CN104269277A - Porous carbon nanometer chain material and preparing method thereof - Google Patents
Porous carbon nanometer chain material and preparing method thereof Download PDFInfo
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- CN104269277A CN104269277A CN201410497054.3A CN201410497054A CN104269277A CN 104269277 A CN104269277 A CN 104269277A CN 201410497054 A CN201410497054 A CN 201410497054A CN 104269277 A CN104269277 A CN 104269277A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910003271 Ni-Fe Inorganic materials 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000010453 quartz Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 235000019441 ethanol Nutrition 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 50
- 229910052786 argon Inorganic materials 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 2
- 241000234282 Allium Species 0.000 abstract 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 abstract 1
- 229910016870 Fe(NO3)3-9H2O Inorganic materials 0.000 abstract 1
- 229910018590 Ni(NO3)2-6H2O Inorganic materials 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000002041 carbon nanotube Substances 0.000 description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 229940101209 mercuric oxide Drugs 0.000 description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a porous carbon nanometer chain material and a preparing method thereof. The porous carbon nanometer chain material is of a chain structure formed by connecting carbonilike nanometer onion units in series. Chain link units are of a hollow ellipsoid structure, and a carbon layer at the joint of every two adjacent chain link units is in a non-closed state. The preparing process comprises the steps that a Fe(NO3)3 9H2O, Ni(NO3)2 6H2O and MgO ethanol solution is prepared, the ethyl alcohol is steamed out, Ni-Fe/MgO powder is obtained through grinding, the powder is heated stage by stage in a quartz tube type furnace and is reacted with a carbon source gas to generate the carbon nanometer chain material wrapping Ni-Fe alloy, the carbon nanometer chain material is mixed with KOH to be ground to obtain the KOH/C mixture, and the porous carbon nanometer chain material is obtained through roasting, washing and drying. The process is simple, the prepared porous carbon nanometer chain material serves as an electrode material of a supercapacitor, and the high electrochemistry performance is achieved.
Description
Technical field
The present invention relates to a kind of porous carbon nano chain material and preparation method thereof, belong to carbon nanomaterial technology.
Background technology
Carbon nanomaterial, owing to having large specific area, suitable pore size distribution, good conductivity and good stability, in fields such as composite material, lithium ion battery and ultracapacitors, have a good application prospect, therefore obtain the extensive concern of researchers.Conventional carbon nanomaterial has carbon nano-onions, carbon nano-tube, Graphene etc.Carbon nano-onions (Carbon nano-onions, CNOs, also known as nano cages, onion-like fullerene) Spectra of Carbon Clusters that is made up of some layers of concentric graphitic layer spherical shell, the carbon nano-tube of its to be the equal of draw ratio be 1:1, it is a kind of special shape of carbon nano-tube, first reported in 1992 by Switzerland scientist Ugarte, its shell spacing is about 0.34 nm.Carbon nano-tube (Carbon Nanotubes, CNTs) can be regarded as the curling sealed tube of graphite flake Alongfixedvector, by Japanese scholars Iijima in Late Cambrian in 1991.As the allotrope of carbon, due to carbon nano-onions and the structure of carbon nano-tube uniqueness and the thermal conductivity of excellence and conductivity, it has important using value in electrode material for super capacitor.
In current existing report, existing about carbon nano-onions and the carbon nano-tube related application at electrode material for super capacitor.But also there is inherent shortcoming in them in application.Although carbon nano-onions has large specific area and suitable pore structure, its conductivity is lower than carbon nano-tube; Meanwhile, carbon nano-tube has excellent conductivity, but its specific area is smaller.Therefore need to look for a kind of can in conjunction with the carbon nano-structured material of both advantages one of focus becoming electrode material for super capacitor research.At present, about porous carbon nano chain material and preparation method thereof, there is not yet relevant report.
Summary of the invention
The present invention aims to provide a kind of porous carbon nano chain material and preparation method thereof, and described porous carbon nano chain material has excellent pore structure, conductivity and chemical stability, and its preparation method process is simple.
The present invention is realized by following technical proposals, a kind of porous carbon nano chain material, it is characterized in that, this material is by the chain structure of class carbon nano-onions units in series, chain length is distributed in tens nanometers in a few micrometer range, and in chain, each link units is ellipsoid shape hollow structure, and the junction carbon-coating of adjacent two link units is in non-occluded state, link units average diameter is 5 ~ 20 nm, and in link units, carbon layers having thicknesses is 2 ~ 5 nm.
The preparation method of above-mentioned porous carbon nano chain material, is characterized in that comprising following process:
1) under mechanical agitation, in absolute ethyl alcohol, by Fe (NO
3)
39H
2o and Ni (NO
3)
26H
2o mol ratio is (0.5 ~ 2): 1, and presses Fe (NO
3)
39H
2o and Ni (NO
3)
26H
2the gross mass of O and the mass ratio of MgO are (0.05 ~ 0.1): 1, are mixed with slaine suspension-turbid liquid; Slaine suspension-turbid liquid carries out stirring in water bath temperature 40 ~ 60 DEG C, steams ethanol, after grinding, obtains Ni-Fe/MgO catalyst fines;
2) the Ni-Fe/MgO catalyst fines of step 1) being placed in Noah's ark, then lying against in quartz tube furnace by Noah's ark, is 50 ~ 300 mLmin at flow
-1argon shield under, with 4 ~ 20 DEG C of min
-1ramp to 500 ~ 600 DEG C after, and at 50 ~ 200 mLmin
-1hydrogen in be incubated 60 min after, with 4 ~ 20 DEG C of min
-1ramp to 750 ~ 800 DEG C, meanwhile, with 10 ~ 60 mLmin
-1methane gas reaction 15 ~ 60 min are passed in tube furnace; Or with methane 10 ~ 60 mLmin
-1, argon gas 50 ~ 300 mLmin
-1ratio in tube furnace, pass into mixed gas reaction 15 ~ 60 min of methane/argon gas, finally at 50 ~ 300 mLmin
-1argon gas atmosphere protection under, cool to room temperature with the furnace, use 1 molL
-1watery hydrochloric acid washs, then uses washed with de-ionized water, drying, obtains the carbon nano chain material of interior coated Ni-Fe alloy;
3) in glove box, by the carbon nano chain material of coated Ni-Fe alloy in obtaining and KOH powder with mass ratio 1:(1 ~ 4) mixed grinding, obtain KOH/C mixture;
4) KOH/C mixture being placed in Noah's ark, being lain against by Noah's ark in quartz tube furnace, is 50 ~ 300 mLmin at flow
-1argon shield under, with 4 ~ 20 DEG C of min
-1ramp to 800 ~ 1000 DEG C, insulation 5 ~ 30 h, finally at 50 ~ 300 mLmin
-1argon gas atmosphere protection under, cool to room temperature with the furnace, the product obtained 1 molL
-1watery hydrochloric acid washs, then uses washed with de-ionized water, drying, obtains porous carbon nano chain material.
Compared with prior art, the invention has the beneficial effects as follows: simple to operate, cost is low.Equipment is common drying box, quartz tube furnace, magnetic stirring apparatus etc., large-scale or complex device without the need to other.Porous carbon nano chain material can be controlled by chemical vapor deposition processes temperature, time, carrier gas ratio, heating rate and KOH ratio, holding temperature, time.Material prepared by the method, as the electrode material of ultracapacitor, can effectively improve its chemical property.
Accompanying drawing explanation
Fig. 1 porous carbon nano chain material TEM obtained by the embodiment of the present invention one schemes.
Fig. 2 porous carbon nano chain material TEM obtained by the embodiment of the present invention two schemes.
Fig. 3 is porous carbon nano chain material obtained by the embodiment of the present invention one, carries out the cyclic voltammetry curve figure of electrochemical property test.
Fig. 4 is porous carbon nano chain material obtained by the embodiment of the present invention one, carries out the constant current charge-discharge curve chart of electrochemical property test.
Embodiment
Below in conjunction with embodiment, the invention will be further described, and these embodiments, just for illustration of the present invention, do not limit the present invention.
Embodiment one
Weigh the Fe (NO of quality 2.02 g
3)
39H
2ni (the NO of O, 1.49 g
3)
26H
2o and 70.2 gMgO, it puts into the beaker of 2000 mL, and adds the absolute ethyl alcohol of 1200 mL, 200 rmin
-1mechanical agitation 2 h, to be mixed evenly after, stirring in water bath is carried out under temperature 40 DEG C of conditions, steam ethanol, be precipitated thing, after mortar grinder, obtain Ni-Fe/MgO catalyst fines, get 6 g Ni-Fe/MgO catalyst fineses and be placed in Noah's ark, being lain against by Noah's ark in quartz tube furnace, is 100 mLmin at flow
-1argon shield under, with 10 DEG C of min
-1ramp to 550 DEG C after, then with 100 mLmin
-1hydrogen atmosphere in be incubated 60 min, with 10 DEG C of min
-1ramp to 750 DEG C, press methane 60 mLmin simultaneously
-1cH is passed in tube furnace
4gas reaction 30 min, finally with 200 mLmin
-1argon gas atmosphere protection under, cool to room temperature with the furnace, use 1 molL
-1after watery hydrochloric acid washing, use washed with de-ionized water again, dry under 80 DEG C of condition of normal pressure, obtain carbon nano chain material 6.376 g of interior coated Ni-Fe alloy, then in glove box, by the carbon nano chain material of coated Ni-Fe alloy in obtaining and 6.376 g KOH powder mixed grindings, obtain KOH/C mixture; KOH/C mixture being placed in Noah's ark, being lain against in quartz tube furnace, is 300 mLmin at flow
-1argon shield under, with 10 DEG C of min
-1ramp to 800 DEG C, be incubated 10 h, finally at 300 mLmin
-1argon gas atmosphere protection under, cool to room temperature with the furnace, 1 excessive molL of the product obtained
-1watery hydrochloric acid washs, and through washed with de-ionized water, drying, obtains porous carbon nano chain material.
Nickel foam is cut into the even size of 1 cm × 2.5 cm, priority deionized water, acetone, absolute ethyl alcohol thoroughly clean, by the mixing of ratio uniform of the active electrode material prepared and acetylene black, PTFE emulsion 75:15:10 in mass ratio, obtain required electrode slurry.Above-mentioned electrode slurry sheet glass uniform ground is coated on cm × 1, the foam nickel electrode sheet one end 1 cm area of known quality, then vacuum constant temperature drying box 80 DEG C of vacuumize 24 h are put into, under 10 MPa pressure, 3 min are maintained with tablet press machine, dried electrode slice is pressed into sheet, obtains work electrode.Test employing three electrode test system, electrolyte solution selects 6 molL
-1kOH solution, using platinized platinum as to electrode, mercury-mercuric oxide electrode is as reference electrode, at room temperature with the test of CHI 660D electrochemical workstation, probe temperature is 25 DEG C, in cyclic voltammetry, and setting sweep speed is 5 mV/s, 10 mV/s, 20 mV/s, 50 mV/s, 100 mV/s, 200 mV/s, 300 mV/s and 500 mV/s.In constant current charge-discharge test, setting current density is 0.5 A/g, 1A/g, 2 A/g, 5 A/g, 10 A/g and 20 A/g.
Embodiment two
Weigh the Fe (NO of quality 4.04 g
3)
39H
2ni (the NO of O, 2.98 g
3)
26H
2o and 70.2 gMgO, it puts into the beaker of 2000 mL, and adds the absolute ethyl alcohol of 1200 mL, 300 rmin
-1mechanical agitation 2 h, to be mixed evenly after, stirring in water bath is carried out under temperature 50 C condition, steam ethanol, be precipitated thing, after mortar grinder, obtain Ni-Fe/MgO catalyst fines, get 12 g Ni-Fe/MgO catalyst fineses and be placed in Noah's ark, being lain against in quartz tube furnace, is 200 mLmin at flow
-1argon shield under, with 10 DEG C of min
-1ramp to 550 DEG C after, then at 200 mLmin
-1hydrogen atmosphere in be incubated 60min, with 10 DEG C of min
-1ramp to 800 DEG C, press methane 60 mLmin simultaneously
-1cH is passed in tube furnace
4gas reaction 40 min, finally at 200 mLmin
-1argon gas atmosphere protection under, cool to room temperature with the furnace, wash with excessive watery hydrochloric acid, through washed with de-ionized water, dry under 80 DEG C of condition of normal pressure, obtain carbon nano chain material 12.593 g of interior coated Ni-Fe alloy, then in glove box, by the carbon nano chain material of coated Ni-Fe alloy in obtaining and 12.593 g KOH powder mixed grindings, obtain KOH/C mixture; KOH/C mixture being placed in Noah's ark, being lain against in quartz tube furnace, is 200 mLmin at flow
-1argon shield under, with 10 DEG C of min
-1ramp to 1000 DEG C, be incubated 15 h, finally at 300 mLmin
-1argon gas atmosphere protection under, cool to room temperature with the furnace, 1 excessive molL of the product obtained
-1watery hydrochloric acid washs, and through washed with de-ionized water, drying, obtains porous carbon nano chain material.
Nickel foam is cut into the even size of 1 cm × 2.5 cm, priority deionized water, acetone, absolute ethyl alcohol thoroughly clean, by the mixing of ratio uniform of the active electrode material prepared and acetylene black, PTFE emulsion 75:15:10 in mass ratio, obtain required electrode slurry.Above-mentioned electrode slurry sheet glass uniform ground is coated on cm × 1, the foam nickel electrode sheet one end 1 cm area of known quality, then vacuum constant temperature drying box 80 DEG C of vacuumize 24 h are put into, under 10 MPa pressure, 3 min are maintained with tablet press machine, dried electrode slice is pressed into sheet, obtains work electrode.Test employing three electrode test system, electrolyte solution selects 6 molL
-1kOH solution, using platinized platinum as to electrode, mercury-mercuric oxide electrode is as reference electrode, at room temperature with the test of CHI 660D electrochemical workstation, probe temperature is 25 DEG C, in cyclic voltammetry, and setting sweep speed is 5 mV/s, 10 mV/s, 20 mV/s, 50 mV/s, 100 mV/s, 200 mV/s, 300 mV/s and 500 mV/s.In constant current charge-discharge test, setting current density is 0.5 A/g, 1A/g, 2 A/g, 5 A/g, 10 A/g and 20 A/g.
Embodiment three
Weigh the Fe (NO of quality 2.02 g
3)
39H
2ni (the NO of O, 1.49 g
3)
26H
2o and 70.2 gMgO, it puts into the beaker of 2000 mL, and adds the absolute ethyl alcohol of 800 mL, 200 rmin
-1mechanical agitation 2 h, to be mixed evenly after, stirring in water bath is carried out under temperature 60 C condition, steam ethanol, be precipitated thing, after mortar grinder, obtain Ni-Fe/MgO catalyst fines, get 7.5 g Ni-Fe/MgO catalyst fineses and be placed in Noah's ark, being lain against in quartz tube furnace, is 200 mLmin at flow
-1argon shield under, with 15 DEG C of min
-1ramp to 550 DEG C after, then at 100 mLmin
-1hydrogen in be incubated 60 min, with 15 DEG C of min
-1ramp to 800 DEG C, press methane 60 mLmin simultaneously
-1with argon gas 200 mLmin
-1flow in tube furnace, pass into CH
4/ Ar mixed gas reaction 50 min, finally at 300 mLmin
-1argon gas atmosphere protection under, cool to room temperature with the furnace, wash with excessive watery hydrochloric acid, through washed with de-ionized water, dry under 80 DEG C of condition of normal pressure, obtain carbon nano chain material 8.021 g of interior coated Ni-Fe alloy, then in glove box, by the carbon nano chain material of coated Ni-Fe alloy in obtaining and 16.042 g KOH powder mixed grindings, obtain KOH/C mixture; KOH/C mixture being placed in Noah's ark, being lain against in quartz tube furnace, is 200 mLmin at flow
-1argon shield under, with 10 DEG C of min
-1ramp to 900 DEG C, be incubated 20 h, finally at 200 mLmin
-1argon gas atmosphere protection under, cool to room temperature with the furnace, 1 excessive molL of the product obtained
-1watery hydrochloric acid washs, and through washed with de-ionized water, drying, obtains porous carbon nano chain material.
Nickel foam is cut into the even size of 1 cm × 2.5 cm, priority deionized water, acetone, absolute ethyl alcohol thoroughly clean, by the mixing of ratio uniform of the active electrode material prepared and acetylene black, PTFE emulsion 75:15:10 in mass ratio, obtain required electrode slurry.Above-mentioned electrode slurry sheet glass uniform ground is coated on cm × 1, the foam nickel electrode sheet one end 1 cm area of known quality, then vacuum constant temperature drying box 80 DEG C of vacuumize 24 h are put into, under 10 MPa pressure, 3 min are maintained with tablet press machine, dried electrode slice is pressed into sheet, obtains work electrode.Test employing three electrode test system, electrolyte solution selects 6 molL
-1kOH solution, using platinized platinum as to electrode, mercury-mercuric oxide electrode is as reference electrode, at room temperature with the test of CHI 660D electrochemical workstation, probe temperature is 25 DEG C, in cyclic voltammetry, and setting sweep speed is 5 mV/s, 10 mV/s, 20 mV/s, 50 mV/s, 100 mV/s, 200 mV/s, 300 mV/s and 500 mV/s.In constant current charge-discharge test, setting current density is 0.5 A/g, 1A/g, 2 A/g, 5 A/g, 10 A/g and 20 A/g.
Claims (2)
1. a porous carbon nano chain material, it is characterized in that, this material is by the chain structure of class carbon nano-onions units in series, chain length is distributed in tens nanometers in a few micrometer range, in chain, each link units is ellipsoid shape hollow structure, and the junction carbon-coating of adjacent two link units is in non-occluded state, link units average diameter is 5 ~ 20 nm, and in link units, carbon layers having thicknesses is 2 ~ 5 nm.
2., by a preparation method for porous carbon nano chain material according to claim 1, it is characterized in that comprising following process:
Under mechanical agitation, in absolute ethyl alcohol, by Fe (NO
3)
39H
2o and Ni (NO
3)
26H
2o mol ratio is (0.5 ~ 2): 1, and presses Fe (NO
3)
39H
2o and Ni (NO
3)
26H
2the gross mass of O and the mass ratio of MgO are (0.05 ~ 0.1): 1, are mixed with slaine suspension-turbid liquid; Slaine suspension-turbid liquid carries out stirring in water bath temperature 40 ~ 60 DEG C, steams ethanol, after grinding, obtains Ni-Fe/MgO catalyst fines;
2) the Ni-Fe/MgO catalyst fines of step 1) being placed in Noah's ark, then lying against in quartz tube furnace by Noah's ark, is 50 ~ 300 mLmin at flow
-1argon shield under, with 4 ~ 20 DEG C of min
-1ramp to 500 ~ 600 DEG C after, and at 50 ~ 200 mLmin
-1hydrogen in be incubated 60 min after, with 4 ~ 20 DEG C of min
-1ramp to 750 ~ 800 DEG C, meanwhile, with 10 ~ 60 mLmin
-1methane gas reaction 15 ~ 60 min are passed in tube furnace; Or with methane 10 ~ 60 mLmin
-1, argon gas 50 ~ 300 mLmin
-1ratio in tube furnace, pass into mixed gas reaction 15 ~ 60 min of methane/argon gas, finally at 50 ~ 300 mLmin
-1argon gas atmosphere protection under, cool to room temperature with the furnace, use 1 molL
-1watery hydrochloric acid washs, then uses washed with de-ionized water, drying, obtains the carbon nano chain material of interior coated Ni-Fe alloy;
3) in glove box, by the carbon nano chain material of coated Ni-Fe alloy in obtaining and KOH powder with mass ratio 1:(1 ~ 4) mixed grinding, obtain KOH/C mixture;
4) KOH/C mixture being placed in Noah's ark, being lain against by Noah's ark in quartz tube furnace, is 50 ~ 300 mLmin at flow
-1argon shield under, with 4 ~ 20 DEG C of min
-1ramp to 800 ~ 1000 DEG C, insulation 5 ~ 30 h, finally at 50 ~ 300 mLmin
-1argon gas atmosphere protection under, cool to room temperature with the furnace, the product obtained 1 molL
-1watery hydrochloric acid washs, then uses washed with de-ionized water, drying, obtains porous carbon nano chain.
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|---|---|---|---|---|
| CN105217616A (en) * | 2015-10-20 | 2016-01-06 | 天津大学 | Porous graphene load carbon nano-onions three-dimensional composite material preparation method |
| CN107352528A (en) * | 2017-08-31 | 2017-11-17 | 清华大学 | A kind of preparation method and nano chain of metal oxide nano chain |
| CN111115617A (en) * | 2019-12-24 | 2020-05-08 | 谢春艳 | Large-scale preparation method of high-purity hollow carbon nano-onion |
| CN113086969A (en) * | 2021-04-02 | 2021-07-09 | 南昌大学 | High-quality carbon nano-pearl chain structure and large-scale preparation method thereof |
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| CN101891182A (en) * | 2010-07-07 | 2010-11-24 | 天津大学 | Method for preparing carbon nano-onions with core-shell structure by using gamma-Fe-Ni alloy as catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105217616A (en) * | 2015-10-20 | 2016-01-06 | 天津大学 | Porous graphene load carbon nano-onions three-dimensional composite material preparation method |
| CN105217616B (en) * | 2015-10-20 | 2017-03-29 | 天津大学 | Porous graphene loads carbon nano-onions three-dimensional composite material preparation method |
| CN107352528A (en) * | 2017-08-31 | 2017-11-17 | 清华大学 | A kind of preparation method and nano chain of metal oxide nano chain |
| CN111115617A (en) * | 2019-12-24 | 2020-05-08 | 谢春艳 | Large-scale preparation method of high-purity hollow carbon nano-onion |
| CN113086969A (en) * | 2021-04-02 | 2021-07-09 | 南昌大学 | High-quality carbon nano-pearl chain structure and large-scale preparation method thereof |
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