CN106976861B - A kind of preparation method of thin-walled Carbon foam-carbon nano tube compound material - Google Patents
A kind of preparation method of thin-walled Carbon foam-carbon nano tube compound material Download PDFInfo
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- CN106976861B CN106976861B CN201710222774.2A CN201710222774A CN106976861B CN 106976861 B CN106976861 B CN 106976861B CN 201710222774 A CN201710222774 A CN 201710222774A CN 106976861 B CN106976861 B CN 106976861B
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Abstract
The invention discloses a kind of preparation methods of thin-walled Carbon foam-carbon nano tube compound material, it is characterized in that: using the mold being made of bottom plug, cyclic annular housing, the weight for being placed in the slidable piston of cyclic annular jacket internal and being pressed on piston;Filter cake is filtered to obtain after starch and mixed acid are mixed;Filter cake is placed on bottom plug, cyclic annular housing and bottom plug are socketed, piston, pressed weight are placed on filter cake, is placed in baking oven and is warming up to 150 DEG C of 1~3 h of maintenance;Filter cake, that is, thin-walled Carbon foam is taken out, is thinly sliced, drying is taken out after impregnating the ethanol solution containing nickel salt, the thin-walled Carbon foam thin slice for having loaded catalyst is made;The thin slice is placed in calcination in alcolhol burner internal flame, then is placed in sulfuric acid solution after immersion, neutrality is washed with distilled water to and dries, obtain thin-walled Carbon foam-carbon nano tube compound material.Gained composite material is compound securely, has pore structure abundant, is widely used as electrode material, catalyst carrier and electromagnetic shielding material etc..
Description
Technical field
The invention belongs to the preparations of charcoal-carbon composite, are related to a kind of system of thin-walled Carbon foam-carbon nano tube compound material
Preparation Method.Thin-walled Carbon foam-carbon nano tube compound material prepared by the present invention is suitable for electrode material, catalyst carrier, electromagnetism
The fields such as shielding material.
Background technique
Foam carbon material is a kind of three-dimensional spongiform novel carbonaceous material of class, have low density, high temperature resistant, it is corrosion-resistant,
The material with high thermal conductivity or heat-proof quality can be made in the features such as anti-oxidant as needed.The exploitation of foam carbon material starts from
The end of the sixties in century.The nineties in last century, United States Air Force research laboratory, Oak Ridge National Laboratory, the U.S. were extra large so far
Army and US National Aeronautics and Space Administration (NASA) start to expand the material research in succession.In recent years, foam carbon material is navigating
The dual-use field such as empty space flight, energy storage, electromagnetic shielding, environmental protection, catalysis, sensing, medicine all shows huge
Application potential, become a member important in carbonaceous material family.Carbon nanotube is that a kind of radial dimension is nanometer scale, axial
One-dimensional Quantum material having a size of micron dimension can be divided into single-walled carbon nanotube (abbreviation SWCNTs) and multi-walled carbon nanotube (letter
Claim MWCNTs).It is found so far from the nineties in last century, carbon nanotube is because of the performances such as its good mechanics, conduction, thermally conductive,
It is widely used in the fields such as composite material, electromagnetic shielding, electrochemical energy storage, hydrogen storage, catalysis.
Carbon foam and carbon nanotube is compound, prepare Carbon foam-carbon nano tube compound material, can play Carbon foam easily at
The advantages of type, self-supporting, at the same using carbon nanotube it is excellent it is conductive, thermally conductive, electromagnetic shielding the features such as, realize one-plus-one it is big
In two effect.It can be widely used for the fields such as electrode material, catalyst carrier, electromagnetic shielding material.In the prior art, preparation bubble
There are mainly two types of foam charcoal-carbon nano tube compound material methods: first is that carbonizing after resin foam is impregnated carbon nano tube dispersion liquid;
Second is that first carbon nanotube is blended with high molecular material, foaming then is carried out to carbon nanotube-macromolecule mixture, later
High temperature carbonization processing is carried out to foamed product again.CN105197912A discloses a kind of preparation method of Foam carbon composite material,
For this method using medium temperature coal pitch as matrix material, acidification carbon nanotube is reinforcement mixing, and it is compound that carbon nanotube/coal tar pitch is made
Then raw material carries out Hydrothermal Upgrading to the raw material, the compound precursor of carbon nanotube/mesophase pitch is made, then in high temperature, height
Pressure, the fugitive constituent by thermally decomposing generation in mesophase pitch obtain carbon nanotube/Foam carbon composite material life from foaming
Material, is finally carbonized again, is graphitized to obtain carbon nanotube/Foam carbon composite material.The prior art is in preparation Carbon foam-carbon nanometer
When pipe composite material, mostly carried out using finished product carbon nanotube obtained it is compound, it is some there are carbon nanotube with
The weak problem of Carbon foam binding force, some then makes carbon nanotube be embedded in Carbon foam skeletal internal, though carbon nanotube is utilized
Mechanical property enhances foam carbon material, but also masks the unique design feature of carbon nanotube simultaneously, makes some of it
Property cannot be played sufficiently.
Summary of the invention
The purpose of the present invention is intended to overcome deficiency in the prior art, and it is compound to provide a kind of thin-walled Carbon foam-carbon nanotube
The preparation method of material.Using the Carbon foam of thin-walled made from the method for the present invention-carbon nano tube compound material, composite construction is different
In existing Carbon foam-carbon nano tube compound material, carbon nanotube is grown on foam carbon surface with cluster-shaped in the present invention, compound
Securely (even if being still able to maintain combined state through ultrasonication 10min), and keep the unique structure of carbon nanotube exposed, make
Material has pore structure abundant, and (material specific surface area is up to 250~400m2/ g), so can be widely used as electrode material,
Catalyst carrier and electromagnetic shielding material etc..
The contents of the present invention are: a kind of preparation method of thin-walled Carbon foam-carbon nano tube compound material, are in place of feature
Include the following steps:
A, thin-walled Carbon foam is prepared:
Prepare mold, cyclic annular housing (2) which is socketed by bottom plug (5), lower section and bottom plug (5) upper section is placed in ring-type
Housing (2) is internal and the slidable cylindric piston (3) that is bonded with cyclic annular housing (2) and is pressed on cylindric piston (3)
Weight (1) constitute;
At room temperature, starch and mixed acid are filtered (be preferably filtered by vacuum) after mixing, obtained filter cake (4);
Filter cake (4) is placed on the bottom plug (5) of mold, the lower section of cyclic annular housing (2) and bottom plug (5) upper section are socketed, on filter cake (4)
Cylindric piston (3) are placed, a pressed weight (1), obtains die assembly on cylindric piston (3);Die assembly is set again
In baking oven, temperature is increased to 150 DEG C with the heating rate of 2~5 DEG C/min, and maintain 1~3h in 150 DEG C of temperature;Take out mould
Have component, after being naturally cooling to room temperature, disassembles die assembly, take out filter cake (4) (filter cake is foamed and carbonized at this time), i.e.,
For thin-walled Carbon foam (6) obtained;
The mixed acid is the mixed acid of sulfuric acid and phosphoric acid;
The purpose that (vacuum) filters after starch is mixed with mixed acid is a certain amount of in order to be distributed in starch particle surface
Acid and moisture, after die assembly is put into baking oven, as the temperature gradually increases, starch is in sour hydrolysis and moisture
Paste and molten condition are presented under gelatinization, after temperature further increases, the evaporation of moisture, acid solution and starch react with
And the decomposition of acid solution itself makes filter cake foam all by the starch producing bubbles inside of gelatinization and molten condition;Meanwhile with temperature
The dehydration carbonization effect of the raising of degree, acid solution carbonizes the starch foam to be formed, its pumiceous texture is enable to remain;
B, preparation has loaded the thin-walled Carbon foam thin slice of catalyst:
Thin-walled Carbon foam (6) obtained in step a is cut into the thin slice of long 1cm, width 1cm, thickness 3mm, then thin slice is soaked
Stain takes out (thin-walled Carbon foam) thin slice after placing 1~3h in the ethanol solution containing nickel salt, then being placed in temperature is 30~60 DEG C
Baking oven in ethyl alcohol is dried, be made and loaded the thin-walled Carbon foam thin slice of catalyst;
There are great amount of hydroxy group, carboxyl or carbonyl isoreactivity and polar groups for the thin-walled foam carbon surface as prepared by step a
Group, thus the catalyst in step b can uniform load in the charcoal wall surface of thin-walled Carbon foam;
By thin-walled Carbon foam be cut into several long 1cm, width 1cm, thickness 3mm thin slice be in order to adapt in next step (burning
) size when growing carbon nanotube in alcolhol burner internal flame needs, which can be according to specific (burning) alcolhol burner internal flame ruler
Very little adjusting has such as expanded flame size using the alcolhol burner of special designing, then the thin-walled Carbon foam Aspect Ratio in this step can
Appropriate amplification is done according to flame size;In addition, thin-walled Carbon foam thickness is advisable with 2~5mm, it is preferable to 3mm, if too thin
Thin-walled Carbon foam is unable to self-supporting and is destroyed when then will lead to calcination, and too thick, is not easy to grow inside thin-walled Carbon foam
Carbon nanotube;
C, thin-walled Carbon foam-carbon nano tube compound material is prepared:
The thin-walled Carbon foam thin slice obtained in step b for having loaded catalyst is placed in (burning) alcolhol burner internal flame and is burnt
It burns, the growth of carbon nanotube is completed in thin-walled Carbon foam, obtains the thin-walled Carbon foam that grown carbon nanotube;It will grown again
The thin-walled Carbon foam of carbon nanotube is placed in 1mol/L aqueous sulfuric acid impregnate (removal catalyst) for 24 hours after, be washed with distilled water
It to neutrality and dries, thin-walled Carbon foam-carbon nano tube compound material as obtained.
Thin-walled Carbon foam prepared by step a, which is utilized, in the growth of carbon nanotube can bear (burning) alcolhol burner internal flame temperature
The characteristics of spending, using well known flame method, this method belongs to the scope of chemical vapor deposition (i.e. CVD) method, with common CVD
Method is different using gaseous carbon sources, which is using liquid fuel alcohol as carbon source, and equipment is simple, easy to operate.
In the contents of the present invention: starch described in step a can be cornstarch, pea starch, tapioca, potato
Any one of starch, starch from sweet potato, wheaten starch and green starch.
In the contents of the present invention: the aqueous sulfuric acid and 1mol/L that mixed acid described in step a is 1mol/L by concentration
1:9~9:1 is mixed phosphate aqueous solution by volume.
In the contents of the present invention: filter cake described in step a (4) be preferably placed in temperature 60 C baking oven place 0~for 24 hours
(partial moisture is evaporated, moisture is the key that regulation thin-walled Carbon foam hole bubble size, thin-walled foam obtained under the conditions of low moisture
Charcoal hole steep size it is smaller, under the conditions of high-moisture thin-walled Carbon foam obtained hole bubble size it is larger) after filter cake;Further, it evaporates
The diameter of filter cake (4) after falling partial moisture, the diameter of bottom plug (5), cyclic annular housing (2) internal diameter and cylindric piston (3)
Diameter be preferably 5cm.
In the contents of the present invention: the concentration of the ethanol solution described in step b containing nickel salt is preferably 0.1~0.5mol/
L。
In the contents of the present invention: nickel salt described in step b can be any in nickel nitrate, nickel acetate and nickel chloride
Kind.
In the contents of the present invention: the thin-walled Carbon foam thin slice that catalyst has been loaded described in step c is placed in alcolhol burner internal flame
The time of calcination is 1~5min in (the alcolhol burner internal flame to burn), must uninterrupted tipping load catalyst during calcination
Thin-walled Carbon foam thin slice, make carbon nanotube that can be uniformly distributed growth on the thin-walled Carbon foam thin slice for having loaded catalyst.
In the contents of the present invention: after starch is uniformly mixed with mixed acid described in step a through filter obtain filter cake (4) compared with
Good be by starch and mixed acid after mixing, place 1~3h, then filtered and (be preferably filtered by vacuum) filter cake obtained
(4)。
In the contents of the present invention: the pressure that weight described in step a (1) is pressed on cylindric piston (3) is preferably 250
~2500Pa;By adjusting the quality of weight (1) pressed on cylindric piston (3), the foaming that gained Carbon foam is adjusted is high
Degree and compactness extent.
In the contents of the present invention: when starch described in step a is mixed with mixed acid, starch: the mass ratio of mixed acid compared with
Good is 1:5~15.
In the contents of the present invention: in thin-walled Carbon foam-carbon nano tube compound material obtained described in step c, the foam
Charcoal hole bulb diameter is adjusted in 100~800 μ ms, charcoal wall thickness is adjusted within the scope of 25~100nm, the carbon nanometer
Pipe is caliber adjustable, length adjustable multi-walled carbon nanotube in 0.5~3 μ m within the scope of 15~100nm;Its
In, the moisture that Carbon foam hole bulb diameter and charcoal wall thickness mainly pass through in control (after evaporating partial moisture) filter cake (4) contains
Amount is adjusted, and the concentration and thin-walled Carbon foam that the diameter and length of carbon nanotube mainly pass through the ethanol solution of control nickel salt are in (combustion
Burning) calcination time in alcolhol burner internal flame adjusts.
Thin-walled Carbon foam-the carbon nano tube compound material prepared using the method for the present invention, by with three-dimensional foam shape structure
Foam carbon material and be combined with the carbon nanotube that cluster-shaped is grown on the thin charcoal wall of the nanometer grade thickness of Carbon foam.
The thin-walled Carbon foam macroshape for using mold of the present invention to obtain, can also be according to needed for Carbon foam to be cylindric
Shape by mold design at other shapes, it is such as cubic;Mold material preferably uses acidproof and high temperature resistant material, such as quartz, ceramics
Or polytetrafluoroethylene (PTFE).
Compared with prior art, the present invention have following features and the utility model has the advantages that
(1) using the present invention, thin-walled Carbon foam-carbon nano tube compound material of preparation overcomes existing biomass starch base
Deficiency in thin-walled foam carbon material technology of preparing, whole preparation process mild condition are not necessarily to inert gas shielding, gained thin-walled
Carbon foam block materials forming realizes thin-walled Carbon foam hole bulb diameter adjustable, charcoal wall thickness in 100~800 μ ms
Degree within the scope of 25~100nm be adjusted, and be grown on thin-walled Carbon foam charcoal wall carbon nanotube diameter, length is also adjustable
Section, not only enriches the structure and function of Carbon foam, is also more advantageous in application process and carries out Effective Regulation to material property;
(2) using the present invention, the carbon of thin-walled Carbon foam-carbon nano tube compound material of preparation its diameter, adjustable in length
Nanotube is grown on foam carbon surface with cluster-shaped, and usual foam charcoal-carbon that this complex method is different from existing report is received
Mitron composite construction had both enable the unique structure of carbon nanotube exposed, and so that the material is had pore structure abundant, (material compares table
Area is up to 250~400m2/ g), Carbon foam and the respective design feature of carbon nanotube have been fully demonstrated, has in turn ensured the two energy
It is enough securely compound, it realizes the effect that one-plus-one is greater than two, has widened the application range of Carbon foam and carbon nanotube, can have been used extensively
Make electrode material, catalyst carrier and electromagnetic shielding material etc.;
(3) preparation method of thin-walled Carbon foam-carbon nano tube compound material provided by the invention is easy to operate, practicability
By force, and starch, alcohol derive from biomass material, have the characteristics that it is reproducible, be conducive to sustainable development.
Detailed description of the invention
Fig. 1 is the mold for preparing thin-walled Carbon foam and the preparation process schematic diagram of thin-walled Carbon foam;
Fig. 2 is the preparation process schematic diagram of thin-walled Carbon foam-carbon nano tube compound material of the present invention;
Fig. 3 is (aperture bulb diameter) thin-walled Carbon foam scanning electron microscope that the hole bubble average diameter of embodiment 2 is 100 μm
Figure;
Fig. 4 is (macropore bulb diameter) thin-walled Carbon foam scanning electron microscope that the hole bubble average diameter of embodiment 1 is 700 μm
Figure;
Fig. 5 is 2 thin-walled Carbon foam of embodiment-carbon nano tube compound material low magnification scanning electron microscope (SEM) photograph;
Fig. 6 is 2 thin-walled Carbon foam of embodiment-carbon nano tube compound material high-amplification-factor scanning electron microscope (SEM) photograph;
In figure: 1-weight, 2-cyclic annular housings, 3-cylindric pistons, 4-filter cakes, 5-bottom plugs, 6-thin-walled Carbon foams,
7-thin-walled Carbon foam hole steep that walls, 8-have loaded the thin-walled Carbon foam hole steep that wall of catalyst, 9-have completed carbon nano tube growth
Thin-walled Carbon foam hole steep that wall, 10-thin-walled Carbon foams-carbon nano tube compound material;I- foaming charing;II- supported catalyst;
III- grows carbon nanotube;IV- removes catalyst.
Specific embodiment
The embodiments given below are intended to further illustrate the invention, but is not to be construed as to the scope of the present invention
Limitation, some nonessential improvement and tune that person skilled in art makes the present invention according to the content of aforementioned present invention
It is whole, still fall within protection scope of the present invention.
Examples 1 to 21: referring to attached drawing.
A kind of preparation method of thin-walled Carbon foam-carbon nano tube compound material, including the following steps:
A, thin-walled Carbon foam is prepared:
Prepare mold, cyclic annular housing 2 which is socketed by bottom plug 5, lower section and 5 upper section of bottom plug is placed in cyclic annular housing 2
Portion and the slidable cylindric piston 3 being bonded with cyclic annular housing 2 and the weight 1 being pressed on cylindric piston 3 composition;
At room temperature, it is filtered and (is preferably filtered by vacuum) after starch being uniformly mixed with mixed acid, obtain filter cake 4;
Filter cake 4 is placed on the bottom plug 5 of mold, the lower section of cyclic annular housing 2 and 5 upper section of bottom plug are socketed, placed on filter cake 4 cylindric
Piston 3, a pressed weight 1, obtains die assembly on cylindric piston 3;Die assembly is placed in baking oven again, with 2~5
DEG C/heating rate of min increases temperature to 150 DEG C, and maintains 1~3h in 150 DEG C of temperature;Take out die assembly, Temperature fall
To room temperature, die assembly is disassembled, is taken out filter cake 4 (filter cake is foamed and carbonized at this time), thin-walled foam as obtained
Charcoal 6;The mixed acid is the mixed acid of sulfuric acid and phosphoric acid;
B, preparation has loaded the thin-walled Carbon foam thin slice of catalyst:
Thin-walled Carbon foam 6 obtained in step a is cut into the thin slice of long 1cm, width 1cm, thickness 3mm, then thin slice is impregnated
In the ethanol solution containing nickel salt, (thin-walled Carbon foam) thin slice is taken out after placing 1~3h, then being placed in temperature is 30~60 DEG C
Ethyl alcohol is dried in baking oven, the thin-walled Carbon foam thin slice for having loaded catalyst is made;
C, thin-walled Carbon foam-carbon nano tube compound material is prepared:
The thin-walled Carbon foam thin slice obtained in step b for having loaded catalyst is placed in (burning) alcolhol burner internal flame and is burnt
It burns, the growth of carbon nanotube is completed in thin-walled Carbon foam, obtains the thin-walled Carbon foam that grown carbon nanotube;It will grown again
The thin-walled Carbon foam of carbon nanotube is placed in 1mol/L aqueous sulfuric acid impregnate (removal catalyst) for 24 hours after, be washed with distilled water
It to neutrality and dries, thin-walled Carbon foam-carbon nano tube compound material as obtained.
Each step each component raw material and ratio, design parameter condition and thin-walled Carbon foam-obtained in Examples 1 to 7
Carbon nano tube compound material (result) etc. see the table below:
Each component raw material and ratio, design parameter condition and thin-walled foam obtained in each step of embodiment 8~14
Charcoal-carbon nano tube compound material (result) etc. see the table below:
Each component raw material and ratio, design parameter condition and thin-walled foam obtained in each step of embodiment 15~21
Charcoal-carbon nano tube compound material (result) etc. see the table below:
Embodiment 22: referring to attached drawing.
A kind of preparation method of thin-walled Carbon foam-carbon nano tube compound material, including the following steps:
A, thin-walled Carbon foam is prepared:
Prepare mold, cyclic annular housing 2 which is socketed by bottom plug 5, lower section and 5 upper section of bottom plug is placed in cyclic annular housing 2
Portion and the slidable cylindric piston 3 being bonded with cyclic annular housing 2 and the weight 1 being pressed on cylindric piston 3 composition;
At room temperature, it is filtered and (is preferably filtered by vacuum) after starch being uniformly mixed with mixed acid, obtain filter cake 4;
Filter cake 4 is placed on the bottom plug 5 of mold, the lower section of cyclic annular housing 2 and 5 upper section of bottom plug are socketed, placed on filter cake 4 cylindric
Piston 3, a pressed weight 1, obtains die assembly on cylindric piston 3;Die assembly is placed in baking oven again, with 2 DEG C/
The heating rate of min increases temperature to 150 DEG C, and maintains 1h in 150 DEG C of temperature;Die assembly is taken out, room temperature is naturally cooling to
Afterwards, die assembly is disassembled, is taken out filter cake 4 (filter cake is foamed and carbonized at this time), thin-walled Carbon foam 6 as obtained;
By the phosphate aqueous solution of aqueous sulfuric acid and 1mol/L that concentration is 1mol/L, 1:9 is mixed the mixed acid by volume
It closes;
When the starch is mixed with mixed acid, starch: the mass ratio of mixed acid is 1:5;
B, preparation has loaded the thin-walled Carbon foam thin slice of catalyst:
Thin-walled Carbon foam 6 obtained in step a is cut into the thin slice of long 1cm, width 1cm, thickness 3mm, then thin slice is impregnated
In the ethanol solution containing nickel salt, (thin-walled Carbon foam) thin slice is taken out after placing 1h, then is placed in the baking oven that temperature is 60 DEG C
Ethyl alcohol is dried, the thin-walled Carbon foam thin slice for having loaded catalyst is made;
The concentration of the ethanol solution containing nickel salt is preferably 0.1mol/L;
C, thin-walled Carbon foam-carbon nano tube compound material is prepared:
The thin-walled Carbon foam thin slice obtained in step b for having loaded catalyst is placed in (burning) alcolhol burner internal flame and is burnt
It burns, the growth of carbon nanotube is completed in thin-walled Carbon foam, obtains the thin-walled Carbon foam that grown carbon nanotube;It will grown again
The thin-walled Carbon foam of carbon nanotube is placed in 1mol/L aqueous sulfuric acid impregnate (removal catalyst) for 24 hours after, be washed with distilled water
It to neutrality and dries, thin-walled Carbon foam-carbon nano tube compound material as obtained.
Embodiment 23: referring to attached drawing.
A kind of preparation method of thin-walled Carbon foam-carbon nano tube compound material, including the following steps:
A, thin-walled Carbon foam is prepared:
Prepare mold, cyclic annular housing 2 which is socketed by bottom plug 5, lower section and 5 upper section of bottom plug is placed in cyclic annular housing 2
Portion and the slidable cylindric piston 3 being bonded with cyclic annular housing 2 and the weight 1 being pressed on cylindric piston 3 composition;
At room temperature, it is filtered and (is preferably filtered by vacuum) after starch being uniformly mixed with mixed acid, obtain filter cake 4;
Filter cake 4 is placed on the bottom plug 5 of mold, the lower section of cyclic annular housing 2 and 5 upper section of bottom plug are socketed, placed on filter cake 4 cylindric
Piston 3, a pressed weight 1, obtains die assembly on cylindric piston 3;Die assembly is placed in baking oven again, with 5 DEG C/
The heating rate of min increases temperature to 150 DEG C, and maintains 3h in 150 DEG C of temperature;Die assembly is taken out, room temperature is naturally cooling to
Afterwards, die assembly is disassembled, is taken out filter cake 4 (filter cake is foamed and carbonized at this time), thin-walled Carbon foam 6 as obtained;
By the phosphate aqueous solution of aqueous sulfuric acid and 1mol/L that concentration is 1mol/L, 9:1 is mixed the mixed acid by volume
It closes;
When the starch is mixed with mixed acid, starch: the mass ratio of mixed acid is 1:15;
B, preparation has loaded the thin-walled Carbon foam thin slice of catalyst:
Thin-walled Carbon foam 6 obtained in step a is cut into the thin slice of long 1cm, width 1cm, thickness 3mm, then thin slice is impregnated
In the ethanol solution containing nickel salt, (thin-walled Carbon foam) thin slice is taken out after placing 3h, then is placed in the baking oven that temperature is 30 DEG C
Ethyl alcohol is dried, the thin-walled Carbon foam thin slice for having loaded catalyst is made;
The concentration of the ethanol solution containing nickel salt is preferably 0.5mol/L;
C, thin-walled Carbon foam-carbon nano tube compound material is prepared:
The thin-walled Carbon foam thin slice obtained in step b for having loaded catalyst is placed in (burning) alcolhol burner internal flame and is burnt
It burns, the growth of carbon nanotube is completed in thin-walled Carbon foam, obtains the thin-walled Carbon foam that grown carbon nanotube;It will grown again
The thin-walled Carbon foam of carbon nanotube is placed in 1mol/L aqueous sulfuric acid impregnate (removal catalyst) for 24 hours after, be washed with distilled water
It to neutrality and dries, thin-walled Carbon foam-carbon nano tube compound material as obtained.
Embodiment 24: referring to attached drawing.
A kind of preparation method of thin-walled Carbon foam-carbon nano tube compound material, including the following steps:
A, thin-walled Carbon foam is prepared:
Prepare mold, cyclic annular housing 2 which is socketed by bottom plug 5, lower section and 5 upper section of bottom plug is placed in cyclic annular housing 2
Portion and the slidable cylindric piston 3 being bonded with cyclic annular housing 2 and the weight 1 being pressed on cylindric piston 3 composition;
At room temperature, it is filtered and (is preferably filtered by vacuum) after starch being uniformly mixed with mixed acid, obtain filter cake 4;
Filter cake 4 is placed on the bottom plug 5 of mold, the lower section of cyclic annular housing 2 and 5 upper section of bottom plug are socketed, placed on filter cake 4 cylindric
Piston 3, a pressed weight 1, obtains die assembly on cylindric piston 3;Die assembly is placed in baking oven again, with 3 DEG C/
The heating rate of min increases temperature to 150 DEG C, and maintains 2h in 150 DEG C of temperature;Die assembly is taken out, room temperature is naturally cooling to
Afterwards, die assembly is disassembled, is taken out filter cake 4 (filter cake is foamed and carbonized at this time), thin-walled Carbon foam 6 as obtained;
The mixed acid by aqueous sulfuric acid and 1mol/L that concentration is 1mol/L phosphate aqueous solution 1:4.5 by volume
It mixes;
When the starch is mixed with mixed acid, starch: the mass ratio of mixed acid is 1:10;
B, preparation has loaded the thin-walled Carbon foam thin slice of catalyst:
Thin-walled Carbon foam 6 obtained in step a is cut into the thin slice of long 1cm, width 1cm, thickness 3mm, then thin slice is impregnated
In the ethanol solution containing nickel salt, (thin-walled Carbon foam) thin slice is taken out after placing 2h, then is placed in the baking oven that temperature is 45 DEG C
Ethyl alcohol is dried, the thin-walled Carbon foam thin slice for having loaded catalyst is made;
The concentration of the ethanol solution containing nickel salt is preferably 0.3mol/L;
C, thin-walled Carbon foam-carbon nano tube compound material is prepared:
The thin-walled Carbon foam thin slice obtained in step b for having loaded catalyst is placed in (burning) alcolhol burner internal flame and is burnt
It burns, the growth of carbon nanotube is completed in thin-walled Carbon foam, obtains the thin-walled Carbon foam that grown carbon nanotube;It will grown again
The thin-walled Carbon foam of carbon nanotube is placed in 1mol/L aqueous sulfuric acid impregnate (removal catalyst) for 24 hours after, be washed with distilled water
It to neutrality and dries, thin-walled Carbon foam-carbon nano tube compound material as obtained.
Embodiment 25: referring to attached drawing.
A kind of preparation method of thin-walled Carbon foam-carbon nano tube compound material, including the following steps:
A, thin-walled Carbon foam is prepared:
Prepare mold, cyclic annular housing 2 which is socketed by bottom plug 5, lower section and 5 upper section of bottom plug is placed in cyclic annular housing 2
Portion and the slidable cylindric piston 3 being bonded with cyclic annular housing 2 and the weight 1 being pressed on cylindric piston 3 composition;
At room temperature, it is filtered and (is preferably filtered by vacuum) after starch being uniformly mixed with mixed acid, obtain filter cake 4;
Filter cake 4 is placed on the bottom plug 5 of mold, the lower section of cyclic annular housing 2 and 5 upper section of bottom plug are socketed, placed on filter cake 4 cylindric
Piston 3, a pressed weight 1, obtains die assembly on cylindric piston 3;Die assembly is placed in baking oven again, with 3 DEG C/
The heating rate of min increases temperature to 150 DEG C, and maintains 1.5h in 150 DEG C of temperature;Die assembly is taken out, room is naturally cooling to
Wen Hou disassembles die assembly, takes out filter cake 4 (filter cake is foamed and carbonized at this time), thin-walled Carbon foam 6 as obtained;
The mixed acid by aqueous sulfuric acid and 1mol/L that concentration is 1mol/L phosphate aqueous solution 1:2.5 by volume
It mixes;
When the starch is mixed with mixed acid, starch: the mass ratio of mixed acid is 1:7;
B, preparation has loaded the thin-walled Carbon foam thin slice of catalyst:
Thin-walled Carbon foam 6 obtained in step a is cut into the thin slice of long 1cm, width 1cm, thickness 3mm, then thin slice is impregnated
In the ethanol solution containing nickel salt, (thin-walled Carbon foam) thin slice is taken out after placing 1.5h, then is placed in the baking oven that temperature is 40 DEG C
It is middle to dry ethyl alcohol, the thin-walled Carbon foam thin slice for having loaded catalyst is made;
The concentration of the ethanol solution containing nickel salt is preferably 0.2mol/L;
C, thin-walled Carbon foam-carbon nano tube compound material is prepared:
The thin-walled Carbon foam thin slice obtained in step b for having loaded catalyst is placed in (burning) alcolhol burner internal flame and is burnt
It burns, the growth of carbon nanotube is completed in thin-walled Carbon foam, obtains the thin-walled Carbon foam that grown carbon nanotube;It will grown again
The thin-walled Carbon foam of carbon nanotube is placed in 1mol/L aqueous sulfuric acid impregnate (removal catalyst) for 24 hours after, be washed with distilled water
It to neutrality and dries, thin-walled Carbon foam-carbon nano tube compound material as obtained.
Embodiment 26: referring to attached drawing.
A kind of preparation method of thin-walled Carbon foam-carbon nano tube compound material, including the following steps:
A, thin-walled Carbon foam is prepared:
Prepare mold, cyclic annular housing 2 which is socketed by bottom plug 5, lower section and 5 upper section of bottom plug is placed in cyclic annular housing 2
Portion and the slidable cylindric piston 3 being bonded with cyclic annular housing 2 and the weight 1 being pressed on cylindric piston 3 composition;
At room temperature, it is filtered and (is preferably filtered by vacuum) after starch being uniformly mixed with mixed acid, obtain filter cake 4;
Filter cake 4 is placed on the bottom plug 5 of mold, the lower section of cyclic annular housing 2 and 5 upper section of bottom plug are socketed, placed on filter cake 4 cylindric
Piston 3, a pressed weight 1, obtains die assembly on cylindric piston 3;Die assembly is placed in baking oven again, with 4 DEG C/
The heating rate of min increases temperature to 150 DEG C, and maintains 2.5h in 150 DEG C of temperature;Die assembly is taken out, room is naturally cooling to
Wen Hou disassembles die assembly, takes out filter cake 4 (filter cake is foamed and carbonized at this time), thin-walled Carbon foam 6 as obtained;
By the phosphate aqueous solution of aqueous sulfuric acid and 1mol/L that concentration is 1mol/L, 7:1 is mixed the mixed acid by volume
It closes;
When the starch is mixed with mixed acid, starch: the mass ratio of mixed acid is 1:13;
B, preparation has loaded the thin-walled Carbon foam thin slice of catalyst:
Thin-walled Carbon foam 6 obtained in step a is cut into the thin slice of long 1cm, width 1cm, thickness 3mm, then thin slice is impregnated
In the ethanol solution containing nickel salt, (thin-walled Carbon foam) thin slice is taken out after placing 2h, then is placed in the baking oven that temperature is 50 DEG C
Ethyl alcohol is dried, the thin-walled Carbon foam thin slice for having loaded catalyst is made;
The concentration of the ethanol solution containing nickel salt is preferably 0.4mol/L;
C, thin-walled Carbon foam-carbon nano tube compound material is prepared:
The thin-walled Carbon foam thin slice obtained in step b for having loaded catalyst is placed in (burning) alcolhol burner internal flame and is burnt
It burns, the growth of carbon nanotube is completed in thin-walled Carbon foam, obtains the thin-walled Carbon foam that grown carbon nanotube;It will grown again
The thin-walled Carbon foam of carbon nanotube is placed in 1mol/L aqueous sulfuric acid impregnate (removal catalyst) for 24 hours after, be washed with distilled water
It to neutrality and dries, thin-walled Carbon foam-carbon nano tube compound material as obtained.
Embodiment 27: referring to attached drawing.
A kind of preparation method of thin-walled Carbon foam-carbon nano tube compound material, including the following steps:
A, thin-walled Carbon foam is prepared:
Prepare mold, cyclic annular housing 2 which is socketed by bottom plug 5, lower section and 5 upper section of bottom plug is placed in cyclic annular housing 2
Portion and the slidable cylindric piston 3 being bonded with cyclic annular housing 2 and the weight 1 being pressed on cylindric piston 3 composition;
At room temperature, it is filtered and (is preferably filtered by vacuum) after starch being uniformly mixed with mixed acid, obtain filter cake 4;
Filter cake 4 is placed on the bottom plug 5 of mold, the lower section of cyclic annular housing 2 and 5 upper section of bottom plug are socketed, placed on filter cake 4 cylindric
Piston 3, a pressed weight 1, obtains die assembly on cylindric piston 3;Die assembly is placed in baking oven again, with 3.5 DEG C/
The heating rate of min increases temperature to 150 DEG C, and maintains 2h in 150 DEG C of temperature;Die assembly is taken out, room temperature is naturally cooling to
Afterwards, die assembly is disassembled, is taken out filter cake 4 (filter cake is foamed and carbonized at this time), thin-walled Carbon foam 6 as obtained;
By the phosphate aqueous solution of aqueous sulfuric acid and 1mol/L that concentration is 1mol/L, 1:7 is mixed the mixed acid by volume
It closes;
When the starch is mixed with mixed acid, starch: the mass ratio of mixed acid is 1:7;
B, preparation has loaded the thin-walled Carbon foam thin slice of catalyst:
Thin-walled Carbon foam 6 obtained in step a is cut into the thin slice of long 1cm, width 1cm, thickness 3mm, then thin slice is impregnated
In the ethanol solution containing nickel salt, (thin-walled Carbon foam) thin slice is taken out after placing 1~3h, then is placed in the baking oven that temperature is 40 DEG C
It is middle to dry ethyl alcohol, the thin-walled Carbon foam thin slice for having loaded catalyst is made;
The concentration of the ethanol solution containing nickel salt is preferably 0.2mol/L;
C, thin-walled Carbon foam-carbon nano tube compound material is prepared:
The thin-walled Carbon foam thin slice obtained in step b for having loaded catalyst is placed in (burning) alcolhol burner internal flame and is burnt
It burns, the growth of carbon nanotube is completed in thin-walled Carbon foam, obtains the thin-walled Carbon foam that grown carbon nanotube;It will grown again
The thin-walled Carbon foam of carbon nanotube is placed in 1mol/L aqueous sulfuric acid impregnate (removal catalyst) for 24 hours after, be washed with distilled water
It to neutrality and dries, thin-walled Carbon foam-carbon nano tube compound material as obtained.
Embodiment 28: referring to attached drawing.
A kind of preparation method of thin-walled Carbon foam-carbon nano tube compound material, including the following steps:
A, thin-walled Carbon foam is prepared:
Prepare mold, cyclic annular housing 2 which is socketed by bottom plug 5, lower section and 5 upper section of bottom plug is placed in cyclic annular housing 2
Portion and the slidable cylindric piston 3 being bonded with cyclic annular housing 2 and the weight 1 being pressed on cylindric piston 3 composition;
At room temperature, it is filtered and (is preferably filtered by vacuum) after starch being uniformly mixed with mixed acid, obtain filter cake 4;
Filter cake 4 is placed on the bottom plug 5 of mold, the lower section of cyclic annular housing 2 and 5 upper section of bottom plug are socketed, placed on filter cake 4 cylindric
Piston 3, a pressed weight 1, obtains die assembly on cylindric piston 3;Die assembly is placed in baking oven again, with 3 DEG C/
The heating rate of min increases temperature to 150 DEG C, and maintains 2h in 150 DEG C of temperature;Die assembly is taken out, room temperature is naturally cooling to
Afterwards, die assembly is disassembled, is taken out filter cake 4 (filter cake is foamed and carbonized at this time), thin-walled Carbon foam 6 as obtained;
The mixed acid by aqueous sulfuric acid and 1mol/L that concentration is 1mol/L phosphate aqueous solution 4.5:1 by volume
It mixes;
When the starch is mixed with mixed acid, starch: the mass ratio of mixed acid is 1:8;
B, preparation has loaded the thin-walled Carbon foam thin slice of catalyst:
Thin-walled Carbon foam 6 obtained in step a is cut into the thin slice of long 1cm, width 1cm, thickness 3mm, then thin slice is impregnated
In the ethanol solution containing nickel salt, (thin-walled Carbon foam) thin slice is taken out after placing 2h, then is placed in the baking oven that temperature is 50 DEG C
Ethyl alcohol is dried, the thin-walled Carbon foam thin slice for having loaded catalyst is made;
The concentration of the ethanol solution containing nickel salt is preferably 0.3mol/L;
C, thin-walled Carbon foam-carbon nano tube compound material is prepared:
The thin-walled Carbon foam thin slice obtained in step b for having loaded catalyst is placed in (burning) alcolhol burner internal flame and is burnt
It burns, the growth of carbon nanotube is completed in thin-walled Carbon foam, obtains the thin-walled Carbon foam that grown carbon nanotube;It will grown again
The thin-walled Carbon foam of carbon nanotube is placed in 1mol/L aqueous sulfuric acid impregnate (removal catalyst) for 24 hours after, be washed with distilled water
It to neutrality and dries, thin-walled Carbon foam-carbon nano tube compound material as obtained.
In above-described embodiment 22~28: starch described in step a can be cornstarch, pea starch, tapioca, horse
Any one of bell sweet potato starch, starch from sweet potato, wheaten starch and green starch.
In above-described embodiment 22~28: filter cake 4 described in step a be preferably placed in temperature 60 C baking oven place 1~
Middle any time evaporates the filter cake after partial moisture for 24 hours;Further, diameter, the bottom plug of the filter cake 4 after evaporating partial moisture
The diameter of 5 diameter, the internal diameter of cyclic annular housing 2 and cylindric piston 3 is preferably 5cm.
In above-described embodiment 22~28: nickel salt described in step b can be in nickel nitrate, nickel acetate and nickel chloride
It is any.
In above-described embodiment 22~28: the thin-walled Carbon foam thin slice that catalyst has been loaded described in step c is placed in alcolhol burner
The time of calcination can be any time in 1~5min in internal flame (the alcolhol burner internal flame to burn), during calcination must not between
Break the tipping load thin-walled Carbon foam thin slice of catalyst, makes carbon nanotube on the thin-walled Carbon foam thin slice for having loaded catalyst
Growth can be uniformly distributed.
In above-described embodiment 22~28: obtaining filter cake 4 through filtering after being uniformly mixed starch with mixed acid described in step a
Preferably after mixing by starch and mixed acid, 1~3h (middle any time) is placed, then through filtering (preferably vacuum
Filter) obtain filter cake 4.
In above-described embodiment 22~28: the pressure that weight 1 described in step a is pressed on cylindric piston 3 is preferably 250
~2500Pa.
In above-described embodiment 22~28: described in thin-walled Carbon foam-carbon nano tube compound material obtained described in step c
Carbon foam hole bulb diameter in 100~800 μ ms, charcoal wall thickness within the scope of 25~100nm, the carbon nanotube be caliber
Within the scope of 15~100nm, multi-walled carbon nanotube of the length in 0.5~3 μ m.
Thin-walled Carbon foam-carbon nano tube compound material prepared by above-described embodiment 22~28, by with three-dimensional foam shape knot
It the foam carbon material of structure and is combined with the carbon nanotube that cluster-shaped is grown on the thin charcoal wall of the nanometer grade thickness of Carbon foam.
In above-described embodiment: used each raw material is commercial product.
In above-described embodiment: it is not specifically specified in used percentage, be quality (weight) percentage or
Well known to a person skilled in the art percentages;Described quality (weight) part can be gram or kilogram.
In above-described embodiment: technological parameter (temperature, time, concentration etc.) and dosage of each component numerical value in each step etc. are
Range, any point is applicable.
The technology contents being not specifically delineated in the content of present invention and above-described embodiment are compared with technology.
The present invention is not limited to the above embodiments, can be implemented described in the content of present invention and has the good result.
Claims (10)
1. a kind of preparation method of thin-walled Carbon foam-carbon nano tube compound material, it is characterized by including the following steps:
A, thin-walled Carbon foam is prepared:
Prepare mold, cyclic annular housing (2) which is socketed by bottom plug (5), lower section and bottom plug (5) upper section is placed in cyclic annular housing
(2) the internal and slidable cylindric piston (3) being bonded with cyclic annular housing (2) and the weight being pressed on cylindric piston (3)
Object (1) is constituted;
At room temperature, starch is filtered after mixing with mixed acid, is obtained filter cake (4);Filter cake (4) is placed in the bottom plug of mold
(5) on, the lower section of cyclic annular housing (2) and bottom plug (5) upper section is socketed, cylindric piston (3) are placed on filter cake (4), in circle
A pressed weight (1), obtains die assembly on plunger piston (3);Die assembly is placed in baking oven again, with 2~5 DEG C/min's
Heating rate increases temperature to 150 DEG C, and maintains 1~3 h in 150 DEG C of temperature;Die assembly is taken out, room temperature is naturally cooling to
Afterwards, die assembly is disassembled, is taken out filter cake (4), thin-walled Carbon foam (6) as obtained;
The mixed acid is the mixed acid of sulfuric acid and phosphoric acid;
B, preparation has loaded the thin-walled Carbon foam thin slice of catalyst:
Thin-walled Carbon foam (6) obtained in step a is cut into the thin slice of long 1 cm, wide 1 cm, 3 mm of thickness, then thin slice is impregnated
In the ethanol solution containing nickel salt, thin slice is taken out after placing 1~3 h, then is placed in second in the baking oven that temperature is 30~60 DEG C
Alcohol drying, is made the thin-walled Carbon foam thin slice for having loaded catalyst;
C, thin-walled Carbon foam-carbon nano tube compound material is prepared:
The thin-walled Carbon foam thin slice obtained in step b for having loaded catalyst is placed in calcination in alcolhol burner internal flame, is steeped in thin-walled
The growth that carbon nanotube is completed on foam charcoal, obtains the thin-walled Carbon foam that grown carbon nanotube;Carbon nanotube will be grown again
Thin-walled Carbon foam is placed in 1 mol/L aqueous sulfuric acid impregnate 24 h after, be washed with distilled water to neutrality and dry, as be made
Thin-walled Carbon foam-carbon nano tube compound material.
2. by thin-walled Carbon foam-carbon nano tube compound material preparation method described in claim 1, it is characterized in that: institute in step a
Stating starch is cornstarch, pea starch, tapioca, potato starch, starch from sweet potato, wheaten starch and green starch
Any one of.
3. by thin-walled Carbon foam-carbon nano tube compound material preparation method described in claim 1, it is characterized in that: institute in step a
Stating mixed acid, 1:9~9:1 is mixed by volume by the phosphate aqueous solution of aqueous sulfuric acid and 1 mol/L that concentration is 1 mol/L
It forms.
4. by thin-walled Carbon foam-carbon nano tube compound material preparation method described in claim 1, it is characterized in that: institute in step a
It states filter cake (4) and is placed in the filter cake placed after 0~24 h in temperature 60 C baking oven.
5. by thin-walled Carbon foam-carbon nano tube compound material preparation method described in claim 1, it is characterized in that: institute in step b
The concentration for stating the ethanol solution containing nickel salt is 0.1~0.5 mol/L.
6. the preparation method of the thin-walled Carbon foam-carbon nano tube compound material of claim 1 or 5 is pressed, it is characterized in that: step b
Described in nickel salt be any one of nickel nitrate, nickel acetate and nickel chloride.
7. by thin-walled Carbon foam-carbon nano tube compound material preparation method described in claim 1, it is characterized in that: institute in step c
State loaded catalyst thin-walled Carbon foam thin slice be placed in calcination in alcolhol burner internal flame time be 1~5 min.
8. by thin-walled Carbon foam-carbon nano tube compound material preparation method described in claim 1, it is characterized in that: institute in step a
State filtered after being uniformly mixed starch with mixed acid obtain filter cake (4) be by starch and mixed acid after mixing, place 1~
3 h, then through filtering the filter cake (4) obtained.
9. by thin-walled Carbon foam-carbon nano tube compound material preparation method described in claim 1, it is characterized in that: described in step a
It is 250~2500 Pa that weight (1), which is pressed on the pressure on cylindric piston (3),.
10. by claim 1,3 or the preparation method of the 8 thin-walled Carbon foam-carbon nano tube compound materials, it is characterized in that: step
When starch described in rapid a is mixed with mixed acid, starch: the mass ratio of mixed acid is 1:5~15.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102674316A (en) * | 2012-05-09 | 2012-09-19 | 清华大学 | Method for preparing composition of carbon nano tube and graphene by using sheet material |
CN102765713A (en) * | 2012-08-16 | 2012-11-07 | 西南石油大学 | Fast preparation method for carbon nano tube/ graphene sandwich structure mateirals |
KR20150062611A (en) * | 2013-11-29 | 2015-06-08 | 한국기계연구원 | Manufacturing method of metal foam, the metal foam manufactured thereby and catalyst support consisting of the metal foam used for exhaust gas purification filter |
CN106185885A (en) * | 2016-06-30 | 2016-12-07 | 天津大学 | There is isotropism height heat conduction, elastic three-dimensional grapheme and the preparation method of carbon nano tube compound material |
CN106367717A (en) * | 2016-08-19 | 2017-02-01 | 中国科学院重庆绿色智能技术研究院 | Patterned growth method of one-dimensional nanotube and three-dimensional graphene composite material |
CN107986261A (en) * | 2018-01-09 | 2018-05-04 | 郑州大学 | The apparatus and method for preparing the three-dimensional porous block of oversize carbon nanotubes |
-
2017
- 2017-04-07 CN CN201710222774.2A patent/CN106976861B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102674316A (en) * | 2012-05-09 | 2012-09-19 | 清华大学 | Method for preparing composition of carbon nano tube and graphene by using sheet material |
CN102765713A (en) * | 2012-08-16 | 2012-11-07 | 西南石油大学 | Fast preparation method for carbon nano tube/ graphene sandwich structure mateirals |
KR20150062611A (en) * | 2013-11-29 | 2015-06-08 | 한국기계연구원 | Manufacturing method of metal foam, the metal foam manufactured thereby and catalyst support consisting of the metal foam used for exhaust gas purification filter |
CN106185885A (en) * | 2016-06-30 | 2016-12-07 | 天津大学 | There is isotropism height heat conduction, elastic three-dimensional grapheme and the preparation method of carbon nano tube compound material |
CN106367717A (en) * | 2016-08-19 | 2017-02-01 | 中国科学院重庆绿色智能技术研究院 | Patterned growth method of one-dimensional nanotube and three-dimensional graphene composite material |
CN107986261A (en) * | 2018-01-09 | 2018-05-04 | 郑州大学 | The apparatus and method for preparing the three-dimensional porous block of oversize carbon nanotubes |
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