CN110371956A - Carbon nano tube/graphene laminated film of N doping and preparation method thereof - Google Patents

Carbon nano tube/graphene laminated film of N doping and preparation method thereof Download PDF

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Publication number
CN110371956A
CN110371956A CN201910745133.4A CN201910745133A CN110371956A CN 110371956 A CN110371956 A CN 110371956A CN 201910745133 A CN201910745133 A CN 201910745133A CN 110371956 A CN110371956 A CN 110371956A
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preparation
laminated film
doping
nano tube
carbon nano
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CN110371956B (en
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方小红
管飞
张鹏博
陈小源
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Pylon Technologies Co Ltd
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Shanghai Advanced Research Institute of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/02—Single layer graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/30—Purity

Abstract

The present invention provides a kind of carbon nano tube/graphene laminated film and preparation method thereof of N doping.The preparation method comprising steps of 1) provide substrate, substrate is placed in vapor deposition apparatus；2) hexamethylenetetramine solid is placed in vapor deposition apparatus, heat resolve is carried out to hexamethylenetetramine solid, and forms the carbon nano tube/graphene laminated film of N doping in substrate surface using low-pressure chemical vapor deposition process in reducibility gas atmosphere.The present invention, for unique carbon nitrogen source, has obtained the carbon nano tube/graphene laminated film of N doping using low-pressure chemical vapor deposition one-step method with cheap hexamethylenetetramine.The preparation method has many advantages, such as equipment and processing step is simple, raw material are cheap and easy to get.The carbon nanotube in carbon nano tube/graphene laminated film being prepared based on preparation method of the invention has high orientation, mutually indepedent between each carbon nanotube, is evenly distributed, film performance is obviously improved.

Description

Carbon nano tube/graphene laminated film of N doping and preparation method thereof
Technical field
The present invention relates to optoelectronic film research fields, compound more particularly to a kind of carbon nano tube/graphene of N doping Film and preparation method thereof.
Background technique
As the carbon nanotube and graphene of material of the same clan, because its electricity in terms of excellent properties due to by Extensive concern.However the smaller radius of curvature of carbon nanotube limits active material in the absorption on its surface；Graphene sheet layer it Between since there are strong van der Waals interactions, will cause the aggregation of graphene fragment, not only reduce the electricity of its vertical direction Lotus transmission, and its specific surface area is reduced, while also reducing carrier mobility.And carbon nano tube/graphene THIN COMPOSITE Film using the synergistic effect between graphene and carbon nanotube and the fault of construction both eliminated by making it in super capacitor The fields such as device, energy storage and sensor have a good application prospect, and become current research hotspot.In addition, graphene/carbon The doping vario-property of nanometer tube composite materials may make that its application is further expanded, such as in graphene/carbon nano-tube compound electric Extremely upper addition CdTe (cadmium antimonide) quantum dot makes optoelectronic switch, and doping metals particle then can be used for making field emission dress It sets.
Many methods use multistep in synthesizing carbon nanotubes/graphene composite material, such as Choi et al. by development and application Method synthesis, first in the SiO for being coated with nickel film2The surface /Si prepares graphene film, then uses FeCl3Solution removal nickel film, then Iron film is deposited on graphene film, deposits multi-walled carbon nanotube on its surface using iron film as catalyst, then etching gets rid of iron Film obtains carbon nano tube/graphene composite material and (is detailed in record: Choi H, Kim H, Hwang S, et after transfer al.Electrochemical electrodes of graphene-based carbon nanotubes grown by chemical vapor deposition[J].Scrip Materialia,2011,64(7):601-604).Dong etc. is with second Alcohol is modified by chemical vapour deposition technique synthesizing graphite alkene/carbon nano tube compound material using nano silicon particles as presoma Copper foil as matrix, graphene homoepitaxial on matrix, carbon nanotube grown using nano silicon particles as starting point to be formed it is netted Structure, and the graphene/carbon nano-tube prepared shows excellent field effect behavior, with chemical vapor deposition (Chemical Vapor Deposition, abbreviation CVD) graphene of method growth is greatly improved compared to conductivity and (is detailed in record: Dong X,Li B,Wei A,et al.One-step growth of graphene–carbon nanotube hybrid materials by chemical vapor deposition[J].Carbon,2011,49(9):2944-2949.)。
But aforementioned these preparation methods are there are complex process, preparation cost is high, film quality is not high, doping regulates and controls difficulty etc. Deficiency, and the carbon nanotube for preparing and non-perpendicular to graphene surface, it is unobvious there are distribution of orientations the disadvantages of.
Summary of the invention
In view of the foregoing deficiencies of prior art, simple, preparation that the purpose of the present invention is to provide a kind of preparation processes The preparation method of the carbon nano tube/graphene laminated film of low-cost N doping, and according to this preparation method prepare it is a kind of high The carbon nano tube/graphene laminated film of the N doping of quality.
In order to achieve the above objects and other related objects, the carbon nano tube/graphene that the present invention provides a kind of N doping is answered The preparation method of film is closed, the substrate is placed in vapor deposition apparatus by the preparation method comprising steps of offer substrate； Hexamethylenetetramine solid is placed in the vapor deposition apparatus, heat resolve is carried out to the hexamethylenetetramine solid, And form the carbon nanometer of N doping in the substrate surface using low-pressure chemical vapor deposition process in reducibility gas atmosphere Pipe/graphene composite film.
In an optinal plan, the substrate is copper foil, and the preparation method further includes that the substrate is placed in the gas The step of cleaning and chemical polishing are carried out to the substrate before phase depositing device.
Optionally, the preparation method further includes carrying out high temperature to the substrate after carrying out chemical polishing to the substrate The step of annealing, the temperature of the high annealing are 800~1200 DEG C.
More optionally, the chemical polishing includes the chemical polishing carried out using acetic acid, nitric acid or hydrochloric acid, or in phosphoric acid item One or both of the electrochemical polish carried out under part.
In another optinal plan, the substrate is the composite substrate that surface is coated with copper metal layer.
Optionally, the reducibility gas is hydrogen.
Optionally, the vapor deposition apparatus includes the first warm area and the second warm area, forms the carbon nanometer of the N doping During pipe/graphene composite film, the substrate is located at second warm area, and the hexamethylenetetramine solid is located at institute The first warm area is stated, the temperature of second warm area is greater than the temperature of first warm area.
Optionally, the temperature of first warm area is 100~200 DEG C, and the temperature of second warm area is 700~1000 ℃。
Optionally, in the step 2), the time for forming the carbon nano tube/graphene laminated film of the N doping is 5 ~100min.
The present invention also provides a kind of carbon nano tube/graphene laminated film of N doping, the carbon nanotube of the N doping/ Graphene composite film is based on aforementioned described in any item preparation methods and is prepared.
The present invention with cheap hexamethylenetetramine be unique carbon nitrogen source, using low-pressure chemical vapor deposition (Chemical Vapor Deposition) one-step method obtained the carbon nano tube/graphene laminated film of N doping.The preparation method, which has, to be set It is standby and the advantages that processing step is simple, raw material are cheap and easy to get.The carbon nanotube being prepared based on preparation method of the invention/ Graphene composite film can realize that carbon nanotube vertical arrangement on single-layer or multi-layer graphene film surface, has high orientation, It is mutually indepedent between each carbon nanotube, it is evenly distributed, and realize effective N doping to improve the electrical property of the laminated film Can, expand its following application field.
Detailed description of the invention
Fig. 1 is shown as the process of the preparation method of the carbon nano tube/graphene laminated film of N doping provided by the invention Figure.
Fig. 2 is shown as the structural schematic diagram of chemical vapor depsotition equipment used in preparation method of the invention.
Fig. 3 and Fig. 4 is shown as the carbon nano tube/graphene laminated film of the N doping of preparation method preparation under this invention Raman spectrogram.
Fig. 5 and Fig. 6 is shown as the carbon nano tube/graphene laminated film of the N doping of preparation method preparation under this invention AFM (atomic force microscope) figure.
Fig. 7 is shown as the TEM of the carbon nano tube/graphene laminated film of the N doping of preparation method preparation under this invention (transmission electron microscope) figure.
Fig. 8 is shown as the SEM of the carbon nano tube/graphene laminated film of the N doping of preparation method preparation under this invention (scanning electron microscope) figure.
Fig. 9 to Figure 11 is shown as the carbon nano tube/graphene THIN COMPOSITE of the N doping of preparation method preparation under this invention XPS (X-ray photoelectron spectroscopic analysis) spectrogram of film.
Component label instructions
10 quartz ampoules
11 first warm areas
12 second warm areas
13 substrates
14 raw material holding trays
15 first heaters
16 ring flanges
17 secondary heating mechanisms
S1~S2 step
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from Various modifications or alterations are carried out under spirit of the invention.
Fig. 1 is please referred to Figure 11.It should be noted that diagram provided in the present embodiment only illustrates this in a schematic way The basic conception of invention, only show in tunnel diagram with related component in the present invention rather than package count when according to actual implementation Mesh, shape and size are drawn, when actual implementation form, quantity and the ratio of each component can arbitrarily change for one kind, and its Assembly layout form may also be increasingly complex.
Referring to Fig. 1, the present invention provides a kind of preparation method of the carbon nano tube/graphene laminated film of N doping, institute State preparation method comprising steps of
S1: substrate 13 is provided, the substrate 13 is placed in vapor deposition apparatus；
S2: hexamethylenetetramine solid is placed in the vapor deposition apparatus, to the hexamethylenetetramine solid into Row heats so that it is decomposed into gaseous state, and uses low-pressure chemical vapor deposition process in the substrate in reducibility gas atmosphere The carbon nano tube/graphene laminated film of 13 surfaces formation N doping.
The present invention with cheap hexamethylenetetramine be unique carbon nitrogen source, using low-pressure chemical vapor deposition (Chemical Vapor Deposition) one-step method obtained the carbon nano tube/graphene laminated film of N doping.The preparation method, which has, to be set It is standby and the advantages that processing step is simple, raw material are cheap and easy to get.The carbon nanotube being prepared based on preparation method of the invention/ Graphene composite film can realize that carbon nanotube vertical arrangement on single-layer or multi-layer graphene film surface, has high orientation, It is mutually indepedent between each carbon nanotube, it is evenly distributed, and realize effective N doping to improve the electrical property of the laminated film Can, expand its following application field.
As shown in Fig. 2, as an example, the chemical vapor depsotition equipment has a quartz ampoule 10,10 quilt of quartz ampoule It is divided into the first warm area 11 and second warm area 12 adjacent with first warm area 11, the inlet port setting of the quartz ampoule 10 There is ring flange 16, first warm area 11 and second warm area 12 can pass through different temperature control device progress temperature (not shown) Control.Be provided in first warm area 11 raw material holding tray 14 and positioned at 14 lower section of the raw material holding tray and for institute The first heater 15 that raw material holding tray 14 is heated is stated, the first heater 15 may include pedestal (not shown) With the resistance heater being located in the base-plates surface or the pedestal, the pedestal can heat for ceramic heating plate, mica One of plate, sheet metal heating, graphite heating plate or carbon fiber heating plate or at least two combination；Second warm area 12 It can be heated by the inclusion of the secondary heating mechanism 17 of multiple halogen lamp.In the present embodiment, mixed as an example, forming the nitrogen During miscellaneous carbon nano tube/graphene laminated film, the substrate 13 is located at the second warm area 12 of the quartz ampoule 10, institute Hexamethylenetetramine solid is stated to be located at the first warm area 11 of the quartz ampoule 10 and be located in the raw material holding tray 14, described the The temperature of two warm areas 12 is greater than the temperature of first warm area 12.And in the present embodiment, the temperature of first warm area 11 is preferred It is 100~200 DEG C, the temperature of second warm area 12 is preferably 700~1000 DEG C.By the temperature setting of first warm area 11 It may insure that the decomposition rate of the hexamethylenetetramine solid is in more stable state for 100~200 DEG C, avoid decomposing The deterioration of the too fast or too slow exception for leading to gas-phase deposition and/or quality of forming film.
In one example, the substrate 13 is copper foil, is also wrapped before the substrate 13 is placed in the vapor deposition apparatus It includes and pretreated step is carried out to the substrate 13, which includes at least cleaning and chemical polishing.Than substrate as will be described 13 are cleaned by ultrasonic in acetone and ethyl alcohol respectively, the substrate 13 are put into orthophosphoric acid solution later, in the electricity of 2~5V Electrochemical polish is carried out under the conditions of pressure, polishing time is 5~15min (minute), or using acetic acid, nitric acid or hydrochloric acid Optical polishing takes out the substrate 13 after completing polishing, uses deionized water rinsed clean later, finally with being dried with nitrogen, leads to It crosses this series of processes process and improves cleannes and the flatness of the copper foil surface in order to which subsequent film deposits.Before completion High annealing can also be carried out to the substrate 13 after stating a series of processing routine, be placed in describedization than substrate 13 as will be described It learns in vapor deposition apparatus and is passed through hydrogen, it is high under 800~1200 DEG C of conditions (for example being 800 DEG C, 900 DEG C, 1000 DEG C etc.) Warm annealing, raises to increase the crystalline substance of the substrate 13 and eliminates dislocation and stress in 13 copper foil of substrate.
In another example, the substrate 13 is that surface is coated with the composite substrate of copper metal layer, for example, for silicon wafer, glass, Ceramics or other metal substrate surfaces are coated with the composite substrate of copper metal layer, not stringent limitation in the present embodiment, if certainly It is composite substrate it is also preferred that carrying out the pretreatment such as cleaning polishing to copper metal layer to ensure the cleannes peace on copper metal layer surface Smooth degree.
As an example, the hexamethylenetetramine in the present embodiment using solid powdery is as unique carbon nitrogen source (i.e. this Shen Please in only use this source material of hexamethylenetetramine), in order to avoid the oxidation stain in chemical vapor deposition processes, this is heavy Product process carries out under reducibility gas atmosphere, and the reducing gas is preferably hydrogen.The hexamethylenetetramine solid powder It is placed in the raw material holding tray 14 of first warm area 11 and is heated, the gas after being thermally decomposed can pass through load Gas, for example be transported in second warm area 12 by hydrogen, under 700~1000 DEG C of growth temperature, through preset life After long-time, the carbon nano tube/graphene laminated film of the N doping of 13 Surface Creation required thickness of Yu Suoshu substrate.This In embodiment, as an example, the growth time is 5~100min (minute).
After completing film growth, first warm area 11 and second warm area 12 all stop heating, at the same continue to Reducibility gas is passed through in second warm area 12 until the substrate 13 is cooled to room temperature.
Invention is further explained combined with specific embodiments below.
Specific embodiment
Copper foil after two-sided electrobrightening is placed on quartz glass gasket, then gasket push-in is had to the chemistry in dual temperature area (it is located in the second warm area) among the quartz ampoule of vapor deposition apparatus.The hexamethylenetetramine for weighing 0.0150g is put into quartz ampoule Quartz boat (boat) in, quartz boat was put on source region heating plate (be located at the first warm area in), later closed quartz tube both ends Ring flange.After to gas circuit cleaning, whole process is passed through the hydrogen (preferably 15sccm) of 10~20sccm, by tube furnace liter To desired temperature (700~1000 DEG C).Source region temperature, which is risen to 120 DEG C, at this time makes hexamethylenetetramine start to distil.Growth 5~ Stop heating after 90min and be down to room temperature to temperature (to may be flowed into hydrogen or other inert gases during this to prevent sky The pollution such as gas), that is, it can be taken off sample.
By the carbon nano tube/graphene laminated film of the N doping of formation after the chemical vapor deposition process Being transferred to surface has the silicon chip surface of 300nm thick silicon oxide layer to carry out subsequent characterizations.As the Raman Characterization of Fig. 3 and Fig. 4 is sent out It is existing, in 1345cm-1、1590cm-1And 2673cm-1Place detects tri- characteristic peaks of D, G and 2D of graphene, 150cm-1With 298cm-1Neighbouring free vibration climacteric (Radical Breathing Modes, RBM) is the characteristic peak of carbon nanotube.And AFM (atomic force microscope) image of Fig. 5 and Fig. 6 can see the good carbon nanotube of arrangement and be evenly distributed on graphene film Surface, the average height of carbon nanotube is 50nm, and root diameter (RD) is 50~100nm, is decreased to 20~60nm at tip.Fig. 7 TEM (transmission electron microscope) figure show that the root of carbon nanotube has more amorphous carbon, and its tip is then less, this result It is consistent with the bottom grown process of carbon nanotube set forth above, and SEM (scanning electron microscope) figure in Fig. 8 shows graphene The hexagonal array structure of carbon atom in film shows that graphene is the list of advantages of good crystallization in carbon nano tube/graphene laminated film Layer structure.As shown in figure 9, occurring the C 1s positioned at 284.5eV in the total spectrogram of XPS (X-ray photoelectron spectroscopic analysis) power spectrum Peak and N 1s positioned at 399.9eV.To its further careful calculating, as shown in Figure 10, the peak C 1s can be divided into 284.5eV, Tri- peaks 285.3eV and 285.9eV, respectively indicate the carbon sp in graphene-structured2Hybrid structure, the N atom and sp of introducing2It is miscellaneous Change and sp3Hydridization C atomic bonding structure.As shown in figure 11, the peak N 1s includes three at 398.8eV, 401.1eV and 401.9eV A small peak respectively indicates pyrrolesization nitrogen, pyridine nitrogen and graphitization nitrogen key, by calculating the N doping stone it can be concluded that prepared Nitrogen average content about 3.5at% in black alkene, this makes it with preferable electric conductivity.
The present invention also provides a kind of carbon nano tube/graphene laminated film of N doping, the carbon nanotube of the N doping/ Graphene composite film is based on aforementioned described in any item preparation methods and is prepared.It can be seen that, this is based on by foregoing teachings The carbon nano tube/graphene laminated film that the preparation method of invention is prepared can realize carbon nanotube vertical arrangement in single layer or Multi-layer graphene film surface, it is mutually indepedent between each carbon nanotube with high orientation, it is evenly distributed, and realized The N doping of effect improves its electric property, this has the carbon nano tube/graphene laminated film of N doping of the invention extensively Wealthy application prospect.
To sum up, the present invention provides a kind of carbon nano tube/graphene laminated film and preparation method thereof of N doping.The system Preparation Method comprising steps of 1) provide substrate, the substrate is placed in vapor deposition apparatus；2) hexamethylenetetramine solid is set In the vapor deposition apparatus, heat resolve is carried out to the hexamethylenetetramine solid, and in reducibility gas atmosphere The carbon nano tube/graphene laminated film of N doping is formed in the substrate surface using low-pressure chemical vapor deposition process.This Invention with cheap hexamethylenetetramine be unique carbon nitrogen source, using low-pressure chemical vapor deposition (Chemical Vapor Deposition) one-step method has obtained the carbon nano tube/graphene laminated film of N doping.The preparation method has equipment and work The advantages that skill step is simple, raw material are cheap and easy to get.The carbon nano tube/graphene being prepared based on preparation method of the invention Laminated film can realize that carbon nanotube vertical arrangement on single-layer or multi-layer graphene film surface, has high orientation, each carbon It is mutually indepedent between nanotube, it is evenly distributed, and realize effective N doping to improve its electric property, so that nitrogen of the invention The carbon nano tube/graphene laminated film of doping has broad application prospects.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as At all equivalent modifications or change, should be covered by the claims of the present invention.

Claims (10)

1. a kind of preparation method of the carbon nano tube/graphene laminated film of N doping, which is characterized in that the preparation method packet Include following steps:
Substrate is provided, the substrate is placed in vapor deposition apparatus；
Hexamethylenetetramine solid is placed in the vapor deposition apparatus, heating point is carried out to the hexamethylenetetramine solid Solution, and received using low-pressure chemical vapor deposition process in the carbon that the substrate surface forms N doping in reducibility gas atmosphere Mitron/graphene composite film.
2. the preparation method of the carbon nano tube/graphene laminated film of N doping according to claim 1, feature exist In: the substrate is copper foil, and the preparation method further includes before the substrate to be placed in the vapor deposition apparatus to described Substrate carries out the step of cleaning and chemical polishing.
3. the preparation method of the carbon nano tube/graphene laminated film of N doping according to claim 2, feature exist Further include the steps that carrying out high annealing to the substrate after carrying out the substrate chemical polishing in: the preparation method, The temperature of the high annealing is 800~1200 DEG C.
4. the preparation method of the carbon nano tube/graphene laminated film of N doping according to claim 2, feature exist In: the chemical polishing includes the chemical polishing carried out using acetic acid, nitric acid or hydrochloric acid, or the electrification carried out under the conditions of phosphoric acid One or both of optical polishing.
5. the preparation method of the carbon nano tube/graphene laminated film of N doping according to claim 1, feature exist In: the substrate is the composite substrate that surface is coated with copper metal layer.
6. the preparation method of the carbon nano tube/graphene laminated film of N doping according to claim 1, feature exist In: the reducibility gas is hydrogen.
7. the preparation method of the carbon nano tube/graphene laminated film of N doping according to any one of claims 1 to 6, It is characterized by: the vapor deposition apparatus includes the first warm area and the second warm area, carbon nanotube/stone of the N doping is formed During black alkene laminated film, the substrate is located at second warm area, and the hexamethylenetetramine solid is located at described the One warm area, the temperature of second warm area are greater than the temperature of first warm area.
8. the preparation method of the carbon nano tube/graphene laminated film of N doping according to claim 7, feature exist In: the temperature of first warm area is 100~200 DEG C, and the temperature of second warm area is 700~1000 DEG C.
9. the preparation method of the carbon nano tube/graphene laminated film of N doping according to claim 7, feature exist In: in the step 2), the time for forming the carbon nano tube/graphene laminated film of the N doping is 5~100min.
10. a kind of carbon nano tube/graphene laminated film of N doping, it is characterised in that: carbon nanotube/stone of the N doping Black alkene laminated film is based on the described in any item preparation methods of claim 1 to 9 and is prepared.
CN201910745133.4A 2019-08-13 2019-08-13 Nitrogen-doped carbon nanotube/graphene composite film and preparation method thereof Active CN110371956B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114068927A (en) * 2020-08-04 2022-02-18 北京大学 Graphene carbon nanotube composite material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN103407982A (en) * 2013-07-16 2013-11-27 清华大学 Nitrogen-doped carbon nano-tube array and graphene hybrid and preparation method thereof
CN103910349A (en) * 2014-03-13 2014-07-09 吉林大学 Method of preparing nitrogen-doped oriented bamboo-like carbon nanotube/graphene composite metal oxide
WO2017164963A2 (en) * 2016-01-07 2017-09-28 William Marsh Rice University Facile preparation of carbon nanotube hybrid materials by catalyst solutions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103407982A (en) * 2013-07-16 2013-11-27 清华大学 Nitrogen-doped carbon nano-tube array and graphene hybrid and preparation method thereof
CN103910349A (en) * 2014-03-13 2014-07-09 吉林大学 Method of preparing nitrogen-doped oriented bamboo-like carbon nanotube/graphene composite metal oxide
WO2017164963A2 (en) * 2016-01-07 2017-09-28 William Marsh Rice University Facile preparation of carbon nanotube hybrid materials by catalyst solutions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114068927A (en) * 2020-08-04 2022-02-18 北京大学 Graphene carbon nanotube composite material and preparation method thereof
CN114068927B (en) * 2020-08-04 2023-10-13 北京大学 Graphene carbon nanotube composite material and preparation method thereof

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