CN103180497A - Method for producing carbon nanofibers, carbon composite and method for producing same - Google Patents
Method for producing carbon nanofibers, carbon composite and method for producing same Download PDFInfo
- Publication number
- CN103180497A CN103180497A CN2011800507114A CN201180050711A CN103180497A CN 103180497 A CN103180497 A CN 103180497A CN 2011800507114 A CN2011800507114 A CN 2011800507114A CN 201180050711 A CN201180050711 A CN 201180050711A CN 103180497 A CN103180497 A CN 103180497A
- Authority
- CN
- China
- Prior art keywords
- carbon
- fiber
- manufacture method
- carbon nano
- catalyst
- 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
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/1278—Carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Thermal Sciences (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Fibers (AREA)
Abstract
The present invention provides: a production method for efficiently producing highly conductive carbon nanofibers that reduces variation in quality; and a carbon composite having excellent dispersibility and ability to impart conductivity, and a method for producing the same. The present invention pertains to: a method for producing carbon nanofibers by causing a catalyst to contact carbide furnace gas used as a starting material; a carbon black/carbon nanofiber carbon composite that is characterized by having a carbon black particle or particle aggregate as a nucleus, and having carbon black and carbon nanofibers joined to one another; and a method for producing a carbon composite by holding a carbon nanofiber-forming catalyst to carbon black, and causing carbide furnace gas to contact the same.
Description
Technical field
The present invention relates to the manufacture method of carbon nano-fiber.In addition, the invention still further relates to carbon complex and the manufacture method thereof of using carbon nano-fiber.
Background technology
In the past, made resin, rubber etc. contain carbon black and gave electric conductivity to it.Particularly acetylene black has the chain structure of carbon granule, and therefore the carbon black with routine compares, and electric conductivity is given the ability excellence.In addition, carbon black can be brought into play its excellent electric conductivity and give ability, as the conductive material of electrode for secondary battery.But in recent years, people's demand does not make the characteristic of the script of resin, battery material etc. reduce and just can give the conductive material of higher electric conductivity.
For these problems, the scheme of use carbon nano-fiber (CNF) as conductive material proposed.CNF is that wire diameter is the fibrous carbon about tens nanometer～100 nanometers, has the excellent character such as high conductivity, high-termal conductivity, and the electroconductive stuffing or the high-termal conductivity filler that therefore can be used as in base materials such as being filled in resin are used in industrial circle.The shape of the CNF that raw material is contacted with catalyst and get mostly is greatly hollow fiber.Sometimes it can be called especially CNT (CNT).
For CNF, although compare with carbon black, its crystallinity is high, the resistance value of powder is low, and because the form of the aggregation that forms with its Filament-wound Machine exists, therefore, the bad dispersibility when mixing with resin etc. can't be given full play to electric conductivity and give ability.Therefore, also make aggregation disperse to be studied to processing by acid treatment or mechanical agitation, but CNF often is cut off shortlyer, and loses speciality originally.So people are studied the compound of carbon black and CNF.For example, the scheme (patent documentation 1) at the on-the-spot CNF of generation of the reaction of acetylene black has been proposed, but because acetylene black is different from the formation condition of CNF, if so generate simultaneously in same generation place, have the unsettled problem of quality.The somebody has proposed to obtain at carbon black generation place importing CNF the scheme (patent documentation 2) of compound, but CNF assembles due to raw material, therefore can't improve the containing ratio of CNF in compound, the mobility while that existence is difficult to the conductive composition that obtains keeping mixing with other material such as resin is reduced the problem of resistance value, does not find yet satisfactory solution at present.
In addition, the method (patent documentation 4) of the method (patent documentation 3) that also contacts with catalyst by the hydrocarbon that makes benzene etc. of CNF, the hydrocarbon that makes benzene etc. and the reaction of catalyst metals fluor-complex, make carbon monoxide (CO) and hydrogen (H
2) the manufacturings such as method (patent documentation 5) that contact with the catalyst granules that contains metal or metal oxide of mist.In the situation that use hydrocarbon as raw material, hydrocarbon is cheap, easily obtain, but on the other hand can secondary soft coal cigarette (cigarette ash), easily sneak in product (CNF).Electric conductivity, the thermal conductivity of coal smoke are poorer than CNF, therefore, have the problem of the performance reduction of the CNF owing to sneaking into.
On the other hand, using CO and H
2The situation of mist as raw material under, the living advantage of pair that easy inhibition coal smoke is arranged, but on the other hand, the yield of CNF or physical property easily produce deviation, therefore aspect productivity, problem is arranged, in addition, be not easy to obtain as the CO of the raw material of industry, higher than price with hydrocarbon phase, the price that therefore has a CNF that generates is the problem such as high also.
[prior art file]
[patent documentation]
Patent documentation 1:WO/2007/013678
Patent documentation 2: TOHKEMY 2010-248397 communique
Patent documentation 3: the clear 62-500943 communique of Japanese Unexamined Patent Application Publication
Patent documentation 4: TOHKEMY 2003-146633 communique
Patent documentation 5: TOHKEMY 2004-300631 communique
Summary of the invention
(inventing problem to be solved)
The present invention provides the method that can reduce the quality deviation and can make expeditiously high conductivity CNF for the problem that solves described CNF manufacture method existence in the past proposes.In addition, the present invention also provides dispersiveness and electric conductivity to give carbon complex and the manufacture method thereof of ability excellence.
(means of dealing with problems)
That is, the present invention adopts following methods in order to solve above-mentioned problem.
(1) a kind of manufacture method of carbon nano-fiber is characterized in that: use calcium carbide furnace gas as raw material, catalyst is contacted with raw material.
(2) manufacture method of above-mentioned (1) described carbon nano-fiber is characterized in that: use and removed the calcium carbide furnace gas of moisture as raw material.
(3) manufacture method of above-mentioned (1) or (2) described carbon nano-fiber is characterized in that: catalyst is the simple substance of iron family element (iron, cobalt or nickel) or the compound that contains iron family element.
(4) manufacture method of above-mentioned (3) described carbon nano-fiber is characterized in that: the compound that contains iron family element is oxide or the hydroxide of iron family element.
(5) manufacture method of above-mentioned (1) or (2) described carbon nano-fiber is characterized in that: catalyst is the compound that contains the iron group mischmetal or contain the iron group mischmetal.
(6) manufacture method of above-mentioned (5) described carbon nano-fiber is characterized in that: the compound that contains the iron group mischmetal is oxide or the hydroxide that contains the iron group mischmetal.
(7) manufacture method of the described carbon nano-fiber of any one in above-mentioned (1)～(6), it is characterized in that: catalyst comprises powdered substance, and under the temperature/pressure condition of Formed nanofiber, not using simultaneously with catalyst fines with the material of the calcium carbide furnace gas reaction body that supports as catalyst, and contact with calcium carbide furnace gas.
(8) manufacture method of above-mentioned (7) described carbon nano-fiber is characterized in that: the body that supports of catalyst is magnesia and/or aluminium oxide.
(9) manufacture method of the described carbon nano-fiber of any one in above-mentioned (1)～(8), is characterized in that: configured catalyst in the carbon nano-fiber synthesizer after, at first with in the reducibility gas gatherer, then import calcium carbide furnace gas.
(10) manufacture method of above-mentioned (9) described carbon nano-fiber is characterized in that: reducibility gas is hydrogen.
(11) a kind of carbon black/carbon nano-fiber carbon complex is characterized in that: having the particle of carbon black or aggregated particle as core, is that carbon black and carbon nano-fiber link.
(12) above-mentioned (11) described carbon complex is characterized in that: the surface selectivity ground of the top ends of carbon nano-fiber and the particle of carbon black or aggregated particle links, and the fibre length of carbon nano-fiber is longer than the length of the particle of carbon black or aggregated particle.
(13) above-mentioned (11) described carbon complex, it is characterized in that: carbon black is acetylene black.
(14) manufacture method of above-mentioned (11) described carbon complex is characterized in that: carbon nano-fiber is generated with catalyst loading on carbon black, and it is contacted with calcium carbide furnace gas.
(15) manufacture method of above-mentioned (14) described carbon complex is characterized in that: use and removed the calcium carbide furnace gas of moisture as raw material.
(16) manufacture method of above-mentioned (14) described carbon complex is characterized in that: it is the simple substance of iron family element (iron, cobalt or nickel) or the compound that contains iron family element with catalyst that carbon nano-fiber generates.
(17) manufacture method of above-mentioned (16) described carbon complex is characterized in that: the compound that contains iron family element is oxide or the hydroxide of iron family element.
(18) manufacture method of above-mentioned (14) described carbon complex is characterized in that: it is the compound that contains the iron group mischmetal or contain the iron group mischmetal with catalyst that carbon nano-fiber generates.
(19) manufacture method of above-mentioned (18) described carbon complex is characterized in that: the compound that contains the iron group mischmetal is oxide or the hydroxide that contains the iron group mischmetal.
(20) manufacture method of above-mentioned (14) described carbon complex, it is characterized in that: configuration has supported the carbon nano-fiber generation with after the carbon black of catalyst in the carbon nano-fiber generating apparatus, at first with in the reducibility gas gatherer, then import calcium carbide furnace gas.
(21) manufacture method of above-mentioned (20) described carbon complex is characterized in that: reducibility gas is hydrogen.
(22) a kind of conductive composition is characterized in that: above-mentioned (11) described carbon complex is filled in resin and/or rubber forms.
(invention effect)
By adopting the manufacture method of carbon nano-fiber of the present invention (CNF), can reduce the deviation of quality and make expeditiously the CNF of high conductivity, can promote the application as electroconductive stuffing or high-termal conductivity filler of CNF, therefore large to the contribution of industrial development.And in the situation that use calcium carbide furnace gas to act as a fuel, in calcium carbide furnace gas, burning occurs and with carbon dioxide (CO in the major part of contained CO
2) form discharge into the atmosphere, but method of the present invention is to utilize CO contained in calcium carbide furnace gas to make CNF, the CO that therefore discharges into the atmosphere
2Reduce, for the reduction of carrying capacity of environment, contribution is arranged also.
In addition, according to the present invention, can obtain dispersiveness and electric conductivity and give the carbon complex of ability excellence, stay in grade.
Description of drawings
Fig. 1 is an example of the structure of carbon complex of the present invention.
Fig. 2 generates an example of the structure of the on-the-spot carbon complex that imports carbon nano-fiber and obtain at carbon black.
The specific embodiment
(embodiment 1)
In the present invention, calcium carbide refers to calcium carbide (CaC
2).Calcium carbide is the acetylene (C as the raw material of industry or fuel use
2H
2) or as the nitrolim (CaCN of nitrogenous fertilizer composition
2) etc. raw material, therefore synthesized widely industrial.Common calcium carbide is synthetic is that carbon (C) with quick lime (CaO) and coke etc. is used as raw material, and within being called as the high temperature furnace of furnace of calcium carbide, the synthesis procedure of the reaction by utilizing formula 1 carries out.
CaO+3C → CaC
2+ CO (formula 1)
In the calcium carbide synthesis procedure, as shown in Equation 1, secondary carbon monoxide (CO) gas of giving birth to.CO is harmful, can not directly discharge, and therefore normally furnace of calcium carbide is made the structure of hermetic type, collects secondary angry body (calcium carbide furnace gas), then carries out harmless treatment by the use that acts as a fuel (formula 2).
CO+(1/2) O
2→ CO
2(formula 2)
Secondary industrial furnace of giving birth to the gas that contains CO is not limited to furnace of calcium carbide, and the secondary angry body of the coke oven that for example uses in Iron industry, blast furnace (oven gas, blast furnace gas) also contains CO.But oven gas, contained hydrocarbon, the carbon dioxide (CO of blast furnace gas
2) etc. the composition beyond CO many, the content of CO be only the 30%(volume) following left and right, so be not suitable for the raw material of CNF.Calcium carbide furnace gas contains CO with 50～90% high concentration, and generates hydrogen (H by the reaction (water gas reaction) of moisture contained in quick lime or coke and carbon
2), therefore, with respect to CO, with CO:H
2=60:40～90:10(volume ratio) ratio contains H
2In the present invention, will be in the calcium carbide synthesis procedure secondary that give birth to, secondary angry body that mainly contain CO and hydrogen is defined as calcium carbide furnace gas.
Can think that the generation of carrying out CNF by the CO raw material makes the reaction shown in formula 3 carry out realizing under the existence of catalyst.By formula 3 as can be known, as only existing CO just can generate CNF as raw material, if but in fact do not make H
2Coexist, reactivity significantly reduces.Its reason may be due to the secondary CO that gives birth to when CNF generates
2Make the cause of catalyst oxidation inactivation, and think due to H
2Coexist and the reason of improving reactivity is due to H
2Reduction suppressed the inactivation of catalyst.
2CO → C(CNF)+CO
2(formula 3)
With CO and H
2Mist open and known in patent documentation 5 as the method for the raw material of CNF.Mist in the past is with industrial raw material CO gas and H
2Gas is with CO:H
2=40:60～90:10 isotactic certainty ratio mixes and obtains.At this moment, mixing is carried out usually at normal temperatures.
On the other hand, the synthetic of calcium carbide carries out under the high temperature of 1600～2000 ℃ usually.Contained CO, H in calcium carbide furnace gas
2Also at high temperature mix, therefore can think, admixture is different near the mist in the past that mixes normal temperature.Inventors etc. newly recognize: like this with the CO and the H that mix under high temperature
2Mist be used in the situation of raw material, with in the past CNF synthetic method relatively, the yield of the CNF of generation significantly improves/stabilisation, therefore the little CNF of quality bills of materials deviation expeditiously, and the characteristic of electrical conductivity also improves/stabilisation, thereby has completed the present invention.
The principal component of calcium carbide furnace gas is carbon monoxide (CO) and hydrogen (H
2), usually also contain nitrogen (N
2) as safety gas.The concentration of each composition is: CO is 50～80 volume %, H
2Be 10～30 volume %, N
2Be several～30 volume %.In addition, remove CO, H in calcium carbide furnace gas
2And N
2Outside, also contain CO
2, the impurity such as hydrocarbon, hydrogen sulfide, nitrogen oxide and/or oxysulfide, be trace, on the almost not impact of generation of CNF.In addition also contain the solid impurity (dust) that produces in calcium carbide generation operation, they can be by filtering (dry method) or washing (wet method) and remove.Removed by wet method in the calcium carbide furnace gas of dust and contained a few %(volumes) steam, this may make catalysqt deactivation, therefore preferably removes to below 0.1% with drying machine or dehydration column etc.
The calcium carbide furnace gas that obtains is like this imported in the CNF synthetic furnace, synthesize CNF by contacting with catalyst.Calcium carbide furnace gas can further be used the inert gas dilutions such as nitrogen, argon.The temperature of preferred synthetic furnace is 300～700 ℃, and pressure is 0.01MPa～1MPa.Lower than 300 ℃ or when surpassing 700 ℃ or pressure lower than 0.01MPa, reaction occurs hardly, and is therefore not preferred in temperature.In addition, when pressure surpassed 1MPa, the withstand voltage scheme of device was comparatively numerous and diverse, and not obvious yield or physical property improve effect, therefore not preferred.Reaction time is preferably 1～24 hour.Lower than 1 hour growing amount pettiness of CNF, in addition, can significantly not increase even surpass 24 hours growing amounts yet, therefore all not preferred.
Catalyst can use the simple substance of iron family element (iron, cobalt or nickel) or contain the compound of iron family element, the for example oxide of iron family element or hydroxide, also can use the compound that contains the iron group mischmetal or contain the iron group mischmetal, for example contain oxide or the hydroxide of iron group mischmetal.These materials can use separately, also can use simultaneously two or more materials.
In addition, use the powder of above-mentioned substance as catalyst, further also can with above-mentioned catalyst fines use simultaneously the said temperature/pressure condition that generates CNF not with the calcium carbide furnace gas reaction, materials such as magnesia and/or aluminium oxide is as the body that supports of catalyst.
Preferably, after the configuration catalyst, carried out in advance the activation (activate and process) of catalyst before importing calcium carbide furnace gas in stove.Particularly, at first configure catalyst in synthetic furnace, after being adjusted to the temperature/pressure that generates CNF in stove, imported about tens of minutes～one hour H in stove before importing calcium carbide furnace gas
2Deng reducibility gas, except deoxidation or moisture, can make catalyst activity from catalyst surface thus.
The CNF that generates can convection drying or is processed to remove dry after residual catalyst and make powder with aqueous acid, perhaps supplies with practical application as the slurry that is scattered in water or organic solvent.
(embodiment 2)
The carbon complex of present embodiment of the present invention is that carbon black and CNF link.Here, link is not simple contact, and refers to merge reasoningly by Carbonaceous matter, be not easy to separate with common mechanically actuated, and electronics can not move freely with thering is no contact resistance between the carbon black that links and CNF.Therefore, when mixing with other materials such as resin, battery materials, carbon black and CNF also exist with the state that links, and can obtain good dispersiveness, are endowed simultaneously high conductivity.In the situation that contain separately carbon black, must increase addition for resin etc. in order to give electric conductivity, the mobility of gained conductive composition is impaired, in the situation that contain separately CNF, be orientated, be wound around when mixing with resin etc., therefore be difficult to obtain good dispersiveness, aspect electric conductivity, deviation can occur.In addition, in the situation that merely carbon black is mixed with CNF, both contact conditions easily change, so deviation can further increase.
Carbon complex of the present invention is the carbon complex with following characteristics, namely has the particle of carbon black or aggregated particle as core, is that carbon black and CNF are formed by connecting.The inventor gives the ability raising and conducts in-depth research for the dispersiveness and the electric conductivity that make carbon complex, found that, the structure of carbon complex is large on the impact of these characteristics.That is, by obtaining centered by carbon black pellet or aggregated particle, have CNF and structure that both link at its peripheral part, when resin etc. mixes, the area change that the CNF of excellent electric conductivity and resin etc. contact.In addition, in said structure, the gathering of CNF reduces, and therefore is difficult to be orientated, be wound around, thereby can increases to the amount of the CNF of the mixing such as resin, and the electric conductivity ability of giving is significantly improved.On the other hand, carbon complex in the past is the structure that carbon black surrounds the peripheral part of the CNF that assembles, therefore the contact area with resin etc. reduces, and the major part that contact with resin etc. is carbon black, so can't give full play in carbon complex the electric conductivity of CNF and give ability.Fig. 1 represents an example of the structure of carbon complex of the present invention, and Fig. 2 is illustrated in the example of structure that carbon black generates the carbon complex in the past of the on-the-spot CNF of importing gained.
In the present invention, preferably, the surface selectivity ground of the top ends of CNF and the particle of carbon black or aggregated particle links, and the fibre length of CNF is larger than the particle diameter of the particle of carbon black or aggregated particle.Here, the top ends of CNF refers to that CNF generates and the end of the direction of extending.In the situation that the fibre length of CNF is larger than the particle diameter of the particle of carbon black or aggregated particle, even the amount of adding the carbon complex in resin etc. to is with in the past identical, also easily wide scope ground diffusion in resin etc., therefore can effectively bring into play the conductive path function.The fibre length of CNF can be regulated by reaction of formation temperature, reaction of formation time, more preferably more than 1 μ m.
The kind that consists of the carbon black of carbon complex of the present invention is not particularly limited, such as using thermal black, furnace black, dim, channel black, acetylene black etc., and more preferably acetylene black wherein.This is to have the structure of the primary particle connection chaining of high-purity, high crystalline so excellent electric conductivity due to acetylene black.
CNF content in carbon complex of the present invention is preferably 10～80 quality %.If the content of CNF can't obtain sufficient electric conductivity lower than 10 quality %, if surpass 80 quality %, because the gathering of CNF etc. makes dispersed the reduction.CNF content can be regulated with amount, reaction of formation temperature, the reaction of formation time of catalyst, carbon black by the CNF generation that joins in the CNF generating apparatus.
The manufacture method of carbon complex of the present invention is not particularly limited, and for example can generate and to use catalyst by support CNF on carbon black, and it is contacted with calcium carbide furnace gas, at the Surface Creation CNF of carbon black pellet and make its link.Owing in embodiment 1, calcium carbide furnace gas being illustrated, therefore description is omitted here.
The calcium carbide furnace gas that obtains like this can be imported in the CNF generating apparatus and it is contacted with catalyst, generating thus CNF.Calcium carbide furnace gas can further be used the inert gas dilutions such as nitrogen, argon.Preferably, the temperature of synthetic furnace is 300～700 ℃, and pressure is 0.01MPa～1MPa.If temperature is lower than 300 ℃ or surpass 700 ℃ or pressure lower than 0.01MPa, reaction occurs hardly, and is therefore not preferred.In addition, if pressure surpasses 1MPa, the withstand voltage scheme of device is numerous and diverse, and not obvious yield, physical property improve effect, therefore not preferred.Preferred 1～24 hour of reaction time.If lower than 1 hour, the growing amount pettiness of CNF, even surpass 24 hours in addition, growing amount can not enlarge markedly yet, and is therefore all not preferred.
The CNF generation can be used the simple substance of iron family element (iron, cobalt or nickel) with catalyst or contain the compound of iron family element, the for example oxide of iron family element or hydroxide, also can use the compound that contains the iron group mischmetal or contain the iron group mischmetal, for example contain oxide or the hydroxide of iron group mischmetal.These materials can use separately, also can use simultaneously two or more materials.
Preferably, CNF generates with catalyst loading on carbon black.Loading method is not particularly limited, such as can be so that the simple substance of iron family element or the CNF such as compound that contain iron family element generate with catalyst suspends or be dissolved in the liquid such as ethanol, add carbon black in this liquid, stirring, mixing, dehydration, drying support thus.The material powder that obtains is thus contacted with calcium carbide furnace gas in the CNF generating apparatus, obtain thus carbon complex, this carbon complex is characterised in that: having the particle of carbon black or aggregated particle as core, is that carbon black and CNF link.Moreover because the particle of carbon black or the aggregated particle form with core exists, so the top ends of CNF optionally links, and CNF is grown along multiple directions, can suppress to assemble.In addition, in method in the past, for example samely generating the on-the-spot method that generates simultaneously carbon black and CNF, generating at carbon black and on-the-spotly add the method for CNF, the carbon complex that is difficult to obtain to have structure of the present invention.
When generating CNF, preferably carried out in advance the activation (activate and process) of catalyst before importing calcium carbide furnace gas.Particularly, configuration has supported CNF and has generated carbon black with catalyst in the CNF generating apparatus, after being adjusted to the temperature/pressure that generates CNF in stove, imports the H about dozens of minutes～one hour in the device
2Deng reducibility gas, remove deoxidation or moisture, activating catalyst thus from catalyst surface.Afterwards, promote the generation of CNF by importing calcium carbide furnace gas.
The carbon complex that generates can convection drying or is processed to remove dry after residual catalyst and make powder with aqueous acid, perhaps as being scattered in the slurry in water or organic solvent and supplying with practical application.By carbon complex of the present invention is filled in resin or rubber etc., can obtain the conductive composition than in the past excellent electric conductivity.
Embodiment
Describe by the following examples manufacture method, carbon complex and the manufacture method thereof of carbon nano-fiber of the present invention in detail with comparative example.But the present invention is not limited to following embodiment in being no more than the scope of its aim.
[embodiment 1]
Use closed type calcium carbide furnace, quick lime (CaO) and petroleum coke (C) are joined in stove, then the central upper from stove is inserted into the electric power that graphite electrode in stove applies 25,000kW, make to be heated to 2000 ℃ in stove, make CaO and C react to synthesize calcium carbide (CaC
2).Collect secondary calcium carbide furnace gas of giving birth to this moment, wash in order to remove dust, then be stored in the hydrolock air accumulator.Extract the part of the calcium carbide furnace gas that stores, (Shimadzu Seisakusho Ltd. makes, and GC-14B) analyzes principal component, analyzes micro constitutent with gas detecting tube (GASTEC manufacturing), and result is as shown in table 1 with gas chromatograph.
[table 1]
Fill in the reaction vessel of quartz glass system and contain cobalt oxide (Co
3O
4) (Sigma aldrich company makes, and " 637025 ", purity 99.8%, (Sigma aldrich company makes, " 549649 ", average grain diameter 12.8nm, specific area 130m for average grain diameter 20～30nm) and magnesia (MgO)
2Then/g) the catalyst of mixed-powder fills in container in the CNF synthesizer.Use inert gas (N in device
2) fill, making pressure is to be warming up to 600 ℃ after 0.1MPa, with reducibility gas (H
2) replace and kept 30 minutes, the above-mentioned calcium carbide furnace gas that then will be stored in air accumulator imports in stove and kept 8 hours.Then, use N
2Calcium carbide furnace gas is replaced and stopped heating, be cooled to open system after room temperature, reclaim product from reaction vessel.These condition summary sheets are shown in Table 2.
[table 2]
Product is the powder of black.The output (weight portion) of every 1 corresponding product of weight portion of the catalyst that calculating is used is as yield.Utilize transmission electron microscope (TEM: NEC manufacturing, transmission electron microscope 2000FX, accelerating potential 200kV, 200,000 times of observation multiplying powers) to observe micro-structural, result is the carbon nano-fiber (CNF) of hollow fiber.By the external diameter of 10 CNF of TEM image measurement, with its mean value as the CNF diameter.For electric conductivity, (Mitsubishi Chemical ANALYTECH Co., Ltd. makes, and LORESTAGP), has measured the powder resistance value with load 4.9kN, four probe method to use the powder resistance measuring instrument.Implement under the same conditions synthetic test 10 times, mean value and the standard deviation of calculated yield, CNF diameter and powder resistance value.These as a result summary sheet be shown in Table 3.
[table 3]
[embodiment 2～4]
Use the calcium carbide furnace gas of embodiment 1, synthesize according to condition shown in table 2 respectively.The morphologic observation of the micro-structural of products therefrom and the result of calculation summary sheet of yield, CNF diameter and powder resistance value are shown in Table 3.
[embodiment 5～7]
Use the calcium carbide furnace gas of the composition shown in table 1, synthesize according to condition shown in table 2 respectively.The morphologic observation of the micro-structural of products therefrom and the result of calculation summary sheet of yield, CNF diameter and powder resistance value are shown in Table 3.
[embodiment 8～14]
Same with embodiment 1～7, (daily use chemicals Seiko is made, and dried post DC-L4), is reduced to 0.01 volume % with moisture by dehydration column to make the calcium carbide furnace gas that is stored in the hydrolock air accumulator.With the principal component of gas chromatograph analytical gas, analyze micro constitutent with gas detecting tube, result is as shown in table 1.Then according to synthesizing with the same condition of embodiment 1～7, the morphologic observation of the micro-structural of products therefrom and the result of calculation summary sheet of yield, CNF diameter and powder resistance value are shown in Table 3.
[comparative example 1～7]
As unstrpped gas, use the gas that commercially available CO gas (purity 99.95%) and hydrogen (purity 99.99%) are at room temperature mixed according to ratio shown in table 4 to replace calcium carbide furnace gas, in addition according to synthesizing with the same condition of embodiment 1～7, the morphologic observation of the micro-structural of products therefrom and the result of calculation summary sheet of yield, CNF diameter and powder resistance value are shown in Table 3.
As shown in Table 3, comparative example 1～7 and synthesis condition except unstrpped gas all identical embodiment (for example comparative example 1 and embodiment 1 and embodiment 8, comparative example 2 and embodiment 2 and embodiment 9, below same) compare, and yield is low, fibre diameter is thin, and the powder resistance value is high.And their standard deviation value is large, and deviation is large.
[comparative example 8～9]
As unstrpped gas, use the oven gas that produces when with coke oven, coal being carried out destructive distillation to replace calcium carbide furnace gas, in addition synthesize according to condition similarly to Example 1, have no the generation of CNF.The blast furnace gas that use produces when utilizing the blast furnace coke reducing iron ore also has no the generation of CNF during as unstrpped gas.The constituent analysis result of the oven gas that uses and blast furnace gas is as shown in table 1.
By embodiment and comparative example as can be known,, can reduce the quality deviation and make expeditiously the CNF with high conductivity the manufacture method of calcium carbide furnace gas as the carbon nano-fiber (CNF) of raw material according to of the present invention.And can use in the calcium carbide synthesis procedure secondary calcium carbide furnace gas of giving birth to as raw material, therefore with the situation of using commercially available CO gas and hydrogen relatively, can cut down carbon dioxide (CO
2) burst size, and can make at low cost CNF.
Embodiment 15 uses calcium carbide furnace gas synthetic in embodiment 1 to make carbon complex.With 50g furnace black (East Sea charcoal element company make, " SEAST SO ") and 0.5g cobalt oxide (Co
3O
4) powder (Sigma aldrich company makes, and " 637025 ", purity 99.8%, average grain diameter 20～30nm) join in 500g ethanol, mix 1 hour with ball mill.Then filter/drying, obtain material powder.Then, the gained material powder is filled in the reaction vessel of quartz glass system, container is filled in the carbon nano-fiber generating apparatus.Making in device is vacuum atmosphere, then fills inert gas (N
2), to make pressure be 0.1Mpa and be warming up to 600 ℃.Then, the above-mentioned calcium carbide furnace gas that is stored in the hydrolock air accumulator is imported in stove and kept 6 hours.Then, use N
2Calcium carbide furnace gas is replaced and stopped heating, be cooled to room temperature, then open system, reclaim product from reaction vessel.Their formation condition is as shown in table 4.
[table 4]
The assessment item of product and evaluation method thereof are as shown below.
(1) have or not link, bond sites about carbon nano-fiber, observe fine structure by transmission electron microscope (Jeol Ltd. makes, and " transmission electron microscope JEM-2000FX " observes 100,000 times of multiplying powers), confirm.
(2) about the fibre length of carbon nano-fiber, measure 10 with transmission electron microscope (observing 5000 times of multiplying powers), ask its mean value.In addition, estimate too about the aggregated particle of carbon black, be 500nm.
(3) about the containing ratio of carbon nano-fiber, deduct the weight of material powder from the weight of the product that reclaims, ask the weight of the carbon nano-fiber that generates to calculate.
(4) give ability about the electric conductivity of carbon complex, by being estimated by the specific insulation of following resin complexes of trying to achieve.10 parts by mass carbon complexes are engaged in 90 parts by mass PS resins (Toyo Styrene Co., Ltd.'s manufacturing " H700 "), (Japan's essence mechanism is done manufacturing to use mixing roll, " LABO PLASTOMILL "), mixing 10 minutes with blade rotational speed 30rpm, 220 ℃ of temperature.Should be heated to 200 ℃ by mixing thing, with the exert pressure moulding of 9.8 * 106Pa, make the test film of 2 * 2 * 70mm, use digital multimeter (Yokogawa Motor Co., Ltd, " digital multimeter 7562 "), according to the test method measuring specific insulation of SRI2301.
(5) about the mobility of the dispersiveness in resin and resin combination, by following MFI(melt flow index of trying to achieve) estimate.The test film that uses during specific insulation is measured is cut into the size of 2 * 2 * 5mm, (Japan's essence mechanism is done manufacturing with the mobility measuring instrument, melt index apparatus A-111), measure the quality of the resin combination of every 10 minutes that flows out from the nozzle of internal diameter 2mm under the load under the heating of 200 ℃, at 5kg.
These results are as shown in table 5.
[table 5]
[embodiment 16]
The raw material carbon black is changed to acetylene black (electrochemical industry is made, " HS-100 "), in addition similarly to Example 15, obtain carbon complex.Evaluation result is as shown in table 6.
[embodiment 17]
Fill inert gas (N
2) and to make pressure be 0.1MPa, be warming up to 600 ℃ after with reducibility gas (NH
3) replace and kept 30 minutes, the calcium carbide furnace gas that is stored in the hydrolock air accumulator is imported in stove, in addition similarly to Example 16, obtain carbon complex.Evaluation result is as shown in table 6.
[embodiment 18]
Reducibility gas is changed to H
2, in addition similarly to Example 17, obtain carbon complex.Evaluation result is as shown in table 6.
[embodiment 19,20]
Carbon nano-fiber is generated with catalyst change to cobalt metal (manufacturing of Sigma aldrich company, " 266639 ", purity 99.8%, average grain diameter 2 μ m), iron-manganese-cobalt alloy (forms 5:2.5:2.5, average grain diameter 30nm), in addition similarly to Example 18, obtain carbon complex.Evaluation result is as shown in table 6.
[embodiment 21～26]
Make the calcium carbide furnace gas that is stored in the hydrolock air accumulator by dehydration column (daily use chemicals Seiko is made, " dried post DC-L4 "), in addition same with embodiment 15～20, obtain carbon complex.Evaluation result is as shown in table 6.
[embodiment 27～29]
As shown in table 4 reaction of formation temperature and reaction of formation time are changed, in addition similarly to Example 24, obtain carbon complex.Evaluation result is as shown in table 5.
[embodiment 30]
Cobalt oxide (the Co that will mix with 50g acetylene black
3O
4) the quantitative change 0.7g more of powder, in addition similarly to Example 29, obtain carbon complex.Evaluation result is as shown in table 6.
[comparative example 10]
With 0.5g cobalt oxide (Co
3O
4) powder is filled in the reaction vessel of quartz glass system, container is filled in the carbon nano-fiber generating apparatus.Making in device is vacuum atmosphere, then fills inert gas (N
2), making pressure is 0.1MPa, and is warming up to 600 ℃.Then use reducibility gas (H
2) replace and kept 30 minutes, then, will import in stove by the calcium carbide furnace gas of dehydration column and keep 6 hours.Then with calcium carbide furnace gas N
2Displacement and stopped heating are cooled to open system after room temperature, reclaim the carbon nano-fiber simple substance that generates from reaction vessel.Evaluation result is as shown in table 6.
[comparative example 11]
With ball mill, the carbon nano-fiber that obtains in comparative example 10 is mixed with acetylene black, obtain mixed powder.Evaluation result is as shown in table 5.
[comparative example 12]
As unstrpped gas, the gas that use mixes with the ratio of the nitrogen (purity 99.99%) of the hydrogen (purity 99.99%) of the commercially available CO gas (purity 99.95%) of 70 volume %, 15 volume %, 15 volume %, in addition similarly to Example 24, obtain carbon complex.Evaluation result is as shown in table 6.
(industrial applicability)
The CNF that is obtained by manufacture method of the present invention is filled in as the high conductivity filler in the matrix such as resin, can be used as composite and uses in various industrial circles.In addition, carbon complex of the present invention can be as for the electric conductivity imparting agent of rubber etc., as battery conductive materials such as one-shot battery, secondary cell, fuel cell, capacitors.
(explanation of Reference numeral)
1: carbon black; 2: carbon nano-fiber
Claims (22)
1. the manufacture method of a carbon nano-fiber, is characterized in that: use calcium carbide furnace gas as raw material, catalyst is contacted with described raw material.
2. the manufacture method of carbon nano-fiber according to claim 1, is characterized in that: use and removed the calcium carbide furnace gas of moisture as raw material.
3. the manufacture method of carbon nano-fiber according to claim 1, it is characterized in that: catalyst is the simple substance of iron family element (iron, cobalt or nickel) or the compound that contains iron family element.
4. the manufacture method of carbon nano-fiber according to claim 3, it is characterized in that: the compound that contains iron family element is oxide or the hydroxide of iron family element.
5. the manufacture method of carbon nano-fiber according to claim 1, it is characterized in that: catalyst is the compound that contains the iron group mischmetal or contain the iron group mischmetal.
6. the manufacture method of carbon nano-fiber according to claim 5, it is characterized in that: the compound that contains the iron group mischmetal is oxide or the hydroxide that contains the iron group mischmetal.
7. the manufacture method of carbon nano-fiber according to claim 1, it is characterized in that: catalyst comprises powdered substance, and under the temperature/pressure condition of Formed nanofiber, not use simultaneously with catalyst fines and to contact with calcium carbide furnace gas with the material of the calcium carbide furnace gas reaction body that supports as catalyst.
8. the manufacture method of carbon nano-fiber according to claim 7, it is characterized in that: the body that supports of catalyst is magnesia and/or aluminium oxide.
9. the manufacture method of carbon nano-fiber according to claim 1, is characterized in that: after the configuration catalyst, at first with in the reducibility gas gatherer, then import calcium carbide furnace gas in the carbon nano-fiber synthesizer.
10. the manufacture method of carbon nano-fiber according to claim 9, it is characterized in that: reducibility gas is hydrogen.
11. carbon black/carbon nano-fiber carbon complex is characterized in that: having the particle of carbon black or aggregated particle as core, is that carbon black and carbon nano-fiber link.
12. carbon complex according to claim 11 is characterized in that: the surface selectivity ground of the top ends of carbon nano-fiber and the particle of carbon black or aggregated particle links, and the fibre length of carbon nano-fiber is longer than the length of the particle of carbon black or aggregated particle.
13. carbon complex according to claim 11 is characterized in that: carbon black is acetylene black.
14. the manufacture method of carbon complex according to claim 11 is characterized in that: carbon nano-fiber is generated with catalyst loading on carbon black, and it is contacted with calcium carbide furnace gas.
15. the manufacture method of carbon complex according to claim 14 is characterized in that: use and removed the calcium carbide furnace gas of moisture as raw material.
16. the manufacture method of carbon complex according to claim 14 is characterized in that: it is the simple substance of iron family element (iron, cobalt or nickel) or the compound that contains iron family element with catalyst that carbon nano-fiber generates.
17. the manufacture method of carbon complex according to claim 16 is characterized in that: the compound that contains iron family element is oxide or the hydroxide of iron family element.
18. the manufacture method of carbon complex according to claim 14 is characterized in that: it is the compound that contains the iron group mischmetal or contain the iron group mischmetal with catalyst that carbon nano-fiber generates.
19. the manufacture method of carbon complex according to claim 18 is characterized in that: the compound that contains the iron group mischmetal is oxide or the hydroxide that contains the iron group mischmetal.
20. the manufacture method of carbon complex according to claim 14, it is characterized in that: configuration has supported the carbon nano-fiber generation with after the carbon black of catalyst in the carbon nano-fiber generating apparatus, at first with in the reducibility gas gatherer, then import calcium carbide furnace gas.
21. the manufacture method of carbon complex according to claim 20 is characterized in that: reducibility gas is hydrogen.
22. a conductive composition is characterized in that: the described carbon complex of claim 11 is filled in resin and/or rubber forms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510092416.5A CN104746181A (en) | 2010-10-20 | 2011-09-29 | Method for producing carbon nanofibers, carbon composite and method for producing same |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010235795 | 2010-10-20 | ||
| JP2010-235795 | 2010-10-20 | ||
| JP2011-202727 | 2011-09-16 | ||
| JP2011202727 | 2011-09-16 | ||
| PCT/JP2011/072385 WO2012053334A1 (en) | 2010-10-20 | 2011-09-29 | Method for producing carbon nanofibers, carbon composite and method for producing same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510092416.5A Division CN104746181A (en) | 2010-10-20 | 2011-09-29 | Method for producing carbon nanofibers, carbon composite and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103180497A true CN103180497A (en) | 2013-06-26 |
| CN103180497B CN103180497B (en) | 2015-08-26 |
Family
ID=45975053
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180050711.4A Active CN103180497B (en) | 2010-10-20 | 2011-09-29 | The manufacture method of carbon nano-fiber, carbon complex and manufacture method thereof |
| CN201510092416.5A Pending CN104746181A (en) | 2010-10-20 | 2011-09-29 | Method for producing carbon nanofibers, carbon composite and method for producing same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510092416.5A Pending CN104746181A (en) | 2010-10-20 | 2011-09-29 | Method for producing carbon nanofibers, carbon composite and method for producing same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5960059B2 (en) |
| CN (2) | CN103180497B (en) |
| WO (1) | WO2012053334A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105980301A (en) * | 2014-02-05 | 2016-09-28 | 电化株式会社 | Production method for carbon nanofibers, and carbon nanofibers |
| CN107847917A (en) * | 2015-07-31 | 2018-03-27 | 电化株式会社 | The manufacture method of carbon nano-fiber |
| CN108136375A (en) * | 2015-08-17 | 2018-06-08 | 电化株式会社 | The manufacturing method of carbon nano-fiber complex and carbon nano-fiber complex |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6135166B2 (en) * | 2013-02-13 | 2017-05-31 | 日本ゼオン株式会社 | Redox catalyst, electrode material, electrode, solar cell, fuel cell, and nitrogen oxide removal catalyst |
| US10714746B2 (en) | 2014-08-11 | 2020-07-14 | Denka Company Limited | Conductive composition for electrode, electrode using same, and lithium ion secondary battery |
| JP2017006888A (en) * | 2015-06-26 | 2017-01-12 | デンカ株式会社 | Catalyst for producing carbon nanofiber, method for producing carbon nanofiber, and carbon nanofiber |
| JP2017141370A (en) * | 2016-02-10 | 2017-08-17 | デンカ株式会社 | Conductive polymer material and molded article using the same |
| EP3512012B1 (en) | 2016-09-07 | 2021-09-01 | Denka Company Limited | Conductive composition for electrodes, and electrode and battery using same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1344674A (en) * | 2000-09-26 | 2002-04-17 | 天津南开戈德集团有限公司 | Prepn of nano-carbon tube |
| JP2003342840A (en) * | 2002-05-27 | 2003-12-03 | Mitsubishi Heavy Ind Ltd | Method and apparatus for producing fibrous nano carbon |
| JP2004300631A (en) * | 2003-03-31 | 2004-10-28 | Mitsubishi Materials Corp | Carbon nanofiber and method for producing the same |
| JP2005219950A (en) * | 2004-02-04 | 2005-08-18 | Nikon Corp | Carbon material, method of manufacturing carbon material, gas adsorption apparatus and composite material |
| JP2006137669A (en) * | 2005-12-05 | 2006-06-01 | Sumitomo Chemical Co Ltd | Method for producing phosgene |
| CN101283055A (en) * | 2005-07-27 | 2008-10-08 | 丹卡新加坡私人有限公司 | Carbon black, method for producing the same, and its use |
| CN101304945A (en) * | 2005-04-14 | 2008-11-12 | 罗伯特·施勒格尔 | Nanosized carbon material-activated carbon composite |
-
2011
- 2011-09-29 JP JP2012539657A patent/JP5960059B2/en active Active
- 2011-09-29 CN CN201180050711.4A patent/CN103180497B/en active Active
- 2011-09-29 CN CN201510092416.5A patent/CN104746181A/en active Pending
- 2011-09-29 WO PCT/JP2011/072385 patent/WO2012053334A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1344674A (en) * | 2000-09-26 | 2002-04-17 | 天津南开戈德集团有限公司 | Prepn of nano-carbon tube |
| JP2003342840A (en) * | 2002-05-27 | 2003-12-03 | Mitsubishi Heavy Ind Ltd | Method and apparatus for producing fibrous nano carbon |
| JP2004300631A (en) * | 2003-03-31 | 2004-10-28 | Mitsubishi Materials Corp | Carbon nanofiber and method for producing the same |
| JP2005219950A (en) * | 2004-02-04 | 2005-08-18 | Nikon Corp | Carbon material, method of manufacturing carbon material, gas adsorption apparatus and composite material |
| CN101304945A (en) * | 2005-04-14 | 2008-11-12 | 罗伯特·施勒格尔 | Nanosized carbon material-activated carbon composite |
| CN101283055A (en) * | 2005-07-27 | 2008-10-08 | 丹卡新加坡私人有限公司 | Carbon black, method for producing the same, and its use |
| JP2006137669A (en) * | 2005-12-05 | 2006-06-01 | Sumitomo Chemical Co Ltd | Method for producing phosgene |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105980301A (en) * | 2014-02-05 | 2016-09-28 | 电化株式会社 | Production method for carbon nanofibers, and carbon nanofibers |
| CN105980301B (en) * | 2014-02-05 | 2018-03-06 | 电化株式会社 | The manufacture method and carbon nano-fiber of carbon nano-fiber |
| CN107847917A (en) * | 2015-07-31 | 2018-03-27 | 电化株式会社 | The manufacture method of carbon nano-fiber |
| CN108136375A (en) * | 2015-08-17 | 2018-06-08 | 电化株式会社 | The manufacturing method of carbon nano-fiber complex and carbon nano-fiber complex |
| CN108136375B (en) * | 2015-08-17 | 2021-09-03 | 电化株式会社 | Method for producing carbon nanofiber composite and carbon nanofiber composite |
| CN113754927A (en) * | 2015-08-17 | 2021-12-07 | 电化株式会社 | Method for producing carbon nanofiber composite and carbon nanofiber composite |
| US11208741B2 (en) | 2015-08-17 | 2021-12-28 | Denka Company Limited | Method for producing carbon nanofiber composite and carbon nanofiber composite |
| CN113754927B (en) * | 2015-08-17 | 2023-09-15 | 电化株式会社 | Method for producing carbon nanofiber composite and carbon nanofiber composite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104746181A (en) | 2015-07-01 |
| CN103180497B (en) | 2015-08-26 |
| WO2012053334A1 (en) | 2012-04-26 |
| JP5960059B2 (en) | 2016-08-02 |
| JPWO2012053334A1 (en) | 2014-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103180497B (en) | The manufacture method of carbon nano-fiber, carbon complex and manufacture method thereof | |
| Al-Enizi et al. | Utilization of waste polyethylene terephthalate bottles to develop metal-organic frameworks for energy applications: A clean and feasible approach | |
| Zhang et al. | Synthesis of hollow carbon nano-onions and their use for electrochemical hydrogen storage | |
| Nahil et al. | Influence of metal addition to Ni-based catalysts for the co-production of carbon nanotubes and hydrogen from the thermal processing of waste polypropylene | |
| Liu et al. | A single-step route for large-scale synthesis of core–shell palladium@ platinum dendritic nanocrystals/reduced graphene oxide with enhanced electrocatalytic properties | |
| Van Dommele et al. | Tuning nitrogen functionalities in catalytically grown nitrogen-containing carbon nanotubes | |
| EP2778266B1 (en) | Composite carbon fibers | |
| KR101446116B1 (en) | Metal catalyst for producing carbon nanotubes and method for preparing carbon nanotubes using thereof | |
| TWI452189B (en) | Method for producing composite carbon fiber | |
| JP6449251B2 (en) | Catalytic degradation of lower hydrocarbons to produce carbon oxide free hydrogen and bamboo structure carbon nanotubes | |
| EP2682517A2 (en) | Composite carbon fibers | |
| Saka | Metal-free catalysts with phosphorus and oxygen doped on carbon-based on Chlorella Vulgaris microalgae for hydrogen generation via sodium borohydride methanolysis reaction | |
| CN105980301B (en) | The manufacture method and carbon nano-fiber of carbon nano-fiber | |
| Li et al. | Mesoporous RGO/NiCo2O4@ carbon composite nanofibers derived from metal-organic framework compounds for lithium storage | |
| Xiong et al. | Synthesis and catalytic performance of a novel RuCuNi/CNTs nanocomposite in hydrolytic dehydrogenation of ammonia borane | |
| CN103998134A (en) | Support for supporting metals, metal-supported catalyst, methanation reaction apparatus, and method relating to these | |
| Dong et al. | Pyrolysis gas from biomass and plastics over X-Mo@ MgO (X= Ni, Fe, Co) catalysts into functional carbon nanocomposite: Gas reforming reaction and proper process mechanisms | |
| Yang et al. | Symmetrical growth of carbon nanotube arrays on FeSiAl micro-flake for enhancement of lithium-ion battery capacity | |
| Kumar et al. | Heazlewoodite, Ni3S2: An electroactive material for supercapacitor application | |
| Li et al. | A comparative study of the electrochemical hydrogen storage properties of activated carbon and well-aligned carbon nanotubes mixed with copper | |
| Ma et al. | Covalent organic polymer assisted synthesis of bimetallic electrocatalysts with multicomponent active dopants for efficient oxygen evolution reaction | |
| Liu et al. | Oxygen vacancy modulation in interfacial engineering Fe3O4 over carbon nanofiber boosting ambient electrocatalytic N2 reduction | |
| Manasa et al. | Improved H2 yields over rice husk derived SiO2 nanoparticles supported Ni catalyst during non-oxidative methane cracking | |
| Pallavolu et al. | CoNi bimetallic engineering on porous carbon for high energy density hybrid supercapacitors | |
| Kim et al. | Fabrication of carbon nanotube with high purity and crystallinity by methane decomposition over ceria-supported catalysts |
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 |