CN101260574A - Method for preparing nano carbon fiber by solid-state carbon source - Google Patents
Method for preparing nano carbon fiber by solid-state carbon source Download PDFInfo
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Abstract
The invention relates to a method for manufacturing nanometer carbon fiber. The method uses a solid state carbon source as the carbon source; the solid state carbon source is graphite, carbon black, or active carbon, and the average grain diameter of the carbon source is less than or equal to 100 microns. The carbon source undergoes preprocessing by adding acid or grinding, the combination with the former body of metal catalyst and carbonization during which carbonizing reactions occurs under the protection of nitrogen gas at a temperature of between 1000 and 1600 DEG C for 0.5 to 5 hours, and thus the nanometer carbon fiber is obtained. The diameter of obtained nanometer carbon fiber ranges from 20 to 200 nanometers, the length ranges from 300 nanometers to 50 microns, and the fiber content of the product is up to 60 percent. The method adopts pure solid carbon material, which is widely available, as the carbon source, and the source of the carbon source is exceedingly abundant. The method has the characteristics of safety, cheapness, simpleness and high conversion rate of carbon source, etc., and the method is easy to realize mass production.
Description
Technical field
The present invention relates to a kind of method for preparing carbon nano-fiber, raw material uses solid-state carbon source, and by solid-state carbon source is carried out preliminary treatment, compound and charing is handled and obtained carbon nano-fiber with the transition metal compound catalyst presoma.
Background technology
Carbon nano-fiber is the fibrous nano material with carbon element that is curled and formed by the multilayer graphite flake, and its diameter is at 1nm～100nm, and length is at 0.1～1000 μ m.Carbon nano-fiber also has advantages such as defective is few, specific area is big, electrical and thermal conductivity performance is good, compact structure except the characteristic with common carbon fibers.Can be widely used as catalyst carrier, ion secondary battery cathode material lithium, electrode material for electric double layer capacitor, high-efficiency adsorbent, release agent, enhancing structural material, field emission electron material etc.
At present, people successfully prepare the carbon nano-fiber of different-shape, for example: linear pattern, screw type, flexure type etc.The preparation method of carbon nano-fiber mainly contains arc discharge method, chemical vapour deposition technique (being called for short CVD), flame method, method of electrostatic spinning etc.Arc discharge method is the common method of preparation fullerene and CNT (carbon nano-tube), is used to prepare that carbon nano-fiber exists that yield is low, poor controllability, product purity are low, be difficult to shortcoming such as large-scale production.Chemical vapour deposition technique is the common method of preparation carbon nano-fiber, be catalyst promptly with magnesium-yttrium-transition metal Fe, Co, Ni etc. and their alloy, with lower carbon number hydrocarbons (for example: methane, acetylene, propine, benzene, ethanol etc.) is carbon source, hydrogen is carrier gas, under 600 ℃～1200 ℃, by carbon deposition preparation carbon nano-fiber.As Chai[S.P.Chaiet al, Synthesizing carbon nanotubes and carbon nanofibers oversupported-nickel oxide catalysts via catalytic decomposition ofmethane, Diamond and Related Materials 2007:16:1656-1664] at SiO
2Spraying the Ni powder on the matrix and make catalyst, is carbon source with methane, and hydrogen is carrier gas, reacts under the 550-700 ℃ of hot conditions, obtains diameter and is distributed in 50～80nm, the carbon nano-fiber about length 1 μ m.The employed carbon source of CVD preparation method all is gaseous state or liquid lower carbon number hydrocarbons such as methane, ethene, acetylene, propylene, carbon monoxide, benzene, ethanol, has only the carbon source that contacts with nanocatalyst particles just can be converted into fibrous carbon.There is carbon source conversion ratio low (being generally less than 20%) in this method, and catalyst granules distributes and is difficult to evenly, and the nano-scale fiber proportion is few in the product, always generates with accessory substances such as carbon black, unformed charcoal or CNT (carbon nano-tube).Flame method also is a kind of method for preparing carbon nano-fiber, and it is to utilize gaseous state, liquid hydrocarbon to decomposite carbon when flame combustion, makes it then to be deposited on to obtain carbon nano-fiber on the quartz base plate.For example: R.L.Vander Wal[R.L.Vander Wal et al, flame synthesis of Fe catalyzed single-walled carbonnanotubes and Ni catalyzed nanofibers:growth mechanisms andconsequences, chem.phy.lett.2001:349:178-184] etc. human diffusion flame method make reaction gas with acetylene, hydrogen/helium mix thing is done carrier gas, and nickel is that Preparation of Catalyst goes out carbon nano-fiber.This method complicated operation, severe reaction conditions, and certain risk is arranged, be difficult to obtain target product with high purity.Method of electrostatic spinning is a kind of new method for preparing carbon nano-fiber of reporting in recent years.This method applies several kilovolts high-pressure electrostatic to polymer solution or melt, charged polymer liquid drops in and is accelerated to electric field force under the effect of electric field power and can overcomes surface tension when enough big and form and spray thread and drop on the receiving device, form the fibrofelt of similar cloth shape, fibrofelt through about 250 ℃, 20min in air pre-oxidation and at N
2850 ℃ charing obtains carbon nano-fiber in the atmosphere.[Ko F et al such as Ko F, Electrospinning of continuous carbon nanotube-filled nanofiberyarns, Adv.Mater.2003:15 (14): 1161-1165] prepared polyacrylonitrile (PAN) base nano carbon fibre that diameter is about 50～400nm with method of electrostatic spinning.This method is in the laboratory exploratory stage at present, and a lot of technology and equipment problems are still unresolved, have problems such as equipment requirement height, investment cost height, preparation of spinning solution difficulty, complicated operating process, length consuming time in addition.Therefore, the method for preparing carbon nano-fiber that seek a kind of simple possible, is easy to control is one of emphasis of these direction research and development at present.
Summary of the invention
The purpose of this invention is to provide a kind of carbon nano-fiber simply, preparation method efficiently, its preparation method adopt solid-state carbon source through preliminary treatment and under the effect of transition metal catalyst precursor body high temperature carbonization obtain carbon nano-fiber.
Preparation method's step that the present invention proposes is as follows:
(1) preliminary treatment: carbon source is solid-state carbon source, and solid-state carbon source is graphite, carbon black or active carbon, the average grain diameter of carbon source≤100 micron; Carbon source is carried out preliminary treatment with nitration mixture processing method or grinding processing method, obtain the preliminary treatment thing;
(2) carbon source and metal catalyst precursor bluk recombination: preliminary treatment thing and metal catalyst precursor bluk recombination are obtained compound, the metal catalyst precursor body is chloride, nitrate, acetate or the cyclopentadienyl compound of transition metal, transition metal is Fe, Co or Ni, and the mass percent of Fe, Co or Ni atom and carbon source is 10%～80% in the metal catalyst precursor body;
(3) charing is handled: compound is carried out carbonization reaction under 1000～1600 ℃ of nitrogen protections, be incubated 0.5～5 hour, cool to room temperature and obtain carbon nano-fiber.
The graphite carbon source that the inventive method adopts is behaved and is made graphite, native graphite or expanded graphite.
The pretreated nitration mixture processing method of the inventive method is that carbon source is joined in the mixed solution that volume ratio is 3: 1 the concentrated sulfuric acid and red fuming nitric acid (RFNA), adds thermal agitation 25～200 hours under 80 ℃ of temperature, through filtration, washing, oven dry obtain the preliminary treatment thing.
The pretreated grinding processing method of the inventive method is that carbon source is placed ball mill, and ball milling 24～100 hours obtains the preliminary treatment thing.
The inventive method carbon source and metal catalyst precursor bluk recombination original position additive process: adding metal catalyst precursor body and carbon source are ground in the lump with the grinding processing method preliminary treatment time, obtain compound.
The inventive method carbon source and metal catalyst precursor bluk recombination infusion process: the preliminary treatment product be impregnated in the ethanolic solution that is dissolved with the metal catalyst precursor body, pass through dried again, obtain compound.
The inventive method carbon source is with metal catalyst precursor bluk recombination polishing: the metal catalyst precursor body is ground with the preliminary treatment thing obtain compound.
Preparation method provided by the invention is the growing principle that melts altogether-separate out according to carbon-metal, and the process of reaction is actually the process of a catalyst reduction-nanofiber growth.The nanometer of carbon source and high activity are handled, the metal catalyst precursor body choose and the principle of dissolving each other of metal and carbon is a key of the present invention, the intersolubility of metal and carbon is good more, reactivity is high more, the yield that solid-state carbon source is converted into fiber is high more.
The present invention uses solid-state carbon source, and the raw material source is very abundant, cheap.In preparation process, the pretreated purpose of solid-state carbon source is to make solid-state carbon source grain refine, increases surface functional group and blemish content, improve reactivity with catalyst.Preliminary treatment is the method that adopts nitration mixture processing or milled processed.It is that solid-state carbon source (for example: in the nitric acid of mass concentration 67%) 3: the 1 by volume liquid mixture prepared, handling 25～200 hours under mechanical agitation, 80 ℃ of temperature is continuously joined the concentrated sulfuric acid (for example: mass concentration is 98% sulfuric acid) and red fuming nitric acid (RFNA) that nitration mixture is handled.The purpose that nitration mixture is handled is not only and is made the oxidation of solid-state carbon source appropriateness, and makes the sheet interlayer of carbon produce slip, upsets layer structure, obtains carbon nano microcrystalline (graphene).Nitration mixture pretreatment time in the inventive method is very big to the preparation influential effect, and the too short purpose that does not then reach grain refine, increases surface functional group and defective of nitration mixture processing time causes to be difficult to generate the final goal product; The acidifying reason time is oversize, and then degree of oxidation is too dark, and the oxidized formation carbon dioxide of carbon is overflowed, and causes the final goal product yield to descend.Generally speaking, can use relatively short pretreatment time to the less solid-state carbon source of particle diameter, to particle diameter bigger then need the long period.During the preliminary treatment milled processed, if the particle mean size of solid-state carbon source is big, the milling time that then needs is long, otherwise then short.The too short purpose that does not then reach grain refine, increases blemish of milled processed time; The milled processed time is oversize, and is uneconomical economically.
The metal catalyst precursor body that the present invention uses is transistion metal compound, and metal inorganic compound or the organo-metallic compound of Fe, Co, Ni etc. comprise its chloride, nitrate, acetate, cyclopentadienyl compound etc.These all are commercial chemicals, are that chemical vapour deposition technique is the metal catalyst precursor body commonly used of preparation carbon nano-fiber.The preliminary treatment thing is being mixed with the metal catalyst precursor body in the metal catalyst precursor body and carbon source compound that obtains, and the quality of metallic atoms such as Fe, Co, Ni accounts for 10%～80% of gross weight.The ratio of metal catalyst precursor body is too low, the catalytic activity point in the reaction system very little, that is: the active site of nanofiber growth is unfavorable for the raised growth carbon nano-fiber very little; The ratio of metal catalyst precursor body is too high, and the carbon that the reducing metal consumes is too many, and these improper consumption also are unfavorable for the raised growth carbon nano-fiber; In addition, metal catalyst precursor body adding proportion is too high, and catalyst granules will be easy to reunite and reunion speed can sharply rise and cause the activity of metallic catalyst to reduce.The present invention is by adjusting the usage ratio control carbon source conversion ratio of metal catalyst precursor body, and solid-state carbon source conversion ratio can reach 60%, and the carbon source conversion ratio of chemical vapour deposition technique is generally about 20%.
The present invention mixes with the even of metal catalyst precursor body in order to realize solid-state carbon source, Gu the infusion process of employing and polishing are known solid-liquid or solid-hybrid technology.
In the inventive method; the carbonization reaction that charing is handled is carried out under the nitrogen protection condition; be about to metal catalyst precursor body and carbon source combination product and place high temperature resistance furnace; under inert gas shielding, be warmed up to 1000～1600 ℃; and, reduce the temperature to room temperature again in whole temperature insulation a period of time.According to the growing principle that carbon-metal melts altogether-separates out, heating and temperature-fall period play a part certain to the growth of carbon nano-fiber.In temperature-rise period, metallic compound at first is heated and is decomposed into metal oxide, is the granule with catalytic activity by carbon reduction simultaneously, and carbon and metal congruent melting are melted.In temperature-fall period, carbon incorporate metallic particles and on active crystal face the form with fiber separate out.The carbonization temperature scope that the present invention uses is 1000～1600 ℃.Temperature is too low, and the energy that is provided is less, and catalyst can not liquefy, and does not have catalytic activity, and end-product mainly is the composite of material with carbon element and metallic particles, and the carbon nano-fiber yield is low; Temperature is too high, and catalyst granules will be easy to reunite, and reunion speed can sharply rise and cause activity of such catalysts to reduce, and power consumption is big, to the requirement height of equipment.The temperature retention time scope that the present invention uses is 0.5～5 hour.Temperature retention time is too short, and the energy that is provided is less, and metallic compound decomposes not exclusively, and yield is on the low side; Overlong time, except that generating carbon nano-fiber, the growing amount of on-catalytic agraphitic carbon is also corresponding to be increased, and the purpose product purity is not significantly improved, and time consumption and energy consumption, has improved preparation cost.Suitable temperature retention time is 1 hour.The carbon nano-fiber high orientation growth of this method preparation, and smooth surface, the cross section is rounded, and is thin and even, and the kind that diameter is looked the metal catalyst precursor body is different and different, generally is distributed between 20～200nm, and distribution of lengths is at 300nm～50 μ m.Fiber content can reach 60% at most in the product.This preparation method has carbon source conversion ratio height, characteristics that the fiber selectivity is high.
The inventive method and existing gas, liquid hydrocarbon are that the preparation method of carbon source compares, broken through and used the conventional route of micromolecule as carbon source, and adopt pure solid carbonaceous material as carbon source, the carbon source source is very abundant, have characteristics such as safe, cheap, simple and carbon source conversion ratio height, easily realize large-scale production.
The specific embodiment
Embodiment 1
Present embodiment uses the nitration mixture processing method to the carbon source preliminary treatment, and polishing is used in carbon source and metal catalyst precursor bluk recombination.
Get the Delanium (average grain diameter 20 μ m, carbon content 〉=98%, ash content≤0.01%) of 5g and the concentrated sulfuric acid (mass concentration 98%, the density 1.84g/cm that the 120ml volume ratio is 3: 1
3) and red fuming nitric acid (RFNA) (mass concentration 67%, density 1.42g/cm
3) the blended liquid phase mixing, place there-necked flask, to stir 100 hours down at 80 ℃, centrifugation is cleaned solids, suction filtration repeatedly with deionized water, is neutral until filtrate.Filter residue after the oven dry is a Delanium preliminary treatment thing.Metal catalyst precursor body and function Iron(III) chloride hexahydrate (is analyzed pure, molecular formula: FeCl
36H
2O, with respect to the density of air: 5.61g/cm
3, with respect to the density of water: 2.90g/cm
3).Take by weighing the grinding of 0.50g Delanium preliminary treatment thing and 2.48g Iron(III) chloride hexahydrate and evenly obtain metal catalyst precursor body and carbon source compound, in this compound, the quality of iron atom accounts for 50% of gross mass.Place graphite crucible to send into the horizontal-type high temperature resistance furnace in the lump compound; the high temperature furnace system is vacuumized and charges into the nitrogen of purity 99%; under nitrogen protection, be heated to 1500 ℃ of carbonization temperatures; heating rate is kept 5 ℃/min; be incubated 1 hour down at 1500 ℃; naturally cool to room temperature then, obtain carbon nano-fiber at last, the carbon source conversion ratio is 60%.Confirm that through X-ray diffraction the carbon nano-fiber that obtains has graphite-like structure.The better crystallinity degree of carbon nano-fiber, diffraction maximum position 2 θ of carbon (002) crystal face correspondence=26.321 ° are slightly larger than the graphite characteristic peak.Interlamellar spacing d (002)=0.33832nm is slightly less than ideal graphite d (002) interplanar distance.Through the scanning electron microscope test analysis, find that carbon nano-fiber is divergent shape, high orientation growth and general self assembly bunchy, smooth surface, the cross section is rounded, and it is thin that diameter is about 30nm and even, and distribution of lengths is at 10～50 μ m, and fiber content is 60%.
Embodiment 2
Method of operating is with embodiment 1, and carbon source is used natural graphite powder (average grain diameter 100 μ m, carbon content 〉=95%, ash content≤0.05%) instead, and it is constant to keep all the other conditions, finally obtains diameter and is distributed in 30～50nm, the distribution of lengths carbon nano-fiber at 1～10 μ m.
Embodiment 3
Method of operating is with embodiment 1, and carbon source is used expanded graphite powder (average grain diameter is 20 μ m, and expansion multiplying power is 10 times) instead, and it is constant to keep all the other conditions, finally obtains diameter and is distributed in 30～50 μ m, the distribution of lengths carbon nano-fiber at 2～40 μ m.
Embodiment 4
Method of operating is with embodiment 1, and carbon source is used expanded graphite powder (average grain diameter is 100 μ m, and expansion multiplying power is 60 times) instead, and it is constant to keep all the other conditions, finally obtain diameter about 30nm, distribution of lengths is at the carbon nano-fiber of 1～5 μ m.
Embodiment 5
Method of operating is with embodiment 1, and carbon source is used expanded graphite powder (average grain diameter is 100 μ m, and expansion multiplying power is 85 times) instead, and it is constant to keep all the other conditions, finally obtains diameter and is distributed in 30～50nm, the distribution of lengths carbon nano-fiber at 1～5 μ m.
Embodiment 6
Method of operating is with embodiment 1, and carbon source is used carbon black (average grain diameter is 40nm, carbon content 〉=99%, ash content≤0.03%) instead, and it is constant to keep all the other conditions, finally obtains diameter and is distributed in 20～100nm, the distribution of lengths carbon nano-fiber at 300nm～1 μ m.
Embodiment 7
Method of operating is with embodiment 1, use carbon source instead active carbon (average grain diameter is 50 μ m, carbon content 〉=95%, ash content≤0.05%), it is constant to keep all the other conditions, finally obtains diameter and is distributed in 20～100nm, the distribution of lengths carbon nano-fiber at 300nm～1 μ m.
Embodiment 8
Method of operating is with embodiment 1, and the nitration mixture processing time was reduced to 25 hours by 100 hours, and it is constant to keep all the other conditions, finally obtains diameter about 30nm, and distribution of lengths is at the carbon nano-fiber of 1～20 μ m.
Embodiment 9
Method of operating is with embodiment 1, and the nitration mixture processing time increased to 200 hours by 100 hours, and it is constant to keep all the other conditions, finally obtains diameter and is distributed in 30～50nm, the distribution of lengths carbon nano-fiber at 5～20 μ m.
Embodiment 10
Method of operating is with embodiment 1, change metal catalyst precursor body addition into 0.44g, promptly in ferrous metal catalyst precursor and carbon source compound, the quality of iron atom accounts for 10% of gross mass, it is constant to keep all the other conditions, finally obtain diameter and be distributed in 30～50nm, distribution of lengths is at the carbon nano-fiber of 2～40 μ m.
Embodiment 11
Method of operating is with embodiment 1, change metal catalyst precursor body addition into 5.14g, promptly in ferrous metal catalyst precursor and carbon source compound, the quality of iron atom accounts for 80% of gross mass, it is constant to keep all the other conditions, finally obtain diameter and be distributed in 30～50nm, length range is the carbon nano-fiber of 2～40 μ m.
Embodiment 12
Method of operating is with embodiment 1, and the metal catalyst precursor structural reform (is analyzed pure, molecular formula: Ni (NO with 2.13g nine nitric hydrate nickel
3)
39H
2O, with respect to the density of water: 2.05g/cm
3).The result shows that the diffraction peak of C (002) the face correspondence of the carbon nano-fiber of preparation is changed to 2 θ=26.240 °, d (002)=0.33934nm; Carbon nano-fiber is grown radially, smooth surface, and the cross section is regular hexagonal, and diameter is distributed in 50～200nm, and distribution of lengths is at 2～40 μ m.
Embodiment 13
Method of operating is with embodiment 12, change metal catalyst precursor body addition into 0.77g, promptly in nickel-metal catalyst presoma and carbon source compound, the quality of nickel metallic atom accounts for 18% of gross mass, it is constant to keep all the other conditions, the diameter that finally obtains is distributed in 50～200nm, and distribution of lengths is at the carbon nano-fiber of 2～40 μ m.
Embodiment 14
Method of operating is with embodiment 12, change metal catalyst precursor body addition into 9.86g, promptly in nickel-metal catalyst presoma and carbon source compound, the quality of nickel metallic atom accounts for 80% of gross mass, it is constant to keep all the other conditions, finally obtain diameter and be distributed in 50～200nm, distribution of lengths is at the carbon nano-fiber of 2～40 μ m.
Embodiment 15
Method of operating is with embodiment 1, and the metal catalyst precursor structural reform (is analyzed pure, molecular formula: Co (NO with 2.47g nine nitric hydrate cobalts
3)
29H
2O, with respect to the density of water: 1.87g/cm
3).At this moment, in cobalt metal catalyst precursor body and carbon source compound, the quality of cobalt metallic atom accounts for 50% of gross mass, and it is constant to keep all the other conditions, finally obtains average diameter 50nm, and distribution of lengths is at the carbon nano-fiber of 1～10 μ m.
Embodiment 16
Carbon source and metal catalyst precursor bluk recombination original position additive process.Take by weighing Delanium (the average grain diameter 20 μ m of 0.50g, carbon content 〉=98%, ash content≤0.01%) place the agate jar of ball mill special use with the 2.48g Iron(III) chloride hexahydrate, set 24 hours ball milling time, ball milling is ended to take out and can be obtained metal catalyst precursor body and carbon source compound.The carbonization reaction condition finally obtains diameter and is distributed in 30～50nm with embodiment 1, and distribution of lengths is at the carbon nano-fiber of 1～5 μ m.
Embodiment 17
Method of operating is with embodiment 16, and the ball milling time extended to 100 hours by 24 hours, and it is constant to keep all the other conditions.Finally obtain diameter and be distributed in 30～50nm, distribution of lengths is at the carbon nano-fiber of 1～5 μ m.
Embodiment 18
The metal catalyst precursor body is different with embodiment 1 with the carbon source complex method, and the complex method of metal catalyst precursor body is changed to infusion process by polishing, and the method for operating of all the other preliminary treatment, carbonization reaction is with embodiment 1.Get 100ml ethanolic solution (molecular formula: C
2H
5OH, concentration: 78%, with respect to the density of water: 0.79g/cm
3) pour in the beaker, weighing 2.84g Iron(III) chloride hexahydrate is dissolved in the ethanol, again with 0.5g native graphite (average grain diameter 100 μ m, carbon content 〉=95%, ash content≤0.05%) the preliminary treatment thing impregnated in the above-mentioned solution, left standstill 24 hours, then directly dry ethanolic solution, obtain compound.All the other carbonization reaction operating conditions are identical with embodiment 1, finally obtain diameter and are distributed in 30～50nm, and distribution of lengths is at the carbon nano-fiber of 2～10 μ m.
Embodiment 19
Method of operating is with embodiment 1, and carbonization temperature changes 1000 ℃ into by 1500 ℃, and it is constant to keep all the other conditions.Finally obtain carbon nano-fiber.
Embodiment 20
Method of operating is with embodiment 16, and carbonization temperature changes 1000 ℃ into by 1500 ℃, and it is constant to keep all the other conditions.Finally obtain diameter and be distributed in 30～50nm, distribution of lengths is at a small amount of carbon nano-fiber of 1～5 μ m.
Embodiment 21
Method of operating is with embodiment 1, and carbonization temperature changes 1600 ℃ into by 1500 ℃, and it is constant to keep all the other conditions.Finally obtain average diameter 30nm, distribution of lengths is at the carbon nano-fiber of 1～5 μ m, and fiber content is 40% in the product.
Embodiment 22
Method of operating is with embodiment 1, and the charing temperature retention time changed 0.5 hour into by 1 hour, and it is constant to keep all the other conditions.Prepare average diameter 30nm, the carbon nano-fiber of distribution of lengths about 1～40 μ m.
Embodiment 23
Method of operating is with embodiment 1, and the charing temperature retention time changed 5 hours into by 1 hour, and it is constant to keep all the other conditions.Prepare average diameter 50nm, the carbon nano-fiber of distribution of lengths about 10～50 μ m.
Claims (7)
1, a kind of method for preparing carbon nano-fiber, carbon source are handled through preliminary treatment, with metal catalyst precursor bluk recombination and charing and are obtained carbon nano-fiber, it is characterized in that:
(1) preliminary treatment: carbon source is solid-state carbon source, and solid-state carbon source is: graphite, carbon black or active carbon, and the average grain diameter of carbon source≤100 micron are carried out preliminary treatment with carbon source with nitration mixture processing method or grinding processing method, obtain the preliminary treatment thing;
(2) carbon source and metal catalyst precursor bluk recombination: preliminary treatment thing and metal catalyst precursor bluk recombination are obtained compound, the metal catalyst precursor body is chloride, nitrate, acetate or the cyclopentadienyl compound of transition metal, transition metal is Fe, Co or Ni, and the mass percent of Fe, Co or Ni atom and carbon source is 10%～80% in the metal catalyst precursor body;
(3) charing is handled: compound is carried out carbonization reaction under 1000～1600 ℃ of nitrogen protections, be incubated 0.5～5 hour, cool to room temperature and obtain carbon nano-fiber.
2, method according to claim 1 is characterized in that: graphite is Delanium, native graphite or expanded graphite.
3, method according to claim 1, it is characterized in that: pretreated nitration mixture processing method is that carbon source is joined in the mixed solution that volume ratio is 3: 1 the concentrated sulfuric acid and red fuming nitric acid (RFNA), under 80 ℃ of temperature, added thermal agitation 25～200 hours, obtain the preliminary treatment thing through filtering, wash, drying.
4, method according to claim 1 is characterized in that: pretreated grinding processing method is that carbon source is placed ball mill, and ball milling 24～100 hours obtains the preliminary treatment thing.
5, method according to claim 1 is characterized in that: carbon source and metal catalyst precursor bluk recombination original position additive process: adding metal catalyst precursor body and carbon source are ground in the lump with the grinding processing method preliminary treatment time, obtain compound.
6, method according to claim 1 is characterized in that: carbon source and metal catalyst precursor bluk recombination infusion process: the preliminary treatment thing be impregnated in the ethanolic solution that is dissolved with the metal catalyst precursor body, pass through dried again, obtain compound.
7, method according to claim 1 is characterized in that: carbon source is with metal catalyst precursor bluk recombination polishing: the metal catalyst precursor body is ground with the preliminary treatment thing obtain compound.
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