CN101397652A - 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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- CN101397652A CN101397652A CNA2008102021134A CN200810202113A CN101397652A CN 101397652 A CN101397652 A CN 101397652A CN A2008102021134 A CNA2008102021134 A CN A2008102021134A CN 200810202113 A CN200810202113 A CN 200810202113A CN 101397652 A CN101397652 A CN 101397652A
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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 monoblock 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 (carbon nano-tube), microcell and surface properties regulation and control, growth mechanism and application start extensive and deep research, feasible relation to CNT (carbon nano-tube) 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 (carbon nano-tube).
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; Easily 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 (to be subjected to the obstruct of macromolecule adhesive, 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).Activated carbon fiber (10～13 millimeters of diameters) cloth, owing to can make the form of paper, cloth, felt as required and be easy to folding forming, and caused people's attention; But its abundant microporous easily causes 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 carbon fiber/carbon ball that is bonded on the gauze.
Summary of the invention
A kind of high surface area monoblock type sintering metal fento-nano carbon composite material with open bore structure of providing at the deficiencies in the prior art is provided, and it need not binding agent, 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 monoblock 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; Described content is weight percentage.
Described metal fento is nickel, cobalt, iron or ferruginous metal alloy fento.
Described carbon source is alkane, alkene, alkynes, low-carbon alcohol or carbon monoxide.
A kind of preparation method of above-mentioned matrix material, get monoblock type sintering metal fento and place reactor, high purity nitrogen purges under the room temperature, in nitrogen, be warming up to 700 ℃, it is mixed to switch to carbon source and hydrogen, 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 monoblock 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 reduce to room temperature in nitrogen atmosphere, made nanocarbon-metal fento matrix material.
The present invention has the following advantages:
(1) need not binding agent, have three-dimensional open pore structure, make the nano-sized carbon surface elevation can near and its surface property kept.
(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 monoblock type sintering Ni metal fento matrix
Fig. 2 is the SEM figure of monoblock 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
The following examples will specifically describe the present invention:
It at first is the preparation of monoblock type sintering metal fento matrix
Adopt papermaking/back sintering technology, preparation has the sintering metal microfibrillar structure matrix of big voidage, tridimensional network, and (Appl.Catal.A 2007,328:77 for concrete preparation process reference literature; AIChEJ 2007,53:1845); 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 monoblock 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 scanning electron microscope (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 be cooled to room temperature make nano-sized carbon-Ni metal fento matrix material in nitrogen atmosphere, 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, scanning electron microscope (SEM) and transmission electron microscope (TEM) figure consult Fig. 3, Fig. 4 and Fig. 5; By Fig. 4 and Fig. 5 as seen, nano-sized carbon mainly is that diameter is the carbon nanotube of 50～60 nanometers, and end-blown.
Embodiment 4-8
Except for the following differences, 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 as seen from Figure 6, existing carbon nanotube has decolorizing carbon again.
Embodiment 9-11
Except for the following differences, 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 scanning electron microscope (SEM) figure consults Fig. 7, as seen from Figure 7, generation be nano carbon microsphere.
Embodiment 12-15
Except for the following differences, 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, by Fig. 8 and Fig. 9 as seen, and 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 for the following differences, 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 for the following differences, 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 scanning electron microscope (SEM) figure consults Figure 10, as seen from Figure 10, generation be the mixture of irregular nano carbon particle and CNT (carbon nano-tube).
Embodiment 19-20
Except for the following differences, 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 for the following differences, 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 and 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, are electrolytic solution with the potassium hydroxide aqueous solution of 5 mol, 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, a kind of metal fento-nano carbon composite material is characterized in that: this material is to be matrix with monoblock 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%; Described content is weight percentage.
2, matrix material according to claim 1 is characterized in that described metal fento is nickel, cobalt, iron or ferruginous metal alloy fento.
3, matrix material according to claim 1 is characterized in that described carbon source is alkane, alkene, alkynes, low-carbon alcohol or carbon monoxide.
4, the preparation method of the described matrix material of a kind of claim 1, it is characterized in that: get monoblock type sintering metal fento and place reactor, high purity nitrogen purges under the room temperature, in nitrogen, be warming up to 700 ℃, it is mixed to switch to carbon source and hydrogen, 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 monoblock 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 reduce to room temperature in nitrogen atmosphere, made nanocarbon-metal fento matrix material.
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Cited By (5)
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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 |
| WO2019019412A1 (en) * | 2017-07-26 | 2019-01-31 | 中能中科（天津）新能源科技有限公司 | Carbon nanoparticle-porous framework composite material, lithium metal complex of carbon nanoparticle-porous framework composite material, preparation methods therefor, and applications thereof |
| JP6810841B1 (en) * | 2020-07-09 | 2021-01-13 | 浙江研基科技有限公司 | Method for manufacturing carbon nanoball electrode material of silver nanowires |
| 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 |
| US11462741B2 (en) | 2017-07-26 | 2022-10-04 | China Energy Cas Technology Co., Ltd. | Metallic lithium-skeleton carbon composite material having a hydrophobic cladding layer, preparation method and use thereof |
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- 2008-10-31 CN CN2008102021134A patent/CN101397652B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| WO2019019412A1 (en) * | 2017-07-26 | 2019-01-31 | 中能中科（天津）新能源科技有限公司 | Carbon nanoparticle-porous framework composite material, lithium metal complex of carbon nanoparticle-porous framework composite material, preparation methods therefor, and applications thereof |
| 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 |
| JP2020509566A (en) * | 2017-07-26 | 2020-03-26 | 中能中科（天津）新能源科技有限公司 | Nanocarbon particles-porous skeletal composites, their lithium metal composites, their preparation methods and applications |
| US11462741B2 (en) | 2017-07-26 | 2022-10-04 | China Energy Cas Technology Co., Ltd. | Metallic lithium-skeleton carbon composite material having a hydrophobic cladding layer, preparation method and use thereof |
| US11866332B2 (en) | 2017-07-26 | 2024-01-09 | China Energy Cas Technology Co., Ltd. | Carbon nanoparticle-porous skeleton composite material, its composite with lithium metal, and their preparation methods and use |
| JP6810841B1 (en) * | 2020-07-09 | 2021-01-13 | 浙江研基科技有限公司 | Method for manufacturing carbon nanoball electrode material of silver nanowires |
| JP2022022930A (en) * | 2020-07-09 | 2022-02-07 | 浙江研基科技有限公司 | Preparation method for carbon nanosphere electrode material containing silver nanowire |
| 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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