CN105256312A - Preparing method for graphene and carbon nano tube composite porous electrode material - Google Patents
Preparing method for graphene and carbon nano tube composite porous electrode material Download PDFInfo
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- CN105256312A CN105256312A CN201510713246.8A CN201510713246A CN105256312A CN 105256312 A CN105256312 A CN 105256312A CN 201510713246 A CN201510713246 A CN 201510713246A CN 105256312 A CN105256312 A CN 105256312A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/343—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one DLC or an amorphous carbon based layer, the layer being doped or not
Abstract
The invention discloses a preparing method for a graphene and carbon nano tube composite porous electrode material. A layer of metal catalyst is deposited on the surface of a porous metal matrix to grow graphene, then a layer of metal catalyst is deposited on the surface of the graphene to grow a carbon nano tube, and the electrode material compounding the graphene, the carbon nano tube and porous metal is obtained. The electrode material has the beneficial effects of being low in weight, high in specific area and conductivity, good in stability and long in service life, good electrochemical performance is shown, and very good application value is achieved on the aspect of electrode application.
Description
Technical field
The present invention relates to a kind of preparation method of porous electrode material, particularly the preparation method of a kind of Graphene and carbon nanotube composite porous electrode material.
Background technology
Along with the popularization and application of global renewable energy source, the developing rapidly and the construction of intelligent grid of ev industry, energy storage technology becomes the key link that restriction promotes energy development.Current renewable energy technologies mainly contains wind energy, sun power, water power, but because they all exist larger unpredictable and dramatic performance, causes great impact, therefore applied not yet on a large scale the reliability of electrical network.And the development of energy storage technology can head it off effectively, the essence of energy storage realizes the storage to electric energy, discharges, thus make renewable energy technologies to store with a kind of stable form and to apply when needs.In addition, as the developing direction of following electrical network, intelligent grid carries out peak load regulation network by energy storage device, to increase capacity and the optimization efficiency of electrical power trans mission/distribution system, at the generating of whole power industry, conveying, the links such as distribution and use, energy storage technology can both be widely used.From within 1859, having strangled since Krona thanks to invention lead acid cell, electrochemical energy storage has been deep in the middle of various multi-form energy storage system, becomes most important integral part in energy storage field.
At present, the research to electrochemical energy storage technology is all being strengthened in countries in the world.The main determining factor of the overall performance of electrochemical energy storing device is the chemical property of electrode materials, so the research of new electrode materials becomes the focus of research in field for this reason.
Graphene is a kind of graphite material of monoatomic layer thickness, and its lattice is the sexangle that carbon atom is formed is honeycomb structure.These characteristics that Graphene shows make it show extraordinary application prospect in various fields such as electronics, optics, inductions.Wherein because Graphene has superhigh specific surface area and excellent conduction, heat conductivility, be suitable for very much three-dimensional porous carbon dioxide process carbon electrode.
Carbon nanotube be curling by single or multiple lift graphene layer after the seamless nano level pipe that is formed by connecting, its diameter, between 0.4nm to tens nanometer, has close to desirable 1-dimention nano space.Carbon nanotube has high-specific surface area, snappiness, high strength, heat-resisting, corrosion-resistant, heat transfer and the excellent properties such as good conductivity, makes it have huge using value in electrode materials application aspect.
When preparing electrode materials, select Graphene, carbon nanotube and porous metal compound, greatly can increase specific surface area and the electric conductivity of electrode, and prepared electrode weight is light, there is the unexistent internal space of plate electrode, the capacity of electrochemical energy storing device can be increased.Direct growth Graphene and carbon nanotube on porous metal, also can avoid the process of both transfers, improves stability and the work-ing life of electrode, be also easy to realize continuous prodution simultaneously.
In existing technology, such as, application number is 201310146410.2(preparation method based on the electrode of super capacitor of nickel foam and products thereof) the middle a kind of electrode materials announced, by depositing one deck graphene oxide on nickel foam substrate, then obtain by electrochemical reduction the nickel foam depositing Graphene, then on Graphene, water applies one deck carbon nanotube.But, method at present for the production of graphene oxide is oxidized Graphite Powder 99 mainly through strong oxidizers such as sulfuric acid, nitric acid, potassium permanganate, thus make to be strutted by oxygen-containing functional group the object reaching lamella and be separated between graphite flake layer, the method finally by chemical reduction obtains Graphene.Use the Graphene that aforesaid method obtains, the oxy radical on lamella is difficult to absolutely be reduced, thus greatly reduces its specific surface area and chemical property thereof.Further, utilize water coating method to transfer to carbon nanotube on graphene layer, be wound around each other and reunite very serious, greatly reducing its specific surface area and electric conductivity.
Application number is 201210250077.5(three-dimensional graphene-carbon nitrogen nanotube composite preparation method) in a kind of matrix material of producing of a kind of preparation method of announcing, be by direct production on nickel foam substrate one layer graphene, then on Graphene, flood layer of Ni (NO
3)
2as catalyst growth carbon nanotube.But because nickel foam skeleton surface is very coarse, there is a lot of crystal boundary, projection, pit, fold, even also there is crackle and surface oxidation phenomenon.And the surface tissue of metal asperity can exert an adverse impact to the quality of the Graphene grown thereon, the step-like structure of metallic surface may make the crystal orientation of Graphene deflect, thus forms the defects such as crystal boundary; Graphene tends in defect and microtexture coarse place nucleation, increase to nuclear density, cause less in nickel foam skeleton epontic Graphene grain-size, the number of plies is uneven and be difficult to control, often there is thicker Graphene in grain boundaries, few layer graphene becomes unordered stacking, and these defects greatly reduce the conductive capability of Graphene.The method has selectivity for the composition of porous metal simultaneously, and matrix can only adopt metal Graphene to catalytic growth effect.The method with the addition of polyoxyethylene glycol as catalyst n i (NO
3)
2binding agent, electrode internal resistance can be caused to increase, and the active area of catalyzer reduces, and activity decrease, causes adverse influence to the growth of carbon nanotube.
Summary of the invention
In order to overcome the shortcoming and defect that currently available products exists, the invention provides the electrode materials of a kind of Graphene, carbon nanotube and porous metal compound.In this electrode materials, grow that Graphene area on perforated substrate is large, the number of plies is controlled, good conductivity; Carbon nanotube impurity is few, uniform sequential, consistence is good, specific surface area is high, electric conductivity is high, thus improves its performance as electrode materials.
Technical scheme of the present invention is:
A preparation method for Graphene and carbon nanotube composite porous electrode material, comprises the following steps:
(1), with porous metal be matrix take porous metal as matrix, porous metal have the 3-D solid structure of perforate, average pore diameter is 100 μm ~ 3000 μm, thickness is 0.3mm ~ 70mm;
(2) on (1) described matrix, use Vacuum Deposition process deposits First Transition metal level, wherein Vacuum Deposition technique refers to vacuum magnetic-control sputtering technology, vacuum evaporation technology, vacuum ionic coating technology, Vacuum Deposition optimal process vacuum magnetic-control sputtering technology, its working parameter is: vacuum chamber base vacuum≤5 × 10
-2pa, vacuum chamber internal pressure≤1Pa during sputter coating, the target power density of every decimeter of target wide cut applying is 0.1 kilowatt ~ 1 kilowatt, and the mean thickness of First Transition metal level is 5nm ~ 2000nm;
(3), First Transition metal level described in (2) uses process for preparing graphenes by chemical vapour deposition layer: the porous metal processed through step (2) are placed in vacuum furnace chamber, be evacuated to furnace chamber internal background vacuum≤2Pa, be warming up to 650 DEG C ~ 1000 DEG C again, pass into the mixed gas of hydrogen and argon gas simultaneously, be incubated 10 minutes ~ 45 minutes, continue to be warming up to 800 DEG C ~ 1100 DEG C, then pass into carbon-source gas to react, 0.5 minute ~ 30 minutes reaction times, reaction terminates rear stopping and passing into carbon-source gas, at argon gas or hydrogen, both argon gas mixed gas protected under be cooled to room temperature, the thickness of the graphene layer prepared is 0.34nm ~ 100nm,
(4) on (3) described graphene layer, use Vacuum Deposition process deposits Second Transition layer, wherein Vacuum Deposition technique refers to vacuum magnetic-control sputtering technology, vacuum evaporation technology, vacuum ionic coating technology, Vacuum Deposition optimal process vacuum magnetic-control sputtering technology, its working parameter is: vacuum chamber base vacuum≤5 × 10
-2pa, vacuum chamber internal pressure≤1Pa during sputter coating, the target power density of every decimeter of target wide cut applying is 0.1 kilowatt ~ 1 kilowatt, and the thickness of Second Transition layer is 5nm ~ 2000nm;
(5), on the Second Transition layer described in (4) with chemical vapor deposition for carbon nanotubes: the porous metal processed through step (2) are placed in vacuum furnace chamber, be evacuated to furnace chamber internal background vacuum≤2Pa, be warming up to 650 DEG C ~ 900 DEG C again, argon gas is passed into as protection gas in temperature-rise period, carbon-source gas is passed into after reaching design temperature, the volume ratio of carbon-source gas and argon gas is 1:20 ~ 1:1, react after 10 minutes ~ 100 minutes and terminate, stop passing into carbon-source gas, under the protection of argon gas atmosphere, be cooled to room temperature; The mean diameter of carbon nanotube is 2nm ~ 50nm, and mean length is 1 μm ~ 100 μm.
Described porous metal are the monometallic materials formed by any metalloid in Ni, Cu, Fe, Al, Co, Ag, Pd, Cr, or the multiple layer metal more than any two classes or two classes formed in above-mentioned metal species or alloy.
Described First Transition metal level is the single metal layer formed by any metalloid in Ni, Cu, Co, Pt, Pd, or the multiple layer metal that formed of the metal in above-mentioned metal species more than any two classes or two classes or alloy layer.
Described Second Transition layer is the single metal layer formed by any metalloid in Ni, Co, Fe, or the multiple layer metal that formed of the metal in above-mentioned metal species more than any two classes or two classes or alloy layer.
Described carbon-source gas is one or more mixtures in methane, ethane, ethene, acetylene, benzene,toluene,xylene.
The present invention by depositing First Transition metal level as catalyst growth Graphene on porous metal matrix, graphene layer deposits Second Transition layer as catalyst growth carbon nanotube, obtain the electrode materials of a kind of Graphene, carbon nanotube and porous metal compound.The advantage of the program is:
(1), porous metal have the advantages that specific surface area is high, good conductivity, quality light, easily process, the feature of the electricity of the excellence that they possess itself, mechanical property and high-specific surface area can be made full use of with Graphene, carbon nanotube compound tense, prepare the electrode of electrochemical performance.
(2), at porous metal matrix deposited on silicon one deck, Graphene is had to the metallic membrane of katalysis, compare directly at porous metal matrix surface direct growth Graphene, the selectivity of Graphene to porous metal component can be eliminated, growing graphene on any porous matrix can be realized; Can fill and lead up and cover crystal boundary and the defect on porous metal skeleton surface, improve the quality of Graphene; This layer has the metallic membrane of katalysis, can be pure metal, also can be alloy, by the collocation of different components and the selecting of technological line, can control the number of plies of Graphene, plays an important role to the quality of raising Graphene.
(3), use vacuum magnetic-control sputtering technology, vacuum evaporation technology, vacuum ionic coating technology on graphene layer, deposit Second Transition layer as carbon nano-tube catalyst, there is catalytic activity high, the advantage that effective catalysis area is large, the carbon nanotube impurity grown on this basis is few, uniform sequential, consistence is good, specific surface area is high, electric conductivity is high.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
The preparation method of a kind of Graphene of the present invention and carbon nanotube composite porous electrode material is further illustrated below in conjunction with specific embodiment.
Embodiment 1:
Take nickel foam as matrix, the average pore diameter of selected nickel foam is 100 μm, and thickness is 0.3 ㎜, and use vacuum magnetic-control sputtering technology at matrix surface deposition Cu as First Transition metal level, its working parameter is: vacuum chamber base vacuum≤5 × 10
-2pa, vacuum chamber internal pressure≤1Pa during sputter coating, the target power density of every decimeter of target wide cut applying is 0.1 kilowatt ~ 1 kilowatt, the mean thickness of First Transition metal level is 5nm, nickel foam through surface deposition Cu is placed in vacuum furnace chamber, be evacuated to furnace chamber internal background vacuum≤2Pa, be warming up to 900 DEG C again, pass into the mixed gas of hydrogen and argon gas simultaneously, be incubated 13 minutes, continue to be warming up to 1040 DEG C, then pass into benzene gas to react, 0.5 minute reaction times, reaction terminates rear stopping and passing into benzene gas, room temperature is cooled in the mixed atmosphere of hydrogen and argon gas, prepare graphene layer.Work in-process are taken out and preserves.
Use vacuum magnetic-control sputtering technology at half-finished graphene layer surface deposition Co as Second Transition layer, its working parameter is: vacuum chamber base vacuum≤5 × 10
-2pa, vacuum chamber internal pressure≤1Pa during sputter coating, the target power density of every decimeter of target wide cut applying is 0.1 kilowatt ~ 1 kilowatt, the mean thickness of Second Transition layer is 5nm, work in-process through surface deposition Co are placed in vacuum furnace chamber, be evacuated to furnace chamber internal background vacuum≤2Pa, be warming up to 800 DEG C again, argon gas is passed into as protection gas in temperature-rise period, ethane gas is passed into after reaching design temperature, the volume ratio of ethane gas and argon gas is 1:5, react after 20 minutes and terminate, stop passing into ethane gas, room temperature is cooled under the protection of argon gas atmosphere, thus obtain a kind of Graphene and carbon nanotube composite porous electrode material, finally product is taken out and preserve.
Embodiment 2:
Take foamed aluminium as matrix, the average pore diameter of selected foamed aluminium is 400 μm, and thickness is 0.8 ㎜, and use vacuum magnetic-control sputtering technology at matrix surface deposition Cu-Ni alloy as First Transition metal level, its working parameter is: vacuum chamber base vacuum≤5 × 10
-2pa, vacuum chamber internal pressure≤1Pa during sputter coating, the target power density of every decimeter of target wide cut applying is 0.1 kilowatt ~ 1 kilowatt, the mean thickness of First Transition metal level is 300nm, foamed aluminium through surface deposition Cu-Ni alloy is placed in vacuum furnace chamber, be evacuated to furnace chamber internal background vacuum≤2Pa, be warming up to 800 DEG C again, pass into the mixed gas of hydrogen and argon gas simultaneously, be incubated 20 minutes, continue to be warming up to 975 DEG C, then pass into ethylene gas to react, 12 minutes reaction times, reaction terminates rear stopping and passing into ethylene gas, room temperature is cooled under the protection of argon gas atmosphere, prepare graphene layer.Work in-process are taken out and preserves.
Use vacuum magnetic-control sputtering technology at half-finished graphene layer surface deposition Ni as Second Transition layer, its working parameter is: vacuum chamber base vacuum≤5 × 10
-2pa, vacuum chamber internal pressure≤1Pa during sputter coating, the target power density of every decimeter of target wide cut applying is 0.1 kilowatt ~ 1 kilowatt, the mean thickness of Second Transition layer is 400nm, work in-process through surface deposition Ni are placed in vacuum furnace chamber, be evacuated to furnace chamber internal background vacuum≤2Pa, be warming up to 700 DEG C again, argon gas is passed into as protection gas in temperature-rise period, methane gas is passed into after reaching design temperature, the volume ratio of methane gas and argon gas is 1:2, react after 30 minutes and terminate, stop passing into methane gas, room temperature is cooled under the protection of argon gas atmosphere, thus obtain a kind of Graphene and carbon nanotube composite porous electrode material, finally product is taken out and preserve.
Embodiment 3:
With foam ferronickel for matrix, the average pore diameter of selected foam ferronickel is 500 μm, and thickness is 1.5 ㎜, and use vacuum magnetic-control sputtering technology at matrix surface deposition Co-Ni alloy as First Transition metal level, its working parameter is: vacuum chamber base vacuum≤5 × 10
-2pa, vacuum chamber internal pressure≤1Pa during sputter coating, the target power density of every decimeter of target wide cut applying is 0.1 kilowatt ~ 1 kilowatt, the mean thickness of First Transition metal level is 400nm, foam ferronickel through surface deposition Co-Ni alloy is placed in vacuum furnace chamber, be evacuated to furnace chamber internal background vacuum≤2Pa, be warming up to 850 DEG C again, pass into the mixed gas of hydrogen and argon gas simultaneously, be incubated 30 minutes, continue to be warming up to 1000 DEG C, then pass into methane gas to react, 20 minutes reaction times, reaction terminates rear stopping and passing into methane gas, room temperature is cooled in the mixed atmosphere of hydrogen and argon gas, prepare graphene layer.Work in-process are taken out and preserves.
Use vacuum magnetic-control sputtering technology in half-finished graphene layer surface deposition Fe-Co alloy/C as Second Transition layer, its working parameter is: vacuum chamber base vacuum≤5 × 10
-2pa, vacuum chamber internal pressure≤1Pa during sputter coating, the target power density of every decimeter of target wide cut applying is 0.1 kilowatt ~ 1 kilowatt, the mean thickness of Second Transition layer is 500nm, work in-process through surface deposition Fe-Co alloy/C are placed in vacuum furnace chamber, be evacuated to furnace chamber internal background vacuum≤2Pa, be warming up to 750 DEG C again, argon gas is passed into as protection gas in temperature-rise period, methane gas is passed into after reaching design temperature, the volume ratio of methane gas and argon gas is 1:2, react after 45 minutes and terminate, stop passing into methane gas, room temperature is cooled under the protection of argon gas atmosphere, thus obtain a kind of Graphene and carbon nanotube composite porous electrode material, finally product is taken out and preserve.
Embodiment 4:
With foam copper nickel for matrix, the average pore diameter of selected foam copper nickel is 3000 μm, and thickness is 70 ㎜, and use vacuum magnetic-control sputtering technology at matrix surface deposition Ni as First Transition metal level, its working parameter is: vacuum chamber base vacuum≤5 × 10
-2pa, vacuum chamber internal pressure≤1Pa during sputter coating, the target power density of every decimeter of target wide cut applying is 0.1 kilowatt ~ 1 kilowatt, the mean thickness of First Transition metal level is 2000nm, foam copper nickel through surface deposition Ni is placed in vacuum furnace chamber, be evacuated to furnace chamber internal background vacuum≤2Pa, be warming up to 900 DEG C again, pass into the mixed gas of hydrogen and argon gas simultaneously, be incubated 45 minutes, continue to be warming up to 1060 DEG C, then pass into methane gas to react, 30 minutes reaction times, reaction terminates rear stopping and passing into methane gas, room temperature is cooled in the mixed atmosphere of hydrogen and argon gas, prepare graphene layer.Work in-process are taken out and preserves.
Use vacuum magnetic-control sputtering technology in half-finished graphene layer surface deposition Fe-Ni alloy/C as Second Transition layer, its working parameter is: vacuum chamber base vacuum≤5 × 10
-2pa, vacuum chamber internal pressure≤1Pa during sputter coating, the target power density of every decimeter of target wide cut applying is 0.1 kilowatt ~ 1 kilowatt, the mean thickness of Second Transition layer is 2000nm, work in-process through surface deposition Fe-Ni alloy/C are placed in vacuum furnace chamber, be evacuated to furnace chamber internal background vacuum≤2Pa, be warming up to 750 DEG C again, argon gas is passed into as protection gas in temperature-rise period, acetylene gas is passed into after reaching design temperature, the volume ratio of acetylene gas and argon gas is 1:2.5, react after 60 minutes and terminate, stop passing into acetylene gas, room temperature is cooled under the protection of argon gas atmosphere, thus obtain a kind of Graphene and carbon nanotube composite porous electrode material, finally product is taken out and preserve.
Claims (5)
1. a preparation method for Graphene and carbon nanotube composite porous electrode material, is characterized in that comprising the following steps:
(1), with porous metal be matrix take porous metal as matrix, porous metal have the 3-D solid structure of perforate, average pore diameter is 100 μm ~ 3000 μm, thickness is 0.3mm ~ 70mm;
(2) on (1) described matrix, use Vacuum Deposition process deposits First Transition metal level, wherein Vacuum Deposition technique refers to vacuum magnetic-control sputtering technology, vacuum evaporation technology, vacuum ionic coating technology, Vacuum Deposition optimal process vacuum magnetic-control sputtering technology, its working parameter is: vacuum chamber base vacuum≤5 × 10
-2pa, vacuum chamber internal pressure≤1Pa during sputter coating, the target power density of every decimeter of target wide cut applying is 0.1 kilowatt ~ 1 kilowatt, and the mean thickness of First Transition metal level is 5nm ~ 2000nm;
(3), First Transition metal level described in (2) uses process for preparing graphenes by chemical vapour deposition layer: the porous metal processed through step (2) are placed in vacuum furnace chamber, be evacuated to furnace chamber internal background vacuum≤2Pa, be warming up to 650 DEG C ~ 1000 DEG C again, pass into the mixed gas of hydrogen and argon gas simultaneously, be incubated 10 minutes ~ 45 minutes, continue to be warming up to 800 DEG C ~ 1100 DEG C, then pass into carbon-source gas to react, 0.5 minute ~ 30 minutes reaction times, reaction terminates rear stopping and passing into carbon-source gas, at argon gas or hydrogen, both argon gas mixed gas protected under be cooled to room temperature, the thickness of the graphene layer prepared is 0.34nm ~ 100nm,
(4) on (3) described graphene layer, use Vacuum Deposition process deposits Second Transition layer, wherein Vacuum Deposition technique refers to vacuum magnetic-control sputtering technology, vacuum evaporation technology, vacuum ionic coating technology, Vacuum Deposition optimal process vacuum magnetic-control sputtering technology, its working parameter is: vacuum chamber base vacuum≤5 × 10
-2pa, vacuum chamber internal pressure≤1Pa during sputter coating, the target power density of every decimeter of target wide cut applying is 0.1 kilowatt ~ 1 kilowatt, and the mean thickness of Second Transition layer is 5nm ~ 2000nm;
(5), on the Second Transition layer described in (4) with chemical vapor deposition for carbon nanotubes: the porous metal processed through step (2) are placed in vacuum furnace chamber, be evacuated to furnace chamber internal background vacuum≤2Pa, be warming up to 650 DEG C ~ 900 DEG C again, argon gas is passed into as protection gas in temperature-rise period, carbon-source gas is passed into after reaching design temperature, the volume ratio of carbon-source gas and argon gas is 1:20 ~ 1:1, react after 10 minutes ~ 100 minutes and terminate, stop passing into carbon-source gas, under the protection of argon gas atmosphere, be cooled to room temperature; The mean diameter of carbon nanotube is 2nm ~ 50nm, and mean length is 1 μm ~ 100 μm.
2. the preparation method of a kind of Graphene according to claim 1 and carbon nanotube composite porous electrode material, it is characterized in that described porous metal are the monometallic materials formed by any metalloid in Ni, Cu, Fe, Al, Co, Ag, Pd, Cr, or the multiple layer metal more than any two classes or two classes formed in above-mentioned metal species or alloy.
3. the preparation method of a kind of Graphene according to claim 1 and carbon nanotube composite porous electrode material, it is characterized in that described First Transition metal level is the single metal layer formed by any metalloid in Ni, Cu, Co, Pt, Pd, or the multiple layer metal that formed of the metal in above-mentioned metal species more than any two classes or two classes or alloy layer.
4. the preparation method of a kind of Graphene according to claim 1 and carbon nanotube composite porous electrode material, it is characterized in that described Second Transition layer is the single metal layer formed by any metalloid in Ni, Co, Fe, or the multiple layer metal that formed of the metal in above-mentioned metal species more than any two classes or two classes or alloy layer.
5. the preparation method of a kind of Graphene according to claim 1 and carbon nanotube composite porous electrode material, is characterized in that described carbon-source gas is one or more mixtures in methane, ethane, ethene, acetylene, benzene,toluene,xylene.
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| CN105551860A (en) * | 2016-02-26 | 2016-05-04 | 济南大学 | Preparation method of nickel-plated graphene/silver-nickel electrical contact material |
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| CN106653389A (en) * | 2016-11-25 | 2017-05-10 | 安徽瑞研新材料技术研究院有限公司 | Preparation method of graphene and carbon nanotube composite electrode material |
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| CN113092537A (en) * | 2021-03-30 | 2021-07-09 | 海南聚能科技创新研究院有限公司 | Quadrupole type conductivity electrode capable of improving seawater conductivity measurement accuracy and preparation method and application thereof |
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