CN106082176A - A kind of preparation method of three-dimensional grapheme - Google Patents
A kind of preparation method of three-dimensional grapheme Download PDFInfo
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- CN106082176A CN106082176A CN201610352387.6A CN201610352387A CN106082176A CN 106082176 A CN106082176 A CN 106082176A CN 201610352387 A CN201610352387 A CN 201610352387A CN 106082176 A CN106082176 A CN 106082176A
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Abstract
The invention discloses the preparation method of a kind of three-dimensional grapheme, comprise the following steps: (1), using high polymer as solute, using polar liquid or nonpolar liquid as solvent, prepares high polymeric solution；(2) nikel powder is added in high polymeric solution, be subsequently poured in the mould of molding, obtain the complex of nikel powder and high polymer；(3) complex of nikel powder with high polymer is placed in heated constant temperature in reacting furnace to react, obtains the three-dimensional grapheme being wrapped on nickel skeleton；(4) three-dimensional grapheme being wrapped on nickel skeleton is put in the acid solution that can dissolve nickel, nickel skeleton is removed, is carried out and is dried, it is thus achieved that pure three-dimensional grapheme.The present invention is convenient, safe, controllably prepare the three-dimensional grapheme of difformity, aperture, porosity and electrical conductivity, breaches the restriction of prior art, and prepared three-dimensional grapheme can extensively applying electronic device material and Bio-Nano-Materials.
Description
Technical field
The present invention relates to the preparation method of a kind of grapheme material, be specifically related to the preparation method of a kind of three-dimensional grapheme.
Background technology
Single-layer graphene exists with two dimensional crystal structure, and thickness only has 0.334nm, and it is to construct other dimension carbonaceous material
Elementary cell, it can wrap up the fullerene forming zero dimension, roll and form one-dimensional CNT, pile up shape layer by layer
Become three-dimensional graphite.Graphene is the nano material that known world is the thinnest, the hardest, and it is almost fully transparent, only inhales
Receive the light of 2.3%；Heat conductivity is up to 5300W/m K, and higher than CNT and diamond, under room temperature, its electron mobility exceedes
15000cm2/ V s, again ratio CNT or silicon wafer height, and resistivity only has 1 Ω m, lower than copper or silver, in the world
The material that resistivity is minimum.The performance of these excellences make Graphene nano electron device, gas sensor, energy storage and
There is the application prospect of light in the fields such as composite.
Due to captivation strong between graphene sheet layer, the Graphene of solid-state is caused to lose single dispersing due to gathering
The excellent properties such as the high-specific surface area that Graphene has.Simultaneously at the energy, environment, sensing and biological field, by two-dimensional graphene
It is assembled into three dimensional structure the most necessary in the application of material based on Graphene.For solving this puzzlement, researchers
If every piece of graphite alkene is joined together to form three-dimensional honeycomb shape framing structure by imagination, then the Graphene of solid-state can be made to represent
The excellent properties similar to monolithic graphite alkene.
Grapheme foam [Three-dimensional flexible and conductive interconnected
Graphene networks grown by chemical vapour deposition(NATURE MATERIALS VOL 10
JUNE 2011 P424-P428)] it is a kind of three-dimensional grapheme prepared for masterplate with nickel skeleton, it is existed by graphene sheet layer
Nickel surface grows and is connected as an entirety, therefore inherits that nickel skeleton is isotropic, the three dimensional skeletal structure of porous.Use
Carbon source mostly be the liquid (gaseous state) of gas or volatilization, such as methane, ethanol.Three-dimensional grapheme prepared by nickel foam steeps because of template nickel
The parameter of foam limits, and its porosity is 95%, and pore size is in 100-500 μm, and electrical conductivity is at 10S cm simultaneously-1。
Along with Graphene application is more and more extensive, need the three-dimensional grapheme of difformity and porosity with reply
Different occasions.So needing to be processed the three-dimensional grapheme of finished product and cut, but processing and cutting necessarily cause three-dimensional
, there is the inequality of structure, fracture in the distortion of graphene-structured and destruction.The three-dimensional grapheme of same shape size, electric conductivity
Can decline because porosity increases, and this point for three-dimensional grapheme as a kind of conductive material, be the most disadvantageous.
In sum, the preparation of current three-dimensional grapheme, it is carried out shape transformation and must increase new step, its process
Complicated, loaded down with trivial details, its structure of destructible.The three-dimensional grapheme porosity that simultaneously prepared by finished product nickel foam cannot be any with pore size
Allotment, therefore electric conductivity also can be restricted.
Summary of the invention
Solve the technical problem that: for the deficiencies in the prior art, the invention provides the preparation side of a kind of three-dimensional grapheme
Method, convenient, safe, controllably prepare the three-dimensional grapheme of difformity and porosity, specifically mix with high polymer with nikel powder,
Wherein nikel powder is catalyst, and high polymer, as solid carbon source, utilizes different element contained by high polymer simultaneously, sinks with chemical gaseous phase
Area method carries out the preparation of three-dimensional grapheme；The three-dimensional grapheme prepared can extensively applying electronic device material and biological nano material
Material.
Technical scheme: the preparation method of a kind of three-dimensional grapheme that the present invention provides, it includes following preparation process:
(1) using linear carbon chains resin high polymer as solute, using polar liquid or nonpolar liquid as solvent, both are mixed in
Stirring and dissolving 1-10 hour at 25-150 DEG C, mixing speed is 100-3000rpm, is configured to mass fraction and more than 10% and is less than
The high polymeric solution of solute saturated concentration；
(2) particle size range is pressed the mass ratio 1:(0.25-4 with step (1) described solute at the nikel powder of 0.1-1000 μm) add
In step (1) gained high polymeric solution, being stirred shaking until solution mix homogeneously, mixing speed is 100-500rpm, so
After mixed solution poured in the mould of molding, continue drying out at 25-150 DEG C 1-48 hour, make liquid flux volatilize,
Complex to nikel powder Yu high polymer；
(3) complex of step (2) gained nikel powder Yu high polymer is put into high temperature-resistant vessel is placed in heating region in reacting furnace,
It is passed through the noble gas of argon or nitrogen while using vacuum pump evacuation, furnace temperature is risen to reaction temperature 800-1000 DEG C,
Keep isothermal reaction 10-60 minute；High temperature-resistant vessel was taken out after terminating when furnace temperature is down to room temperature by reaction, obtained being wrapped in nickel
Three-dimensional grapheme on skeleton；
(4) three-dimensional grapheme that step (3) gained is wrapped on nickel skeleton is put in the acid solution that can dissolve nickel, in temperature
Degree, for 25-80 DEG C, keeps 12-48 hour, is removed by nickel skeleton, is carried out and is dried, can obtain pure three
Dimension Graphene.
Described linear carbon chains resin high polymer is the non-three-dimensional-structure macromole that main chain is made up of carbon atom completely, and it is often
Temperature is lower is solid-state, semisolid, reaches the straight chain linear structure high polymer of 1:1000, such as vinyl polymerization for molecular diameter and length ratio
The polyvinyl alcohol of thing or polypropylene, or linear macromolecule main chain is with the line style side chain high polymer of some side chains, and side chain is the shortest
The best, the polymethyl methacrylate of such as acid lipid aggregate thing or polyamino acid methyl ester.The height that the prioritizing selection degree of polymerization is high gathers
Thing.
Described polar liquid is water or acetone；Described nonpolar liquid is chloroform or chlorobenzene.Need to be according to high polymer
Polarity selects close liquid, and the polyvinyl alcohol of such as polarity uses water as solvent, nonpolar polymethyl methacrylate
Use chloroform as solvent.Polar polymer dissolubility in a liquid is bigger, prioritizing selection.
The mass fraction of described high polymer solute, its numerical value is the highest, and high polymeric solution gets over thickness, too high and too low the most not
It is beneficial to the mixing of high polymeric solution and nikel powder.And high polymer solute saturated concentration is this high polymer solute can dissolve in a solvent
Highest mass fractions.So on the premise of the high polymer solute mass fraction less than saturated concentration, preferably high polymer is molten
Matter mass fraction is 20%.
Described nikel powder needs unified particle diameter, to control the pore size of three-dimensional grapheme, the fine grained ball of preferably 5-10 μm
Shape nikel powder.
Described nikel powder and the mass ratio of high polymer solute, be used for controlling porosity and the electrical conductivity of three-dimensional grapheme, quality
Ratio is the highest, and porosity is the biggest, and electrical conductivity is the least；Preferably nikel powder is 1:0.67 with the mass ratio of high polymer solute, now with hole
The rising of rate, electrical conductivity declines the slowest.
The mould of described molding is any three-dimensional shape, such as cuboid, shape triangular prism shaped, irregular, is used for controlling
The shape of three-dimensional grapheme processed, please use difform mould corresponding to different application scenarios.
Described acid solution is: prepared the aqueous solution obtained, such as hydrochloric acid solution by acid；Or prepared by strong acid weak base salt
The aqueous solution become, such as liquor ferri trichloridi；Or the aqueous solution of arbitrary proportion mixing both, the salt of preferably 3mol/L
The ferric chloride aqueous solutions of aqueous acid and 3mol/L presses the aqueous solution of 1:1 mixing；Mixed aqueous solution is used to take into account removal nickel
Speed and cost, so prioritizing selection.
Beneficial effect: the present invention compared with prior art, has following features and an effect:
(1) difform mould is utilized can to obtain difform three-dimensional grapheme, it is not necessary to increase processing and shear step, soon
Prompt convenient.
(2) nikel powder of different-grain diameter size is utilized, it is achieved the preparation of different pore size size three-dimensional grapheme.Pore size exists
0.1 μm-1000 μm, breaches nickel foam and prepares the restriction in 100-500 μm of the three-dimensional grapheme pore size.
(3) utilize nikel powder different from high polymer Solute mass ratio, control the porosity of three-dimensional grapheme, the highest hole of mass ratio
Gap rate is the biggest, it is achieved the preparation of the three-dimensional grapheme of different porosities and electrical conductivity.Porosity is at 20%-80%, due to its ratio
The most controlled, breach nickel foam and prepare the restriction of three-dimensional grapheme porosity 95%.
(4) three-dimensional grapheme of different porosities, under same shape size, electrical conductivity is different, and porosity is the biggest, conductance
Rate is the least.Electrical conductivity is at 12-33Scm-1, breach nickel foam and prepare the electrical conductivity of three-dimensional grapheme at 10Scm-1Restriction.
Accompanying drawing explanation
Fig. 1 is difform nikel powder and High polymer compounds, and wherein (a) is the triangular prism shaped of embodiment 1, and (b) is real
Execute the irregular shape of example 2；
Fig. 2 be the three-dimensional grapheme (a) of embodiment 7, the scanning electron microscope image (c) of (b) and conventional three-dimensional Graphene,
(d)；
Fig. 3 is the three-dimensional grapheme Raman spectrogram with conventional three-dimensional Graphene of embodiment 7；
Fig. 4 is that the three-dimensional grapheme of embodiment 1-7 contrasts with conventional three-dimensional Graphene electrical conductivity.
Detailed description of the invention
Further illustrate the present invention below by the mode of embodiment, but the most therefore protection scope of the present invention is confined to
Following embodiment, but limited by description and claims of this specification.
Embodiment 1
One, the method preparing three-dimensional grapheme with high polymer for solid carbon source described in the present embodiment, comprises the steps:
The preparation of the poly-vinyl alcohol solution of mass fraction 20%: use polyvinyl alcohol and water to mix according to mass ratio 2:8 and pour container into
In, container is heated to 95 DEG C, carry out 4 hours, rotating speed be the stirring of 400rpm, allow polyvinyl alcohol be completely dissolved, clarified
Poly-vinyl alcohol solution stand-by.
Being that 1:0.25 weighs nikel powder according to nikel powder and polyvinyl alcohol mass ratio, the unification of nikel powder particle diameter is 5 μm.Nikel powder is added
Poly-vinyl alcohol solution.Suitable stirring concussion, until nikel powder is mixed thoroughly with solution.Mixing liquid is poured into triangular prism shaped
In the mold for forming of shape, heating 80 DEG C and keep 6 hours, make water volatilize, polyvinyl alcohol solute is solidified togather with nikel powder.Obtain
Nikel powder and the complex of polyvinyl alcohol.
The complex of the nikel powder being cured with polyvinyl alcohol is removed from the molds, puts into high temperature-resistant vessel and be placed in reacting furnace
Middle heating region, seals reacting furnace, opens vacuum pump, is passed through argon simultaneously, is inert gas atmosphere in making stove.By reacting furnace liter
Warm to 1000 DEG C, constant temperature 20 minutes.After to be grown, it be down to room temperature and take out.Obtain the three-dimensional graphite being wrapped on nickel skeleton
Alkene.Said process all keeps vacuum pump work and is passed through argon.
The removal of nickel skeleton: the three-dimensional grapheme/nickel skeleton prepared is placed in hydrochloric acid solution and the 3mol/L of 3mol/L
Liquor ferri trichloridi 1:1 mixed aqueous solution in, 50 DEG C keep 36 hours.Nickel skeleton is completely dissolved removal, finally gives
The three-dimensional grapheme of foaming structure.
Two, the present embodiment effect: three-dimensional grapheme is shaped as triangular prism shaped, as shown in Fig. 1 (a), pore size average out to 5
μm, porosity is 80%, and electrical conductivity is 12Scm-1。
Embodiment 2
One, the method preparing three-dimensional grapheme with high polymer for solid carbon source described in the present embodiment, comprises the steps:
The preparation of the poly-vinyl alcohol solution of mass fraction 20%: use polyvinyl alcohol and water to mix according to mass ratio 2:8 and pour container into
In, container is heated to 95 DEG C, carry out 4 hours, rotating speed be the stirring of 400rpm, allow polyvinyl alcohol be completely dissolved, clarified
Poly-vinyl alcohol solution stand-by.
Being that 1:4 weighs nikel powder according to nikel powder and polyvinyl alcohol mass ratio, the unification of nikel powder particle diameter is 5 μm.Nikel powder is added poly-
Glycohol solution.Suitable stirring concussion, until nikel powder is mixed thoroughly with solution.Mixing liquid is poured into irregularly shaped
Mold for forming in, heat 80 DEG C keep 6 hours, make water volatilize, polyvinyl alcohol solute is solidified togather with nikel powder.Obtain nickel
Powder and the complex of polyvinyl alcohol.
The complex of the nikel powder being cured with polyvinyl alcohol is removed from the molds, puts into high temperature-resistant vessel and be placed in reacting furnace
Middle heating region, seals reacting furnace, opens vacuum pump, is passed through argon simultaneously, is inert gas atmosphere in making stove.By reacting furnace liter
Warm to 1000 DEG C, constant temperature 20 minutes.After to be grown, it be down to room temperature and take out.Obtain the three-dimensional graphite being wrapped on nickel skeleton
Alkene.Said process all keeps vacuum pump work and is passed through argon.
The removal of nickel skeleton: the three-dimensional grapheme/nickel skeleton prepared is placed in hydrochloric acid solution and the 3mol/L of 3mol/L
Liquor ferri trichloridi 1:0.25 mixed aqueous solution in, 50 DEG C keep 36 hours.Nickel skeleton is completely dissolved removal, final
Three-dimensional grapheme to foaming structure.
Two, the present embodiment effect: three-dimensional grapheme is shaped as irregular shape, as shown in Fig. 1 (b), pore size average out to 5
μm, porosity is 20%, and electrical conductivity is 33Scm-1。
Embodiment 3
One, the method preparing three-dimensional grapheme with high polymer for solid carbon source described in the present embodiment, comprises the steps:
The preparation of the poly-vinyl alcohol solution of mass fraction 10%: use polyvinyl alcohol and water to mix according to mass ratio 1:9 and pour container into
In, container is heated to 95 DEG C, carry out 4 hours, rotating speed be the stirring of 400rpm, allow polyvinyl alcohol be completely dissolved, clarified
Poly-vinyl alcohol solution stand-by.
Being that 1:0.67 weighs nikel powder according to nikel powder and polyvinyl alcohol mass ratio, the unification of nikel powder particle diameter is 0.1 μm.Nikel powder is added
Enter poly-vinyl alcohol solution.Suitable stirring concussion, until nikel powder is mixed thoroughly with solution.Pour mixing liquid into cuboid
In the mold for forming of shape, heating 80 DEG C and keep 6 hours, make water volatilize, polyvinyl alcohol solute is solidified togather with nikel powder.?
Complex to nikel powder Yu polyvinyl alcohol.
The complex of the nikel powder being cured with polyvinyl alcohol is removed from the molds, puts into high temperature-resistant vessel and be placed in reacting furnace
Middle heating region, seals reacting furnace, opens vacuum pump, is passed through argon simultaneously, is inert gas atmosphere in making stove.By reacting furnace liter
Warm to 1000 DEG C, constant temperature 20 minutes.After to be grown, it be down to room temperature and take out.Obtain the three-dimensional graphite being wrapped on nickel skeleton
Alkene.Said process all keeps vacuum pump work and is passed through argon.
The removal of nickel skeleton: the three-dimensional grapheme/nickel skeleton prepared is placed in hydrochloric acid solution and the 3mol/L of 3mol/L
Liquor ferri trichloridi 1:0.5 mixed aqueous solution in, 50 DEG C keep 36 hours.Nickel skeleton is completely dissolved removal, final
Three-dimensional grapheme to foaming structure.
Two, the present embodiment effect: three-dimensional grapheme is shaped as cuboid, pore size average out to 0.1 μm, and porosity is
63%, electrical conductivity is 18.5Scm-1。
Embodiment 4
One, the method preparing three-dimensional grapheme with high polymer for solid carbon source described in the present embodiment, comprises the steps:
The preparation of the poly-vinyl alcohol solution of mass fraction 10%: use polyvinyl alcohol and water to mix according to mass ratio 1:9 and pour container into
In, container is heated to 95 DEG C, carry out 4 hours, rotating speed be the stirring of 400rpm, allow polyvinyl alcohol be completely dissolved, clarified
Poly-vinyl alcohol solution stand-by.
Being that 1:0.67 weighs nikel powder according to nikel powder and polyvinyl alcohol mass ratio, the unification of nikel powder particle diameter is 1000 μm.By nikel powder
Add poly-vinyl alcohol solution.Suitable stirring concussion, until nikel powder is mixed thoroughly with solution.Mixing liquid is poured into rectangular
In the mold for forming of shape, heating 80 DEG C and keep 6 hours, make water volatilize, polyvinyl alcohol solute is solidified togather with nikel powder.
Obtain the complex of nikel powder and polyvinyl alcohol.
The complex of the nikel powder being cured with polyvinyl alcohol is removed from the molds, puts into high temperature-resistant vessel and be placed in reacting furnace
Middle heating region, seals reacting furnace, opens vacuum pump, is passed through argon simultaneously, is inert gas atmosphere in making stove.By reacting furnace liter
Warm to 1000 DEG C, constant temperature 20 minutes.After to be grown, it be down to room temperature and take out.Obtain the three-dimensional graphite being wrapped on nickel skeleton
Alkene.Said process all keeps vacuum pump work and is passed through argon.
The removal of nickel skeleton: the three-dimensional grapheme/nickel skeleton prepared is placed in hydrochloric acid solution and the 3mol/L of 3mol/L
Liquor ferri trichloridi 1:1 mixed aqueous solution in, 50 DEG C keep 36 hours.Nickel skeleton is completely dissolved removal, finally gives
The three-dimensional grapheme of foaming structure.
Two, the present embodiment effect: three-dimensional grapheme is shaped as cuboid, pore size average out to 1000 μm, porosity
Being 66%, electrical conductivity is 17.5Scm-1。
Embodiment 5
One, the method preparing three-dimensional grapheme with high polymer for solid carbon source described in the present embodiment, comprises the steps:
The preparation of the poly-vinyl alcohol solution of mass fraction 10%: use polyvinyl alcohol and water to mix according to mass ratio 1:9 and pour container into
In, container is heated to 95 DEG C, carry out 4 hours, rotating speed be the stirring of 400rpm, allow polyvinyl alcohol be completely dissolved, clarified
Poly-vinyl alcohol solution stand-by.
Being that 1:0.67 weighs nikel powder according to nikel powder and polyvinyl alcohol mass ratio, the unification of nikel powder particle diameter is 5 μm.Nikel powder is added
Poly-vinyl alcohol solution.Suitable stirring concussion, until nikel powder is mixed thoroughly with solution.Pour mixing liquid into cuboid
In the mold for forming of shape, heating 80 DEG C and keep 6 hours, make water volatilize, polyvinyl alcohol solute is solidified togather with nikel powder.Obtain
Nikel powder and the complex of polyvinyl alcohol.
The complex of the nikel powder being cured with polyvinyl alcohol is removed from the molds, puts into high temperature-resistant vessel and be placed in reacting furnace
Middle heating region, seals reacting furnace, opens vacuum pump, is passed through argon simultaneously, is inert gas atmosphere in making stove.By reacting furnace liter
Warm to 1000 DEG C, constant temperature 20 minutes.After to be grown, it be down to room temperature and take out.Obtain the three-dimensional graphite being wrapped on nickel skeleton
Alkene.Said process all keeps vacuum pump work and is passed through argon.
The removal of nickel skeleton: the three-dimensional grapheme/nickel skeleton prepared is placed in hydrochloric acid solution and the 3mol/L of 3mol/L
Liquor ferri trichloridi 1:1 mixed aqueous solution in, 50 DEG C keep 36 hours.Nickel skeleton is completely dissolved removal, finally gives
The three-dimensional grapheme of foaming structure.
Two, the present embodiment effect: three-dimensional grapheme is shaped as cuboid, pore size average out to 5 μm, and porosity is
61%, electrical conductivity is 19Scm-1。
Embodiment 6
One, the method preparing three-dimensional grapheme with high polymer for solid carbon source described in the present embodiment, comprises the steps:
The preparation of the polymethyl methacrylate solution of mass fraction 20%: use polymethyl methacrylate and chloroform liquid
Body according to mass ratio 2:8 mixing pours in container, container is heated to 50 DEG C, carry out 4 hours, rotating speed be the stirring of 400rpm,
Allowing polymethyl methacrylate be completely dissolved, the polymethyl methacrylate solution obtaining clarification is stand-by.
Being that 1:0.67 weighs nikel powder according to nikel powder and polymethyl methacrylate mass ratio, the unification of nikel powder particle diameter is 5 μm.Will
Nikel powder adds polymethyl methacrylate solution.Suitable stirring concussion, until nikel powder is mixed thoroughly with solution.Will mixing
Liquid is poured in the mold for forming of rectangular shape, is heated to 40 DEG C and keeps 6 hours, makes chloroform volatilize, polyvinyl alcohol
Solute is solidified togather with nikel powder.Obtain the complex of nikel powder and polyvinyl alcohol.
The complex of the nikel powder being cured with polyvinyl alcohol is removed from the molds, puts into high temperature-resistant vessel and be placed in reacting furnace
Middle heating region, seals reacting furnace, opens vacuum pump, is passed through argon simultaneously, is inert gas atmosphere in making stove.By reacting furnace liter
Warm to 1000 DEG C, constant temperature 20 minutes.After to be grown, it be down to room temperature and take out.Obtain the three-dimensional graphite being wrapped on nickel skeleton
Alkene.Said process all keeps vacuum pump work and is passed through argon.
The removal of nickel skeleton: the three-dimensional grapheme/nickel skeleton prepared is placed in hydrochloric acid solution and the 3mol/L of 3mol/L
Liquor ferri trichloridi 1:1 mixed aqueous solution in, 50 DEG C keep 36 hours.Nickel skeleton is completely dissolved removal, finally gives
The three-dimensional grapheme of foaming structure.
Two, the present embodiment effect: three-dimensional grapheme is shaped as cuboid, pore size average out to 5 μm, and porosity is
61%, electrical conductivity is 19Scm-1。
Embodiment 7
One, the method preparing three-dimensional grapheme with high polymer for solid carbon source described in the present embodiment, comprises the steps:
The preparation of the poly-vinyl alcohol solution of mass fraction 20%: use polyvinyl alcohol and water to mix according to mass ratio 2:8 and pour container into
In, container is heated to 95 DEG C, carry out 4 hours, rotating speed be the stirring of 400rpm, allow polyvinyl alcohol be completely dissolved, clarified
Poly-vinyl alcohol solution stand-by.
Being that 1:0.67 weighs nikel powder according to nikel powder and polyvinyl alcohol mass ratio, the unification of nikel powder particle diameter is 5 μm.Nikel powder is added
Poly-vinyl alcohol solution.Suitable stirring concussion, until nikel powder is mixed thoroughly with solution.Mixing liquid is poured into triangular prism shaped
In the mold for forming of shape, heating 80 DEG C and keep 6 hours, make water volatilize, polyvinyl alcohol solute is solidified togather with nikel powder.Obtain
Nikel powder and the complex of polyvinyl alcohol.
The complex of the nikel powder being cured with polyvinyl alcohol is removed from the molds, puts into high temperature-resistant vessel and be placed in reacting furnace
Middle heating region, seals reacting furnace, opens vacuum pump, is passed through argon simultaneously, is inert gas atmosphere in making stove.By reacting furnace liter
Warm to 1000 DEG C, constant temperature 20 minutes.After to be grown, it be down to room temperature and take out.Obtain the three-dimensional graphite being wrapped on nickel skeleton
Alkene.Said process all keeps vacuum pump work and is passed through argon.
The removal of nickel skeleton: the three-dimensional grapheme/nickel skeleton prepared is placed in hydrochloric acid solution and the 3mol/L of 3mol/L
Liquor ferri trichloridi 1:1 mixed aqueous solution in, 50 DEG C keep 36 hours.Nickel skeleton is completely dissolved removal, finally gives
The three-dimensional grapheme of foaming structure.
Two, the present embodiment effect: the scanning electron microscope image of the three-dimensional grapheme obtained by the present embodiment is shown in Fig. 2
(a) and 2 (b).Image clearly shows that three dimensional structure and graphene film Rotating fields, its lamella exists fold, demonstrates it
Feature.Compared with the scanning electron microscope image 2 (c) of ordinary graphite alkene and 2 (d), it can clearly be seen that ordinary graphite alkene
Porosity be 95%, pore size is in 200 μm, and the three-dimensional grapheme obtained by the present embodiment, and its porosity is 60%, aperture
Size is 5 μm.
The Raman spectrum of the three-dimensional grapheme obtained by the present embodiment is shown in Fig. 3, and its G peak, 2D peak are obvious, and D hardly may be used at peak
See.Compared with the Raman spectrum of conventional three-dimensional Graphene unanimously, show that preparation is as three-dimensional grapheme.
Three-dimensional grapheme is shaped as triangular prism shaped, pore size average out to 5 μm, and porosity is 60%, and electrical conductivity is
19.5Scm-1。
The electrical conductivity performance of product prepared by product prepared by embodiment 1-7 and conventional method is shown in Fig. 4.
Claims (8)
1. the preparation method of a three-dimensional grapheme, it is characterised in that include following preparation process:
(1) using linear carbon chains resin high polymer as solute, using polar liquid or nonpolar liquid as solvent, both are mixed in
Stirring and dissolving 1-10 hour at 25-150 DEG C, mixing speed is 100-3000rpm, is configured to mass fraction and more than 10% and is less than
The high polymeric solution of solute saturated concentration；
(2) particle size range is pressed the mass ratio 1:(0.25-4 with step (1) described solute at the nikel powder of 0.1-1000 μm) add
In step (1) gained high polymeric solution, being stirred shaking until solution mix homogeneously, mixing speed is 100-500rpm, so
After mixed solution poured in the mould of molding, continue drying out at 25-150 DEG C 1-48 hour, make liquid flux volatilize,
Complex to nikel powder Yu high polymer；
(3) complex of step (2) gained nikel powder Yu high polymer is put into high temperature-resistant vessel is placed in heating region in reacting furnace,
It is passed through the noble gas of argon or nitrogen while using vacuum pump evacuation, furnace temperature is risen to reaction temperature 800-1000 DEG C,
Keep isothermal reaction 10-60 minute；High temperature-resistant vessel was taken out after terminating when furnace temperature is down to room temperature by reaction, obtained being wrapped in nickel
Three-dimensional grapheme on skeleton；
(4) three-dimensional grapheme that step (3) gained is wrapped on nickel skeleton is put in the acid solution that can dissolve nickel, in temperature
Degree, for 25-80 DEG C, keeps 12-48 hour, is removed by nickel skeleton, is carried out and is dried, can obtain pure three
Dimension Graphene.
The preparation method of a kind of three-dimensional grapheme the most according to claim 1, it is characterised in that step (1) described Linear carbon
Chain resin high polymer is the non-three-dimensional-structure macromole that main chain is made up of carbon atom completely, and it is solid-state, semisolid at normal temperatures,
For molecular diameter and length than reaching the straight chain linear structure high polymer of 1:1000 or linear macromolecule main chain with some side chains
Line style side chain high polymer.
The preparation method of a kind of three-dimensional grapheme the most according to claim 2, it is characterised in that described molecular diameter and length
The straight chain linear structure high polymer of Du Bida 1:1000 is polyvinyl alcohol or polypropylene.
The preparation method of a kind of three-dimensional grapheme the most according to claim 2, it is characterised in that described linear macromolecule master
Chain is polymethyl methacrylate or polyamino acid methyl ester with the line style side chain high polymer of some side chains.
The preparation method of a kind of three-dimensional grapheme the most according to claim 1, it is characterised in that step (1) described polar liquid
Body is water or acetone.
The preparation method of a kind of three-dimensional grapheme the most according to claim 1, it is characterised in that step (1) is described nonpolar
Liquid is chloroform or chlorobenzene.
The preparation method of a kind of three-dimensional grapheme the most according to claim 1, it is characterised in that step (4) is described can be molten
Solve nickel acid solution be by acid prepare obtain aqueous solution, the aqueous solution prepared by strong acid weak base salt or both in any proportion
The aqueous solution of mixing.
The preparation method of a kind of three-dimensional grapheme the most according to claim 1, it is characterised in that step (4) is described can be molten
The aqueous solution that the ferric chloride aqueous solutions of the aqueous hydrochloric acid solution that acid solution is 3mol/L and 3mol/L that solve nickel is mixed by 1:1.
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