CN101397652B - Metal microfiber-nano carbon composite material and preparation method - Google Patents
Metal microfiber-nano carbon composite material and preparation method Download PDFInfo
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- CN101397652B CN101397652B CN2008102021134A CN200810202113A CN101397652B CN 101397652 B CN101397652 B CN 101397652B CN 2008102021134 A CN2008102021134 A CN 2008102021134A CN 200810202113 A CN200810202113 A CN 200810202113A CN 101397652 B CN101397652 B CN 101397652B
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Abstract
The invention discloses a metal microfiber-nano-carbon composite material. The material takes integral sintered metal microfiber as a matrix and is obtained by carbon deposition on the surface of the matrix; wherein, the obtained material contains 1 percent to 65 percent of carbon and 35 percent to 99 percent of the metal microfiber according to weight ratio. The material needs no agglomerant, has 3-d open pore structure, excellent electric conductivity and thermal conductivity, wide application prospect in the electrochemistry, catalytic field and other fields and can be prepared on a large area, with low cost.
Description
Technical field
The present invention relates to the material technology field, particularly a kind of high surface area monobloc(k)type sintering metal fento-nano carbon composite material and preparation method with open bore structure.
Background technology
Nano-sized carbon is as the carbon-based material of a new generation, because the polytropy and the controllability of its microstructure and surperficial physico-chemical property have great application prospect at aspects such as heterogeneous catalyst, electrocatalysis, electrode materialss.New energy conversion and memory technology such as fuel cell, secondary cell and ultracapacitor etc. have evoked the research boom of people to nano-sized carbon (particularly carbon nanotube) to the expectation of high performance carbon electrode/electro catalytic material.Since the nineties in last century; People are synthetic to the controllable structure of CNT, microcell and surface properties regulation and control, growth mechanism and application start extensive and deep research; Feasible relation to CNT microstructure-surperficial physico-chemical property-application performance has had very deep understanding, and this has established solid theories and technical foundation for the application of CNT.
Yet, but run into the moulding problem identical in its practical application with the absorbent charcoal powder body material.Such as, the requirement of the application counter electrode material of super capacitor or the sub technology of purifying waste water of electric capacity disengaging etc. is: satisfactory electrical conductivity; Bigger effective ratio area; The open bore structure of reinforcing mass transfer; Good chemistry and electrochemical stability; Be prone to be shaped.The electrode that adopts carbon nano fiber to make; Generally need macromolecule adhesive; And macromolecule adhesive not only can the sacrificial electrode material specific surface area; Also cause very high conduction of current and mass transfer resistance (receive the obstruct of macromolecule adhesive, the contact between the carbon nano fiber is not tight successive, causes very high resistance); Simultaneously, the increase of thickness of electrode and stacking bed big potential difference.Charcoal-aero gel is a kind of lightweight, porous, nano level amorphous carbon material, has bigger specific surface area and good electrical conductivity, but this material price is expensive, big area one-piece construction electrode preparation difficulty big (Advanced Materials, 20 (2008) 815).NACF (10～13 millimeters of diameters) cloth, owing to can process the form of paper, cloth, felt as required and be easy to folding forming, and caused people's attention; But its abundant microporous is prone to cause the space that " eclipsing effect " takes place and is unfavorable for the formation of electrostatic double layer.
There is bibliographical information (Appl.Phys.Lett.89 (2006) 053127/1-053127/3) on nickel foil, to adopt chemical vapour deposition technique growing nano-tube carbon and is used for the electric capacity desalination; The loading capacity of unit weight is identical with charcoal-aero gel, and the loading capacity of unit volume is 100 times and hundreds of times of the latter; But the one-dimensional plane structure of this material is unfavorable for radially mass transfer etc.Bordjiba etc. (Chem.Phys.Lett.441 (2007) 88-93) have reported the carbon paper material that a kind of multi-walled carbon nano-tubes is modified; But carbon nanotube (CNTs) loading amount is limited, and between carbon nanotube (CNTs) and carbon paper and be unrealized " fusion " contact and cause high impedance.Renken etc. (Surf.Coatings Technol.202 (2008) 3029-3042) are being coated with La
2NiO
4Carry out methane cracking on the 304 stainless steel gauzes of film (200 microns of netting twine diameters) and prepared the thomel/carbon ball that is bonded on the gauze.
Summary of the invention
A kind of high surface area monobloc(k)type sintering metal fento-nano carbon composite material with open bore structure that the objective of the invention is to be directed against the deficiency of prior art and provide, it need not sticker, has three-dimensional open pore structure, good conductive, thermal conductivity.
The concrete technical scheme that realizes the object of the invention is:
A kind of metal fento-nano carbon composite material, this material are to be matrix with monobloc(k)type sintering metal fento, get to this matrix surface deposit carbon; Wherein: gained material carbon containing is 1～65%, and the containing metal fento is 35～99%, and carbon is nano level; Said content is weight percentage.
Said metal fento is nickel, cobalt, iron or ferruginous metal alloy fento.
Said carbon source is alkane, alkene, alkynes, low-carbon alcohol or carbon monoxide.
A kind of preparation method of above-mentioned matrix material; Get monobloc(k)type sintering metal fento and place reactor drum; High purity nitrogen purges under the room temperature, in nitrogen, is warming up to 700 ℃, switches to carbon source and hydrogen and mixes; Carbon source flow wherein: gas 50～100 ml/min, liquid 0.1～0.15 ml/min, hydrogen flow rate 300 ml/min; Under 700 ℃, carbon source is at monobloc(k)type sintering metal fento surface deposition carbon; The time that feeds carbon source and hydrogen was controlled at 2～60 minutes, switched to high pure nitrogen afterwards and fully purged, and in nitrogen atmosphere, reduce to room temperature, made nanocarbon-metal fento matrix material.
The present invention has the following advantages:
(1) need not sticker, have three-dimensional open pore structure, make the nano-sized carbon surface elevation can near and its surface property be able to keep.
(2) can large-area preparation, and can directly use and post-modification.
(3) favorable conductive/heat conductivility makes this material have broad prospect of application in fields such as electrochemistry, catalysis.
(4) be easy to make, manufacturing expense is little.
Description of drawings
Fig. 1 is the optical picture of monobloc(k)type sintering Ni metal fento matrix
Fig. 2 is the SEM figure of monobloc(k)type sintering Ni metal fento matrix
Fig. 3 is the optical picture of embodiment 2 nano-sized carbon-Ni metal fento matrix material
Fig. 4 is the SEM figure of embodiment 2 nano-sized carbon-Ni metal fento matrix material
Fig. 5 is the TEM figure of embodiment 2 nano-sized carbon-Ni metal fento matrix material
Fig. 6 is the TEM figure of embodiment 5 nano-sized carbon-Ni metal fento matrix material
Fig. 7 is the SEM figure of embodiment 10 nano-sized carbon-Ni metal fento matrix material
Fig. 8 is the TEM figure of embodiment 13 nano-sized carbon-Ni metal fento matrix material
Fig. 9 is the TEM figure of embodiment 15 nano-sized carbon-Ni metal fento matrix material
Figure 10 is the SEM figure of embodiment 18 nano-sized carbon-SS-316L metal fento matrix material
Embodiment
Following embodiment will specifically describe the present invention:
It at first is the preparation of monobloc(k)type sintering metal fento matrix
Adopt papermaking/back sintering technology, preparation has the sintering metal microfibrillar structure matrix of big voidage, tridimensional network, specifically prepares process reference literature (Appl.Catal.A2007,328:77; AIChEJ2007,53:1845); Steel fiber is respectively: the Ni fiber of 8 micron diameters, 12 microns stainless steel (alloy, SS-316L) the Al fiber of the Fe fiber of the Co fiber of the Cu fiber of fiber, 8 micron diameters, 8 micron diameters, 8 micron diameters and 8 micron diameters; The sintering process for preparing whole big area microfibrillar structure is carried out in nitrogen atmosphere, and sintering temperature is respectively: 950 ℃, and 1100 ℃, 900 ℃, 950 ℃, 1000 ℃ and 650 ℃.
The monobloc(k)type sintering metal fento matrix that makes is expressed as respectively: SF
Ni, SF
SS, SF
Cu, SF
Co, SF
FeAnd SF
AlThe thickness of sintering metal fento matrix is that 5 millimeters, voidage are respectively 90% (volume), 85% (volume), 80% (volume), 93% (volume), 73% (volume) and 75% (volume).
Sintering Ni metal fento matrix SF
NiOptics and ESEM (SEM) figure consult Fig. 1 and Fig. 2.
Embodiment 1-3
Cut the sintering Ni metal fento matrix SF of 8.5 centimetres of diameters
Ni, as for the quartz tube reactor of 8.5 centimetres of internal diameters, high purity nitrogen purges with abundant displaced air under the room temperature; In nitrogen, be warming up to 700 ℃ then, switch to ethene/hydrogen mixed air, therein ethylene flow 100 ml/min, hydrogen flow rate 300 ml/min; Under 700 ℃, ethene is at SF
NiKatalysis decompose down and at Ni metal fento matrix surface deposit carbon; The time that control feeds ethene/hydrogen mixed air was respectively 2 minutes, 30 minutes and 60 minutes, switched to high pure nitrogen afterwards and fully purged and in nitrogen atmosphere, be cooled to room temperature and make nano-sized carbon-Ni metal fento matrix material, was designated as NC-SF respectively
Ni-1, NC-SF
Ni-2 and NC-SF
Ni-3, its carbon laydown amount is respectively 1% (weight), 52% (weight) and 62% (weight).
NC-SF
Ni-2 optics, ESEM (SEM) and transmission electron microscope (TEM) figure consult Fig. 3, Fig. 4 and Fig. 5; Visible by Fig. 4 and Fig. 5, nano-sized carbon mainly is that diameter is the carbon nanotube of 50～60 nanometers, and end-blown.
Embodiment 4-8
Except that following difference, other condition is all with embodiment 2.
Replace ethene with carbon monoxide, methane, ethane, propane and butane respectively; When adopting methane to be carbon source, control reaction temperature is 750 ℃; When adopting propane and butane to be carbon source, its gas flow rate is 50 ml/min.
The nano-sized carbon that makes-Ni metal fento matrix material is designated as NC-SF respectively
Ni-4, NC-SF
Ni-5, NC-SF
Ni-6, NC-SF
Ni-7 and NC-SF
Ni-8, its carbon laydown amount is respectively 35% (weight), 44% (weight), 49% (weight), 52% (weight) and 56% (weight).
NC-SF
Ni-5 transmission electron microscope (TEM) figure consults Fig. 6, and visible by Fig. 6, existing carbon nanotube has decolorizing carbon again.
Embodiment 9-11
Except that following difference, other condition is all with embodiment 2.
Replace ethene with acetylene, propylene and butylene respectively; When adopting propylene and butylene to be carbon source, its gas flow rate is 50 ml/min.
The nano-sized carbon that makes-Ni metal fento matrix material is designated as NC-SF respectively
Ni-9, NC-SF
Ni-10 and NC-SF
Ni-11, its carbon laydown amount is respectively 55% (weight), 53% (weight) and 58% (weight).
NC-SF
Ni-10 ESEM (SEM) figure consults Fig. 7, and is visible by Fig. 7, generation be nano carbon microsphere.
Embodiment 12-15
Except that following difference, other condition is all with embodiment 2.
Replace ethene with methyl alcohol, ethanol, propyl alcohol and butanols respectively, its liquid feeding flow velocity is respectively 0.15 ml/min, 0.12 ml/min, 0.13 ml/min and 0.1 ml/min.
The nano-sized carbon that makes-Ni metal fento matrix material is designated as NC-SF respectively
Ni-12, NC-SF
Ni-13, NC-SF
Ni-14 and NC-SF
Ni-15, its carbon laydown amount is respectively 35% (weight), 44% (weight), 40% (weight) and 43% (weight).
NC-SF
Ni-13 and NC-SF
Ni-15 transmission electron microscope (TEM) figure consults Fig. 8 and Fig. 9, and is visible by Fig. 8 and Fig. 9, NC-SF
NiWhat generate on-13 mainly is the vermiform nanometer carbon line of the superimposed growth of sheet carbon, NC-SF
NiOn-15 with the master that is generated as of Nano carbon fibers peacekeeping vermiform carbon.
Embodiment 16-17
Except that following difference, other condition is all with embodiment 2.
With sintering Ni metal fento matrix SF
NiIn the aluminum nitrate solution of 60 ℃ 0.5 mol, magnesium nitrate aqueous solution, soak after 60 minutes, through the SF of the modification of 200 ℃ of bakings
NiMatrix also is used to prepare nano-sized carbon-Ni metal fento matrix material; The matrix material that makes is designated as NC-SF respectively
Ni-16 and NC-SF
Ni-17, its carbon laydown amount is 60% (weight), 63% (weight).
Embodiment 18
Except that following difference, other condition is all with embodiment 2.
With sintering SS-316L (stainless steel) metal fento matrix SF
SSReplace agglomerating Ni fento matrix SF
Ni, the temperature of reaction of catalytic deposition carbon is 750 ℃ in ethene/hydrogen mixed air.
The nano-sized carbon that makes-SS-316L metal fento matrix material is designated as NC-SF
SS-1, its carbon laydown amount is 49% (weight).
NC-SF
SS-1 ESEM (SEM) figure consults Figure 10, and is visible by Figure 10, generation be the mixture of irregular nano carbon particle and CNT.
Embodiment 19-20
Except that following difference, other condition is all with embodiment 2.
With sintering Co, Fe metal fento matrix SF
Co, SF
FeReplace agglomerating Ni metal fento matrix.
The nano-sized carbon metal fento matrix material that makes is designated as NC-SF
Co-1, NC-SF
Fe-1, its carbon laydown amount is 51% (weight), 53% (weight).
Embodiment 21-22
Except that following difference, other condition is all with embodiment 2.
With sintering Cu, Al metal microfibrillar structure matrix SF
Cu, SF
AlReplace agglomerating Ni metal fento matrix, and with the growth that is used for nano-sized carbon after the nickel nitrate aqueous solution incipient impregnation of 1 mol, oven dry, the 550 ℃ of roastings.
The nano-sized carbon metal fento matrix material that makes is designated as NC-SF
Cu-1, NC-SF
Al-1, its carbon laydown amount is 51% (weight), 52% (weight).
Embodiment 23-24
Nano-sized carbon-Ni metal fento matrix material NC-SF with embodiment 2
Ni-2 with nano-sized carbon-Ni metal fento matrix material NC-SF of embodiment 13
Ni-13 for working electrode and counter electrode, dried mercury electrode are the three-electrode electro Chemical system of reference electrode, uses the potassium hydroxide aqueous solution of 5 mol to be electrolytic solution, the employing cyclic voltammetry its electrochemical capacitor amount; When potential scan speed was 2 millivolts/second, the electrical capacity that records was respectively 47 faraday/grams (carbon) and 70 faraday/grams (carbon).
Claims (4)
1. metal fento-nano carbon composite material is characterized in that: this material is to be matrix with monobloc(k)type sintering metal fento, gets to this matrix surface deposit carbon; Wherein: gained material carbon containing is 1～65%, and the containing metal fento is 35～99%; Said content is weight percentage; Said nano-sized carbon is that existing carbon nanotube has indefiniteness carbon, nano carbon microsphere again or mainly is the vermiform nanometer carbon line of the superimposed generation of sheet carbon.
2. matrix material according to claim 1 is characterized in that said metal fento is nickel, cobalt, iron or ferruginous metal alloy fento.
3. matrix material according to claim 1 is characterized in that said carbon source is alkane, alkene, alkynes, low-carbon alcohol or carbon monoxide.
4. matrix material according to claim 1; It is characterized in that this preparation methods is: get monobloc(k)type sintering metal fento and place reactor drum; High purity nitrogen purges under the room temperature, in nitrogen, is warming up to 700 ℃, switches to carbon source and hydrogen and mixes; Carbon source flow wherein: gas 50～100 ml/min, liquid 0.1～0.15 ml/min, hydrogen flow rate 300 ml/min; Under 700 ℃, carbon source is at monobloc(k)type sintering metal fento surface deposition carbon; The time that feeds carbon source and hydrogen was controlled at 2～60 minutes, switched to high pure nitrogen afterwards and fully purged, and in nitrogen atmosphere, reduce to room temperature, made nanocarbon-metal fento matrix material.
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| CN107321349A (en) * | 2017-06-26 | 2017-11-07 | 华南理工大学 | A kind of fento coated carbon nano-tube composite material of carried metal active component and its preparation and application |
| CN109309203A (en) * | 2017-07-26 | 2019-02-05 | 中能中科（天津）新能源科技有限公司 | Nano carbon particle-stephanoporate framework composite material, its lithium metal compound, their preparation method and application |
| CN109309200B (en) | 2017-07-26 | 2021-02-26 | 中能中科（天津）新能源科技有限公司 | Metal lithium-framework carbon composite material with hydrophobic coating layer, and preparation method and application thereof |
| CN111755261A (en) * | 2020-07-09 | 2020-10-09 | 浙江奚态生物科技有限公司 | Preparation method of silver nanowire doped nano carbon ball electrode material |
| CN113201362A (en) * | 2021-05-07 | 2021-08-03 | 中国石油化工股份有限公司 | Method for preparing alkylate oil by sulfuric acid catalysis |
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