CN100369809C - Carbon wool ball material and its preparation method and uses - Google Patents
Carbon wool ball material and its preparation method and uses Download PDFInfo
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- CN100369809C CN100369809C CNB2004100986182A CN200410098618A CN100369809C CN 100369809 C CN100369809 C CN 100369809C CN B2004100986182 A CNB2004100986182 A CN B2004100986182A CN 200410098618 A CN200410098618 A CN 200410098618A CN 100369809 C CN100369809 C CN 100369809C
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Abstract
The present invention relates to a carbon wool ball material and a preparation method and application thereof. The material comprises a core carbon material and a one-dimensional carbon nanofiber or/and a carbon nanotube growing on the surface of the material, wherein the average particle size of the core carbon material is from 100 nm to 1mm, the diameter of the one-dimensional nanofiber or the carbon nanotube is from 1 to 500 nm, and the length of the one-dimensional nanofiber or the carbon nanotube is from 10 nm to 100 mum. The novel carbon/carbon composite material is prepared by a chemical gas-phase deposition method, and the chemical gas-phase deposition method comprises: an alcohol solution using salts of metal iron, cobalt, nickel or molybdenum as catalysts is prepared; the core carbon material is added; pretreatment is carried out, and target temperature is reached by temperature programming; products are obtained after the products are purified. The carbon wool ball material has the advantages of stable structure and large specific surface area, and therefore, has multiple functions. The carbon wool ball material can be used as cathode materials of lithium ion cells, supporters of direct methanol fuel cell catalysts, electrode materials of dye-sensitized solar cells, supporters of supported catalysts, etc.
Description
Technical field
The invention belongs to the carbon material field, specifically relate to a kind of carbon/carbon composite nano-material and its production and use.
Background technology
Carbon material mainly contains sp at nature
2The natural graphite of structure, sp
3The diamond of structure and mixing sp
2And sp
3The indefiniteness carbon material of structure, acetylene black for example, carbon black, coke etc.People have also found soccerballene (C recently
60, C
70) and carbon nanotube.The geometric shape of occurring in nature carbon material is varied, but is mainly the natural graphite of sheet structure, fibrous carbon fiber, the carbon black class material of needle coke and irregular geometric properties.By synthetic, can prepare the synthetic graphite of subglobular, have perfect spherical design the hard carbon ball (Wang Qing, Li Hong, yellow-study outstanding person, Chen Liquan, a kind of micropore hard carbon ball, CN106225.5), the carbon nano fiber that length-to-diameter ratio is bigger, CNT (carbon nano-tube).
Spherical carbon material has advantage such as higher tap density, maximum structural stability and has lower surface one volume ratio (specific surface area).In some field, low specific surface area has special advantage.But as carrier class material, lower specific surface area is unfavorable for by the high-content load of load material.On the other hand, Nano carbon fibers peacekeeping CNT (carbon nano-tube) with one-dimentional structure (comprises Single Walled Carbon Nanotube, double-wall carbon nano-tube and multiple-wall carbon nanotube) because its unique Electronic Performance, mechanical property, thermal property and chemical stability etc. cause great concern in the Science and Technology field.But have one-dimentional structure, the Nano carbon fibers peacekeeping CNT (carbon nano-tube) preparation back that length-to-diameter ratio is bigger is difficult to disperse.Its lighter weight is inhaled into respiratory tract easily, is unfavorable for people's health.As carrier, be difficult for fixing when in fluid medium, using, move with carrier gas easily.
In many Application Areass, support of the catalyst for example, the electrode materials in chemical power source and the electric chemical super capacitor, the element material in the transmitter had both needed stable structure, needed bigger specific surface area again.Existing carbon material and carbon composite are not well positioned to meet this demand.
Summary of the invention
It is low to the objective of the invention is to overcome spherical carbon material specific surface area, the unsettled defective of monodimension nanometer material geometry, thus a kind of stable structure that both had is provided, the carbon wool ball material that has bigger specific surface area again, and its production and use.
The objective of the invention is to realize by the following technical solutions:
Carbon wool ball material provided by the invention is first the one dimension carbon material to be grown in the core carbon material surface with large-size, obtains a matrix material with bobbles geometry appearance.We define this novel carbon/carbon compound material at this and are " carbon bobbles ".
Carbon/carbon compound material provided by the invention, i.e. carbon wool ball material, have following feature: it comprises a core carbon material, and is grown in the 1-dimention nano carbon fiber on the described core carbon material surface.
The median size of described core carbon material is 100nm～1mm, both can be graphited carbon material, also can be the carbon material of disordered structure, and preferred geometric shape is spherical.
The diameter of described 1-dimention nano carbon fiber is 1～500nm, and length is 10nm～100 μ m, and length-to-diameter ratio is 5～105; This 1-dimention nano carbon fiber both can have straight geometry appearance, also can have crooked geometry appearance.
The invention provides a kind of preparation method of above-mentioned carbon wool ball material, this carbon/carbon compound material can prepare by chemical gaseous phase depositing process, mainly may further comprise the steps:
(1) preparation of catalyst solution
Take by weighing in metallic iron, cobalt, nickel or the molybdenum salt one or more as catalyzer, add alcoholic solvent, put into container, stirring and dissolving makes the catalyst solution that concentration is 0.0001～0.1M;
Described molysite is Fe (NO
3)
39H
2O, FeSO
47H
2O or Fe (OH) (CH
3COO)
2
Described cobalt salt is Co (NO
3)
26H
2O or Co (CH
3COO)
24H
2O;
Described nickel salt is Ni (NO
3)
26H
2O;
Described molybdenum salt is (NH
4)
6Mo
7O
244H
2O;
Described alcoholic solvent is one or more in ethanol, methyl alcohol, Virahol, ethylene glycol or the glycerol solution;
(2) catalyst cupport
Take by weighing the core carbon material and add in the alcoholic solution-catalyst solution of above-mentioned metal ion, metal catalyst (M) is M: C=1 with the mass ratio (w/w) of core carbon material (C): 1～1: 1000; And abundant stir about 30 minutes～2 hours, left standstill about 1～72 hour, separate drying;
(3) chemical vapour deposition
The material that step (2) is obtained is placed in the thermally resistant container (as graphite boat, aluminium oxide boat), the tube furnace that the resistance to air loss of packing into then is good (also can be with vacuum extractor), charge into the gas mixture of argon gas or argon gas and hydrogen, or carry out pre-treatment, temperature programming to 400 then～1200 ℃ temperature with ammonia; After being raised to target temperature, gas being converted to carbon-source gas (acetylene, ethene, methane or carbon monoxide) or being converted to the gas mixture of argon gas, nitrogen or hydrogen and above-mentioned carbon-source gas, after constant temperature 10 minutes carried out chemical vapour deposition to 48 hours; Naturally cool to room temperature;
(4) product purifies
Product is packed in the container into HNO 70%
3In refluxed 4～24 hours in 110～160 ℃ of temperature; Naturally after the cooling, fully dilute with deionized water, remove supernatant liquid after the centrifugation, lower floor's solid matter with deionized water repetitive scrubbing promptly gets product-novel carbon wool ball material more than three times.
In the carbon wool ball material that aforesaid method synthesizes, the diameter of epontic 1-dimention nano carbon fiber is 1～500nm, and length is 10nm～100 μ m, and length-to-diameter ratio is 5～105.Diameter, length, length-to-diameter ratio and the density of the 1-dimention nano carbon fiber of core carbon material surface growth can be by catalyzer the kind, flow, the ratio of different carrier gas compositions, the temperature and time of reaction of the carrier gas of being adopted of particle diameter, content, distribution and chemical vapour deposition of catalyzer during at the core supported on carbon surface regulated and control.
Above-mentioned carbon wool ball material provided by the invention serves many purposes.In energy storage and switching device, as the negative material of lithium ion battery, as the carrier of direct methanol fuel cell catalyzer, or as the electrode materials of dye sensitization solar battery; In catalyst field, as carrier of loaded catalyst etc.
Carbon wool ball material provided by the invention is a kind of carbon/carbon compound material that is proposed first by the inventor, compare with existing carbon material, its advantage is: combine the core carbon material and have stable structure, and epontic carbon nano fiber has the advantage than bigger serface and big voidage, thereby as support of the catalyst, when electrode materials in chemical power source and the electric chemical super capacitor and the element material in the transmitter, shown good dynamic performance, thermostability, chemical stability and structural stability.In addition, preparation method provided by the invention is at core carbon surface controllable growth one dimension carbon nanofiber, the technology that is adopted is simple, good reproducibility, required plant and instrument all is the equipment that chemistry and material industry are used always, the prepared product purity height that goes out, and geometry is controlled, steady quality is suitable for large-scale industrialization production.
Description of drawings
The field emission scan electron microscopic pattern of the carbon bobbles that Fig. 1 obtains for embodiment 10;
The field emission scan electron microscopic pattern of the low magnification of the carbon bobbles that Fig. 2 obtains for embodiment 10 (10000 times);
The field emission scan electron microscopic pattern of the high-amplification-factor of the carbon bobbles that Fig. 3 obtains for embodiment 10 (40000 times);
The field emission scan electron microscopic pattern of the high-amplification-factor of the carbon bobbles that Fig. 4 obtains for embodiment 10 (200000 times).
Embodiment
Embodiment 1,
Measure the 0.01MCo (NO of 100ml
3)
26H
20.0001M (the NH of O and 100ml
4)
6Mo
7O
244H
2The ethanol of O and the mixing solutions of methyl alcohol add the 1g natural flake graphite as the core carbon material in beaker, its median size is 10 μ m, Co/ natural flake graphite=5.8% (w/w), Mo/ natural flake graphite=0.7% (w/w) stirred 2 hours, after leaving standstill about 72 hours, separation, drying; The gained material is placed in the graphite boat, the tube furnace of packing into then, charge into argon gas and hydrogen gas mixture (92: 8, v/v), total flux is 100sccm, after the temperature programming to 400 ℃, with gas be converted to hydrogen and carbon monoxide gas mixture (1: 4, v/v), total flux is 100sccm, constant temperature naturally cooled to room temperature after carrying out chemical vapour deposition in 50 minutes; The purification of product is at 70% HNO with product
3In refluxed 24 hours in 160 ℃, naturally after the cooling, fully dilute with deionized water, remove supernatant liquid after the centrifugation, lower floor's solid matter with deionized water repetitive scrubbing promptly gets the novel carbon wool ball material of product more than three times, is natural flake graphite/carbon nano fiber matrix material, the mean diameter of carbon nano fiber is 10nm, and length is 20 μ m.Length-to-diameter ratio is 2 * 10
3
The negative material of described material as lithium ion battery used.The preparation method of negative pole is described below: with described natural flake graphite/carbon nano fiber matrix material, carbon black mixes the formation slurry at normal temperatures and pressures with the cyclohexane solution of polyvinylidene difluoride (PVDF), evenly be coated on the Copper Foil substrate as collector, the about 20 μ m. of the film thickness of gained with the film that obtains at 150 ℃ down after the oven dry, at 20Kg/cm
2Under compress, continue 150 ℃ of oven dry 12 hours down.Oven dry back natural flake graphite/carbon nano fiber matrix material (85nm), the weight percent of carbon black and polyvinylidene difluoride (PVDF) is 40: 40: 20, then film being cut to area is 1cm
2Thin rounded flakes as negative pole.
With commodity positive electrode material LiFePO
4Mix formation slurry (active material: acetylene black: PVDF=75: 15: 10) at normal temperatures and pressures with the cyclohexane solution of acetylene black and 10% polyvinylidene difluoride (PVDF) (PVDF), evenly be coated on the aluminum substrates, about 2～20 μ m of the film thickness of gained are as the positive pole of battery.Electrolytic solution is 1mol LiPF
6Be dissolved in the mixed solvent of 1LEC and DMC (volume ratio 1: 1).With all battery materials, comprise positive pole, negative pole, battery case, barrier film, dry back is added electrolytic solution and is assembled into Experimental cell in the argon filling glove box or in the drying room.
Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.The charging stopping potential is 4.2V, and discharge cut-off voltage is 2.0V.Studies have shown that, described natural flake graphite/carbon nano fiber matrix material is as the lithium ion battery negative active material, and its reversible capacity at 0.1C is 330mAh/g, and the reversible capacity of 1C is 300mAh/g, the reversible capacity of 10C is 250mAh/g, has shown dynamic behavior preferably.The cyclicity that obtains lithium ion battery is better.
Embodiment 2,
Measure the 0.03M Co (NO of 100ml
3)
26H
20.00045M (the NH of O and 100ml
4)
6Mo
7O
244H
2The ethanol of O and the mixing solutions of methyl alcohol add the 1g refinery coke then as the core carbon material in beaker, its median size is 200 μ m, Co/ refinery coke=17% (w/w), Mo/ refinery coke=3% (w/w) stirred 0.5 hour, after leaving standstill about 24 hours, separation, drying; Chemical vapor deposition processes is with embodiment 1, and the time of chemical vapour deposition is 2 hours; The purification of product is at 70% HNO with product
3In refluxed 4 hours in 110 ℃, naturally after the cooling, fully dilute with deionized water, remove supernatant liquid after the centrifugation, lower floor's solid matter with deionized water repetitive scrubbing is more than three times, and products therefrom is novel carbon wool ball material, be refinery coke/carbon nano fiber matrix material, the mean diameter of carbon nano fiber is 50nm, and length is 500nm, and length-to-diameter ratio is 10.
Embodiment 3,
Measure the 0.1M Co (NO of 40ml
3)
26H
20.0015M (the NH of O and 40ml
4)
6Mo
7O
244H
2The ethanol of O and the mixing solutions of methyl alcohol add 1g granulation gac then as the core carbon material in beaker, its median size is 1mm, Co/ gac=23.3% (w/w), Mo/ gac=4% (w/w) stirred 1 hour, after leaving standstill about 72 hours, separation, drying; Chemical vapor deposition processes is with embodiment 1, and wherein the total flux of hydrogen and carbon mono oxide mixture is 500sccm, and the time of chemical vapour deposition is 2 hours; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is gac/carbon nano fiber matrix material, and the mean diameter of carbon nano fiber is 20nm, and length is 100 μ m, and length-to-diameter ratio is 5 * 10
3
Described material is used as support of the catalyst.Take by weighing described gac/carbon nano fiber matrix material 0.722g, adding is dissolved with 0.02gK
2PtCl
6200ml ethylene glycol and the solution of 5ml water in; fully stir after 1 hour; refluxed about 8 hours under argon shield in 140 ℃; after naturally cooling to room temperature; product is washed repeatedly with ethanol and deionized water, and products therefrom is gac/carbon nano fiber matrix material loaded with nano Pt catalyzer, and the Pt charge capacity is 2wt.%; the Pt high dispersing is in its surface, and its mean diameter is 2.0nm.The reformation effect that this catalyzer is used for petroleum fractions is with to load on activated carbon surface active high 3 times, long 5 times of life-span.
Embodiment 4,
Measure the 0.01MFeSO of 60ml
47H
2The ethylene glycol of O and methyl alcohol (1: 1, mixing solutions V/V) adds the hard charcoal ball of 1g then as the core carbon material in beaker, its median size is 100nm, the hard charcoal ball of Fe/=3.3% (w/w) stirred 30 minutes, leave standstill about 1 hour after, separate, drying; The gained dried feed is placed in the aluminium oxide boat, pack into then in the tube furnace, charge into argon gas, flow is 100sccm, after the temperature programming to 1200 ℃, gas is converted to methane, flow is 100sccm, constant temperature was converted to argon gas with gas after carrying out chemical vapour deposition in 48 hours, naturally cooled to room temperature; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is hard charcoal ball/Single Walled Carbon Nanotube matrix material, and wherein the mean diameter of Single Walled Carbon Nanotube is 1nm, and length is 10nm, and length-to-diameter ratio is 10.
Embodiment 5,
Measure the 0.01M FeSO47H of 120 ml
2The ethylene glycol of O and methyl alcohol (1: 1, mixing solutions V/V) adds the hard charcoal ball of 1g then as the core carbon material in beaker, its median size is 500nm, the hard charcoal ball of Fe/=6.6% (w/w) stirred 30 minutes, leave standstill about 24 hours after, separate, drying; Chemical vapor deposition processes is with embodiment 4, and the time of chemical vapour deposition is 2 hours; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is hard charcoal ball/Single Walled Carbon Nanotube matrix material, and wherein the mean diameter of Single Walled Carbon Nanotube is 4.2nm, and length is 100 μ m, and length-to-diameter ratio is 2.3 * 10
4
Embodiment 6,
Measure 0.0045MFe (the OH) (CH of 60ml
3COO)
20.004MCo (CH with 60ml
3COO)
24H
2The ethanolic soln of O adds the hard charcoal ball of 1g then as the core carbon material in beaker, its median size is 1 μ m, the hard charcoal ball of Fe/=3% (w/w), the hard charcoal ball of Co/=1.4% (w/w) stirred 2 hours, leave standstill about 72 hours after, separate, drying; The gained dried feed is placed in the aluminium oxide boat, pack into then in the tube furnace, charge into argon gas, flow is 100sccm, after the temperature programming to 1200 ℃, gas is converted to the gas mixture of methane and hydrogen, its ratio is 3: 2 (v/v), and total flux is 100sccm, after constant temperature carried out chemical vapour deposition in 20 minutes, gas is converted to argon gas, naturally cools to room temperature; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is hard charcoal ball/double-walled carbon nano-tube matrix material, and wherein the mean diameter of double-walled carbon nano-tube is 2.5nm, and length is 60 μ m, and length-to-diameter ratio is 2.4 * 10
4
Embodiment 7,
Measure 0.0045M Fe (the OH) (CH of 120ml
3COO)
20.004MCo (CH with 120ml
3COO)
24H
2The ethanolic soln of O adds the hard charcoal ball of 1g then as the core carbon material in beaker, its median size is 5 μ m, the hard charcoal ball of Fe/=6% (w/w), the hard charcoal ball of Co/=2.8% (w/w) stirred 2 hours, leave standstill about 72 hours after, separate, drying; Chemical vapor deposition processes is with embodiment 6, and the time of chemical vapour deposition is 1 hour; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is hard charcoal ball/double-walled carbon nano-tube matrix material, and wherein the mean diameter of double-walled carbon nano-tube is 6nm, and length is 30nm, and length-to-diameter ratio is 5.
Embodiment 8,
Measure the 0.009M Ni (NO of 100ml
3)
26H
2The methanol solution of O adds the graphited carbonaceous mesophase spherules of 1g (MCMB 2800) then in beaker, Ni/MCMB=5.2% (w/w), its median size is 20 μ m, stirs 30 minutes, leave standstill about 48 hours after, separate, drying; The gained dried feed is placed in the graphite boat, in the tube furnace of packing into then, after vacuumizing, charge into the gas mixture of argon gas and hydrogen, its ratio is 92: 8 (v/v), and total flux is 100sccm, after temperature programming to the 800 ℃ temperature, gas is converted to ammonia, flow is 50sccm, after constant temperature carried out pre-treatment in 20 minutes, gas is converted to acetylene, and flow is 20sccm, after constant temperature carried out chemical vapour deposition in 20 minutes under uniform temp, gas is converted to argon gas, naturally cools to room temperature; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is the MCMB/ multi-wall carbon nano-tube composite material, and wherein the carbon nanotube mean diameter is 50nm, and length is 50 μ m, and length-to-diameter ratio is 1 * 10
3
Embodiment 9,
Measure the 0.009MNi (NO of 50ml
3)
26H
2The methanol solution of O adds 1gMCMB then as the core carbon material in beaker, its median size is 20 μ m, and Ni/MCMB=2.6% (w/w) stirred 30 minutes, leave standstill about 48 hours after, separate, drying; Chemical vapor deposition processes is with embodiment 8, and the time of chemical vapour deposition is 1 hour; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is the MCMB/ multi-wall carbon nano-tube composite material, and wherein its mean diameter of carbon nanotube is 20nm, and length is 100 μ m, and length-to-diameter ratio is 5 * 10
3
Embodiment 10,
Measure the 0.01M Fe (NO of 100ml
3)
39H
2The Virahol of O and methyl alcohol (2: 1, mixing solutions V/V) adds 1gMCMB1000 (1000 ℃ of processing) then as the core carbon material in beaker, its median size is 20 μ m, and Fe/MCMB=5.6% (w/w) stirred 30 minutes, after leaving standstill about 72 hours, separation, drying; The gained dried feed is placed in the graphite boat, pack into then in the tube furnace, charge into the gas mixture of argon gas and hydrogen, its ratio is 92: 8 (v/v), and total flux is 100sccm, after the temperature programming to 650 ℃, gas is converted to the gas mixture of argon gas and acetylene, and its ratio is 100: 9 (v/v), and total flux is 109sccm, constant temperature naturally cooled to room temperature after carrying out chemical vapour deposition in 50 minutes; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is the MCMB/ multi-wall carbon nano-tube composite material, and wherein the multi-walled carbon nano-tubes mean diameter is 50nm, and length is 10 μ m, and length-to-diameter ratio is 200.The stereoscan photograph of the different amplification of gained sample is referring to Fig. 1～4.
Embodiment 11,
Measure the 0.01M Fe (NO of 20ml
3)
39H
2The Virahol of O and methyl alcohol (2: 1, mixing solutions V/V) adds 1g MCMB2800 then as the core carbon material in beaker, its median size is 20 μ m, Fe/MCMB=1.12% (w/w) stirred 30 minutes, leave standstill about 72 hours after, separate, drying; Chemical vapor deposition processes is with embodiment 10, and the time of chemical vapour deposition is 2 hours; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is the MCMB/ multi-wall carbon nano-tube composite material, and wherein the mean diameter of carbon nanotube is 10nm, and length is 100 μ m, and length-to-diameter ratio is 1 * 10
4
Embodiment 12,
Measure the 0.01MFe (NO of 60ml
3)
39H
2The Virahol of O and methyl alcohol (2: 1, mixing solutions V/V) adds 1g carbosphere CMS 2800 then as the core carbon material in beaker, its median size is 20 μ m, and Fe/MCMB=3.36% (w/w) stirred 30 minutes, after leaving standstill about 48 hours, separation, drying; Chemical vapor deposition processes is with embodiment 10, and the time of chemical vapour deposition is 48 hours; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is the MCMB/ multi-wall carbon nano-tube composite material, and wherein the mean diameter of carbon nanotube is 500nm, and length is 10 μ m, and length-to-diameter ratio is 20.
Embodiment 13,
Measure the 0.01MFe (NO of 20ml
3)
39H
2The Virahol of O and methyl alcohol (2: 1, mixing solutions V/V) adds the hard charcoal ball of 1g then as the core carbon material in beaker, its median size is 10 μ m, Fe/MCMB=1.12% (w/w) stirred after 30 minutes, leave standstill about 24 hours after, separate, drying; Chemical vapor deposition processes is with embodiment 10, and the time of chemical vapour deposition is 10 minutes; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is hard charcoal ball/multi-wall carbon nano-tube composite material, and wherein the mean diameter of carbon nanotube is 10nm, and length is 5 μ m, and length-to-diameter ratio is 5 * 10
2
Embodiment 14,
Measure the 0.005MFe (NO of 20ml
3)
39H
2The Virahol of O and methyl alcohol (2: 1, mixing solutions V/V) adds the hard charcoal ball of 1g then as the core carbon material in beaker, its median size is 10 μ m, Fe/MCMB=0.56% (w/w) stirred after 30 minutes, leave standstill about 24 hours after, separate, drying; Chemical vapor deposition processes is with embodiment 10, and the time of chemical vapour deposition is 10 minutes; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is hard charcoal ball/multi-wall carbon nano-tube composite material, and wherein the mean diameter of carbon nanotube is 10nm, and length is 500nm, and length-to-diameter ratio is 5 * 10
4
Resulting material is mixed the formation slurry at normal temperatures and pressures with the n-formyl sarcolysine base pyrrolidone solution of polyvinylidene difluoride (PVDF), evenly be coated on the conductive glass ITO, the electrode that the about 20 μ m. of coat thickness of dry back gained obtain uses as the counter electrode of dye sensitization solar battery.With this electrode, with the ITO-TiO that adopts N3 dyestuff surface sensitizing
2Electrode is formed dye sensitization solar battery, uses the LiI-3HPN-SiO2 solid electrolyte, and under the radiation of 1.5 M sun units, the efficiency of conversion of solar cell can reach 5.4%.Suitable with the counter electrode performance that adopts surface-coated Pt.
Embodiment 15,
Measure the 0.005M Fe (NO of 20ml
3)
39H
2The glycerol of O and ethylene glycol (1: 1, mixing solutions v/v) adds the hard charcoal ball of 1g then as the core carbon material in beaker, its median size is 10 μ m, Fe/MCMB=0.56% (w/w) stirred after 30 minutes, leave standstill about 24 hours after, separate, drying; Chemical vapor deposition processes is with embodiment 10, and the time of chemical vapour deposition is 10 minutes; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is hard charcoal ball/multi-wall carbon nano-tube composite material, and wherein the mean diameter of carbon nanotube is 10nm, and length is 100nm, and length-to-diameter ratio is 1 * 10
4
Embodiment 16,
Measure the 0.01MFe (NO of 60ml
3)
39H
20.006M Ni (the NO of O and 60ml
3)
26H
2The methanol solution of O adds the 0.0546g natural flake graphite then as the core carbon material in beaker, its median size is 50 μ m, (Fe+Ni)/natural flake graphite=1: 1 (w/w), stirs 2 hours, leave standstill about 60 hours after, separate, drying; The gained dried feed is placed in the graphite boat, pack into then in the tube furnace, charge into the gas mixture of argon gas and hydrogen, its ratio is 85: 15 (v/v), after the temperature programming to 700 ℃, gas is converted to ethene, flow is 50sccm, constant temperature was converted to nitrogen with gas after carrying out chemical vapour deposition in 2 hours, naturally cooled to room temperature; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is natural flake graphite/multi-wall carbon nano-tube composite material, and the mean diameter of multi-walled carbon nano-tubes is 20nm, and length is 100 μ m, and length-to-diameter ratio is 5 * 10
3
Embodiment 17,
Measure the 0.01MFe (NO of 6m1
3)
39H
20.006MNi (the NO of O and 6ml
3)
26H
2The methyl alcohol of O, ethanol and glycerol (3: 2: 1, v/v) mixing solutions is in beaker, add the artificial spherical graphite of 5.46g then as the core carbon material, its median size is 20 μ m, (Fe+Ni)/and artificial spherical graphite=1: 1000, stirred 2 hours, leave standstill about 60 hours after, separate, drying; Chemical vapor deposition processes is with embodiment 16; The purification of product is with embodiment 1; Products therefrom is novel carbon wool ball material, is natural flake graphite/multi-wall carbon nano-tube composite material, and its mean diameter is 10nm, and length is 100 μ m, and length-to-diameter ratio is 1 * 10
4
Claims (10)
1. carbon wool ball material, it is characterized in that: this carbon wool ball material comprises a core carbon material, and is grown in the 1-dimention nano carbon fiber on the described core carbon material surface.
2. carbon wool ball material as claimed in claim 1 is characterized in that: described core carbon material is graphited carbon material, or the carbon material of disordered structure; Its median size is 100nm～1mm.
3. carbon wool ball material as claimed in claim 1 is characterized in that: the geometric shape of described core carbon material is for spherical.
4. carbon wool ball material as claimed in claim 1 is characterized in that: the diameter of described 1-dimention nano carbon fiber is 1～500nm, and length is 10nm～100 μ m, and length-to-diameter ratio is 5～10
5
5. the preparation method of the described carbon wool ball material of claim 1 for by the chemical gaseous phase depositing process preparation, mainly may further comprise the steps:
1) preparation of catalyst solution
Take by weighing in metallic iron, cobalt, nickel or the molybdenum salt one or more as catalyzer, add alcoholic solvent, put into container, stirring and dissolving makes the catalyst solution that concentration is 0.0001～0.1M;
2) catalyst cupport
The core carbon material is added in the catalyst solution that step 1) makes, and the mass ratio of metal catalyst and core carbon material is 1: 1～1: 1000; And fully stir, leave standstill, separate drying;
3) chemical vapour deposition
With step 2) material that obtains is placed in the thermally resistant container, and the tube furnace that the resistance to air loss of packing into then is good charges into the gas mixture of argon gas or argon gas and hydrogen, or carries out pre-treatment, temperature programming to 400 then～1200 ℃ temperature with ammonia; After being raised to target temperature, gas is converted to carbon-source gas, perhaps is converted to the gas mixture of argon gas, nitrogen or hydrogen and carbon-source gas, after constant temperature 10 minutes carried out chemical vapour deposition to 48 hours; Naturally cool to room temperature;
4) product purifies
The product that step 3) is made is packed in the container, the HNO 70%
3In refluxed 4～24 hours in 110～160 ℃ of temperature; Naturally after the cooling, fully dilute with deionized water, remove supernatant liquid after the centrifugation, lower floor's solid matter with deionized water repetitive scrubbing obtains carbon wool ball material more than three times.
6. the preparation method of carbon wool ball material as claimed in claim 5, it is characterized in that: the molysite described in the step 1) is Fe (NO
3)
39H
2O, FeSO
47H
2O or Fe (OH) (CH
3COO)
2Described cobalt salt is Co (NO
3)
26H
2O or Co (CH
3COO)
24H
2O; Described nickel salt is Ni (NO
3)
26H
2O; Described molybdenum salt is (NH
4)
6Mo
7O
244H
2O.
7. the preparation method of carbon wool ball material as claimed in claim 5, it is characterized in that: the alcoholic solvent described in the step 1) is one or more in ethanol, methyl alcohol, Virahol, ethylene glycol or the glycerol solution.
8. the preparation method of carbon wool ball material as claimed in claim 5, it is characterized in that: carbon-source gas described in the step 3) is acetylene, ethene, methane or carbon monoxide.
9. the application of the described carbon wool ball material of claim 1 in the secondary lithium battery cathode material.
10. the application of the described carbon wool ball material of claim 1 in the electrode materials of dye sensitization solar battery.
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| CN102264639B (en) * | 2008-12-22 | 2013-11-20 | 爱信精机株式会社 | Composite carbon and manufacturing method therefor |
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| CN103094529B (en) * | 2013-01-30 | 2015-06-24 | 新乡远东电子科技有限公司 | Preparation method of composite cathode material of helical carbon nanotube/graphite |
| CN103247802B (en) * | 2013-05-03 | 2016-01-06 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery composite cathode material of silicon/carbon/graphite, preparation method and lithium ion battery |
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| CN104201386A (en) * | 2014-09-24 | 2014-12-10 | 杭州金色能源科技有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| WO2019014212A1 (en) * | 2017-07-10 | 2019-01-17 | University Of Cincinnati | Carbon nanotube hybrid material fabric, composite fabric, and personal protective apparel and equipment |
| FR3070381A1 (en) * | 2017-08-29 | 2019-03-01 | Nawatechnologies | METHOD FOR MANUFACTURING VERTICALLY ALIGNED CARBON NANOTUBES, AND ELECTROCHEMICAL SUPERCONDENSATORS USING THESE NANOTUBES AS ELECTRODES |
| CN108329048A (en) * | 2018-02-26 | 2018-07-27 | 陕西科技大学 | A kind of connection method of carbon/carbon compound material |
| CN109368615B (en) * | 2018-12-11 | 2022-04-12 | 福建星宏新材料科技有限公司 | Composite nano carbon material and preparation method thereof |
| CN111326726B (en) * | 2020-03-06 | 2021-06-18 | 厦门海麒新能源科技有限公司 | Single-walled carbon nanotube-silicon carbon composite material and preparation method and application thereof |
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| CN113921784A (en) * | 2021-09-29 | 2022-01-11 | 湖北亿纬动力有限公司 | Negative electrode material and preparation method and application thereof |
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