CN104599856B - A kind of single-walled carbon nanotube orthogonal array carbon nano-onions composite material and preparation method thereof and its application in ultracapacitor - Google Patents
A kind of single-walled carbon nanotube orthogonal array carbon nano-onions composite material and preparation method thereof and its application in ultracapacitor Download PDFInfo
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Abstract
A kind of single-walled carbon nanotube orthogonal array carbon nano-onions composite material and preparation method thereof and its application in ultracapacitor, belong to carbon nanomaterial technical field.It is vertical single-wall carbon nanotube array on silicon chip, silicon chip that bottom, which is, and the top of vertical single-wall carbon nanotube array is carbon nano-onions structure.First the vertical-growth single-wall carbon nanotube array on silicon chip, Si layers are deposited on the top of single-wall carbon nanotube array, then utilize Si layers of growth carbon nano-onions structure.Single-walled carbon nanotube orthogonal array carbon nano-onions composite is removed to be used in ultracapacitor after base silicon wafer.
Description
Technical field
The invention belongs to carbon nanomaterial technical field, and in particular to a kind of vertical carbon nanotube array-carbon nano-onions
Composite material and preparation method thereof, and prepare super electricity using single-walled carbon nanotube orthogonal array-carbon nano-onions composite as electrode
The method of container.
Background technology
Ultracapacitor is a kind of new energy storage device, because there is high power, high-energy dress to change efficiency, excellent cycle for it
Performance, as the focus in new chemical energy research.Ultracapacitor is between traditional capacitor and rechargeable battery
A kind of environment-friendly, novel energy-storing, the energy saver that can not be substituted；Compared with traditional capacitor, ultracapacitor had both had fast
The characteristics of fast discharge and recharge, the energy storage mechnism with electrochemical cell, but also with long circulation life, pollution-free, wider
The characteristics of operating temperature range, big consumption.Just because of These characteristics, ultracapacitor is in electric automobile, communication, consumption and gives pleasure to
The application in the fields such as happy electronics, signal monitoring increasingly attracts attention, such as audio-video equipment, PDA, telephone set, facsimile machine and
The communication apparatus such as computer and household electrical appliance etc..Specifically, automobile-used ultracapacitor can meet automobile accelerate, start,
High power requirements when creeping, to protect main storage battery system, this cause the development of ultracapacitor be thus lifted to one it is new
Highly.The appearance of super capacitor, exactly complies with the requirement of era development, it be related to material, the energy, chemical industry, electronics during etc. it is many
Individual field, the focus as cross discipline research, ultracapacitor is expected to the new green power as this century.
CNT is as a kind of new nano material, due to its unique hollow structure and nano-scale, compound
The fields such as Material reinforcement, catalyst, Flied emission have potential application advantage.Its very big draw ratio is additionally, since, relatively
High specific surface area, pore-size distribution concentrates on certain scope, and unique electric conductivity, CNT is considered as super capacitor
The ideal candidates material of device.Nano-sized carbon onion be Ugarte in 1992 etc. in transmission electron microscope by strong electron beam irradiation
Carbon ash and find.Carbon nano-onions are in the fullerene nano particle of near-spherical, are closed in catalyst granules or hollow core curved
Bent concentric graphitic alkene shell coated state.Since self-discovery, due to its unique hollow caged and concentric graphitic Rotating fields,
There is larger development in terms of its preparation, structure and performance, and be expected in hydrogen storage material, superconductor, catalyst carrier
Played a role with terms of biomaterial, thus it is of great interest.
At present, the performance of limitation carbon onion be the problem of further study to lack one kind can prepare tactical rule,
The method of the high carbon onion of crystallization degree.At this stage, preparing the main method of carbon nano-onions has：(1) physical method, including electricity
Arc discharge method and electron beam, laser irradiation.The method can prepare the high carbon onion of high-purity, crystallization degree, but be difficult to control
Reaction process and product processed, carbon onion yield are extremely low.(2) chemical method, wherein high annealing method, acidic treatment, plasma
Enhancing method etc., these methods can realize prepared by the carbon onion product of magnanimity, but often carbon onion structure has surface defect, crystallization
Degree is not high；
In terms of ultracapacitor is prepared, vertical carbon nano pipe array relative to random arrangement CNT network structures more
Tool advantage, is transmitted and conductive channel because it can provide the aperture of rule, straight ion.Vertical carbon nanotube array has
Specific surface area is big, the features such as being easy to growth by CVD method.And in the carbon nanomaterial of a variety of different shapes, carbon nanometer ocean
Green onion is due to its hollow structure, relatively low density, larger specific surface area, stability with good surface wettability energy
Good application prospect is shown in terms of electrochemistry.At present, the most of all interior category covered with gold leaf of the carbon nano-onions of synthesis, is all that carbon is received
Rice onion carbon-coating is tightly fitted with interior metal.In lithium battery or super capacitor application, in charge and discharge process, inner layer metal
Dilation can influence carbon-coating structure, cause electrochemical capacitance stability poor.Meanwhile, electrolyte also cannot be introduced into inside carbon onion,
It can not be made full use of.On seldom without metal inner core carbon nano-onions preparation method report, on single
Pipe orthogonal array-carbon nano-onions composite and its ultracapacitor, there is not yet relevant report.
The content of the invention
It is an object of the invention to provide a kind of HF CVD (hot filament chemical vapor
Deposition) prepare, simple to operate, short preparation period, can large area prepare, the single wall carbon of high-quality, repeatable operation
Nanotube orthogonal array-carbon nano-onions composite material preparation process method, and thus can be used for preparing high power density and energy
The ultracapacitor of metric density.
Single-walled carbon nanotube orthogonal array-carbon nano-onions composite of the present invention：It on silicon chip, silicon chip is vertical that bottom, which is,
Straight single-wall carbon nanotube array, the top of vertical single-wall carbon nanotube array is carbon nano-onions structure.
The present invention is achieved by the following scheme, comprises the following steps：
(1) silicon chip is cleaned by ultrasonic respectively through methanol, acetone and isopropyl acetone, N2Drying, passes through electron beam evaporation system
The Al of 8-12nm thickness is deposited in (E-Beam Evaporator) in silicon chip surface successively2O3With 0.7-1.2nm thickness Fs e；
(2) single-wall carbon nanotube array vertical-growth：It is 700-800 DEG C to set furnace temperature, and total gas couette is：H2:200±
10sccm、C2H2:2 ± 0.5sccm and the H for passing through deionized water2For 200 ± 10sccm, total gas pressure is 25 ± 1Torr, and heated filament is
Single tungsten filament, power is 30-35W；The silicon chip of obtained coating in step (1) is placed in tungsten filament front 0.3-0.5cm (preferably
0.5cm), tungsten filament is parallel with silicon chip so that air-flow reacts through overheating tungsten filament with the coating on silicon chip, by tungsten filament work(after reaction 30s
Rate is set to 0, and total gas pressure completes the growth of single-walled carbon nanotube orthogonal array after being adjusted to 6.4Torr, reaction 15min；
(3) 1- is vertically deposited in the single wall vertical carbon nanotube array top obtained by electron beam evaporation system in (2)
The Si of 3nm thickness；
(4) using the equipment of step (2), 850 DEG C of furnace temperature is set, and total gas couette is H2:200±10sccm、CH4:
0.75sccm, logical deionized water H2For 200 ± 10sccm；Total gas pressure be 25 ± 1Torr, heated filament be replace with four it is in parallel
Tungsten filament, under the conditions of general power is 75-85W, will be made under being deposited and having that Si carbon nano pipe array is parallel and be placed in tungsten filament just in (3)
The preparation of vertical carbon nanotube array-carbon nano-onions composite is completed after side, reaction 2-6h.
CVD stoves used in the present invention are heated filament-CVD stoves, and heated filament used is tungsten filament.Tungsten filament diameter 0.2-0.3mm, length
For 8-12mm, one, or four can be changed to.When being changed to four, four tungsten filament levels, a parallel rows are separated.It is above-mentioned
The Si of evaporation is not specifically limited in step (2), but preferably 1-3nm.
It is transformed SiC the invention reside in Si, the nanometer Buddha's warrior attendant by seeded growth of nano SiC.Nano diamond is through too high
Temperature reduces the carbon nano-onions that are transformed, and ultimately forms vertical carbon nanotube array-carbon nano-onions composite.Step (4)
As Si is transformed SiC, and the nanometer Buddha's warrior attendant by seeded growth of nano SiC, Nano diamond is transformed by high temperature reduction
The process of carbon nano-onions.
The single-walled carbon nanotube orthogonal array of the present invention-carbon nano-onions composite is removed after base silicon wafer for super
In capacitor.
Compared with the prior art, the obvious advantage of present invention process：
(1) vertical carbon nanotube array-carbon nano-onions composite prepared by this technique, carbon nano pipe array keeps hanging down
Straight state, defect is less, free from admixture, the impurity defect such as no amorphous carbon.TEM shape appearance figures show, Si is transformed SiC, to receive
Rice SiC is seeded growth nanometer Buddha's warrior attendant.Nano diamond is transformed carbon nano-onions.Carbon nano-onions are turned by Nano diamond
Change, no metal core, size is tiny, is evenly distributed, crystallization degree is high, free of surface defects.
(2) this process gas raw material is routine experimentation gas, loose to demand, substantially reduces preparation cost.It is required
Instrument is simple, it is only necessary to electron beam evaporation system, CVD stoves.Special atmosphere, pressure atmosphere are not needed, only need to be in low pressure, also Primordial Qi
Atmosphere can complete vertical carbon nanotube array and carbon nano-onions and prepare, and technique simplifies, short preparation period, high excellent of preparation efficiency
Point.
(3) this technique need to pass through the vertical single-wall carbon nanotube array containing Si relative to existing process, only 850 DEG C once
Processing, preparation time is short, and temperature is low, substantially reduces energy consumption.Graphene nanobelt array area prepared by the inventive method is not
Limit, depending on CVD body of heater quartz tubes, general area can reach 20 × 20mm.
(4) this technique, which prepares ultracapacitor, has high-energy-density and power density, power density and energy density point
Wei not 67.3kW/kg and 499.5Wh/kg.Compared with prior art, the present invention passes through HF CVD vertical carbon nanotube-carbon nanometer
Onion composite.Carbon nano-onions size uniformity, in concentric graphitic Rotating fields, is conducive to electrolyte intermediate ion to enter graphene
Transmission, diffusion in nanobelt.In 0.2V/s, its ultracapacitor specific capacitance is respectively 167.62, and maximum energy-density is
499.5Wh/kg, power density is 67.3kW/kg.Because vertical single-walled carbon nanotube-carbon nano-onions composite is good
Electric conductivity, after 10000 charge and discharge cycles, is not reduced, and shows good power-performance and cycle performance.
Brief description of the drawings
Fig. 1 a, b are that embodiment 1 prepares vertical carbon nanotube array-carbon nano-onions composite SEM figures；
Fig. 1 c are that embodiment 1 prepares vertical carbon nanotube array-carbon nano-onions composite Raman figures；
Fig. 1 d are that embodiment 1 prepares vertical carbon nanotube array-carbon nano-onions composite TEM figures；
Fig. 2 a, b are that embodiment 2 prepares vertical carbon nanotube array-carbon nano-onions composite SEM figures；
Fig. 2 c are that embodiment 2 prepares vertical carbon nanotube array-carbon nano-onions composite Raman figures；
Fig. 2 d, e, f are that embodiment 2 prepares vertical carbon nanotube array-carbon nano-onions composite TEM figures；
Fig. 3 a are that embodiment 3 prepares vertical carbon nanotube array-carbon nano-onions composite XPS figures；
Fig. 3 b, c are that embodiment 3 prepares vertical carbon nanotube array-carbon nano-onions composite A FM figures；
Fig. 4 a are that embodiment 4 prepares the obtained ultracapacitor CV of vertical carbon nanotube array-carbon nano-onions composite
Curve；
Fig. 4 b are that embodiment 4 prepares the obtained ultracapacitor energy of vertical carbon nanotube array-carbon nano-onions composite
The graph of a relation of metric density and power density；
Fig. 4 c be embodiment 4 prepare vertical carbon nanotube array-carbon nano-onions composite be made ultracapacitor follow
Ring curve；
Embodiment
Below in conjunction with the accompanying drawings to the present invention embodiment be described in further detail, but the present invention be not limited to
Lower embodiment.Following examples tungsten filament diameter 0.25mm, length is about 8mm.
Embodiment 1：CVD stoves used in the present invention are heated filament-CVD stoves.
(1) silicon chip is cleaned by ultrasonic 15 minutes respectively through methanol, acetone and isopropyl acetone, N2Drying.Steamed by electron beam
10nm Al are deposited in hair system (E-Beam Evaporator) successively2O3, 0.8nm Fe.
(2) at 750 DEG C of furnace temperature, gas flow is respectively H2:200sccm, C2H2:2sccm, passes through the H of deionized water2
For 200sccm, total gas pressure is 25Torr, and heated filament is single tungsten filament, under the conditions of power is 30W, and the silicon chip that will be made in (1) is placed in tungsten
By tungsten filament power setting it is 0 after silk front 0.5cm, reaction 30s, total gas pressure is adjusted to 6.4Torr, completes single after reaction 15min
Wall carbon nano tube orthogonal array grows.
(3) 1nm Si are deposited in the single wall vertical carbon nanotube array obtained by electron beam evaporation system in (2).
(4) at 850 DEG C of furnace temperature, gas flow is respectively H2:200sccm, CH4:0.75sccm, leads to the H of deionized water2
For 200sccm, total gas pressure is 25Torr, and heated filament is four tungsten filaments, under the conditions of general power is 75W, will be made in (3) containing vertical carbon
Nano-tube array and Si silicon chip are placed in immediately below tungsten filament, and it is multiple to complete vertical carbon nanotube array-carbon nano-onions after reaction 2h
The preparation of condensation material.
Fig. 1 a, b can be seen that obtained single-wall carbon nanotube array for SEM shape appearance figures and still keep vertical topography.Fig. 1 c
For Raman spectrograms, show that the vertical permutation of obtained single-walled carbon nanotube-carbon nano-onions defect is less.Fig. 1 d are TEM patterns
Figure, shows have part diamond to be generated around SiC nano particles, part Nano diamond formation nano-onions, forms graphene
Shell structurre.
Embodiment 2：CVD stoves used in the present invention are heated filament-CVD stoves.
(1) silicon chip is cleaned by ultrasonic 15 minutes respectively through methanol, acetone and isopropyl acetone, N2Drying.Steamed by electron beam
10nm Al are deposited in hair system (E-Beam Evaporator) successively2O3, 0.8nm Fe.
(2) at 750 DEG C of furnace temperature, gas flow is respectively H2:200sccm, C2H2:2sccm, passes through the H of deionized water2
For 200sccm, total gas pressure is 25Torr, and heated filament is single tungsten filament, under the conditions of power is 30-35W, and the silicon chip that will be made in (1) is put
By tungsten filament power setting it is 0 after the 0.3cm in front of the tungsten filament, reaction 30s, total gas pressure is adjusted to complete after 6.4Torr, reaction 15min
Into the growth of single-walled carbon nanotube orthogonal array.
(3) 2nm Si are deposited in the single wall vertical carbon nanotube array obtained by electron beam evaporation system in (2).
(4) at 850 DEG C of furnace temperature, gas flow is respectively H2:200sccm, CH4:0.75sccm, leads to the H of deionized water2
For 200sccm, total gas pressure is 25Torr, and heated filament is four tungsten filaments, under the conditions of general power is 80W, will be made in (3) containing vertical carbon
Nano-tube array and Si silicon chip are placed in immediately below tungsten filament, and it is multiple to complete vertical carbon nanotube array-carbon nano-onions after reaction 4h
The preparation of condensation material.
Fig. 2 a, b are SEM shape appearance figures, it can be seen that obtained single-wall carbon nanotube array still keeps vertical topography, and carbon is received
Rice onion is covered in single-wall carbon nanotube array top.Fig. 2 c are Raman spectrograms, show that obtained single-walled carbon nanotube is vertically whole
Row-carbon nano-onions defect is less.Fig. 2 e-f are TEM shape appearance figures, show have nano-onions to be formed, carbon nano-onions are a diameter of
20-100nm, no metal core.
Embodiment 3：CVD stoves used in the present invention are heated filament-CVD stoves.
(1) silicon chip is cleaned by ultrasonic 15 minutes respectively through methanol, acetone and isopropyl acetone, N2Drying.Steamed by electron beam
10nm Al are deposited in hair system (E-Beam Evaporator) successively2O3, 0.8nm Fe.
(2) at 750 DEG C of furnace temperature, gas flow is respectively H2:200sccm, C2H2:2sccm, passes through the H of deionized water2
For 200sccm, total gas pressure is 25Torr, and heated filament is single tungsten filament, under the conditions of power is 30W, and the silicon chip that will be made in (1) is placed in tungsten
By tungsten filament power setting it is 0 after silk front 0.3cm, reaction 30s, total gas pressure is adjusted to 6.4Torr, completes single after reaction 15min
Wall carbon nano tube orthogonal array grows.
(3) 2nm Si are deposited in the single wall vertical carbon nanotube array obtained by electron beam evaporation system in (2).
(4) at 850 DEG C of furnace temperature, gas flow is respectively H2:200sccm, CH4:0.75sccm, leads to the H of deionized water2
For 200sccm, total gas pressure is 25Torr, and heated filament is four tungsten filaments, under the conditions of general power is 80W, will be made in (3) containing vertical carbon
Nano-tube array and Si silicon chip are placed in immediately below tungsten filament, and it is multiple to complete vertical carbon nanotube array-carbon nano-onions after reaction 6h
The preparation of condensation material.
Fig. 3 a are XPS collection of illustrative plates, it can be seen that vertical carbon nanotube array-carbon nano-onions composite is without other miscellaneous
Matter；Fig. 3 b are the AFM figures that embodiment 3 prepares carbon nano-onions in vertical carbon nanotube array-carbon nano-onions composite, can
To find out that carbon nano-onions are annular in shape.
Embodiment 4：CVD stoves used in the present invention are heated filament-CVD stoves.
(1) silicon chip is cleaned by ultrasonic 15 minutes respectively through methanol, acetone and isopropyl acetone, N2Drying.Steamed by electron beam
10nm Al are deposited in hair system (E-Beam Evaporator) successively2O3, 0.8nm Fe.
(2) at 750 DEG C of furnace temperature, gas flow is respectively H2:200sccm, C2H2:2sccm, passes through the H of deionized water2
For 200sccm, total gas pressure is 25Torr, and heated filament is single tungsten filament, under the conditions of power is 35W, and the silicon chip that will be made in (1) is placed in tungsten
By tungsten filament power setting it is 0 after silk front 0.5cm, reaction 30s, total gas pressure is adjusted to 6.4Torr, completes single after reaction 15min
Wall carbon nano tube orthogonal array grows.
(3) 3nm Si are deposited in the single wall vertical carbon nanotube array obtained by electron beam evaporation system in (2).
(4) at 850 DEG C of furnace temperature, gas flow is respectively H2:200sccm, CH4:0.75sccm, leads to the H of deionized water2
For 200sccm, total gas pressure is 25Torr, and heated filament is four tungsten filaments, under the conditions of general power is 85W, will be made in (3) containing vertical carbon
Nano-tube array and Si silicon chip are placed in immediately below tungsten filament, and it is multiple to complete vertical carbon nanotube array-carbon nano-onions after reaction 6h
The preparation of condensation material.
Fig. 4 a are to prepare vertical carbon nanotube array-carbon nano-onions composite ultracapacitor CV curves are made, and are obtained
Going out Electrochemical results, its specific capacitance is respectively 167.62,117.48,105.02 in 0.2V/s, 0.5V/s, 1V/s and 2V/s,
88.92F/g.Fig. 4 b are that embodiment 4 prepares the obtained ultracapacitor energy of vertical carbon nanotube array-carbon nano-onions composite
The graph of a relation of metric density and power density, it can be seen that its maximum energy-density is 499.5Wh/kg, and power density is 67.3kW/
kg.Fig. 4 c are to prepare vertical carbon nanotube array-carbon nano-onions composite ultracapacitor cyclic curve is made, and can be seen
Go out after 10000 circulations, its capacity ratio has almost no change, and shows good cycle characteristics.
Claims (3)
1. the method for single-walled carbon nanotube orthogonal array-carbon nano-onions composite is prepared, single-walled carbon nanotube orthogonal array-
Carbon nano-onions composite bottom is silicon chip, is vertical single-wall carbon nanotube array on silicon chip, vertical single-walled carbon nanotube battle array
The top of row is carbon nano-onions structure, it is characterised in that comprised the following steps：
(1) silicon chip is cleaned by ultrasonic respectively through methanol, acetone and isopropyl acetone, N2Drying, passes through electron beam evaporation system (E-
Beam Evaporator) Al of 8-12nm thickness is deposited in silicon chip surface successively2O3With 0.7-1.2nm thickness Fs e；
(2) single-wall carbon nanotube array vertical-growth：It is 700-800 DEG C to set furnace temperature, and total gas couette is：H2:200±
10sccm、C2H2:2 ± 0.5sccm and the H for passing through deionized water2For 200 ± 10sccm, total gas pressure is 25 ± 1Torr, and heated filament is
Single tungsten filament, power is 30-35W；The silicon chip of obtained coating in step (1) is placed in 0.3-0.5cm in front of tungsten filament, tungsten filament with
Silicon chip is parallel so that coating of the air-flow through overheating on tungsten filament and silicon chip reacts, and by tungsten filament power setting is 0, total gas after reaction 30s
Pressure completes the growth of single-walled carbon nanotube orthogonal array after being adjusted to 6.4Torr, reaction 15min；
(3) it is thick that 1-3nm is vertically deposited in the single wall vertical carbon nanotube array top obtained by electron beam evaporation system in (2)
The Si layers of degree；
(4) using the equipment of step (2), 850 DEG C of furnace temperature is set, and total gas couette is H2:200±10sccm、CH4:
0.75sccm, logical deionized water H2For 200 ± 10sccm；Total gas pressure be 25 ± 1Torr, heated filament be replace with four it is in parallel
Tungsten filament, under the conditions of general power is 75-85W, will be made under being deposited and having that Si carbon nano pipe array is parallel and be placed in tungsten filament just in (3)
The preparation of vertical carbon nanotube array-carbon nano-onions composite is completed after side, reaction 2-6h.
2. according to the method for claim 1, it is characterised in that tungsten filament diameter 0.2-0.3mm, length is 8-12mm；Tungsten filament is four
During root, the parallel row of four tungsten filaments is separated.
3. according to the method for claim 1, it is characterised in that in step (2)：By the obtained silicon chip containing coating in step (1)
It is placed in 0.5cm in front of tungsten filament.
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| CN101811690A (en) * | 2009-02-24 | 2010-08-25 | 国家纳米科学中心 | Method for forming carbon composite structure by using carbon nano tube and graphene |
| CN102369308A (en) * | 2009-02-09 | 2012-03-07 | 应用材料公司 | Mesoporous carbon material for energy storage |
| CN102424375A (en) * | 2011-09-07 | 2012-04-25 | 钟国仿 | Preparation method for vertical carbon nanotube array |
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| CN102369308A (en) * | 2009-02-09 | 2012-03-07 | 应用材料公司 | Mesoporous carbon material for energy storage |
| CN101811690A (en) * | 2009-02-24 | 2010-08-25 | 国家纳米科学中心 | Method for forming carbon composite structure by using carbon nano tube and graphene |
| CN102424375A (en) * | 2011-09-07 | 2012-04-25 | 钟国仿 | Preparation method for vertical carbon nanotube array |
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| Title |
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| Growth of Manganese Oxide Nanoflowers on Vertically-Aligned Carbon Nanotube Arrays for High-Rate Electrochemical Capacitive Energy Storage;Hao Zhang等;《American Chemical Society》;20080821;45484-45491页 * |
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