CN105502359A - Preparation method of low-cost porous graphene - Google Patents
Preparation method of low-cost porous graphene Download PDFInfo
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Abstract
The invention belongs to the field of high-performance carbon materials, and particularly relates to a preparation method of low-cost porous graphene. A low-cost carbon precursor and additives are adopted as raw materials, the raw materials are mixed, and low-temperature carbonization and pickling technology are adopted to prepare the porous graphene. The method has the advantages that the technology is simple, the cost is low, and industrialization popularization is easy; the obtained porous graphite is high in purity, the number of structural defects is small, and pore size distribution in uniform.
Description
Technical field
The invention belongs to carbon materials field, be specifically related to a kind of preparation method of low cost porous graphene.
Background technology
Porous graphene is a kind of grapheme material with tridimensional network.As a kind of novel carbon material, porous graphene, with the three-dimensional structure of its uniqueness and excellent physical and chemical performance, has good application prospect in various electrode of electrochemical device material, support of the catalyst, gas delivery and storage etc.On the one hand, porous graphene possesses the advantages such as the chemical property of Graphene uniqueness, the thermal conductivity of superelevation and specific surface area are large; On the other hand, on this basis, the three-dimensional structure of its uniqueness, effectively can avoid the reunion of grapheme material self and stacking, make full use of the specific surface area of its super large, good electron transfer rate, the premium properties of abundant Graphene, expands the application of this material in energy field, electronic applications etc. further.
At present, main template and the chemical etching method of adopting prepares porous graphene.Template synthesis porous graphene, mainly adopts CVD technology, and magnesium oxide is the controlled porous graphene in Template preparation aperture.Chemical etching method comprises KOH activation method, nitric acid oxidation method, facilitates the methods such as agent oxidation style, and raw material mainly adopts graphene film, etches graphene sheet layer by chemical reaction, significantly to avoid the reunion of Graphene.But aforesaid method, more or less exists that complex process, cost are high, environmental pollution, product defect are many and are difficult to the problem of mass production, limit application and the popularization of porous graphene.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of preparation method of low cost porous graphene is provided.This preparation technology is simple, cost is low, and Industry Promotion is easy, and prepared porous graphene has good three-dimensional porous structure, textural defect is few, and product purity is high.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for low cost porous graphene, comprises the following steps:
1) mixing of raw material: 100:1 ~ 100:100 takes carbon precursor and aluminum contained compound in mass ratio, adds solvent, after stirring 1 ~ 5h at 25 DEG C ~ 150 DEG C, solvent evaporated, is placed in the dry 1 ~ 12h of 40 DEG C ~ 100 DEG C baking ovens by solid residue;
2) low-temperature carbonization: material dried for step 1) is put into atmosphere furnace, keeps 0.1h ~ 10h after being then warming up to 1100 DEG C ~ 2000 DEG C with the temperature rise rate of 1 DEG C/min ~ 50 DEG C/min, is cooled to room temperature and takes out;
3) pickling: by step 2) gained carbonizing production is placed in acid solution and stirs 1 ~ 5h, and deionized water fully washs to neutrality, then puts into after vacuum drying oven carries out drying, obtained porous graphene.
In step 1), the total mass of carbon precursor and aluminum contained compound and the mass values of solvent are: 1:1 ~ 1:10.
Aluminum contained compound described in step 1) is aluminum chloride, Tai-Ace S 150, aluminium carbonate, Burow Solution, aluminum nitrate, aluminium hydroxide, sodium metaaluminate, aluminium nitride, aluminum phosphate, pure aluminium silicate, aluminium carbide, ten sulfate dihydrate aluminium ammonia, metasilicic acid aluminium, trifluoromethanesulfonic acid aluminium, trialkylaluminium, dialkylaluminum chloride, one alkyl al dichloride, trialkyl tri-chlorination two aluminium, aluminum isopropylate, butyl aluminium, aluminum acetate, al formate, oxalic acid aluminium, propionic acid aluminium, poly aluminium chloride, pure aluminium silicate, fluoric acid aluminium, aluminium secondary butylate, praseodynium aluminium, triisobutyl aluminium, oxine aluminium, aluminum perchlorate, aluminum monostearate, aluminium distearate, oxalic acid aluminium, ethyl aluminum dichloride, second squama aluminium, aluminium acetylacetonate, aluminium dihydrogen phosphate, aluminium oleate, aluminum bromide, aluminum iodide, aluminum ethylate, Aluctyl, isocaprylic acid aluminium, one in trioctylaluminum.
Carbon precursor described in step 1) is the one in pitch, sucrose, xylogen and derivative thereof, hemicellulose, Mierocrystalline cellulose, starch, tannin, rosin, chitin, polyvinyl alcohol, polyoxyethylene glycol, polyethylene, trimeric cyanamide and derivative thereof, urea, polyvinylacetal, polyvinyl butyral acetal, polystyrene, urethane, polyimide, resol, furfuryl resin, furfuryl alcohol resin, furane resin, epoxy resin, bimaleimide resin, cyanate ester resin.
Solvent described in step 1) is water, ethanol, methylene dichloride, acetone, chloroform, methyl alcohol, tetrahydrofuran (THF), tetracol phenixin, hexanaphthene, Virahol, 1,2-trichloroethane, triethylamine, toluene, pyridine, quadrol, butanols, acetic acid, chlorobenzene, p-Xylol, dimethylbenzene, N, one in dinethylformamide, pimelinketone, hexalin, N,N-dimethylacetamide, N-METHYLFORMAMIDE, phenol, methyl-sulphoxide, ethylene glycol, N-Methyl pyrrolidone, methane amide, tetramethylene sulfone, glycerine.
Step 2) be N in atmosphere furnace
2or argon gas; Gas flow: 25mL/min ~ 300mL/min.
Acid solution described in step 3) is the one in hydrochloric acid, oxalic acid, sulfuric acid, and the concentration of acid solution is 0.05mol/L ~ 6mol/L, and stirring velocity is 25 ~ 200r/min.
In step 3), the vacuum tightness of vacuum drying oven is 1.0 × 10
-1~ 1.0 × 10
5pa, drying temperature is 40 ~ 100 DEG C.
beneficial effect of the present invention is:
1) specific surface area of porous graphene that the present invention obtains is 100 ~ 1500m
2/ g, the number of plies 1 ~ 15 layer, aperture 2nm ~ 50nm;
2) the raw material abundant raw material source that uses of preparation method of the present invention, price is low; Processing unit is simple, is easy to scale operation; Obtained porous graphene specific surface area is high, textural defect is few, even aperture distribution.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of the porous graphene adopting embodiment 1 technique to prepare;
Fig. 2 is the scanning electron microscopic picture of the porous graphene adopting embodiment 2 technique to prepare;
Fig. 3 is the scanning electron microscopic picture of the porous graphene adopting embodiment 3 technique to prepare;
Fig. 4 is the scanning electron microscopic picture of the porous graphene adopting embodiment 4 technique to prepare;
Fig. 5 is the scanning electron microscopic picture of the porous graphene adopting embodiment 5 technique to prepare.
Specific embodiment
Be below several specific embodiment of the present invention, further illustrate the present invention, but the present invention be not limited only to this.
embodiment 1
1) raw material mixing: Aqua-mesophase and Burow Solution are taken according to mass ratio 100:100, employing deionized water is solvent, and the mass ratio of raw material and solvent is 1:10; Both mixed by mechanical stirring, whipping temp is 25 DEG C, and churning time is 0.5h; To be mixed evenly after, underpressure distillation goes out solvent, is positioned over 60 DEG C of vacuum drying ovens (1.0 × 10
-1pa) dry 4 hours, room temperature is cooled to;
2) carbonize: dry sample is positioned in atmosphere furnace, passes into argon gas (argon flow amount is 100mL/min), be warming up to 1800 DEG C with 10 DEG C/min, insulation 2h, be cooled to room temperature and take out;
3) pickling: carbonizing production is positioned in hydrochloric acid soln (acid solution volumetric molar concentration is 1mol/L), stir 4h, stirring velocity is 120r/min, is washed till neutrality after filtering separation with deionized water; Be positioned over vacuum drying oven (1.0 × 10
-1pa) in, dry 60 DEG C of dryings 8 hours, namely obtain porous graphene;
Prepared porous graphene performance is as follows: the number of plies is 2-10 layer, and aperture size is 2nm-25nm, and specific surface area is 1500m
2/ g.
embodiment 2
1) raw material mixing: sucrose and Tai-Ace S 150 are taken according to mass ratio 100:50, employing acetone is solvent, and the mass ratio of raw material and solvent is 1:3; Both mixed by mechanical stirring, whipping temp is 30 DEG C, and churning time is 1h; To be mixed evenly after, underpressure distillation goes out solvent, is positioned over 35 DEG C of vacuum drying ovens (1.0 × 10
-1pa) dry 2 hours, room temperature is cooled to;
2) carbonize: dry sample is positioned in atmosphere furnace, passes into nitrogen (nitrogen flow is 50mL/min), be warming up to 1400 DEG C with 5 DEG C/min, insulation 1h, be cooled to room temperature and take out;
3) pickling: carbonizing production is positioned in sulphuric acid soln (acid solution volumetric molar concentration is 0.5mol/L), stir 2h, stirring velocity is 60r/min, is washed till neutrality after filtering separation with deionized water; Be positioned over vacuum drying oven (1.0 × 10
-1pa) in, dry 80 DEG C of dryings 4 hours, namely obtain porous graphene;
Prepared porous graphene performance is as follows: the number of plies is 5-15 layer, and aperture size is 10nm-50nm, and specific surface area is 400m
2/ g.
embodiment 3
1) raw material mixing: polystyrene and aluminum isopropylate are taken according to mass ratio 100:70, employing DMF is solvent, and the mass ratio of raw material and solvent is 1:5; Both mixed by mechanical stirring, whipping temp is 120 DEG C, and churning time is 1.5h.To be mixed evenly after, underpressure distillation goes out solvent, is positioned over 80 DEG C of vacuum drying ovens (1.0 × 10
-1pa) dry 10 hours, room temperature is cooled to;
2) carbonize: dry sample is positioned in atmosphere furnace, passes into argon gas (argon flow amount is 120mL/min), be warming up to 2000 DEG C with 15 DEG C/min, insulation 0.5h, be cooled to room temperature and take out;
3) pickling: carbonizing production is positioned in oxalic acid solution (acid solution volumetric molar concentration is 2mol/L), stir 3h, stirring velocity is 80 revs/min, is washed till neutrality after filtering separation with deionized water; Be positioned over vacuum drying oven (1.0 × 10
-1pa) in, dry 70 DEG C of dryings 8 hours, namely obtain porous graphene;
Prepared porous graphene piece performance is as follows: the number of plies is 5-10 layer, and aperture size is 20nm-35nm, and specific surface area is 350m
2/ g.
embodiment 4
1) raw material mixing: xylogen and Aluminum chloride anhydrous are taken according to mass ratio 100:80, employing toluene is solvent, and the mass ratio of raw material and solvent is 1:9; Both mixed by mechanical stirring, whipping temp is 80 DEG C, and churning time is 4h; To be mixed evenly after, underpressure distillation goes out solvent, is positioned over 60 DEG C of vacuum drying ovens (1.0 × 10
-1pa) dry 3 hours, room temperature is cooled to;
2) carbonize: dry sample is positioned in atmosphere furnace, passes into nitrogen (nitrogen flow is 80mL/min), be warming up to 1100 DEG C with 2 DEG C/min, insulation 5h, be cooled to room temperature and take out;
3) pickling: carbonizing production is positioned in hydrochloric acid soln (acid solution volumetric molar concentration is 0.05mol/L), stir 5h, stirring velocity is 40 revs/min, is washed till neutrality after filtering separation with deionized water; Be positioned over vacuum drying oven (1.0 × 10
5pa) in, dry 100 DEG C of dryings 2 hours, namely obtain porous graphene;
Prepared porous graphene performance is as follows: the number of plies is 2-12 layer, and aperture size is 30nm-40nm, and specific surface area is 500m
2/ g.
embodiment 5
1) raw material mixing: novolac resin and aluminum nitrate are taken according to mass ratio 100:30, employing N-METHYLFORMAMIDE is solvent, and the mass ratio of raw material and solvent is 1:4; Both mixed by mechanical stirring, whipping temp is 100 DEG C, and churning time is 3.5h.To be mixed evenly after, underpressure distillation goes out solvent, is positioned over 70 DEG C of vacuum drying ovens (1.0 × 10
2pa) dry 5 hours, room temperature is cooled to;
2) carbonize: dry sample is positioned in atmosphere furnace, passes into argon gas (argon flow amount is 200mL/min), be warming up to 1700 DEG C with 20 DEG C/min, insulation 6h, be cooled to room temperature and take out;
3) pickling: be positioned over by carbonizing production in hydrochloric acid soln (acid solution volumetric molar concentration is 4mol/L), stir 5h, stirring velocity is 90 revs/min, is washed till neutrality after filtering separation with deionized water.Be positioned over vacuum drying oven (1.0 × 10
-1pa) in, dry 60 DEG C of dryings 10 hours, namely obtain porous graphene.Prepared porous graphene performance is as follows: the number of plies is 3-9 layer, and aperture size is 5nm-25nm, and specific surface area is 800m
2/ g.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (8)
1. a preparation method for low cost porous graphene, is characterized in that: comprise the following steps:
1) mixing of raw material: 100:1 ~ 100:100 takes carbon precursor and aluminum contained compound in mass ratio, adds solvent, after stirring 1 ~ 5h at 25 DEG C ~ 150 DEG C, solvent evaporated, is placed in the dry 1 ~ 12h of 40 DEG C ~ 100 DEG C baking ovens by solid residue;
2) low-temperature carbonization: material dried for step 1) is put into atmosphere furnace, keeps 0.1h ~ 10h after being then warming up to 1100 DEG C ~ 2000 DEG C with the temperature rise rate of 1 DEG C/min ~ 50 DEG C/min, is cooled to room temperature and takes out;
3) pickling: by step 2) gained carbonizing production is placed in acid solution and stirs 1 ~ 5h, and deionized water fully washs to neutrality, then puts into after vacuum drying oven carries out drying, obtained porous graphene.
2. the preparation method of low cost porous graphene according to claim 1, is characterized in that: in step 1), the total mass of carbon precursor and aluminum contained compound and the mass values of solvent are: 1:1 ~ 1:10.
3. the preparation method of low cost porous graphene according to claim 1, it is characterized in that: the aluminum contained compound described in step 1) is aluminum chloride, Tai-Ace S 150, aluminium carbonate, Burow Solution, aluminum nitrate, aluminium hydroxide, sodium metaaluminate, aluminium nitride, aluminum phosphate, pure aluminium silicate, aluminium carbide, ten sulfate dihydrate aluminium ammonia, metasilicic acid aluminium, trifluoromethanesulfonic acid aluminium, trialkylaluminium, dialkylaluminum chloride, one alkyl al dichloride, trialkyl tri-chlorination two aluminium, aluminum isopropylate, butyl aluminium, aluminum acetate, al formate, oxalic acid aluminium, propionic acid aluminium, poly aluminium chloride, pure aluminium silicate, fluoric acid aluminium, aluminium secondary butylate, praseodynium aluminium, triisobutyl aluminium, oxine aluminium, aluminum perchlorate, aluminum monostearate, aluminium distearate, oxalic acid aluminium, ethyl aluminum dichloride, second squama aluminium, aluminium acetylacetonate, aluminium dihydrogen phosphate, aluminium oleate, aluminum bromide, aluminum iodide, aluminum ethylate, Aluctyl, isocaprylic acid aluminium, one in trioctylaluminum.
4. the preparation method of low cost porous graphene according to claim 1, it is characterized in that: the carbon precursor described in step 1) is pitch, sucrose, xylogen and derivative thereof, hemicellulose, Mierocrystalline cellulose, starch, tannin, rosin, chitin, polyvinyl alcohol, polyoxyethylene glycol, polyethylene, trimeric cyanamide and derivative thereof, urea, polyvinylacetal, polyvinyl butyral acetal, polystyrene, urethane, polyimide, resol, furfuryl resin, furfuryl alcohol resin, furane resin, epoxy resin, bimaleimide resin, one in cyanate ester resin.
5. the preparation method of low cost porous graphene according to claim 1, it is characterized in that: the solvent described in step 1) is water, ethanol, methylene dichloride, acetone, chloroform, methyl alcohol, tetrahydrofuran (THF), tetracol phenixin, hexanaphthene, Virahol, 1, 2-trichloroethane, triethylamine, toluene, pyridine, quadrol, butanols, acetic acid, chlorobenzene, p-Xylol, dimethylbenzene, N, dinethylformamide, pimelinketone, hexalin, N, N-N,N-DIMETHYLACETAMIDE, N-METHYLFORMAMIDE, phenol, methyl-sulphoxide, ethylene glycol, N-Methyl pyrrolidone, methane amide, tetramethylene sulfone, one in glycerine.
6. the preparation method of low cost porous graphene according to claim 1, is characterized in that: step 2) be N in atmosphere furnace
2or argon gas; Gas flow: 25mL/min ~ 300mL/min.
7. the preparation method of low cost porous graphene according to claim 1, is characterized in that: the acid solution described in step 3) is the one in hydrochloric acid, oxalic acid, sulfuric acid, and the concentration of acid solution is 0.05mol/L ~ 6mol/L, and stirring velocity is 25 ~ 200r/min.
8. the preparation method of low cost porous graphene according to claim 1, is characterized in that: in step 3), the vacuum tightness of vacuum drying oven is 1.0 × 10
-1~ 1.0 × 10
5pa, drying temperature is 40 ~ 100 DEG C.
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| CN107352529A (en) * | 2017-08-14 | 2017-11-17 | 华南理工大学 | A kind of method for preparing grapheme material using discarded object banana skin for raw material |
| CN107381547A (en) * | 2017-07-27 | 2017-11-24 | 华南理工大学 | A kind of method for preparing grapheme material using frangipanis for raw material |
| CN107417965A (en) * | 2017-09-14 | 2017-12-01 | 南通迅达橡塑制造有限公司 | A kind of preparation method of rubber-plastics material graphene composite flame-retardant agent |
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