; The greying temperature rise rate is 50 ℃/min, and the whole temperature of greying is 3000 ℃, is incubated 2 hours.The yield of multi-walled carbon nano-tubes is 20wt.% (based on not melting the micro-nano ball powder), purity about 99%, diameter is between 20-70nm, but charing carbon nanotube degree of graphitization is lower than made multi-walled carbon nano-tubes in [embodiment one], and the degree of graphitization of multi-walled carbon nano-tubes is higher than made multi-walled carbon nano-tubes in [embodiment one] after the greying.
[embodiment nine]
Experimentation, method and condition and [embodiment one] are basic identical, but monomer is the mixture of vinyl cyanide and methyl methacrylate, the mol ratio of methyl methacrylate and vinyl cyanide is that mass ratio is 2: 98, the volume ratio of polymerization single polymerization monomer and deionized water is 1: 10, initiator is an ammonium persulphate, and the initiator add-on is 10mg/100ml, and polymerization temperature is 70 ℃, polymerization time is 4 hours, adds the Potassium Persulphate of relative polyacrylonitrile quality 10% after the polymerization; The oxidation temperature rise rate is 0.1 ℃/min, and the whole temperature of oxidation is 300 ℃, and soaking time is 1 hour; Carbonization heating rate is 30 ℃/min, and the whole temperature of charing is 900 ℃, and carbonization time is 2 hours; The greying temperature rise rate is 10 ℃/min.The yield of multi-walled carbon nano-tubes is 30wt.% (based on not melting the micro-nano ball powder), purity about 99%, diameter is between 20-100nm, but charing multi-walled carbon nano-tubes degree of graphitization is lower than made multi-walled carbon nano-tubes in [embodiment one], and the degree of graphitization of multi-walled carbon nano-tubes is higher than made multi-walled carbon nano-tubes in [embodiment one] after the greying.
Claims (4)
1. one kind prepares the method for multi-walled carbon nano-tubes with the polyacrylonitrile micro-nano ball, it is characterized in that comprising following process:
(1) pure vinyl cyanide or vinyl cyanide and polymer monomers thereof are mixed with 1: 20～1: 5 volume ratio with deionized water, rotating speed stirring with 300～800 rev/mins under nitrogen protection was warming up to 50～80 ℃ after 30 minutes, add initiator for reaction 1-12 hour of 1～90mg/100ml, be cooled to room temperature and directly make or add and make polyacrylonitrile micro-nano ball emulsion after additive mixes;
(2) the polyacrylonitrile micro-nano ball emulsion that step (1) is obtained places freeze drier, obtains polyacrylonitrile micro-nano ball powder after the lyophilize;
(3) the micro-nano ball powder that step (2) is obtained places oxidized still, temperature rise rate with 0.1～5 ℃/min in air is warming up to 200～300 ℃, and carries out oxide treatment in constant temperature 1-10 hour do not melted polyacrylonitrile micro-nano ball powder under this temperature;
(4) the micro-nano ball powder that do not melt that step (3) is obtained places charring furnace, temperature rise rate with 3～100 ℃/min under nitrogen protection is warmed up to 800～1500 ℃, and keeps carrying out in 0.1～10 hour charing handle and to obtain multi-walled carbon nano-tubes under this temperature;
(5) carbon nanotube that step (4) is obtained is warmed up to 2300～3000 ℃ with 10～50 ℃/min speed under argon shield, is incubated the multi-walled carbon nano-tubes that carried out obtaining after the greying high graphitization degree in 1～5 hour.
2. a kind of method for preparing multi-walled carbon nano-tubes with the polyacrylonitrile micro-nano ball according to claim 1, it is characterized in that: the described polymer monomers of step (1) is methylene-succinic acid and derivative thereof, perhaps acrylamide and derivative thereof, perhaps methyl acrylate and derivative thereof, the mol ratio of polymer monomers and vinyl cyanide is 1: 99～10: 90.
3. according to claim 1ly a kind ofly prepare the method for multi-walled carbon nano-tubes with the polyacrylonitrile micro-nano ball, it is characterized in that: the described initiator of step (1) comprises thermolysis type initiators such as Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate.
4. a kind of method for preparing multi-walled carbon nano-tubes with the polyacrylonitrile micro-nano ball according to claim 1, it is characterized in that: the described additive of step (1), comprise metal-salts such as Potassium Persulphate, Potassium ethanoate, iron trichloride, Cobaltous diacetate, addition is 0.1～10% of a polyacrylonitrile quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100511580A CN101555007B (en) | 2009-05-14 | 2009-05-14 | Method for preparing multi-walled carbon nanometer tube by polyacrylonitrile nanometer microsphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100511580A CN101555007B (en) | 2009-05-14 | 2009-05-14 | Method for preparing multi-walled carbon nanometer tube by polyacrylonitrile nanometer microsphere |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101555007A true CN101555007A (en) | 2009-10-14 |
| CN101555007B CN101555007B (en) | 2011-02-16 |
Family
ID=41173321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100511580A Expired - Fee Related CN101555007B (en) | 2009-05-14 | 2009-05-14 | Method for preparing multi-walled carbon nanometer tube by polyacrylonitrile nanometer microsphere |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101555007B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891930A (en) * | 2010-08-17 | 2010-11-24 | 上海交通大学 | Carbon nano tube-containing sulfur-based composite cathode material and preparation method thereof |
| CN102502582A (en) * | 2011-10-31 | 2012-06-20 | 上海理工大学 | Preparation method of three dimensional ordered macroporous charcoal material |
| CN107675281B (en) * | 2017-10-19 | 2020-06-26 | 华北水利水电大学 | Preparation method of PVP/PAN nano composite fiber |
| CN111422886A (en) * | 2020-05-31 | 2020-07-17 | 佛山经纬纳科环境科技有限公司 | Method for treating organic waste salt through low-temperature catalytic pyrolysis and application |
| CN112331483A (en) * | 2020-10-28 | 2021-02-05 | 成都先进金属材料产业技术研究院有限公司 | Zinc oxide-doped nano multi-level structure composite electrode material and preparation method thereof |
-
2009
- 2009-05-14 CN CN2009100511580A patent/CN101555007B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891930A (en) * | 2010-08-17 | 2010-11-24 | 上海交通大学 | Carbon nano tube-containing sulfur-based composite cathode material and preparation method thereof |
| CN102502582A (en) * | 2011-10-31 | 2012-06-20 | 上海理工大学 | Preparation method of three dimensional ordered macroporous charcoal material |
| CN107675281B (en) * | 2017-10-19 | 2020-06-26 | 华北水利水电大学 | Preparation method of PVP/PAN nano composite fiber |
| CN111422886A (en) * | 2020-05-31 | 2020-07-17 | 佛山经纬纳科环境科技有限公司 | Method for treating organic waste salt through low-temperature catalytic pyrolysis and application |
| CN111422886B (en) * | 2020-05-31 | 2020-11-24 | 佛山经纬纳科环境科技有限公司 | Method for treating organic waste salt through low-temperature catalytic pyrolysis and application |
| CN112331483A (en) * | 2020-10-28 | 2021-02-05 | 成都先进金属材料产业技术研究院有限公司 | Zinc oxide-doped nano multi-level structure composite electrode material and preparation method thereof |
| CN112331483B (en) * | 2020-10-28 | 2022-01-28 | 成都先进金属材料产业技术研究院股份有限公司 | Zinc oxide-doped nano multi-level structure composite electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101555007B (en) | 2011-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101555007B (en) | Method for preparing multi-walled carbon nanometer tube by polyacrylonitrile nanometer microsphere | |
| Liu et al. | Synthesis of enantiopure carbonaceous nanotubes with optical activity | |
| CN105772708A (en) | Method for using biomass waste for preparing nitrogen-doped carbon nanotube coated metal particle composite material | |
| CN101830455A (en) | Method for synthesizing continuous carbon nanometer tube film | |
| CN110562960B (en) | Preparation and purification method of coal-based carbon nano tube | |
| CN103508444A (en) | Phosphorus doped graphene and preparation method thereof | |
| CN102730664A (en) | Carbon nano-tube with fluorine-containing surface and preparation method thereof | |
| CN101219784B (en) | Process for producing polyacrylonitrile base carbon nanospheres | |
| CN101633498A (en) | Preparation method of boron nitride nano tube with controllable dimension | |
| CN106082194B (en) | A kind of method for preparing bigger serface and the less graphene of the number of plies | |
| CN107857247A (en) | A kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion | |
| CN106898494B (en) | A kind of preparation method of carbonaceous mesophase spherules-carbon nano tube compound material | |
| CN103043646A (en) | Method for preparing small solid carbon ball and carbon ball prepared thereby | |
| CN103708436B (en) | Nitrogenous carbon nanotube of a kind of high heat resistance and preparation method thereof | |
| CN102505188B (en) | Method for preparing activated carbon fiber by using polyvinylidene chloride as matrix | |
| Chen et al. | Electrospinning of pure polymer-derived SiBCN nanofibers with high yield | |
| CN115057429A (en) | Method for co-production of nitrogen-doped lignin-based carbon nanotube and biochar | |
| CN104466133B (en) | A kind of graphene carbon composite of N doping and preparation method thereof | |
| CN108455565B (en) | Preparation method of nitrogen-doped graphitized nano carbon cage | |
| CN102020267A (en) | Purification method of single-wall carbon nano tube | |
| CN101696005B (en) | Method for preparing acrylonitrile polymer based mesoporous carbon | |
| CN105749949B (en) | The preparation method of the nitrogenous CNT of internal package metal nanoparticle | |
| CN116712976B (en) | Iron carbide loaded composite carbon-based material and preparation method and application thereof | |
| Shen et al. | A general strategy for the synthesis of carbon nanofibers from solid carbon materials | |
| JP4670100B2 (en) | Method for purifying boron nitride nanotubes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110216 Termination date: 20130514 |