CN106744859A - Graphene three-dimensional multistage pore structure powder prepared by a kind of low temperature polymer cracking - Google Patents
Graphene three-dimensional multistage pore structure powder prepared by a kind of low temperature polymer cracking Download PDFInfo
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Abstract
The invention discloses Graphene three-dimensional multistage pore structure powder prepared by a kind of cracking of low temperature polymer：(1) catalyst metal salts are added water, is configured to metal salt solution and mixed with polymers that mass concentration is 10~60%, filtered after 0.1~12h of stirring, take filter residue, cleaned up, dried；(2) reductant solution is added, is filtered after 0.1~12h of stirring, drying；(3) pore-creating agent solution is added, and is stirred, dried；(4) heat, it is 700~1000 DEG C, 0.5~8h of constant temperature to control temperature；(5) by 1~12h of pickling, filtering, drying, that is, Graphene three-dimensional multistage pore structure powder is obtained.The inventive method prepares gained Graphene three-dimensional multistage pore structure powder has specific surface area high, high conductivity, preparing raw material without crushing; finished product does not need ball milling, and preparation flow is greatly shortened, yield is improved, cost is substantially reduced, easy scale and industrialized production.
Description
Technical field
The present invention relates to a kind of Graphene three-dimensional multistage pore structure powder, prepared by more particularly to a kind of low temperature polymer cracking
Graphene three-dimensional multistage pore structure powder.
Background technology
Graphene be one kind by carbon atom through sp2The honeycomb two-dimensional structure material formed after electron orbit hydridization, is C units
Another allotrope of element.By A.K.Geim and K.S.Novoselov in 2004, single crystal graphite is torn with adhesive tape hand thin
The method of film, the Graphene stablized first.Graphene is most thin, most hard, the conductive at room temperature world being currently known
Property preferably and possess the nano material of powerful flexibility, the thickness of single-layer graphene only has 0.34nm, and specific surface area is up to
2630m2/ g, intensity is up to 130GPa, is the best material of current intensity, hardness, is far longer than the metal materials such as steel class.Graphite
Alkene thermal conductivity is more than 2 × 10 in 3000-5000W/mK, carrier density11cm-2.These excellent performances, will cause Graphene
Material is in traditional field and emerging fields such as semiconductor industry, photovoltaic industry, secondary cell, space flight, military project, displays of new generation
Bring revolutionary technological progress.
Originally, scientists take the mode of mechanical stripping to prepare Graphene, using adhesive tape to single crystal graphite repeatedly
Stickup can obtain the grapheme material with a small number of carbon atomic layers, structure stable and superior performance relatively.But the mechanical stripping
Graphene size prepared by mode is smaller, inefficiency.In order to overcome the shortcoming, scientists to take the mode of vapour deposition,
Using Copper Foil as template, CH is being passed through4And H2Under conditions of, in the larger grapheme material of copper foil surface synthesis area, but can be somebody's turn to do
Kind preparation method is complex, and the removal of copper brings larger environmental pollution.In addition, the Hummers methods of classics prepare oxidation
Graphene is most commonly seen, this kind of method low cost, can high efficiency prepare large-area graphene thin layer.But the Graphene for preparing is present
Topological defect, conjugation region is small, above has certain limitation in application.Walt A.de Heer are closed by epitaxial growth substrate of SiC
Influenceed by SiC substrate into equally having carrier mobility high, the Graphene of good electrochemical properties, but this kind of method
Larger, preparation process control is complex, and can not largely make.
The information for being disclosed in the background section is merely intended to increase the understanding to general background of the invention, without answering
In being considered as recognizing or imply in any form that the information structure has been the prior art well known to persons skilled in the art.
The content of the invention
It is contemplated that overcoming the shortcomings of that prior art is present prepares the three-dimensional construction powder body material of Graphene, there is provided it is a kind of with
Polymer without pulverizing processing is raw material, prepares high conductivity, the three-dimensional multistage pore structure graphene powder of morphology controllable
Method.
To achieve the above object, the technical scheme that the present invention is provided is as follows：
Graphene three-dimensional multistage pore structure powder prepared by a kind of low temperature polymer cracking, comprising following operating procedure：
(1) catalyst metal salts are added water, is configured to the metal salt solution that mass concentration is 10~60% and is mixed with polymer
Close, filtered after 0.1~12h of stirring, take filter residue, clean up, dry；
(2) reductant solution is added in gained material to after drying in step (1), and is uniformly mixed, stirring 0.1~
Filtered after 12h, take filter residue, dried；
(3) added relative to raw material than the pore creating material for 0.2-2 in gained filter residue to after drying in step (2), and stirred
It is well mixed, drying, whole drying course polymer therein is without crushing；Wherein, during pore creating material adds solvent, pore-creating is formed
Agent solution；Described solvent is the one kind in water, acetone, methyl alcohol or ethanol；
(4) by gained material after drying in step (3) under protective atmosphere, heating controls temperature for 700~1000 DEG C,
0.5~8h of constant temperature；
(5) during gained material adds acid solution after heating in step (4), 1~12h of pickling, filtering, drying,
The Graphene three-dimensional multistage pore structure powder body material with high-specific surface area, high conductivity is obtained, gently concussion obtains stone
Black alkene three-dimensional multistage pore structure powder.
Wherein, heating rate is 1~10 DEG C/min in heating process in step (4).
Wherein, the catalyst metal salts described in step (1) be molysite, cobalt salt or nickel salt in one or more
Mixture；Wherein, described molysite is iron chloride, frerrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, acetic acid
Iron, ferrous acetate, potassium ferrocyanide, the potassium ferricyanide, sodium ferrocyanide or the sodium ferricyanide；Described cobalt salt is cobalt chloride, chlorination
Sub- cobalt, cobaltous sulfate, Cobaltous sulfate, cobalt nitrate, colbaltous nitrate, cobalt acetate, acetic acid Asia cobalt, hexanitro close cobalt acid sodium or hexanitro conjunction
Cobalt acid potassium；Described nickel salt is nickel chloride, nickel sulfate, nickel nitrate or nickel acetate.
Wherein, the polymer described in step (1) be PKS polymer, phenolic resin, epoxy resin, Corvic,
The mixture of one or more resins in polyester resin, polyamide, polyimide resin.
Wherein, the reductant solution described in step (2) dissolves gained reductant solution for reducing agent is added to the water；Its
In, described reducing agent is the one kind in sodium borohydride, hydrazine hydrate, sodium sulfite, sodium hydrogensulfite, hydrogen sulfide and stannous chloride
Or two or more mixtures.
Wherein, the pore creating material described in step (3) is potassium hydroxide, calcium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, bicarbonate
One or more in sodium or NaOH.
Wherein, the protective atmosphere described in step (4) is the one kind in nitrogen, helium, argon gas.
Wherein, the acid solution described in step (5) be hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid in one kind or
Two or more mixtures.
Wherein, the concentration of the acid solution described in step (5) is 1~5mol/L.
Compared with prior art, the present invention has the advantages that：
The inventive method prepare gained Graphene three-dimensional multistage pore structure powder have specific surface area high, high conductivity,
Without crushing, finished product does not need ball milling to preparing raw material, and preparation flow is greatly shortened, yield is improved, cost is substantially reduced, easy scale
Change and industrialized production；The present invention uses the reducing loaded catalyst metal ion on polymer of low-temperature in-site so that raw material
Polymer can at a lower temperature occur graphitization reaction；Further, temperature reduction, degree of graphitization is improved, so that greatly
It is big to reduce energy consumption, improve material conductivity.The inventive method is not required to by harsh material pre-treatment, without pulverizing and sieving, into
The post processing of product is also without ball milling.The polymer for being used, wide material sources are with low cost, in addition, the preparation that the present invention is provided
Method low cost, yield is high, and technical process is simple, it is easy to accomplish the industrialized production of Graphene.
Brief description of the drawings
Fig. 1 is that the present invention implements the X-ray diffractogram that row 1 prepare products obtained therefrom.
Fig. 2 is that the present invention implements the scanning electron microscope (SEM) photograph that row 2 prepare products obtained therefrom.
Fig. 3 and Fig. 4 are that the present invention implements the transmission electron microscope picture that row 2 prepare products obtained therefrom.
Fig. 5 is that the present invention implements the scanning electron microscope (SEM) photograph that row 3 prepare products obtained therefrom.
Fig. 6 is that the present invention implements the transmission electron microscope picture that row 4 prepare products obtained therefrom.
Specific embodiment
Specific embodiment is described in detail below in conjunction with the accompanying drawings, it is to be understood that protection scope of the present invention is not received
The limitation of specific embodiment.
Embodiment 1
(1) nickel sulfate of 20g is dissolved in 100ml deionized waters, the nickel sulfate that concentration is 20% is formed after stirring and dissolving
Solution, adds 100g polyester resin, and magnetic agitation is uniform in 60 DEG C of water-baths, polyester resin is exchanged metallic nickel ions, stirs
Suction filtration after 12h is mixed, filter residue is taken, is cleaned with deionized water 3 times, the polyester resin after exchanging well is dried in 80 DEG C of baking ovens；
(2) it is reducing agent hydrazine hydrate is soluble in water, the hydrazine hydrate solution that mass fraction is 80% is formed, measure 75ml mass
Fraction is that 80% reducing agent hydrazine hydrate solution is added in the polyester resin by ion exchange in step (1) after drying,
Magnetic agitation is uniform in 60 DEG C of water-baths, suction filtration after stirring 12h, removes filtrate, takes filter residue, obtains final product the polyester tree after reduction
Fat, gained polyester resin is dried in 80 DEG C of baking ovens；
(3) take and be dissolved in 100ml than the 100g pore creating material potassium hydroxide for 1 relative to gained filter residue after drying in step (2)
In deionized water, potassium hydroxide solution is formed, is subsequently adding in step (2) after drying in gained filter residue, and be uniformly mixed,
The vacuum drying at 80 DEG C, whole drying course polymer therein is without crushing；
(4) gained polyester resin after reduction is weighed in the above-mentioned steps of quality (3) such as six parts to be put into tube furnace 350
DEG C, 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, heated under 800 DEG C of respective different temperatures, i.e., be in nitrogen flow
Under the nitrogen of 60mL/min, assigned temperature is risen to from room temperature with the heating rate of 2 DEG C/min, and 2h is incubated in assigned temperature, so
Natural cooling afterwards；
(5) each material of gained is respectively with the chlorohydric acid pickling 6h of 3mol/L, filtering, repeatedly acid after step (4) is heated
Wash twice, take filter residue and cleaned with deionized water to cleaning fluid pH in neutrality, then each drying respectively at 80 DEG C is had
There is the Graphene three-dimensional multistage pore structure powder body material of high-specific surface area, high conductivity, gently concussion obtains Graphene three-dimensional
Hierarchical porous structure powder, respective finely ground rear survey XRD, as shown in Figure 1.
Embodiment 2
(1) Nickel dichloride hexahydrate of 20g is dissolved in 100ml deionized waters, it is 20% that concentration is formed after stirring and dissolving
Nickel dichloride hexahydrate solution, adds 100gPKS polymer, and magnetic agitation is uniform in 60 DEG C of water-baths, makes PKS polymer exchanges
Metallic nickel ions, suction filtration after stirring 10h, take filter residue, are cleaned with deionized water 3 times, and the PKS polymer after exchanging well is at 80 DEG C
Dried in baking oven；
(2) it is reducing agent sodium borohydride is soluble in water, the sodium borohydride solution that mass fraction is 80% is formed, measure 75ml
Mass fraction is that 80% PKS by ion exchange that is added in step (1) after drying of reducing agent sodium borohydride solution gathers
In compound, magnetic agitation is uniform in 60 DEG C of water-baths, suction filtration after stirring 10h, removes filtrate, filter residue is taken, after obtaining final product reduction
PKS polymer, gained PKS polymer is dried in 80 DEG C of baking ovens；
(3) take and be dissolved in deionization than the 100g pore creating material potassium hydroxide for 1 relative to gained filter residue after drying in step (2)
In water, potassium hydroxide solution is formed, be subsequently adding in step (2) after drying in gained filter residue, and be uniformly mixed, at 80 DEG C
Lower vacuum drying, whole drying course polymer therein is without crushing；
(4) gained PKS polymer after reduction in step (3) is put into tube furnace and is heated, i.e., in nitrogen stream
Measure under the protective gas for 60mL/min, rise to 850 DEG C from room temperature with the heating rate of 2 DEG C/min, and protected at a temperature of 850 DEG C
Warm 2h, natural cooling；
(5) each material of gained is respectively with the sulfuric acid washing 6h of 3mol/L, filtering, repeatedly acid after step (4) is heated
Wash twice, take filter residue and cleaned with deionized water to cleaning fluid pH in neutrality, then each drying respectively at 80 DEG C is had
There is the Graphene three-dimensional multistage pore structure powder body material of high-specific surface area, high conductivity, gently concussion obtains Graphene three-dimensional
Hierarchical porous structure powder.
Embodiment 3
(1) the six hydration nickel acetates of 20g are dissolved in 100ml deionized waters, it is 20% that concentration is formed after stirring and dissolving
Six hydration nickel acetate solutions, add 100g phenolic resin, and magnetic agitation is uniform in 60 DEG C of water-baths, phenolic resin is exchanged gold
Category nickel ion, suction filtration after stirring 8h, takes filter residue, is cleaned with deionized water 3 times, and the phenolic resin after exchanging well is in 80 DEG C of baking ovens
Middle drying；
(2) it is reducing agent sodium hydrogensulfite is soluble in water, the solution of sodium bisulfite that mass fraction is 80% is formed, measure
75ml mass fractions be 80% reducing agent solution of sodium bisulfite be added in step (1) after drying by ion exchange
In phenolic resin, magnetic agitation is uniform in 60 DEG C of water-baths, suction filtration after stirring 0.1h, removes filtrate, takes filter residue, obtains final product reduction
Phenolic resin afterwards, gained phenolic resin is dried in 80 DEG C of baking ovens；
(3) take and be dissolved in acetone than the 150g pore creating material ammonium hydrogen carbonate for 1.5 relative to gained filter residue after drying in step (2)
In, ammonium hydrogen carbonate acetone soln is formed, it is subsequently adding in step (2) after drying in gained filter residue, and be uniformly mixed, 80
Vacuum drying at DEG C, whole drying course polymer therein is without crushing；
(4) heated in gained phenolic resin after reduction in (3) being put into tube furnace, i.e., be in nitrogen flow
Under the protective gas of 60mL/min, 700 DEG C are risen to from room temperature with the heating rate of 1 DEG C/min, and be incubated at a temperature of 700 DEG C
8h, natural cooling；
(5) each material of gained is respectively with the nitric acid acidwashing 1h of 5mol/L, filtering, repeatedly acid after step (4) is heated
Wash twice, take filter residue and cleaned with deionized water to cleaning fluid pH in neutrality, then each drying respectively at 80 DEG C is had
There is the Graphene three-dimensional multistage pore structure powder body material of high-specific surface area, high conductivity, gently concussion obtains Graphene three-dimensional
Hierarchical porous structure powder.
Embodiment 4
(1) nickel nitrate of 20g is dissolved in 100ml deionized waters, the nickel nitrate that concentration is 20% is formed after stirring and dissolving
Solution, adds 100g epoxy resin, and magnetic agitation is uniform in 60 DEG C of water-baths, epoxy resin is exchanged metallic nickel ions, stirs
Suction filtration after 6h is mixed, filter residue is taken, is cleaned with deionized water 3 times, the epoxy resin after exchanging well is dried in 80 DEG C of baking ovens；
(2) it is reducing agent sodium sulfite is soluble in water, the sodium sulfite solution that mass fraction is 80% is formed, measure 75ml
Mass fraction is that 80% reducing agent sodium sulfite solution is added to the asphalt mixtures modified by epoxy resin by ion exchange in step (1) after drying
In fat, magnetic agitation is uniform in 60 DEG C of water-baths, suction filtration after stirring 2h, removes filtrate, takes filter residue, obtains final product the epoxy after reduction
Resin, gained epoxy resin is dried in 80 DEG C of baking ovens；
(3) take and be dissolved in deionization than the 200g pore creating material calcium hydroxides for 2 relative to gained filter residue after drying in step (2)
In water, aqua calcis is formed, be subsequently adding in step (2) after drying in gained filter residue, and be uniformly mixed, at 80 DEG C
Lower vacuum drying, whole drying course polymer therein is without crushing；
(4) gained epoxy resin after reduction in step (3) is put into tube furnace and is heated, i.e., in helium gas flow
Under for the protective gas of 60mL/min, 1000 DEG C are risen to from room temperature with the heating rate of 10 DEG C/min, and at a temperature of 1000 DEG C
Insulation 0.5h, natural cooling；
(5) each material of gained is respectively with the acetic acid pickling 12h of 1mol/L, filtering, repeatedly acid after step (4) is heated
Wash twice, take filter residue and cleaned with deionized water to cleaning fluid pH in neutrality, then each drying respectively at 80 DEG C is had
There is the Graphene three-dimensional multistage pore structure powder body material of high-specific surface area, high conductivity, gently concussion obtains Graphene three-dimensional
Hierarchical porous structure powder.
Embodiment 5
(1) Nickel dichloride hexahydrate of 20g is dissolved in 100ml deionized waters, it is 20% that concentration is formed after stirring and dissolving
Nickel dichloride hexahydrate solution, adds 100g Corvics, and magnetic agitation is uniform in 60 DEG C of water-baths, makes polyvinyl chloride tree
Ester exchange metallic nickel ions, suction filtration after stirring 4h, take filter residue, are cleaned with deionized water 3 times, the polyvinyl chloride tree after exchanging well
Fat is dried in 80 DEG C of baking ovens；
(2) it is reducing agent hydrogen sulfide is soluble in water, the hydrogen sulfide solution that mass fraction is 80% is formed, measure 75ml mass
Fraction is that 80% reducing agent hydrogen sulfide solution is added to the Corvic by ion exchange in step (1) after drying
In, magnetic agitation is uniform in 60 DEG C of water-baths, suction filtration after stirring 4h, removes filtrate, takes filter residue, obtains final product the polychlorostyrene second after reduction
Olefine resin, gained Corvic is dried in 80 DEG C of baking ovens；
(3) take and dissolve ionized water than the 20g pore creating material ammonium carbonates for 0.2 relative to gained filter residue after drying in step (2)
In, sal volatile is formed, it is subsequently adding in step (2) after drying in gained filter residue, and be uniformly mixed, it is true at 80 DEG C
Sky drying, whole drying course polymer therein is without crushing；
(4) gained Corvic after reduction in step (3) is put into tube furnace and is heated, i.e., in argon gas
Under flow is for the protective gas of 60mL/min, 800 DEG C are risen to from room temperature with the heating rate of 5 DEG C/min, and at a temperature of 800 DEG C
Insulation 3h, natural cooling；
(5) each material of gained is respectively with the oxalic acid pickling 10h of 2mol/L, filtering, repeatedly acid after step (4) is heated
Wash twice, take filter residue and cleaned with deionized water to cleaning fluid pH in neutrality, then each drying respectively at 80 DEG C is had
There is the Graphene three-dimensional multistage pore structure powder body material of high-specific surface area, high conductivity, gently concussion obtains Graphene three-dimensional
Hierarchical porous structure powder.
Embodiment 6
(1) Nickel dichloride hexahydrate of 50g is dissolved in 100ml deionized waters, it is 50% that concentration is formed after stirring and dissolving
Nickel dichloride hexahydrate solution, adds 100g polyamides, and magnetic agitation is uniform in 60 DEG C of water-baths, hands over polyamide
Metallic nickel ions are changed, suction filtration after stirring 2h takes filter residue, cleaned with deionized water 3 times, and the polyamide after exchanging well is 80
Dried in DEG C baking oven；
(2) it is reducing agent stannous chloride is soluble in water, the stannous chloride solution that mass fraction is 80% is formed, measure 75ml
Mass fraction is that 80% reducing agent stannous chloride solution is added to the polyamide by ion exchange in step (1) after drying
In resin, magnetic agitation is uniform in 60 DEG C of water-baths, suction filtration after stirring 8h, removes filtrate, takes filter residue, obtains final product poly- after reduction
Amide resin, gained polyamide is dried in 80 DEG C of baking ovens；
(3) take and be dissolved in relative to gained pore creating material sodium acid carbonate of the filter residue than the 50g for 0.5 after drying in step (2)
In ionized water, sodium bicarbonate solution is formed, be subsequently adding in step (2) after drying in gained filter residue, and be uniformly mixed,
Vacuum drying at 80 DEG C, whole drying course polymer therein is without crushing；
(4) gained polyamide after reduction in step (3) is put into tube furnace and is heated, i.e., in nitrogen stream
Measure under the protective gas for 60mL/min, rise to 900 DEG C from room temperature with the heating rate of 4 DEG C/min, and protected at a temperature of 900 DEG C
Warm 5h, natural cooling；
(5) each material of gained is respectively with the chlorohydric acid pickling 3h of 4mol/L, filtering, repeatedly acid after step (4) is heated
Wash twice, take filter residue and cleaned with deionized water to cleaning fluid pH in neutrality, then each drying respectively at 80 DEG C is had
There is the Graphene three-dimensional multistage pore structure powder body material of high-specific surface area, high conductivity, gently concussion obtains Graphene three-dimensional
Hierarchical porous structure powder.
Embodiment 7
(1) ferric chloride hexahydrate of 40g is dissolved in 100ml deionized waters, it is 40% that concentration is formed after stirring and dissolving
Ferric chloride hexahydrate solution, adds 100g polyimide resins, and magnetic agitation is uniform in 60 DEG C of water-baths, makes polyimides tree
Ester exchange metal iron ion, suction filtration after stirring 0.1h, takes filter residue, is cleaned with deionized water 3 times, the polyimides after exchanging well
Resin is dried in 80 DEG C of baking ovens；
(2) it is reducing agent sodium borohydride is soluble in water, the sodium borohydride solution that mass fraction is 80% is formed, measure 75ml
Mass fraction is that to be added in step (1) polyamides by ion exchange after drying sub- for 80% reducing agent sodium borohydride solution
In polyimide resin, magnetic agitation is uniform in 60 DEG C of water-baths, suction filtration after stirring 10h, removes filtrate, filter residue is taken, after obtaining final product reduction
Polyimide resin, gained polyimide resin is dried in 80 DEG C of baking ovens；
(3) take and be dissolved in deionization than the 100g pore creating material potassium hydroxide for 1 relative to gained filter residue after drying in step (2)
In water, potassium hydroxide solution is formed, be subsequently adding in step (2) after drying in gained filter residue, and be uniformly mixed, at 80 DEG C
Lower vacuum drying, whole drying course polymer therein is without crushing；
(4) gained polyimide resin after reduction in step (3) is put into tube furnace and is heated, i.e., in nitrogen
Under flow is for the protective gas of 60mL/min, 850 DEG C are risen to from room temperature with the heating rate of 2 DEG C/min, and at a temperature of 850 DEG C
Insulation 2h, natural cooling；
(5) each material of gained is respectively with the sulfuric acid washing 6h of 3mol/L, filtering, repeatedly acid after step (4) is heated
Wash twice, take filter residue and cleaned with deionized water to cleaning fluid pH in neutrality, then each drying respectively at 80 DEG C is had
There is the Graphene three-dimensional multistage pore structure powder body material of high-specific surface area, high conductivity, gently concussion obtains Graphene three-dimensional
Hierarchical porous structure powder.
Embodiment 8
(1) cobalt chloride hexahydrate of 30g is dissolved in 100ml deionized waters, it is 30% that concentration is formed after stirring and dissolving
Cobalt chloride hexahydrate solution, adds 100gPKS polymer, and magnetic agitation is uniform in 60 DEG C of water-baths, makes PKS polymer exchanges
Metal cobalt ions, suction filtration after stirring 12h, takes filter residue, is cleaned with deionized water 3 times, and the PKS polymer after exchanging well is at 80 DEG C
Dried in baking oven；
(2) it is reducing agent hydrazine hydrate is soluble in water, the hydrazine hydrate solution that mass fraction is 80% is formed, measure 75ml mass
Fraction is that 80% reducing agent hydrazine hydrate solution is added in the PKS polymer by ion exchange in step (1) after drying,
Magnetic agitation is uniform in 60 DEG C of water-baths, suction filtration after stirring 12h, removes filtrate, takes filter residue, obtains final product the PKS polymerizations after reduction
Thing, gained PKS polymer is dried in 80 DEG C of baking ovens；
(3) take relative to gained pore creating material NaOH of the filter residue than the 100g for 1 after drying in step (2) be dissolved in from
In sub- water, sodium hydroxide solution is formed, be subsequently adding in step (2) after drying in gained filter residue, and be uniformly mixed, 80
Vacuum drying at DEG C, whole drying course polymer therein is without crushing；
(4) gained PKS polymer after reduction in step (3) is put into tube furnace and is heated, i.e., in nitrogen stream
Measure under the protective gas for 60mL/min, rise to 850 DEG C from room temperature with the heating rate of 2 DEG C/min, and protected at a temperature of 850 DEG C
Warm 2h, natural cooling；
(5) each material of gained is respectively with the chlorohydric acid pickling 6h of 3mol/L, filtering, repeatedly acid after step (4) is heated
Wash twice, take filter residue and cleaned with deionized water to cleaning fluid pH in neutrality, then each drying respectively at 80 DEG C is had
There is the Graphene three-dimensional multistage pore structure powder body material of high-specific surface area, high conductivity, gently concussion obtains Graphene three-dimensional
Hierarchical porous structure powder.
Embodiment 9
(1) cobaltous sulfate of the ferric sulfate iron of 30g and 30g is dissolved in 100ml deionized waters, concentration is formed after stirring and dissolving
It is 60% ferric sulfate iron, cobalt sulfate solution, adds 100g Corvics, magnetic agitation is uniform in 60 DEG C of water-baths,
Corvic is set to exchange metal iron ion and cobalt ions, suction filtration after stirring 12h takes filter residue, cleaned with deionized water 3 times,
Corvic after exchanging well is dried in 80 DEG C of baking ovens；
(2) it is reducing agent sodium sulfite is soluble in water, the sodium sulfite solution that mass fraction is 80% is formed, measure 75ml
Mass fraction is that 80% reducing agent sodium sulfite solution is added to the polychlorostyrene second by ion exchange in step (1) after drying
In olefine resin, magnetic agitation is uniform in 60 DEG C of water-baths, suction filtration after stirring 12h, removes filtrate, filter residue is taken, after obtaining final product reduction
Corvic, gained Corvic is dried in 80 DEG C of baking ovens；
(3) take and dissolve ionized water than the 100g pore creating material calcium hydroxides for 1 relative to gained filter residue after drying in step (2)
In, aqua calcis is formed, it is subsequently adding in step (2) after drying in gained filter residue, and be uniformly mixed, at 80 DEG C
Vacuum drying, whole drying course polymer therein is without crushing；
(4) gained Corvic after reduction in step (3) is put into tube furnace and is heated, i.e., in nitrogen
Under flow is for the protective gas of 60mL/min, 850 DEG C are risen to from room temperature with the heating rate of 2 DEG C/min, and at a temperature of 850 DEG C
Insulation 2h, natural cooling；
(5) each material of gained is respectively with the nitric acid acidwashing 6h of 3mol/L, filtering, repeatedly acid after step (4) is heated
Wash twice, take filter residue and cleaned with deionized water to cleaning fluid pH in neutrality, then each drying respectively at 80 DEG C is had
There is the Graphene three-dimensional multistage pore structure powder body material of high-specific surface area, high conductivity, gently concussion obtains Graphene three-dimensional
Hierarchical porous structure powder.The foregoing description to specific illustrative embodiment of the invention be in order to illustrate and illustration purpose.
These descriptions are not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can carry out
It is many to change and change.The purpose of selecting and describing the exemplary embodiment is that explain certain principles of the invention and its
Practical application, so that those skilled in the art can realize and utilize a variety of exemplary embodiment party of the invention
Case and a variety of selections and change.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (9)
1. the Graphene three-dimensional multistage pore structure powder that prepared by a kind of low temperature polymer cracking, it is characterised in that comprising following behaviour
Make step：
(1) catalyst metal salts are added water, is configured to metal salt solution and mixed with polymers that mass concentration is 10~60%, stirred
Filtered after mixing 0.1~12h, take filter residue, cleaned up, dried；
(2) to being filtered after adding reductant solution, and 0.1~12h of stirring in gained material after drying in step (1), filter residue is taken,
Drying；
(3) added relative to raw material than the pore creating material for 0.2-2 in gained filter residue to after drying in step (2), and stirred, dried
It is dry；
(4) by gained material after drying in step (3) under protective atmosphere, heating, it is 700~1000 DEG C, constant temperature to control temperature
0.5~8h；
(5) during gained material adds acid solution after heating in step (4), 1~12h of pickling, filtering, drying are obtained final product
To Graphene three-dimensional multistage pore structure powder.
2. the Graphene three-dimensional multistage pore structure powder that prepared by low temperature polymer cracking according to claim 1, its feature
It is：Heating rate is 1~10 DEG C/min in heating process in step (4).
3. the Graphene three-dimensional multistage pore structure powder that prepared by low temperature polymer cracking according to claim 1, its feature
It is：Catalyst metal salts described in step (1) are one or more mixtures in molysite, cobalt salt or nickel salt；
Wherein, described molysite is iron chloride, frerrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, ferric acetate, acetic acid
Ferrous iron, potassium ferrocyanide, the potassium ferricyanide, sodium ferrocyanide or the sodium ferricyanide；Described cobalt salt is cobalt chloride, cobalt chloride, sulphur
Sour cobalt, Cobaltous sulfate, cobalt nitrate, colbaltous nitrate, cobalt acetate, acetic acid Asia cobalt, hexanitro close cobalt acid sodium or hexanitro closes cobalt acid potassium；
Described nickel salt is nickel chloride, nickel sulfate, nickel nitrate or nickel acetate.
4. the Graphene three-dimensional multistage pore structure powder that prepared by low temperature polymer cracking according to claim 1, its feature
It is：Polymer described in step (1) is PKS polymer, phenolic resin, epoxy resin, Corvic, polyester tree
The mixture of one or more resins in fat, polyamide, polyimide resin.
5. the Graphene three-dimensional multistage pore structure powder that prepared by low temperature polymer cracking according to claim 1, its feature
It is：Reductant solution described in step (2) dissolves gained reductant solution for reducing agent is added to the water；Wherein, it is described
Reducing agent be sodium borohydride, hydrazine hydrate, sodium sulfite, sodium hydrogensulfite, hydrogen sulfide and stannous chloride in one or two with
Upper mixture.
6. the Graphene three-dimensional multistage pore structure powder that prepared by low temperature polymer cracking according to claim 1, its feature
It is：Pore creating material described in step (3) is potassium hydroxide, calcium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, sodium acid carbonate or hydrogen-oxygen
Change sodium in one or more.
7. the Graphene three-dimensional multistage pore structure powder that prepared by low temperature polymer cracking according to claim 1, its feature
It is：Protective atmosphere described in step (4) is the one kind in nitrogen, helium, argon gas.
8. the Graphene three-dimensional multistage pore structure powder that prepared by low temperature polymer cracking according to claim 1, its feature
It is：Acid solution described in step (5) is one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid
Mixture.
9. the Graphene three-dimensional multistage pore structure powder that prepared by low temperature polymer cracking according to claim 1, its feature
It is：The concentration of the acid solution described in step (5) is 1~5mol/L.
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| CN107601491A (en) * | 2017-09-15 | 2018-01-19 | 广东工业大学 | A kind of preparation method and lithium-ion capacitor of three-dimensional graphite carbon |
| CN108101030A (en) * | 2018-02-09 | 2018-06-01 | 中山大学 | A kind of preparation method of three-dimensional porous grapheme material |
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