CN101661839A - Metal fiber-nanometer carbon fiber-carbon aerogel composite material and preparation method and use thereof - Google Patents
Metal fiber-nanometer carbon fiber-carbon aerogel composite material and preparation method and use thereof Download PDFInfo
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Abstract
The invention discloses a metal fiber-nanometer carbon fiber-carbon aerogel composite material and a preparation method and a use thereof, wherein, the material contains metal fiber, nanometer carbonfiber and carbon aerogel; a binding point of the metal fiber is sintered on a tri-dimensional net structure, the nanometer carbon fiber grows on the metal fiber, and the carbon aerogel is coated on the nanometer carbon fiber. The preparation method comprises the following steps: sintering the metal fiber net structure in a large area on a selected thin layer; allowing the nanometer carbon fiber togrow by catalyzing a selected chemical vapor phase deposition method of a carbon-containing compound under a specified condition; then coating a selected organic polymer on the nanometer carbon fiber, and carbonizing the polymer at a certain temperature to obtain the metal fiber-nanometer carbon fiber-carbon aerogel composite material. The material can be taken as an electrode material of a novelchemical power supply; and the material has a self-supporting integral structure without an organic polymer macromolecular binding agent, has a tri-dimensional layered hole structure which is beneficial to ion transmission and storage, and has high electrical conductivity, small internal resistance and good chemical energy storage performance.
Description
Technical field
The present invention relates to a kind of metal fiber-nanometer carbon fiber dimension-carbon aerogel composite material and preparation method thereof, specifically, relate to a kind of thin layer large tracts of land network that makes up by the micron diameter metallic fiber, grow in Nano carbon fibers peacekeeping on the metallic fiber and be coated on composite material that the carbon aerogels on the carbon nano-fiber forms and preparation method thereof, the technical field of function of dominant material and preparation thereof.
Technical background
Lithium battery (LIB) and ultracapacitor mechanism of new electrochemical power sources technology such as (EDLC), owing to have significant superiority at aspects such as energy-saving and environmental protection and carbon emission reductions, the trend as new forms of energy power development breach is day by day clear for a long time.Mechanism of new electrochemical power sources has been put into National Program for Medium-to Long-term Scientific and Technological Development and " Shanghai City medium-term and long-term scientific and technological development planning outline ", becomes the important front edge in the new energy technology that country wants long-run development.
Electrode material is one of key of decision chemical power source performance.The research and development of high performance electrode material are the core topic of chemical power source research field always.Material with carbon element is widely used in mechanism of new electrochemical power sources such as LIB and EDLC.At present, the regulation and control that also concentrate on the material with carbon element of specific texture and brilliant structure mostly of the research of relevant high-performance chemical power supply carbon electrode material are both at home and abroad synthesized and the research aspect of chemical property.CNT (carbon nano-tube) (CNTs) has big length-footpath than characteristics such as, bigger specific area and high conductivity, find that higher EDLC energy-storage property is arranged (＞100F/g) and the reversible discharge capacity of very high LIB (＞500mAh/g).In addition, carbon aerogels (CAGs) is a kind of promising new construction carbon electrode material, because the characteristics of aperture big (2-10nm), being used for EDLC can avoid in the active carbon abundant microporous space " eclipsing effects " takes place and be unfavorable for that (～the problem that 1nm) forms is used for LIB and then helps the quick insertion of Li+ ion and shift out electric double layer.Yet the application of CNTs and CAG but runs into the moulding problem identical with absorbent charcoal powder body, the striding yardstick preparation and still can't break through of adhesive-free.The use of tradition adhesive not only can the sacrificial electrode material specific area in addition destroy the architectural characteristic of material with carbon element, also cause very high charge-conduction resistance and ion transport resistance.
In recent years, around mechanism of new electrochemical power sources carbon electrode new material system, particularly its research of striding the yardstick preparation is gradually active.(Nano Lett. such as Futaba, 2008,8,2437) reported that employing liquid stream induces method that " CNTs jungle " caves in to prepare the block CNTs material of high density, marshalling, because the intrinsic property of CNTs is kept, the electric capacity of this material can reach 80F/g; This method is the cost height not only, and the storage capacitor amount is also lower.Beguin etc. (Adv.Mater., 2005,17,2380.) attempted with CNTs as the structural strengthening agent mix the polyimides colloid again carbonization prepare the large scale carbon aerogels, effect is very limited; Simultaneously, the material of preparation also only reaches 100F/g in the capacitance of 1M H2SO4; Yet CNTs is difficult to realize even the mixing with the polyimides colloid, causes between part carbon aerogels particle the charge transfer blocking-up and causes its utilization ratio lower (being that electric capacity is lower).Kim etc. (Adv.Mater., 2008,20,466.) adopt the bonding CNTs of the crosslinked DNA silk of respinning to prepare the DNA-CNTs composite fibre, and its electric capacity in organic bath reaches～100F/g (CNTs).Wallace etc. (Adv.Mater., 2008,20,566.) have reported the large scale LIB electrode material of direct growth CNTs on a kind of carbon paper, though obtained the reversible discharge capacity up to 572mAh/g, find the stable dispersion preparation difficulty of CNTs.
Summary of the invention
Purpose of the present invention: first technical problem that solve is to propose the metal fiber-nanometer carbon fiber dimension-carbon aerogel composite material that a kind of yardstick is crossed over macroscopic view, microcosmic and nanometer, the thin layer large tracts of land network that it is made up by the micron diameter metallic fiber, grow in the carbon aerogels that the Nano carbon fibers peacekeeping on the metallic fiber is coated on the carbon nano-fiber and form, have the self-supporting overall structure; Need not the organic polymer high polymer binder; The conductivity height, internal resistance is little; Three-dimensional level pore structure with the ion transfer of being beneficial to and storage; The carbon aerogel load amount is big, can reach 80% (weight); Have unique form factor, can make thin layer large tracts of land structure; Characteristics such as be easy to make, manufacturing expense is little.Second technical problem that solves provides a kind of described preparation methods.
The object of the present invention is achieved like this:
A kind of metal fiber-nanometer carbon fiber dimension-carbon aerogel composite material, characteristics are: the thin layer large tracts of land network that this composite material is made up by the micron diameter metallic fiber, grow in the carbon aerogels that the Nano carbon fibers peacekeeping on the metallic fiber is coated on the carbon nano-fiber and form, each composition weight content is in its material: metallic fiber accounts for 10～40%, carbon nano-fiber accounts for 10～40%, carbon aerogels accounts for 20～80%.
At first pass through the method for catalytic chemical gaseous phase deposition (CCVD) at thin layer large-area metal network of fibers superficial growth carbon nano-fiber (CNFs); Secondly use the solution or the made sample of the sol impregnation first step of carbon aerogels precursor, method through the pyrolysis carbonization is assembled into carbon aerogels on the carbon nano-fiber again, form yardstick and cross over macroscopic view, the self-supporting nanometer carbon fiber-carbon aerogel composite material of microcosmic and nanometer.
Now be described in detail the preparation method of described composite material:
A kind of preparation method of metal fiber-nanometer carbon fiber dimension-carbon aerogel composite material comprises following concrete operations step:
The first step: press document (Applied Catalysis A 2007,328:77-82) preparation thin layer large tracts of land sintered metal fiber network structure material, its disk that cuts into certain size is placed the catalytic chemical gaseous phase deposition reactor, after in inert atmosphere, being warmed up to 600～800 ℃, feeding hydrogen contacts with the sintered metal fiber network structure material with carbon source gas, under the autocatalysis of metallic fiber, carbon nano-fiber is in the metallic fiber superficial growth, make metal fiber-nanometer carbon fiber dimension composite material, wherein carbon nano-fiber weight accounts for 10～60% of this material total weight; Metallic fiber is at least a metal or alloy fiber that contains among Fe, Co, the Ni, and diameter is 2～20 microns; The carbon source that the metallic fiber surface generates carbon nano-fiber is carbon monoxide, methane, ethane, propane, ethene, propylene, acetylene, benzene, ethanol, propyl alcohol or butanols; The volume ratio of the hydrogen/carbon source gas that feeds is controlled at 2～7/1, and hydrogen and carbon source gas overall flow rate by every gram sintered metal fiber network structure material are controlled at 100～500 ml/min;
Second step: use the colloidal sol (sodium carbonate that adds trace in mixed solution plays catalytic action) that contains the mixed solution of P-F or p-phenylenediamine (PPD)-pyromellitic dianhydride or contain phenolic resins-P123 high-molecular copolymer, the metal fiber-nanometer carbon fiber dimension composite material of incipient impregnation first step preparation is also after abundant condensation, 800～1100 ℃ of high temperature cabonizations make metal fiber-nanometer carbon fiber dimension-carbon aerogel composite material in inert atmosphere;
Wherein: contain in the mixed solution of P-F, the phenol/formaldehyde mol ratio is 1/2; The phenolic aldehyde weight content is 50～60% of a total solution weight, and phenol/sodium carbonate mol ratio 1/0.005～1/0.01, phenol formaldehyde condensation are reflected at and carried out under 75～95 ℃ 15～30 hours;
Contain in the mixed solution of p-phenylenediamine (PPD)-pyromellitic dianhydride, pyromellitic dianhydride/p-phenylenediamine (PPD) mol ratio is 1/1, and pyromellitic dianhydride and p-phenylenediamine (PPD) weight content are 7～9% of total solution weight; The amine acylation reaction was carried out under 130～280 ℃ 10～20 hours;
In the colloidal sol of phenolic resins-P123 high-molecular copolymer, the phenolic resins weight content is 8～10% of a colloidal sol total weight, P123 high-molecular copolymer weight content is 9～11% of a colloidal sol total weight, and the hot polymerization of phenolic resins carried out under 90～110 ℃ 15～25 hours;
In second step, in the colloidal sol of phenolic resins-P123 high-molecular copolymer-ethyl orthosilicate, the phenolic resins weight content is 8～10% of a colloidal sol total weight, P123 high-molecular copolymer weight content is 9～11% of a colloidal sol total weight, and the ethyl orthosilicate weight content is 11～13% of a colloidal sol total weight; The hot polymerization of phenolic resins carried out under 90～110 ℃ 15～25 hours.
The material that the present invention makes is used for ultracapacitor energy storage as electrode material.Its material has the self-supporting overall structure, need not to adopt the organic polymer high polymer binder to carry out follow-up moulding.
Compared with prior art, the present invention has following remarkable advantage:
(1), have the self-supporting overall structure, need not follow-up moulding.
(2), has the three-dimensional level pore structure that is beneficial to electrolyte appearance storage, ionic conduction and storage.
(3), conductivity of composite material is good, internal resistance is little.
(4), the regulation and control of composite material texture flexibly.
(5), be easy to make, manufacturing expense is little.
Description of drawings
Fig. 1 is the embodiment of the invention 1 materials A ' SEM figure
Fig. 2 is the SEM figure of the embodiment of the invention 1 materials A
Fig. 3 is the SEM figure of the embodiment of the invention 2 material B
Fig. 4 is the SEM figure of the embodiment of the invention 3 material C
Fig. 5 is the SEM figure of the embodiment of the invention 4 material D
Fig. 6 is the SEM figure of Comparative Examples material E of the present invention
Fig. 7 is embodiment of the invention gained materials A, B, C, the D cyclic voltammetry curve figure under 2 millivolts/second voltage scan rate in the 5 mol KOH aqueous solution
Fig. 8 be the embodiment of the invention 2 material B in the 5 mol KOH aqueous solution under 100 millivolts/second voltage scan rate the electric capacity of 1000 cyclic voltammetrics test figure as a result
Fig. 9 is the embodiment of the invention 3 material C cyclic voltammetry curve figure under different voltage scan rate (1,5,10,20 millivolts/second) in 0.1 mol tetraethylammonium hexafluorophosphate acetonitrile solution
Figure 10 be the embodiment of the invention 3 material C in (1) the 5 mol KOH aqueous solution under 100 millivolts/second the voltage scan rate and in (2) 0.1 mol tetraethylammonium hexafluorophosphate acetonitrile solutions under 20 millivolts of/second voltage scan rate the electric capacity of 1000 cyclic voltammetric tests figure as a result
Embodiment
The following examples will be described concrete feature of the present invention, below all embodiment all carry out according to the technical scheme of the invention described above.
The first step: according to document (Applied Catalysis A 2007,328:77-82), with 8 microns of 5 gram diameters, the nickel metallic fiber that length is 3～4 millimeters has prepared 159 millimeters of diameters, the sintrered nickel metallic fiber network structure that thickness is 1 millimeter, cut 8 centimetres of diameters from the material that makes, the disk of weight 1.2 grams, placing internal diameter is 8 centimetres tubular type catalytic chemical gaseous phase deposition reactor, after in nitrogen atmosphere, being warming up to 700 ℃, flow velocity with 400 ml/min feeds ethene/hydrogen (1/4, volume) gaseous mixture and in 700 ℃ the reaction 45 minutes, and then switch to nitrogen and in nitrogen atmosphere, reduce to room temperature, making the Nano carbon fibers dimension hplc is the nickel metal fiber-nanometer carbon fiber dimension composite material of 60% (weight).This material marking is A '.
Second step: the mixed aqueous solution of pressing the proportional arrangement content of organics 55% (weight) of phenol/formaldehyde mol ratio 1/2, ratio in phenol/sodium carbonate mol ratio 1/0.006 adds sodium carbonate in mixed aqueous solution then, fully stir and form the homogeneous phase settled solution, the nickel metal fiber-nanometer carbon fiber dimension composite material that makes with the above-mentioned aqueous solution incipient impregnation of the gained first step was also placed 30 minutes under room temperature, with the composite material repeated impregnations 3 times that makes and in 85 ℃ of baking ovens, place 24h, after making the abundant condensation of phenol-aldehyde generate phenolic resins, soak 6h with acetone again, take out the back kept at room temperature overnight, subsequently this composite material is positioned in the tubular heater, in high-purity N
2Be heated to 950 ℃ and constant temperature 1 hour with 4 ℃/minute heating rate in the atmosphere, make the phenolic resins carbonization form carbon aerogels, promptly get metal fiber-nanometer carbon fiber dimension-carbon aerogel composite material, consisting of of this composite material: nickel fiber 10.5% (weight), carbon nano-fiber 15.7% (weight), carbon aerogels 73.8% (weight).This material marking is A.
In the first step of present embodiment, the fiber of preparation sintered metal fiber network structure material can be 316L stainless steel fibre (iron content, a nickel), the cobalt metallic fiber.
In the first step of present embodiment, the fibre diameter of preparation sintered metal fiber network structure material can be 2～20 μ m.
In the present embodiment first step, the carbon source presoma that generates carbon nano-fiber can be carbon monoxide, methane, ethane, propane, ethene, propylene, acetylene, benzene, ethanol, propyl alcohol, butanols, and the reaction temperature of carrying out catalytic chemical gaseous phase deposition is 600～800 ℃.
In the present embodiment first step, by changing the reaction time of catalytic chemical gaseous phase deposition, the growing amount of carbon nano-fiber can be 10～60% (weight).
In second step of present embodiment, by changing the concentration of dipping number of times and modulation phenol-aldehyde aqueous solution, the growing amount of aeroge can be 5～80% (weight), and carburizing temperature can be 850～1100 ℃.
Except for the following differences, all the other are all with embodiment 1.
In the first step, be that carbon source makes the nickel metal fiber-nanometer carbon fiber dimension composite material that the Nano carbon fibers dimension hplc is 51% (weight) with ethene.
In second step, be solvent with N-methyl-2 pyrrolidones, configuration contains the mixed solution of 8% (weight) pyromellitic dianhydride and p-phenylenediamine (PPD), and wherein pyromellitic dianhydride/p-phenylenediamine (PPD) mol ratio is 1/1.The nickel metal fiber-nanometer carbon fiber dimension composite material that makes with the above-mentioned solution incipient impregnation of the gained first step was also placed 30 minutes under room temperature; with this composite material repeated impregnations 7 times and at room temperature place the back of spending the night the acylation reaction of amine is fully carried out and after generating polyimide resin, in high-purity N
2Be heated to 950 ℃ and constant temperature 1 hour with 4 ℃/minute heating rate in the atmosphere, make the polyimide resin carbonization form carbon aerogels, promptly get metal fiber-nanometer carbon fiber dimension-carbon aerogel composite material; Consisting of of this composite material: nickel fiber 28.7% (weight), carbon nano-fiber 32.3% (weight), carbon aerogels 39.0% (weight).This material marking is B.
Except for the following differences, all the other are all with embodiment 1.
In the first step, be that carbon source makes the nickel metal fiber-nanometer carbon fiber dimension composite material that the Nano carbon fibers dimension hplc is 51% (weight) with ethene.
In second step, take by weighing 0.92 gram phenol, in flask after 45 ℃ of water-bath heat fused, the NaOH solution that adds 0.2 gram 20% earlier, stirred 10 minutes, and sealed after adding 37% formalins of 1.56 grams then, under 70 ℃ of water-baths heating, stirred 1 hour, the gained mixture is regulated pH value to neutrality with the hydrochloric acid solution of 0.2 mol, under the room temperature decompression distillation dewater the phenolic resins solid sample; The gained solid sample joined in the 4.8g absolute ethyl alcohol to stir left standstill 2 hours after 1 minute, get the colloidal sol that the upper strata contains phenolic resins, slowly be added drop-wise in the clear sol of forming by the hydrochloric acid solution and the 1.6 gram P123 organic polymers of 6.5 gram ethanol, 1.0 grams, 0.2 mol, keep sealing at room temperature to stir 2 hours, make the colloidal sol that contains phenolic resins 9.7% (weight) and P123 organic polymer 10.0% (weight).At room temperature flooding first step gained nickel metal fiber-nanometer carbon fiber dimension composite material with made colloidal sol also at room temperature placed 15 minutes, with this composite material repeated impregnations 7 times and after at room temperature placement is spent the night, hot polymerization is 20 hours in 100 ℃ of baking ovens, put into tubular heater after the taking-up, being warming up to 350 ℃ of heat treatments under the nitrogen protection made the decomposition of P123 organic polymer remove in 2 hours, under nitrogen protection, be heated to 950 ℃ and constant temperature 1 hour with 4 ℃/minute heating rate then, make the phenolic resins carbonization form carbon aerogels, promptly get metal fiber-nanometer carbon fiber dimension-carbon aerogel composite material; Consisting of of this composite material: nickel fiber 32.3% (weight), carbon nano-fiber 33.6% (weight), carbon aerogels 34.1% (weight).This product labelling is C.
Embodiment 4
Except for the following differences, all the other are all with embodiment 3.
In second step, in the colloidal sol that contains phenolic resins and P123 organic polymer that makes, add 2.08 gram ethyl orthosilicates (TEOS), at room temperature stirred after the sealing 2 hours, make and contain phenolic resins 8.1% (weight), P123 organic polymer 9.2% (weight) and TEOS 12.0% (weight) colloidal sol, with the made nickel metal fiber-nanometer carbon fiber dimension of made sol impregnation embodiment 3 first steps composite material, other condition is all with 3 second steps of embodiment; The high temperature cabonization sample is removed silicon dioxide with the dissolving of KOH aqueous solution soaking, promptly gets metal fiber-nanometer carbon fiber dimension-carbon aerogel composite material; Consisting of of this composite material: nickel fiber 31.9% (weight), carbon nano-fiber 33.1% (weight), carbon aerogels 35.0% (weight).This material marking is D.
Comparative Examples
Except for the following differences, all the other are all with embodiment 1.
Directly the sintrered nickel metalolic network structural material with first step preparation was used for for second step.Consisting of of material: nickel fiber 38.3% (weight), carbon aerogels 61.7% (weight).This material marking is E.
Comparing result
Adopt scanning electron microscopy (SEM), nitrogen adsorption-desorption, X-ray powder diffraction that surface topography, texture and the architectural characteristic of embodiment sample are characterized.Fig. 1 is embodiment 1 first step materials A ' the SEM photo, as can be seen, the metallic fiber surface has generated the carbon nano-fiber of one deck even compact.Fig. 2 to Fig. 5 is respectively the SEM photo of embodiment materials A, B, C, D, and Fig. 6 is the SEM photo of Comparative Examples material.Find that relatively the carbon aerogels of materials A, B, C, D is fixed in the three-dimensional net structure equably by carbon nano-fiber, simultaneously, kept open macroporous structure; On the contrary, among the comparative example E, owing to be not rooted in the existence of the carbon nano-fiber on metallic fiber surface, be full of cracks takes place and combines not fastening with metallic fiber in the carbon aerogels of generation.Table 1 is the texture and the architectural characteristic of exemplary embodiments material, and the result shows that the carbon aerogels in the composite material has bigger N
2-BET specific area and obvious bigger mesoporous aperture surface area, simultaneously, the carbon aerogels of generation has higher degree of graphitization.
The physico-chemical property of carbon aerogels in the table 1 embodiment material
A is mesoporous: the hole of aperture 2-50nm; The hole of b micropore: aperture＜2nm; The graphite layers distance of (002) crystal face X-ray powder diffraction peak correspondence of c carbon aerogels.
Be electrode material, be electrolyte with the embodiment material, adopt cyclic voltammetry (CV) on CHI660C type electrochemical workstation, to carry out the test of chemical property at the KOH of 5 mol solution.Three-electrode system is selected in test for use: electrode and work electrode are the embodiment material, and reference electrode is a calomel electrode.Fig. 7 is the CV curve of embodiment materials A, B, C, D, and the result shows that under 2 millivolts/second voltage scanning speed, the capacitance of the every gram carbon aerogels that records is all more than 300F.
Capacitance energy storage performance to embodiment 2 material B has been carried out repeatedly loop test, and the voltage scan rate of selecting for use is 100 millivolts/second, and other condition is with test case 1.Fig. 8 is 1000 loop test results, and as can be seen, after preceding 300 circulations, capacitance has reduced by 10%, and in 700 times follow-up tests, capacitance has only descended 3%, has good stable.
Adopt the CA method on CHI660C type electrochemical workstation, to test to the capacitive property of embodiment 3 material C in the tetraethylammonium hexafluorophosphate acetonitrile solution of 0.1 mol.Three-electrode system is selected in test for use: electrode and work electrode are the embodiment material, and reference electrode is a calomel electrode.Fig. 9 be different voltage scan rate (1 millivolt/second, 5 millivolts/second, 10 millivolts/second, 20 millivolts/second) under the CV curve, as can be seen, every gram carbon aerogels can obtain the capacitance up to 160F in organic bath, simultaneously, with the increase of voltage scan rate, the capacitance decay is also not obvious.
Test case 4
To embodiment 3 material C respectively the capacitive property in the tetraethylammonium hexafluorophosphate acetonitrile solution of 5 mol KOH solution and 0.1 mol carried out repeatedly loop test, the voltage scan rate of selecting for use: being 20 millivolts/second in the organic bath, is 100 millivolts/second in the inorganic electrolyte.Adopt the CA method on CHI660C type electrochemical workstation, to test.Three-electrode system is selected in test for use: electrode and work electrode are the embodiment material, and reference electrode is a calomel electrode.Figure 10 is 1000 loop test results, and as can be seen, after 1000 circulations, no matter at organic bath or in inorganic electrolyte, the attenuation amplitude of capacitance all is lower than 10%, has good stability.
Claims (3)
1, a kind of metal fiber-nanometer carbon fiber dimension-carbon aerogel composite material, it is characterized in that: the thin layer large tracts of land network that this composite material is made up by the micron diameter metallic fiber, grow in the carbon aerogels that the Nano carbon fibers peacekeeping on the metallic fiber is coated on the carbon nano-fiber and form, each composition weight content is in its material: metallic fiber accounts for 10～40%, carbon nano-fiber accounts for 10～40%, carbon aerogels accounts for 20～80%.
2, the preparation method of the described composite material of a kind of claim 1 is characterized in that: this method comprises following concrete operations step:
The first step: with thin layer large tracts of land sintered metal fiber network structure material, after in inert atmosphere, being warmed up to 600～800 ℃, feeding hydrogen contacts with the sintered metal fiber network structure material with carbon source gas, under the autocatalysis of metallic fiber, carbon nano-fiber is in the metallic fiber superficial growth, make metal fiber-nanometer carbon fiber dimension composite material, wherein carbon nano-fiber weight accounts for 10～60% of this material total weight;
Second step: with containing the mixed solution of P-F or p-phenylenediamine (PPD)-pyromellitic dianhydride or containing phenolic resins-P123 high-molecular copolymer or the colloidal sol of phenolic resins-P123 high-molecular copolymer-ethyl orthosilicate, the metal fiber-nanometer carbon fiber dimension composite material of incipient impregnation first step preparation is also after abundant condensation, 800～1100 ℃ of high temperature cabonizations make metal fiber-nanometer carbon fiber dimension-carbon aerogel composite material in inert atmosphere;
Wherein:
In the first step, metallic fiber contains at least a among Fe, Co, the Ni, and the metallic fiber diameter is 2～20 microns;
During the first step and second went on foot, the inert gas in the inert atmosphere was nitrogen, argon gas, helium or carbon dioxide;
In the first step, the carbon source that the metallic fiber surface generates carbon nano-fiber is carbon monoxide, methane, ethane, propane, ethene, propylene, acetylene, benzene, ethanol, propyl alcohol or butanols; In the first step, the volume ratio of hydrogen/carbon source gas is controlled at 2～7/1, and hydrogen and carbon source gas overall flow rate by every gram sintered metal fiber network structure material are controlled at 100～500 ml/min;
In second step, contain in the mixed solution of P-F, the phenol/formaldehyde mol ratio is 1/2; The phenolic aldehyde weight content is 50～60% of a total solution weight, and phenol formaldehyde condensation is reflected at and carried out under 75～95 ℃ 15～30 hours;
In second step, contain in the mixed solution of p-phenylenediamine (PPD)-pyromellitic dianhydride, pyromellitic dianhydride/p-phenylenediamine (PPD) mol ratio is 1/1, and pyromellitic dianhydride and p-phenylenediamine (PPD) weight content are 7～9% of total solution weight; The amine acylation reaction was carried out under 130～280 ℃ 10～20 hours;
In second step, in the colloidal sol of phenolic resins-P123 high-molecular copolymer, the phenolic resins weight content is 8～10% of a colloidal sol total weight, and P123 high-molecular copolymer weight content is 9～11% of a colloidal sol total weight, and the hot polymerization of phenolic resins carried out under 90～110 ℃ 15～25 hours;
In second step, in the colloidal sol of phenolic resins-P123 high-molecular copolymer-ethyl orthosilicate, the phenolic resins weight content is 8～10% of a colloidal sol total weight, P123 high-molecular copolymer weight content is 9～11% of a colloidal sol total weight, and the ethyl orthosilicate weight content is 11～13% of a colloidal sol total weight; The hot polymerization of phenolic resins carried out under 90～110 ℃ 15～25 hours.
3, the purposes of the described composite material of a kind of claim 1 is characterized in that this material is used for ultracapacitor energy storage as electrode material.
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