CN108502873A - A kind of high quality, less defect, the preparation method of the uniform graphene of structure - Google Patents
A kind of high quality, less defect, the preparation method of the uniform graphene of structure Download PDFInfo
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- CN108502873A CN108502873A CN201810665320.7A CN201810665320A CN108502873A CN 108502873 A CN108502873 A CN 108502873A CN 201810665320 A CN201810665320 A CN 201810665320A CN 108502873 A CN108502873 A CN 108502873A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
Abstract
The present invention devises a kind of high quality, few defect, the preparation method of the uniform graphene of structure, which includes the following steps：The pre-treatment of catalyst nickel-coated carbon fibers；It is grown using PECVD；The setting corresponding technological parameter of instrument is grown；Growth terminates, and closes all water, electricity and gas, taking-up growth sample is characterized.The present invention uses nickel-coated carbon fibers for catalyst, and preparation-obtained graphene-structured is uniform, quality is high, impurity is few.
Description
Technical field
The present invention is the preparation field of graphene, and in particular to a kind of high quality, few defect, the uniform graphene of structure
Preparation method.
Background technology
Graphene has unique structure and excellent performance, while also having good flexibility and translucency.Make its
The fields such as electronics, information, the energy, material and biological medicine suffer from wide application prospect.It is this new in order to preferably apply
Proximate matter material, how controlledly synthesis high-quality graphene is a difficulty that must pull against.With chemistry redox method, mechanical stripping
Method is compared with silicon carbide epitaxial growth method, and chemical vapour deposition technique (CVD) can be continuous with growing large-area high quality because of it
Graphene film and receive much attention.Growth mechanism based on graphene, from the point of view of the selected angle of substrate material, the selection pair of substrate
The influence of CVD growth graphene is still very big.
CVD is one of the main stream approach for preparing monocrystalline high-quality graphene at present, and this method is using with methane, second
The carbon containing air source such as alkynes, ethylene is as presoma, and carbon-source gas molecule is cracked to form carbon atom under high temperature, in temperature appropriate
In the case of degree, pressure and gas ratio, carbon atom forms the gradual crystalline film of core on the metallic substrate.Currently used catalyst
Transition metal has two kinds of copper foil and nickel film.But the difference of the growth mechanism on copper and mickel.Deposition on nickel is intended to
Carbon mechanism is analysed in carburizing, and is then surface limiting growth mechanism on copper foil.There is the metallic matrix of higher molten carbon amounts for nickel
For, the pyrolysis carbon atom of carbon source precursor Pintsch process generation penetrates into metal inside and is formed at high temperature with nickel admittedly at high temperature
Solution, with the reduction of temperature, carbon before is gradually precipitated in surface forming core crystalline film.But the growth on nickel is not easy to adjust
Parameters are saved, cause the quality degree of disorder of the film of growth high.
Nickel-coated carbon fibers belong to field of metal matrix composite, are a kind of novel high intensity, high modulus material, have good
Good conductive capability.The composite material of nickel-coated carbon fibers enhancing not only has excellent rigidity and intensity, smaller thermal expansion system
The advantages of number and proportion, while having preferable catalytic performance, therefore this patent just utilizes nickel-coated carbon fibers, invented it is a kind of with
Nickel-coated carbon fibers material is catalyst, and using plasma enhancing chemical vapour deposition technique (PECVD) is prepared for high quality, defect
Less, the method for the uniform graphene of structure.
Invention content
For the problems of the prior art, the present invention provides a kind of high quality, few defect, the systems of the uniform graphene of structure
Preparation Method, it is, using methane as carbon source, at a lower temperature, to grow graphite based on PECVD using nickel-coated carbon fibers as catalyst to use
Alkene.
In order to achieve the above objectives, the present invention is achieved by the following technical solutions：A kind of high quality, less defect, structure
The preparation method of uniform graphene, includes the following steps：
(1) nickel-coated carbon fibers for cutting 10cm length completely remove the slurry agent on nickel-coated carbon fibers with acetone soak 2h, described
Carbon fiber sizing agent content is 1.0%~1.5%；
(2) electricity, gas and device for absorbing tail gas are opened；CH4、H2, Ar master switch, first of pressure reducing valve, second decompression
Valve；
(3) opening PECVD power switches, instrument switch, startup vacuum detecting unit switch, the vacuum degree of detecting instrument,
Keep its vacuum degree in 0.5Pa hereinafter, its pressure holding effect is tested, after vacuum system test, by nickel-coated carbon fibers clip 10cm long
The heating zone of quartz ampoule is put on quartz boat and be positioned over, ring flange furnace chamber door is closed；
(4) it vacuumizes：Flapper valve is opened, tail gas linked set switch is closed, clicks vacuum system device start button, directly
It is reduced to 0.5Pa or less to quartzy overpressure；
(5) it heats：It clicks heat control unit and runs button, until temperature rises to target temperature；
(6) cycle annealing：Open H2Air inlet switchs, and opens and be mixed into gas port switch, clicks auto-admission setting and presses
Button, open plasma switch, is adjusted to target power by power, clicks the ON buttons of plasma, H after 30min2Flow is automatic
It closes；
(7) it grows：Open CH4Air inlet switchs, click auto-admission setting button, H after 15min2Flow is automatically closed,
Plasma power is adjusted to target power, after growth, plasma power is adjusted to 0W, closes plasma shutter,
Click OFF buttons；
(8) cool down：Ar air inlets switch is opened, auto-admission is clicked and button is set, close H2、 CH4Air inlet switchs,
Ar flows are automatically closed after 50min；
(9) cooling sampling：Vacuum detecting unit is closed when furnace body temperature is down to 50 DEG C, is closed Ar air inlets, is mixed into
Gas port switchs, and opens ring flange and takes out sample；
(10) it shuts down：Instrument button is closed to OFF gears, LOCK switches, power switch device is closed and power supply is always opened
It closes, closes all air circuit breaker buttons.
Further, the nickel plating thickness 0.2-1.0mm of the nickel-coated carbon fibers, surface is relatively rough, uneven, directly
Diameter is about 8mm.
Further, the target temperature is 750 DEG C.
Further, the target power that PECVD is adjusted to is 40W.
Further, H when cycle annealing2Flow be 10sccm.
Further, H when growth2Flow be 5sccm, CH4Flow be 4sccm.
Further, Ar flows are 50sccm when cooling.
Advantageous effect of the present invention：The preparation-obtained graphene-structured of the present invention is uniform, quality is high, impurity is few, reaction
Temperature is relatively low, and energy consumption is also fewer, and reaction total time is shorter.
Description of the drawings
Fig. 1 is growth graphene SEM figures above the nickel-coated carbon fibers of the preparation of the embodiment of the present invention 1；
Fig. 2 is the Raman spectrogram that graphene is grown above the nickel-coated carbon fibers of the preparation of the embodiment of the present invention 1；
Fig. 3 is growth graphene SEM figures above the nickel-coated carbon fibers of the preparation of the embodiment of the present invention 2；
Fig. 4 is the Raman spectrogram that graphene is grown above the nickel-coated carbon fibers of the preparation of the embodiment of the present invention 2；
Fig. 5 is growth graphene SEM figures above the nickel-coated carbon fibers of the preparation of the embodiment of the present invention 3；
Fig. 6 is the Raman spectrogram that graphene is grown above the nickel-coated carbon fibers of the preparation of the embodiment of the present invention 3.
Specific implementation mode
Embodiment 1
(1) nickel-coated carbon fibers for cutting 10cm length completely remove the slurry agent on nickel-coated carbon fibers, carbon fiber with acetone soak 2h
Starching agent content is tieed up 1.2%, the starching agent content of same root fiber difference section is basicly stable.
(2) electricity, gas, device for absorbing tail gas, CH are opened4、H2, Ar switch master switch, first of pressure reducing valve, second decompression
Valve.
(3) open plasma enhancing chemical vapor deposition (PECVD) power switch, instrument switch, start vacuum detecting
Unit switch, the vacuum degree (0.5Pa or less) and pressure holding effect of detecting instrument, after vacuum system is out of question, by the plating of figure below
The heating zone of quartz ampoule is put on quartz boat and placed to nickel carbon fiber clip 10cm long, closes ring flange furnace chamber door.
(4) it vacuumizes：Flapper valve is opened, tail gas linked set switch is closed, clicks vacuum system device start button, directly
It is 0.5Pa or less to quartzy overpressure.
(5) technological parameter is set：Target temperature：700 DEG C, the heating-up time：50min, annealing time：30min, when annealing
H2Flow：10sccm, power when annealing：40W, growth time：30min, H when growth2Flow：5sccm, CH when growth4Flow：
4sccm, power when growth：40W, Ar flows are 50sccm when cooling.
(6) it heats：It clicks heat control unit and runs button, until temperature rises to target temperature；
(7) cycle annealing：Open H2Air inlet switchs, and opens and be mixed into gas port switch, clicks auto-admission setting and presses
Power is adjusted to target power by button, open plasma switch, clicks ON buttons, H after 30min2Flow is automatically closed；
(8) it grows：Open CH4Air inlet switchs, click auto-admission setting button, H after 15min2Flow is automatically closed,
Plasma power is adjusted to target power, after growth, plasma power is adjusted to 0W, closes plasma shutter,
Click OFF buttons；
(9) cool down：Ar air inlets switch is opened, auto-admission is clicked and button is set, close H2、 CH4Air inlet switchs,
Ar flows are automatically closed after 50min；
(10) cooling sampling：Vacuum detecting unit is closed when furnace body temperature is down to 50 DEG C, closes Ar air inlets, mixing
Air inlet switchs, and opens ring flange, sample is taken out；
(11) it shuts down：Instrument button is closed to OFF gears, LOCK switches, power switch device is closed and power supply is always opened
It closes, closes all air circuit breaker buttons.
Growth result：Quartzy tube wall does not have blackening, nickel-coated carbon fibers surface not to change significantly, only than growth before
Color has slightly deepened some.
Embodiment 2
(1) (1) in above-mentioned steps~(4) are the same as embodiment 1.
(2) technological parameter is set：Target temperature：750 DEG C, the heating-up time：55min, annealing time：30min, when annealing
H2Flow：10sccm, power when annealing：40W, growth time：30min, H when growth2Flow：5sccm, CH when growth4Flow：
4sccm, power when growth：40W, Ar flows are 50sccm when cooling.
(3) above-mentioned (6)~(11) technical process is the same as embodiment 1.
Growth result：Quartzy tube wall does not have blackening, nickel-coated carbon fibers surface not to change significantly, than the color before growth
Some are slightly deepened.
Embodiment 3
(1) (1) in above-mentioned steps~(4) are the same as embodiment 1.
(2) technological parameter is set：Target temperature：800 DEG C, the heating-up time：70min, annealing time：30min, when annealing
H2Flow：10sccm, power when annealing：40W, growth time：30min, H when growth2Flow：5sccm, CH when growth4Flow：
4sccm, power when growth：40W, Ar flows are 50sccm when cooling.
(3) above-mentioned (6)~(11) technique is the same as embodiment 1.
Growth result：Quartzy tube wall blackening is more black, and nickel-coated carbon fibers surface state does not change significantly, before growth
Color has slightly deepened some.
Graphene prepared by 1-3 of the embodiment of the present invention carries out level of coverage, technique total time, structure uniformly and defect is united
It counts specific data and is shown in Table 1.Table 1
Claims (7)
1. a kind of high quality, defect are few, the preparation method of the uniform graphene of structure, which is characterized in that the method step is：
(1) nickel-coated carbon fibers for cutting 10cm length completely remove the slurry agent on nickel-coated carbon fibers, the carbon fiber with acetone soak 2h
Starching agent content is tieed up 1.0%~1.5%；
(2) electricity, gas and device for absorbing tail gas are opened；CH4、H2, Ar master switch, first of pressure reducing valve, second pressure reducing valve；
(3) PECVD power switches, instrument switch are opened, vacuum detecting unit switch is started, the vacuum degree of detecting instrument is kept
Nickel-coated carbon fibers clip 10cm long hereinafter, test its pressure holding effect, after vacuum system test, is put stone by its vacuum degree in 0.5Pa
Ying Zhou is upper and is positioned over the heating zone of quartz ampoule, closes ring flange furnace chamber door；
(4) it vacuumizes：Flapper valve is opened, tail gas linked set switch is closed, clicks vacuum system device start button, until stone
English overpressure is reduced to 0.5Pa or less；
(5) it heats：It clicks heat control unit and runs button, until temperature rises to target temperature；
(6) cycle annealing：Open H2Air inlet switchs, and opens and be mixed into gas port switch, clicks auto-admission and button is arranged, beat
Plasma shutter is opened, power is adjusted to target power, clicks the ON buttons of plasma, H after 30min2Flow is automatically closed；
(7) it grows：Open CH4Air inlet switchs, click auto-admission setting button, H after 15min2Flow is automatically closed, and will wait
Gas ions power is adjusted to target power, after growth, plasma power is adjusted to 0W, closes plasma shutter, is clicked
OFF buttons；
(8) cool down：Ar air inlets switch is opened, auto-admission is clicked and button is set, close H2、CH4Air inlet switchs, after 50min
Ar flows are automatically closed；
(9) cooling sampling：Vacuum detecting unit is closed when furnace body temperature is down to 50 DEG C, is closed Ar air inlets, is mixed into gas port
Switch opens ring flange and takes out sample；
(10) it shuts down：Instrument button is closed to OFF gears, LOCK switches, power switch device and battery main switch is closed, closes
Close all air circuit breaker buttons.
2. a kind of high quality according to claim 1, few defect, the preparation method of the uniform graphene of structure, feature
It is：The nickel plating thickness 0.2-1.0mm of the nickel-coated carbon fibers, rough surface is uneven, a diameter of 8mm.
3. a kind of high quality according to claim 1, few defect, the preparation method of the uniform graphene of structure, feature
It is：The target temperature is 750 DEG C.
4. a kind of high quality according to claim 1, few defect, the preparation method of the uniform graphene of structure, feature
It is：The target power that PECVD is adjusted to is 40W.
5. a kind of high quality according to claim 1, few defect, the preparation method of the uniform graphene of structure, feature
It is：H when cycle annealing2Flow be 10sccm.
6. a kind of high quality according to claim 1, few defect, the preparation method of the uniform graphene of structure, feature
It is：H when growth2Flow be 5sccm, CH4Flow be 4sccm.
7. a kind of high quality according to claim 1, few defect, the preparation method of the uniform graphene of structure, feature
It is：Ar flows are 50sccm when cooling.
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| WO2020168819A1 (en) * | 2019-02-20 | 2020-08-27 | 南京大学 | Method for efficiently eliminating graphene wrinkles formed by chemical vapor deposition |
| CN113072063A (en) * | 2020-07-10 | 2021-07-06 | 华南理工大学 | Hydrogen-resistant coating based on inner surface of hydrogen storage and transportation equipment and preparation method thereof |
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Address after: 330000 No.278 luozhu Road, Xiaolan economic and Technological Development Zone, Nanchang County, Nanchang City, Jiangxi Province Patentee after: Jiangxi Nanotechnology Research Institute Address before: 330000 no.266 Huiren Avenue, Xiaolan economic and Technological Development Zone, Nanchang City, Jiangxi Province Patentee before: NANCHANG INSTITUTE, SUZHOU INSTITUTE OF NANO-TECH AND NANO-BIONICS, CAS |