CN105621400B - A kind of method that graphene is prepared using carbonate as raw material - Google Patents
A kind of method that graphene is prepared using carbonate as raw material Download PDFInfo
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Abstract
The invention belongs to carbon material preparing technical field, more particularly to a kind of method that graphene is prepared using carbonate as raw material.It will be mixed first using carbonate with high-molecular compound and be used as carbon source predecessor, carbon source predecessor is pumped into double screw extruder, by disperseing screwing element, carbonate is set to be coated in the network structure of high-molecular compound formation, then by being kneaded screwing element, carbon source predecessor is set to be changed into thermoplastic under the conditions of high temperature hot-stretch, pass through devolatilization screwing element again, using under conditions of high temperature high fever, volatile matter is excluded, loose and porous structure is formed, thin slice is formed finally by extruding, reacted again by high-temperature catalytic, and wash and be dried to obtain graphene.The present invention prepares that graphene technique is simple, the extensive cost of raw material sources is low, and yield is high, and purity is high, and large-scale production can be achieved.
Description
Technical field
The invention belongs to carbon material technical field, more particularly to a kind of method that graphene is prepared using carbonate as raw material.
Background technology
Graphene is arranged according to hexagon by carbon atom, is connected with each other, formed as a kind of new two-dimensional material
One carbon molecules, its structure are highly stable；As the amount of carbon atom connected is on the increase, this two-dimentional carbon molecules plane
Constantly expand, molecule also constantly becomes big.Single-layer graphene only has the thickness of a carbon atom, i.e., 0.335 nanometer, equivalent to one
The thickness of 20 a ten thousandths of hair, will nearly there is 1,500,000 layers or so of graphene in the graphite of 1 millimeters thick.And graphene
It is the unique existing Two Dimensional Free state atomic crystal having now been found that.AK Geim, KS since Univ Manchester UK
The researchers such as Novoselov are this with various excellent since 2004 peel off oriented graphite discovery graphene using adhesive tape
The material of different characteristic, illustrated in fields such as electronics, sensing, the energy, composite, medical treatment, energy storage, catalysis, Aero-Space
Wide application prospect.
Up to now, it has been found that graphene has outstanding physics and electrical properties, and its thickness is only that single layer of carbon atom is straight
Footpath, be in the world it is most thin, specific surface area is maximum, intensity highest, thermal conductivity highest, mean free path is most long at room temperature, is easy to repair
Decorations and large-scale production etc..
At present, grapheme material powder can be prepared using a variety of methods, such as mechanical stripping method, oxidation-reduction method, crystalline substance
External epitaxial growth, chemical vapour deposition technique, organic synthesis method and stripping CNT method etc..In these methods, machinery stripping
It is relatively low that graphene destructible graphene-structured, yield are prepared from method and epitaxial growth method, it is difficult to meet large-scale production.Chemical gas
Although phase sedimentation can obtain the continuous graphene film of large scale, it is applied to micro-nano electronic device or electrically conducting transparent is thin
Film, it can not but meet the extensive demand in market.The cost that oxidation-reduction method prepares grapheme material powder is higher, complex process.
China Patent Publication No. 103466608A disclose a kind of graphene ball milling prepare method, the present invention by graphitic carbon with
The mass volume ratio of the hexa-atomic aromatic ring of alkyl or condensed ring polyether nonionic surfactant is 1：2~1：15 and deionized water mixing
Loaded on ball grinder, ball mill is fixed on 200-500rpm rotating speed ball milling 5-30 hours；It is transferred to again in deionized water, with
3000-8000rpm rotating speed centrifugation 10-30min, obtains black upper strata soliquid, it is water-soluble that various concentrations graphene is made
Liquid.The present invention utilizes ball mill destructible graphene crystal structure, and yield is relatively low, can not large-scale production.
China Patent Publication No. 104528696A discloses the preparation method and graphene of a kind of graphene, including following step
Suddenly：A) carbon source and metal agent for capturing are mixed, obtain being modified carbon source, the carbon source includes ion exchange resin, starch, cellulose
With the one or more in amorphous carbon；B) by metallic catalyst and the step A) in modification carbon source mix, adsorbed,
Obtain being adsorbed with the carbon source of metallic catalyst；C) by the step B) in the carbon source for being adsorbed with metallic catalyst heated,
Obtain graphene.The present invention is more using metal agent for capturing adsorbing metal catalyst influence factor, can not effectively obtain graphite
Alkene, yield is relatively low, and cost is high, is unfavorable for large-scale production.
The content of the invention
The present invention is in view of the above-mentioned problems, propose a kind of method that graphene is prepared using carbonate as raw material.Will be with carbonate
Mixed with high-molecular compound and be used as carbon source predecessor, carbon source predecessor is pumped into double screw extruder, pass through scattered screw thread member
Part, carbonate is set to be coated in the network structure of high-molecular compound formation, then by being kneaded screwing element, in high temperature hot-drawn
Carbon source predecessor is set to be changed into thermoplastic under the conditions of stretching, then by devolatilization screwing element, using under conditions of high temperature high fever,
Volatile matter is excluded, forms loose and porous structure, forms thin slice, high-temperature catalytic finally by extruding, and wash and be dried to obtain stone
Black alkene.Preparation method of the present invention is reproducible, environmentally friendly, prepares that graphene technique is simple, the extensive cost of raw material sources is low,
Yield is high, and purity is high, and large-scale production can be achieved, have broad application prospects.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of method that graphene is prepared using carbonate as raw material, it is characterised in that comprise the following steps：
（1）It is 8 in mass ratio by carbonate and high-molecular compound：(2 ~ 3) add in high-speed mixer with 2000 ~
3000rpm speed high-speed stirred disperses 5 ~ 10min and obtains carbon source predecessor；
（2）By step（1）In obtained carbon source predecessor be pumped into screw extruder charge door, screw rod is from feed end to end
End sets gradually scattered screwing element, is kneaded screwing element, devolatilization screwing element, and the scattered screwing element section reaction temperature of setting is
130 ~ 180 DEG C, carbon source predecessor makes carbonate be coated on the network structure of high-molecular compound formation by disperseing screwing element
In；Then by being kneaded screwing element, it is 180 ~ 220 DEG C to set this section of reaction temperature, makes carbon source under the conditions of high temperature hot-stretch
Predecessor is changed into thermoplastic, then by devolatilization screwing element, using under conditions of high temperature high fever, excludes volatile matter,
Loose and porous structure is formed, it is 200 ~ 230 DEG C to set temperature；Thin slice is formed finally by extruding；
（3）By step（2）In obtained thin slice in aqueous by washing, vibrate, be put into tube furnace, 180 ~
15 ~ 30min is dried under 250 DEG C of air atmosphere；
（4）Under the conditions of inert gas shielding, the temperature of tube furnace is warming up to 800 ~ 1000 DEG C, adds catalyst reaction
120 ~ 150min, 25 DEG C are cooled in atmosphere of inert gases, obtain graphene Primary product；
（5）By step（4）Obtained graphene Primary product reacts 8 ~ 12min in hydrochloric acid solution, is then washed with water
To neutrality and dry, finally obtain graphene；
Described carbonate is calcium carbonate, magnesium carbonate, barium carbonate, sodium carbonate, at least one of aluminium carbonate, described height
Molecular compound is PVP, polyacrylamide, polyethylene terephthalate, polyethylene glycol, benzene second
At least one of alkene-butadiene-styrene triblock copolymer, polyimides；
Described catalyst is one kind in cesium salt, aluminium isopropoxide, manganese dioxide, antimony oxide, stannous chloride；
Above-mentioned steps（1）Described in high-speed mixer be conical screw spiral ribbon mixer, the mixer is by cycloidal-pin wheel
Reductor, screw rod, outer layer ribbon etc. form, and are cut carbonate and high-molecular compound edge by centrifugal force caused by quick rotation
Space is thrown in line direction, it is produced strong convection current shearing, diffusion, so as to reach the purpose being quickly well mixed.
Above-mentioned steps（2）Described in screw extruder be conical parallel dual-screw extruding machine, screw slenderness ratio is 60 ~
75：1, screw rod is set gradually as scattered screwing element by feed end terminad, is kneaded screwing element, devolatilization screwing element, compression
Screwing element, screwing element in the same direction, the extruder, extrusion force is big, plasticizing capacity is good, yield is high, energy consumption is low, by carbon source predecessor
Extruding obtains thin slice, makes the effective regular uniform growth of graphene, its graphene purity finally obtained, yield are high.
Above-mentioned steps（4）Described in catalyst its addition catalyst in mass ratio：Carbonate=(0.03 ~ 0.05)：3.
A kind of method that graphene is prepared using carbonate as raw material of the present invention, first will be with carbonate and high-molecular compound
Carbon source predecessor is formed under conditions of high-speed stirred for carbon source, it is sufficiently mixed uniformly, carbon source predecessor is pumped into double spiral shells
Bar extruder, by disperseing screwing element, carbonate is coated in the network structure of high-molecular compound formation, make what is formed
Graphene-structured is uniform, then by being kneaded screwing element, carbon source predecessor is changed into thermoplasticity under the conditions of high temperature hot-stretch
Material, thin slice is obtained beneficial to thermoplasticity processing, then by devolatilization screwing element, using under conditions of high temperature high fever, make volatilization
Point exclude, impurity is reduced, so as to get graphene purity it is high, formed loose and porous structure add with catalyst reaction surface,
Be improved its abundant reaction yield, then by extruding form thin slice, can homoepitaxial obtain graphene.
A kind of method that graphene is prepared using carbonate as raw material of the present invention, the characteristics of protruding compared with prior art with have
The effect of benefit is：
1st, a kind of method that graphene is prepared using carbonate as raw material of the present invention, being handled by double screw extruder makes carbonic acid
Salt is coated in the network structure of high-molecular compound formation, and volatile matter excludes, and forms loose and porous structure extruding increase in flakes
Reaction surface with catalyst, reactivity are improved, and it grows effectively graphene regular uniform, obtained graphite
Alkene purity is high, yield is high.
2nd, a kind of method that graphene is prepared using carbonate as raw material of the present invention, its raw material sources is extensive, and it prepares work
Skill is simple, cost is low, using double screw extruder is easy to spread and the advantages that continuous production.
Embodiment
Embodiment 1
（1）By calcium carbonate and PVP in mass ratio 8:2 add conical screw spiral ribbon mixers in
2000rpm speed high-speed stirred disperses 5min and obtains carbon source predecessor；
（2）By step（1）In obtained carbon source predecessor be pumped into conical parallel dual-screw extruding machine charge door, screw rod by
Feed end terminad sets gradually scattered screwing element, is kneaded screwing element, devolatilization screwing element, sets scattered screwing element section
Reaction temperature is 130 DEG C, and carbon source predecessor makes calcium carbonate be coated on PVP and formed by disperseing screwing element
Network structure in；Then by being kneaded screwing element, it is 180 DEG C to set this section of reaction temperature, under the conditions of high temperature hot-stretch
Carbon source predecessor is changed into thermoplastic, then by devolatilization screwing element, using under conditions of high temperature high fever, make volatile matter
Exclude, form loose and porous structure, it is 200 DEG C to set temperature；Thin slice is formed finally by extruding；
（3）By step（2）In obtained thin slice in aqueous by washing, vibrating, be put into tube furnace, at 180 DEG C
Air atmosphere under dry 15min；
（4）Under the conditions of inert gas shielding, the temperature in tube furnace is warming up to 800 DEG C, in mass ratio cesium salt：Carbonic acid
Calcium=0.03:3 add cesium salt reaction 120min, and 25 DEG C are cooled in atmosphere of inert gases, obtains graphene Primary product.
（5）By step（4）Obtained product reacts 8min in hydrochloric acid solution, is then washed with water to neutral and dries,
Finally obtain graphene
Embodiment 2
（1）It is 8 in mass ratio by magnesium carbonate and polyacrylamide solution：2.1 add conical screw spiral ribbon mixers in
2100rpm speed high-speed stirred disperses 6min and obtains carbon source predecessor；
（2）By step（1）In obtained carbon source predecessor be pumped into conical parallel dual-screw extruding machine charge door, screw rod by
Feed end terminad sets gradually scattered screwing element, is kneaded screwing element, devolatilization screwing element, sets scattered screwing element section
Reaction temperature is 140 DEG C, and carbon source predecessor makes magnesium carbonate be coated on the network of polyacrylamide formation by disperseing screwing element
In structure；Then by being kneaded screwing element, it is 185 DEG C to set this section of reaction temperature, makes carbon source under the conditions of high temperature hot-stretch
Predecessor is changed into thermoplastic, then by devolatilization screwing element, using under conditions of high temperature high fever, excludes volatile matter,
Loose and porous structure is formed, it is 205 DEG C to set temperature；Thin slice is formed finally by extruding；
（3）By step（2）In obtained thin slice in aqueous by washing, vibrating, be put into tube furnace, at 190 DEG C
Air atmosphere under dry 16min；
（4）Under the conditions of inert gas shielding, the temperature in tube furnace is warming up to 850 DEG C, in mass ratio aluminium isopropoxide：
Calcium carbonate=0.032:3, which add aluminium isopropoxide, reacts 130 min, and 25 DEG C, at the beginning of obtaining graphene are cooled in atmosphere of inert gases
Level product；
（5）By step（4）Obtained product reacts 9min in hydrochloric acid solution, is then washed with water to neutral and dries,
Finally obtain graphene.
Embodiment 3
（1）It is 8 in mass ratio by barium carbonate and polyethylene terephthalate solution：2.2 add conical screw ribbon
Mixer disperses 7min with 2200rpm speed high-speed stirred and obtains carbon source predecessor；
（2）By step（1）In obtained carbon source predecessor be pumped into conical parallel dual-screw extruding machine charge door, screw rod by
Feed end terminad sets gradually scattered screwing element, is kneaded screwing element, devolatilization screwing element, sets scattered screwing element section
Reaction temperature is 150 DEG C, and carbon source predecessor makes barium carbonate be coated on polyethylene terephthalate by disperseing screwing element
In the network structure of formation；Then by being kneaded screwing element, it is 195 DEG C to set this section of reaction temperature, in high temperature hot-stretch bar
Carbon source predecessor is changed into thermoplastic under part, then by devolatilization screwing element, using under conditions of high temperature high fever, make to wave
Hair point excludes, and forms loose and porous structure, and it is 210 DEG C to set temperature；Thin slice is formed finally by extruding；
（3）By step（2）In obtained thin slice in aqueous by washing, vibrating, be put into tube furnace, at 220 DEG C
Air atmosphere under dry 20min；
（4）Under the conditions of inert gas shielding, the temperature in tube furnace is warming up to 900 DEG C, in mass ratio manganese dioxide：
Barium carbonate=0.04:3, which add manganese dioxide, reacts 140 min, and 25 DEG C, at the beginning of obtaining graphene are cooled in atmosphere of inert gases
Level product；
（5）By step（4）Obtained product reacts 10min in hydrochloric acid solution, is then washed with water to neutral and dries,
Finally obtain graphene.
Embodiment 4
（1）It is 8 in mass ratio by sodium carbonate and polyglycol solution：2.5 add conical screw spiral ribbon mixers in
2900rpm speed high-speed stirred disperses 9min and obtains carbon source predecessor；
（2）By step（1）In obtained slurry be pumped into conical parallel dual-screw extruding machine charge door, screw rod is by feed end
Terminad sets gradually scattered screwing element, is kneaded screwing element, devolatilization screwing element, sets scattered screwing element section reaction temperature
Spend for 170 DEG C, carbon source predecessor makes sodium carbonate be coated in the network structure of polyethylene glycol formation by disperseing screwing element；
Then by being kneaded screwing element, it is 210 DEG C to set this section of reaction temperature, becomes carbon source predecessor under the conditions of high temperature hot-stretch
For thermoplastic, then by devolatilization screwing element, using under conditions of high temperature high fever, volatile matter is excluded, formed loose
Loose structure, it is 210 DEG C to set temperature；Thin slice is formed finally by extruding；
（3）By step（2）In obtained thin slice in aqueous by washing, vibrating, be put into tube furnace, at 240 DEG C
Air atmosphere under dry 28min；
（4）Under the conditions of inert gas shielding, the temperature in tube furnace is warming up to 950 DEG C, in mass ratio three oxidations two
Antimony：Sodium carbonate=0.045：3 add antimony oxide reaction 145min, and 25 DEG C are cooled in atmosphere of inert gases, obtains graphite
Alkene Primary product；
（5）By step（4）Obtained product reacts 11min in hydrochloric acid solution, is then washed with water to neutral and dries,
Finally obtain graphene.
Embodiment 5
（1）It is 8 in mass ratio by aluminium carbonate and styrene-butadiene-styrene triblock copolymer solution：3 add
10min is disperseed with 3000rpm speed high-speed stirred in conical screw spiral ribbon mixer and obtains carbon source predecessor；
（2）By step（1）In obtained slurry be pumped into double screw extruder charge door, screw rod by feed end terminad according to
Secondary to set scattered screwing element, be kneaded screwing element, devolatilization screwing element, it is 180 to set scattered screwing element section reaction temperature
DEG C, carbon source predecessor makes aluminium carbonate be coated on styrene-butadiene-styrene triblock copolymer by disperseing screwing element
In the network structure that thing is formed；Then by being kneaded screwing element, it is 220 DEG C to set this section of reaction temperature, in high temperature hot-stretch
Under the conditions of carbon source predecessor is changed into thermoplastic, then by devolatilization screwing element, using under conditions of high temperature high fever, make
Volatile matter excludes, and forms loose and porous structure, and it is 230 DEG C to set temperature；Thin slice is formed finally by extruding；
（3）By step（2）In obtained thin slice in aqueous by washing, vibrate, be put into high-temperature reactor,
30min is dried under 250 DEG C of air atmosphere；
（4）Under the conditions of inert gas shielding, the temperature in high-temperature reactor is warming up to 1000 DEG C, in mass ratio chlorination
It is cuprous：Aluminium carbonate=0.05：3, which add stannous chloride, reacts 150 min, and 25 DEG C are cooled in atmosphere of inert gases, obtains graphite
Alkene Primary product；
（5）By step（4）Obtained product reacts 12min in hydrochloric acid solution, is then washed with water to neutral and dries,
Finally obtain graphene.
Claims (2)
- A kind of 1. method that graphene is prepared using carbonate as raw material, it is characterised in that comprise the following steps：（1）It is 8 in mass ratio by carbonate and high-molecular compound：(2 ~ 3) add in high-speed mixer with 2000 ~ 3000rpm Speed high-speed stirred disperse 5 ~ 10min obtain carbon source predecessor；（2）By step（1）In obtained carbon source predecessor be pumped into screw extruder charge door, screw rod by feed end terminad according to It is secondary that scattered screwing element is set, is kneaded screwing element, devolatilization screwing element, set scattered screwing element section reaction temperature be 130 ~ 180 DEG C, carbon source predecessor makes carbonate be coated in the network structure of high-molecular compound formation by disperseing screwing element； Then by being kneaded screwing element, it is 180 ~ 220 DEG C to set this section of reaction temperature, and carbon source forerunner is made under the conditions of high temperature hot-stretch Thing is changed into thermoplastic, then by devolatilization screwing element, using under conditions of high temperature high fever, excludes volatile matter, formed Loose and porous structure, it is 200 ~ 230 DEG C to set temperature；Thin slice is formed finally by extruding；（3）By step（2）In obtained thin slice in aqueous by washing, vibrating, be put into tube furnace, at 180 ~ 250 DEG C Air atmosphere under dry 15 ~ 30min；（4）Under the conditions of inert gas shielding, the temperature of tube furnace is warming up to 800 ~ 1000 DEG C, add catalyst reaction 120 ~ 150min, 25 DEG C are cooled in atmosphere of inert gases, obtain graphene Primary product；（5）By step（4）Obtained graphene Primary product reacts 8 ~ 12min in hydrochloric acid solution, in being then washed with water to Property and drying, finally obtain graphene；Described carbonate is calcium carbonate, magnesium carbonate, barium carbonate, sodium carbonate, at least one of aluminium carbonate, described macromolecule Compound is PVP, polyacrylamide, polyethylene terephthalate, polyethylene glycol, styrene-fourth At least one of diene-styrene triblock copolymer, polyimides；Described catalyst is cesium salt, aluminium isopropoxide, two One kind in manganese oxide, antimony oxide, stannous chloride；Step（1）Described in high-speed mixer be conical screw spiral ribbon mixer, the mixer is by cycloidal planetary gear speed reducer, spiral shell Bar, outer layer ribbon composition, are tangentially thrown to carbonate with high-molecular compound by centrifugal force caused by quick rotation Space, it is set to produce strong convection current shearing, diffusion, so as to reach the purpose being quickly well mixed；Step（2）Described in screw extruder be conical parallel dual-screw extruding machine, screw slenderness ratio is 60 ~ 75：1.
- A kind of 2. method that graphene is prepared using carbonate as raw material according to claim 1, it is characterised in that step（4） Described in catalyst its addition catalyst in mass ratio：Carbonate=(0.03 ~ 0.05)：3.
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| CN106587026B (en) * | 2016-12-28 | 2019-04-02 | 山东理工大学 | Strengthen the preparation method of the three-dimensional nitrogen-doped graphene of quality transmission type multistage pore canal perforation |
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