CN106629641B - A kind of black phosphorus carbon nano tube compound material and its preparation method and application - Google Patents
A kind of black phosphorus carbon nano tube compound material and its preparation method and application Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 114
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 114
- 239000000463 material Substances 0.000 title claims abstract description 49
- -1 black phosphorus carbon nano tube compound Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 80
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000002079 double walled nanotube Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 0.000 claims 1
- 230000005693 optoelectronics Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011521 glass Substances 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
- 239000013067 intermediate product Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003325 tomography Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic System
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention provides a kind of black phosphorus carbon nano tube compound materials, including more carbon nanotubes and the black phosphorus crystal particle for being deposited on the carbon nano tube surface.The composite material has both the adjustable direct band gap characteristic of black phosphorus and highly conductive, the high stability of carbon nanotube, compensates for limitation when black phosphorus or carbon nanotube is used alone, has broad application prospects in fields such as photoelectric devices.The present invention also provides the preparation method and application of the black phosphorus carbon nano tube compound material.
Description
Technical field
The present invention relates to condensation material preparation technical fields, more particularly to a kind of black phosphorus carbon nano tube compound material and its system
Preparation Method and application.
Background technique
Black phosphorus is the two-dimensional material of the another kind novelty found after graphene.Different from the graphite with zero band gap
Alkene, black phosphorus are direct band-gap semicondictor materials, and band gap can show biggish switching current ratio (10 between 0.3~2eV5)
With high carrier mobility (103cm2/ Vs), while there is near infrared light response characteristic.Therefore, in black phosphorus scene effect transistor
The fields such as channel material, dye-sensitized solar cells there is potential application prospect.However, black phosphorus is under the environment such as air
It easily decomposes, hinders the large-scale application of black phosphorus, how to improve the environmental stability of black phosphorus is to need emphasis to consider at present
The problem of.
Carbon nanotube has been known, with splendid environmental stability, electric conductivity, high electron transfer
Rate (104cm2/ Vs) and certain electro catalytic activity, there is important application in photoelectric device and fuel cell.However, carbon
Nanotube suffers from the problem too narrow with zero similar band gap of graphene or band gap, has when so that it is as microelectronic switch
Low on-off ratio.In addition, the nano tubular structure and surface inertness of carbon nanotube make it be difficult to closely connect with other component,
Further limit the application of carbon nanotube.Therefore, it is necessary in conjunction with black phosphorus and the respective excellent properties of carbon nanotube, by both sides
Disadvantage made up, develop and a kind of have both the adjustable direct band gap characteristic of black phosphorus and highly conductive, the Gao Wen of carbon nanotube
Qualitative composite material makes the two have brighter prospect in the application in the fields such as photoelectric device, electro-catalysis.
Summary of the invention
In consideration of it, first aspect present invention provides a kind of black phosphorus carbon nano tube compound material, which has both black
The adjustable direct band gap characteristic of phosphorus and highly conductive, the high stability of carbon nanotube have wide in fields such as photoelectric device, electro-catalysis
Wealthy application prospect.
In a first aspect, the present invention provides a kind of black phosphorus carbon nano tube compound material, including more carbon nanotubes and deposition
In the black phosphorus crystal particle of the carbon nano tube surface.
Wherein, the mass ratio of the carbon nanotube and the black phosphorus crystal particle is 1:(0.1~50).The content of the two can
It is set according to concrete application demand, optionally, the mass ratio of carbon nanotube and black phosphorus crystal particle can be 1:(0.1~1)
Or 1:(2~30) or 1:(40~50).
In black phosphorus carbon nano tube compound material of the present invention, the carbon nanotube is single wall, double-walled and multi-wall carbon nano-tube
One or more of pipe, the more carbon nano-tube oriented arrangements or is intertwined to form porous carbon nanotube mesh structures.
Therefore, the black phosphorus carbon nano tube compound material equally has porous structure.
The black phosphorus crystal particle is evenly distributed in the carbon nanotube mesh structures.
The size of the black phosphorus crystal particle is 3nm~8 μm.More specifically 5nm-100nm, 200nm-800nm or 1 μm
~5 μm.
Optionally, the diameter of the carbon nanotube is 3~200nm, and length is 0.1~100 μm.Suitable diameter and length
Be conducive to carbon nanotube to mix with the uniform of red phosphorus, be conducive to the deposition of black phosphorus crystal particle.
The black phosphorus carbon nano tube compound material that first aspect present invention provides, it is brilliant by depositing black phosphorus in carbon nano tube surface
Body particle makes it have both the adjustable direct band gap characteristic of black phosphorus and the highly conductive of carbon nanotube, high stability, electro catalytic activity,
Compensate for limitation when black phosphorus or carbon nanotube is used alone.
Second aspect, the present invention provides a kind of preparation methods of black phosphorus carbon nano tube compound material, comprising the following steps:
Carbon nanotube and red phosphorus are added in volatile organic solvent or deionized water by certain mass ratio and carry out ultrasound
Dispersion obtains mixed dispersion liquid, then the mixed dispersion liquid is dry, to remove the volatile organic solvent or deionization
Water obtains carbon nanotube and red phosphorus mixture；
It after the carbon nanotube and red phosphorus mixture are carried out hand lapping or ball milling, is placed in reaction chamber, in protection gas
It is first heated to 450~1100 DEG C under atmosphere, keeps the temperature 1~20h, subsequently drops to 120~380 DEG C, keeps the temperature 0.2~4h, heat preservation terminates
After cool down, obtain black phosphorus carbon nano tube compound material, the black phosphorus carbon nano tube compound material includes carbon nanotube and is deposited on
The black phosphorus crystal particle of the carbon nano tube surface.
Optionally, the mass ratio of the carbon nanotube and the red phosphorus is 1:(0.1~50), the content of the two can be according to tool
Body application demand is set, and further, the mass ratio of carbon nanotube and black phosphorus crystal particle can be 1:(0.1~1) or 1:
(2~30) or 1:(40~50).
Optionally, in volatile organic solvent or deionized water described in every 1L carbon nanotube and the gross mass of red phosphorus be 1~
100g.Further, in volatile organic solvent or deionized water described in every 1L carbon nanotube and the gross mass of red phosphorus be 1~
50g or 60-90g.
Optionally, the diameter of the carbon nanotube is 3~200nm, and length is 0.1~100 μm.Suitable diameter and length
Be conducive to carbon nanotube to mix with the uniform of red phosphorus, be conducive to the deposition of black phosphorus crystal particle.
Optionally, the volatile organic solvent includes dehydrated alcohol, acetone, n-hexane, methanol, toluene, dimethylbenzene, four
One of chloromethanes, acetonitrile, ethyl acetate are a variety of.
Optionally, the time of the ultrasonic disperse is 5~40min.Further, the time of ultrasonic disperse is 5-15min,
Or 20-35min.The drying carries out in an oven, and optionally, the temperature of the drying is 50~150 DEG C.Further, it does
Dry temperature is 80-120 DEG C.And the dry time depending on the amount of the mixed dispersion liquid, it is general it is dry to mixture agglomeration,
Occur it is dry and cracked and without wetting until, specifically the dry time can be 4~48h.By ultrasonic disperse and drying, so that carbon nanometer
Pipe is uniformly mixed with red phosphorus powder.
In the present invention, the hand lapping carries out in mortar, and the material of mortar can be glass, stainless steel, agate, oxygen
Change aluminium or zirconium oxide.Optionally, the time of the hand lapping is 5~120min, and grinding rate is 10~60 turns/min.Into one
Step ground, the time of hand lapping are 10~60min.
In the present invention, the ball milling using planetary ball mill carry out, optionally, drum's speed of rotation be 30~720 turns/
Min, Ball-milling Time are 10~120min.Further, drum's speed of rotation be 100~600 turns/min, Ball-milling Time be 20~
60min.The ball milling pearl of the planetary ball mill can be to be spherical or cylindrical, and diameter is 1~30mm, and material is stainless steel, oxygen
Change aluminium or zirconia ceramics.By hand lapping or ball milling, the carbon nanotube and red phosphorus mixture agglomerated after drying is made to smash to pieces, grind
Carefully, and make to mix more uniform.
In the present invention, by 450~1100 DEG C of high-temperature heating process of first stage, red phosphorus is made to decompose volatilization, volatilization
Phosphorus atoms intermediate product is transferred to carbon nano tube surface, is adsorbed, and carbon nano tube surface nucleation, grow up, with phosphorus original
Continuous transmission, absorption, diffusion, nucleation and the growth of son, black phosphorus crystal particle is finally formed in carbon nano tube surface, to obtain
Black phosphorus carbon nano tube compound material.And by 120~380 DEG C of second stage, the cooling insulating process of 0.2~4h is kept the temperature, is avoided
The crystallization as caused by a step direct temperature-fall period not exclusively, make cracked deposit, tomography, crystal grain is tiny, crystal phase not
Phenomena such as consistent.
Optionally, the protective atmosphere is argon gas or nitrogen atmosphere, and purity is >=99.99%.
Optionally, it is first heated to 600~800 DEG C, keeps the temperature 1~20h, subsequently drop to 200~300 DEG C, heat preservation 0.2~
4h。
The size of the black phosphorus crystal particle is 3nm~8 μm.More specifically 5nm-100nm, 200nm-800nm or 1 μm
~5 μm.The size of black phosphorus crystal particle increases with the growth of the high-temperature holding time of first stage.
The preparation method for the black phosphorus carbon nano tube compound material that second aspect of the present invention provides, this method is at low cost, efficiency
High, easy scale.
The third aspect, the present invention provides black phosphorus carbon nano tube compound materials described in a kind of first aspect present invention in light
Application in electrical part.For example, as the application of channel material in scene effect transistor, in dye-sensitized solar cells
As the application of photocathode, and the application as catalyst carrier or non-platinum catalyst in a fuel cell.
Advantages of the present invention will be illustrated partially in the following description, and a part is apparent according to specification
, or can implementation through the embodiment of the present invention and know.
Detailed description of the invention
Fig. 1 is the SEM photograph for the black phosphorus carbon nano tube compound material that the embodiment of the present invention 1 is prepared；
Fig. 2 is the XRD photo for the black phosphorus carbon nano tube compound material that the embodiment of the present invention 1 is prepared；
Fig. 3 is the high-resolution transmission electron microscopy for the black phosphorus carbon nano tube compound material that the embodiment of the present invention 1 is prepared
Mirror photo.
Specific embodiment
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, without departing from the principles of the embodiments of the present invention, several improvements and modifications can also be made, these improvement
Also it is considered as the protection scope of the embodiment of the present invention with retouching.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.Wherein, the embodiment of the present invention is unlimited
Due to specific embodiment below.Within the scope of the unchanged main rights, implementation can appropriate be changed.
Embodiment 1
A kind of preparation method of black phosphorus carbon nano tube compound material, comprising the following steps:
(1) 2g carbon nanotube and 2g red phosphorus are added to progress ultrasonic disperse 20min in 1L dehydrated alcohol, obtain mixing point
Dispersion liquid, then by the mixed dispersion liquid it is dry to agglomerate, occur it is dry and cracked and without wetting until, to remove the dehydrated alcohol, obtain
To carbon nanotube and red phosphorus mixture；
(2) carbon nanotube and red phosphorus mixture are put into agate mortar, with the speed hand lapping of 30 turns/min
After 30min, reaction chamber is packed into using aluminium oxide boat, the argon gas that purity is 99.99% is passed through in reaction chamber as protective atmosphere, and
650 DEG C of holding 6h are heated to, 350 DEG C is subsequently reduced to and keeps 2h, then be down to room temperature, take out sample to get black phosphorus carbon nanometer is arrived
Pipe composite material.
SEM characterization discovery is carried out to sample, carbon nano tube surface is deposited with a large amount of black phosphorus crystal particle, and black phosphorus crystal
Particle is evenly distributed in carbon nanotube network, and particle size is between 0.1~5 μm, as shown in Figure 1,10 being in figure
Black phosphorus crystal particle.XRD characterization is carried out to obtained sample, as shown in Fig. 2, there is apparent carbon nanotube in discovery map
With the characteristic peak of rhombic system black phosphorus, it was confirmed that synthesized sample is black phosphorus carbon nano tube compound material.To obtained sample
Product carry out high resolution transmission electron microscopy characterization, as shown in figure 3, the crystalline substance in carbon nanotube (002) face can wherein be clearly seen
Lattice interplanar distance is 0.336nm and the lattice spacing in black phosphorus (111) face is 0.25nm.
Embodiment 2
A kind of preparation method of black phosphorus carbon nano tube compound material, comprising the following steps:
(1) 20g carbon nanotube and 2g red phosphorus are added to progress ultrasonic disperse 15min in 1L dehydrated alcohol, are mixed
Dispersion liquid, then by the mixed dispersion liquid it is dry to agglomerate, occur it is dry and cracked and without wetting until, to remove the dehydrated alcohol,
Obtain carbon nanotube and red phosphorus mixture；
(2) carbon nanotube and red phosphorus mixture are put into agate mortar, with the speed hand lapping of 20 turns/min
After 60min, reaction chamber is packed into using aluminium oxide boat, the argon gas that purity is 99.99% is passed through in reaction chamber as protective atmosphere, and
800 DEG C of holding 8h are heated to, 250 DEG C is subsequently reduced to and keeps 3.5h, then be down to room temperature, sample is taken out and is received to get to black phosphorus carbon
Mitron composite material.
Embodiment 3
A kind of preparation method of black phosphorus carbon nano tube compound material, comprising the following steps:
(1) 2g carbon nanotube and 80g red phosphorus are added to progress ultrasonic disperse 40min in 1L acetone, obtain mixing dispersion
Liquid, then by the mixed dispersion liquid it is dry to agglomerate, occur it is dry and cracked and without wetting until, to remove the acetone, obtain carbon and receive
Mitron and red phosphorus mixture；
(2) carbon nanotube and red phosphorus mixture are put into planetary ball mill and are ground, with 300 turns/min's
After revolving speed ball milling 60min, reaction chamber is packed into using aluminium oxide boat, the argon gas that purity is 99.99% is passed through in reaction chamber and is used as guarantor
Protect atmosphere, and be heated to 400 DEG C of holdings 18h, be subsequently reduced to 150 DEG C and keep 0.5h, then be down to room temperature, taking-up sample to get
To black phosphorus carbon nano tube compound material.
Embodiment 4
A kind of preparation method of black phosphorus carbon nano tube compound material, comprising the following steps:
(1) 2g carbon nanotube and 40g red phosphorus are added to progress ultrasonic disperse 30min in 1L deionized water, are mixed
Dispersion liquid, then by the mixed dispersion liquid it is dry to agglomerate, occur it is dry and cracked and without wetting until, to remove the deionized water,
Obtain carbon nanotube and red phosphorus mixture；
(2) carbon nanotube and red phosphorus mixture are put into planetary ball mill and are ground, with 600 turns/min's
After revolving speed ball milling 15min, reaction chamber is packed into using aluminium oxide boat, the argon gas that purity is 99.99% is passed through in reaction chamber and is used as guarantor
Atmosphere is protected, and is heated to 1000 DEG C of holding 2h, 380 DEG C is subsequently reduced to and keeps 4h, then be down to room temperature, takes out sample to get arriving
Black phosphorus carbon nano tube compound material.
Embodiment 5
A kind of preparation method of black phosphorus carbon nano tube compound material, comprising the following steps:
(1) 2g carbon nanotube and 20g red phosphorus are added to progress ultrasonic disperse 20min in 1L acetonitrile, obtain mixing dispersion
Liquid, then by the mixed dispersion liquid it is dry to agglomerate, occur it is dry and cracked and without wetting until, to remove the acetonitrile, obtain carbon and receive
Mitron and red phosphorus mixture；
(2) carbon nanotube and red phosphorus mixture are put into planetary ball mill and are ground, with 200 turns/min's
After revolving speed ball milling 100min, reaction chamber is packed into using aluminium oxide boat, the argon gas that purity is 99.99% is passed through in reaction chamber and is used as guarantor
Atmosphere is protected, and is heated to 600 DEG C of holding 12h, 200 DEG C is subsequently reduced to and keeps 3h, then be down to room temperature, takes out sample to get arriving
Black phosphorus carbon nano tube compound material.
It should be noted that according to the above description the announcement of book and with illustrate, those skilled in the art in the invention also
It can change and modify the above embodiment.Therefore, the invention is not limited to specific realities disclosed and described above
Mode is applied, some equivalent modifications of the invention and change should also be as within scope of protection of the claims of the invention.This
Outside, although using some specific terms in this specification, these terms are merely for convenience of description, not to the present invention
Constitute any restrictions.
Claims (10)
1. a kind of black phosphorus carbon nano tube compound material, which is characterized in that including more carbon nanotubes and be deposited on the carbon nanometer
The black phosphorus crystal particle of pipe surface, the black phosphorus carbon nano tube compound material use are made following preparation method, the preparation side
Method the following steps are included:
By carbon nanotube and red phosphorus 1:(0.1~50 in mass ratio) it is added in volatile organic solvent or deionized water and carries out
Ultrasonic disperse, obtains mixed dispersion liquid, then the mixed dispersion liquid is dry, with remove the volatile organic solvent or go from
Sub- water obtains carbon nanotube and red phosphorus mixture；
After the carbon nanotube and red phosphorus mixture are carried out hand lapping or ball milling, it is placed in reaction chamber, under protective atmosphere
600~1100 DEG C are first heated to, 1~20h is kept the temperature, subsequently drops to 120~380 DEG C, keeps the temperature 0.2~4h, it is cold after heat preservation
But, the black phosphorus carbon nano tube compound material is obtained.
2. black phosphorus carbon nano tube compound material as described in claim 1, which is characterized in that the carbon nanotube and the black phosphorus
The mass ratio of crystal grain is 1:(0.1~50).
3. black phosphorus carbon nano tube compound material as described in claim 1, which is characterized in that the more carbon nano-tube oriented rows
Carbon nanotube mesh structures are arranged or are intertwined to form, the black phosphorus crystal particle is evenly distributed on the carbon nanotube mesh knot
In structure.
4. black phosphorus carbon nano tube compound material as described in claim 1, which is characterized in that the size of the black phosphorus crystal particle
For 3nm~8 μm；The carbon nanotube is one or more of single wall, double-walled and multi-walled carbon nanotube, the carbon nanotube
Diameter is 3~200nm, and length is 0.1~100 μm.
5. a kind of preparation method of black phosphorus carbon nano tube compound material, which comprises the following steps:
By carbon nanotube and red phosphorus 1:(0.1~50 in mass ratio) it is added in volatile organic solvent or deionized water and carries out
Ultrasonic disperse, obtains mixed dispersion liquid, then the mixed dispersion liquid is dry, with remove the volatile organic solvent or go from
Sub- water obtains carbon nanotube and red phosphorus mixture；
After the carbon nanotube and red phosphorus mixture are carried out hand lapping or ball milling, it is placed in reaction chamber, under protective atmosphere
600~1100 DEG C are first heated to, 1~20h is kept the temperature, subsequently drops to 120~380 DEG C, keeps the temperature 0.2~4h, it is cold after heat preservation
But, black phosphorus carbon nano tube compound material is obtained, the black phosphorus carbon nano tube compound material includes carbon nanotube and is deposited on described
The black phosphorus crystal particle of carbon nano tube surface.
6. the preparation method of black phosphorus carbon nano tube compound material as claimed in claim 5, which is characterized in that volatilize described in every 1L
Property organic solvent or deionized water in carbon nanotube and the gross mass of red phosphorus be 1~100g.
7. the preparation method of black phosphorus carbon nano tube compound material as claimed in claim 5, which is characterized in that the volatility has
Solvent includes dehydrated alcohol, acetone, n-hexane, methanol, toluene, dimethylbenzene, tetrachloromethane, acetonitrile, one in ethyl acetate
Kind is a variety of.
8. the preparation method of black phosphorus carbon nano tube compound material as claimed in claim 5, which is characterized in that the ultrasonic disperse
Time be 5~40min, the temperature of the drying is 50~150 DEG C, and the dry time is 4~48h.
9. the preparation method of black phosphorus carbon nano tube compound material as claimed in claim 5, which is characterized in that the hand lapping
Time be 5~120min, grinding rate be 10~60 turns/min；The ball milling is carried out using planetary ball mill, ball mill
Revolving speed is 30~720 turns/min, and Ball-milling Time is 10~120min.
10. a kind of application of black phosphorus carbon nano tube compound material according to any one of claims 1-4 in the opto-electronic device.
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| CN111969883B (en) * | 2020-08-24 | 2021-09-03 | 合肥工业大学 | Application of black phosphorus carbon nanotube composite material as non-contact electrostatic response driver |
| CN112018362B (en) * | 2020-08-31 | 2022-07-12 | 华中科技大学 | Phosphorus-carbon material and in-situ synthesis method and application thereof |
| CN114852995B (en) * | 2022-03-31 | 2024-03-22 | 海南师范大学 | Electrocatalytic application of horseradish peroxidase sensor constructed by black phosphorus-based composite material |
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| CN103296261A (en) * | 2012-02-24 | 2013-09-11 | 清华大学 | Preparation method of lithium ion battery cathode material |
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