CN102586946B - High-strength graphene ordered porous fibers and preparation method thereof - Google Patents
High-strength graphene ordered porous fibers and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 73
- 239000000835 fiber Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 35
- 239000010439 graphite Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000009987 spinning Methods 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 5
- 238000005374 membrane filtration Methods 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses high-strength graphene ordered porous fibers and a preparation method thereof. The method comprises the following steps of: oxidizing graphite to obtain graphene oxide; dispersing the graphene oxide in water to obtain 1 to 20 mass percent spinning solution liquid crystal sol; continuously extruding a spinning solution at a constant speed from a spinning head capillary to liquid nitrogen, and solidifying; performing freeze drying to obtain graphene oxide ordered porous fibers; and performing chemical reduction to obtain the graphene ordered porous fibers. The obtained graphene ordered porous fibers are low in density, high in porosity, excellent in mechanical properties and high in toughness, can be used for supporting various catalysts and also can be used as light leads.
Description
Technical field
The present invention relates to a kind of porous graphene fiber, relate in particular to a kind of high-strength graphene ordered porous fibers and preparation method thereof.
Background technology
Graphene is a kind of novel two-dimensional nano material, has caused the research boom of academia and industrial quarters since self-discovery.This material has the intensity that known materials is the highest, excellent electric conductivity and thermal conductivity, the highest carrier transport speed, the large tempting characteristics such as specific area.At present, realize and prepare Graphene macroscopic material, comparatively general method is to take native graphite as raw material preparation oxidation oxidation of precursor Graphene, by chemical oxidation-reducing process, realize again a large amount of preparations (Tung, V. C., the et al. Nature Nanotechnol. of Graphene, 2009
4, 25 – 29).Due to a large amount of organo-functional group in its surface, graphene oxide shows good dissolubility in water; Due to its large flakiness ratio (being generally greater than 1000), graphene oxide can show liquid crystal behavior in water, i.e. spontaneous formation ordered structure simultaneously.The Graphene macroscopic material that being found to be of graphene oxide liquid crystal prepared high-sequential provides a simple effective method.Yet, utilize this characteristic of graphene oxide liquid crystal to prepare Graphene Microscopic order material and remain the challenge realizing in Graphene application.
Summary of the invention
The object of the invention is, for the deficiencies in the prior art, provides a kind of high-strength graphene ordered porous fibers and preparation method thereof.The present invention adopts graphite to carry out the ordered porous fiber of Graphene as raw material, and the ordered porous fiber making has low-density, high-tensile strength and high compression-strength, good toughness and electric conductivity.Process costs of the present invention is low, simple to operate.
The object of the invention is to be achieved through the following technical solutions: a kind of preparation method of high-strength graphene ordered porous fibers, comprises the following steps:
(1) graphite raw material of 1 weight portion, 1 ~ 100 weight portion sulfuric acid, 0.5 ~ 5 weight portion potassium peroxydisulfate and 0.5 ~ 5 weight portion phosphorus pentoxide are mixed, at 25 ~ 100 ℃, stirring reaction is 1 ~ 10 hour, after cool to room temperature, with deionized water, dilute, with filter membrane suction filtration, with deionized water washing, to neutral, air dry obtains intercalated graphite for 10 ~ 50 hours;
(2) intercalated graphite of gained in 1 weight portion step 1,1 ~ 100 weight portion sulfuric acid and 0.5 ~ 10 weight portion potassium permanganate are mixed, at-10 ~ 50 ℃, stirring reaction is after 0.1 ~ 10 hour, add deionized water and 0.1 ~ 10 weight portion hydrogen peroxide of 10 ~ 2000 weight portions to stir 0.1 ~ 10 hour, with membrane filtration, with deionized water cyclic washing, to neutral, air dry obtains graphite oxide;
(3) the graphite oxide ene product of gained in 1 weight portion step 2 is dissolved in the water of 5 ~ 100 weight portions, with the ultrasonic processing of 0 ~ 50KHz 0.1 ~ 10 hour, obtains graphene oxide spinning solution colloidal sol;
(4) get the graphene oxide spinning solution colloidal sol of step 3 gained, extruded velocity with 1 ~ 100 mL/h, it by diameter, is the spinning capillary of 50 ~ 500 μ m, colloidal sol is clamp-oned and in liquid nitrogen, stopped 1 ~ 50s and condense, further freeze drying or critical freeze drying 2-40h, finally obtain ordered porous graphene oxide fiber again;
(5) the graphene oxide fiber of gained in step 4 is placed in to reductant and reduces 0.1 ~ 100h, washing is dry, obtains high-strength graphene ordered porous fibers.
The present invention has following technique effect:
1, adopting graphite is that raw material is prepared graphene fiber, raw material sources extensively, be easy to get;
2, the graphene oxide presoma of highly dissoluble and stable graphene oxide liquid crystal gel have been prepared simplely;
3, adopt spinning-cryodesiccated method to prepare the ordered porous fiber of graphene oxide;
4, the ordered porous fiber of graphene oxide making has very low density, high-tensile strength and high compression-strength, fine toughness;
5, the ordered porous fiber of Graphene making has very low density, high-tensile strength and high compression-strength, fine toughness, has excellent electric conductivity simultaneously.
The specific embodiment
The preparation method of high-strength graphene ordered porous fibers of the present invention, comprises the following steps:
1, the graphite raw material of 1 weight portion, 1 ~ 100 weight portion sulfuric acid, 0.5 ~ 5 weight portion potassium peroxydisulfate and 0.5 ~ 5 weight portion phosphorus pentoxide are mixed, at 25 ~ 100 ℃, stirring reaction is 1 ~ 10 hour, after cool to room temperature, with deionized water, dilute, with filter membrane suction filtration, with deionized water washing, to neutral, air dry obtains intercalated graphite for 10 ~ 50 hours.
Graphite is native graphite or pyrolytic graphite, and sulfuric acid is the sulfuric acid that mass concentration is greater than 80%.
2, the intercalated graphite of gained in 1 weight portion step 1,1 ~ 100 weight portion sulfuric acid and 0.5 ~ 10 weight portion potassium permanganate are mixed, at-10 ~ 50 ℃, stirring reaction is after 0.1 ~ 10 hour, add deionized water and 0.1 ~ 10 weight portion hydrogen peroxide of 10 ~ 2000 weight portions to stir 0.1 ~ 10 hour, with membrane filtration, with deionized water cyclic washing, to neutral, air dry obtains graphite oxide.
Sulfuric acid is the sulfuric acid that mass concentration is greater than 80%.
3, the graphite oxide ene product of gained in 1 weight portion step 2 is dissolved in the water of 5 ~ 100 weight portions, with the ultrasonic processing of 0 ~ 50KHz 0.1 ~ 10 hour, obtains graphene oxide spinning solution colloidal sol;
5, get the graphene oxide spinning solution colloidal sol of step 4 gained, extruded velocity with 1 ~ 100 mL/h, it by diameter, is the spinning capillary of 50 ~ 500 μ m, colloidal sol is clamp-oned and in liquid nitrogen, stopped 1 ~ 50s and condense, further freeze drying or critical freeze drying 2-40h, finally obtain the ordered porous fiber of graphene oxide again;
6, the graphene oxide fiber of gained in step 5 is placed in to reductant and reduces 0.1 ~ 100h, washing is dry, obtains high-strength graphene ordered porous fibers.
One or more the mixing of reductant in hydrazine hydrate, sodium borohydride, hydrobromic acid, hydroiodic acid, acetic acid forms.
The ordered porous fiber of high strength graphene oxide that this method obtains, graphene oxide is arranged vertically and is piled into along fiber axially extending bore, and the diameter of fiber is 5-500 micron, and density is 0.02-0.1g/cm
3, TENSILE STRENGTH is 5-10MPa, and compressive strength is 0.5-2MPa, and elongation at break is 0.3-10%.The high-strength graphene ordered porous fibers that this method obtains, graphene oxide is arranged vertically and is piled into along fiber axially extending bore, and density is 0.01-0.1g/cm
3, TENSILE STRENGTH is 5-20MPa, and compressive strength is 1-5MPa, and the diameter of fiber is 5-500 micron, and elongation at break is 1-10%, conductance is greater than 1000S/m.
Below by embodiment, the present invention is specifically described; the present embodiment is only for the present invention is described further; can not be interpreted as limiting the scope of the invention; those skilled in the art makes some nonessential change and adjustment according to the content of foregoing invention, all belongs to protection scope of the present invention.
embodiment 1:
Step (a): add 10g graphite in reaction bulb, 90% sulfuric acid of 10g, 1 g potassium peroxydisulfate and 1 g phosphorus pentoxide, at 80 ℃, stirring reaction is 5 hours, after cool to room temperature, with deionized water dilution, with filter membrane suction filtration, with deionized water cyclic washing filter cake, repeatedly to neutral, air dry obtains intercalated graphite for 10 hours;
Step (b): the intercalated graphite product that adds gained in 5g step (a) in reaction bulb, 80% sulfuric acid of 20g and 2.5g potassium permanganate, at 50 ℃, stirring reaction is after 2 hours, add 30% hydrogen peroxide of 1kg deionized water and 0.5g to stir 10 hours, with membrane filtration, with deionized water cyclic washing filter cake, to neutral, air dry obtains graphite oxide;
Step (c): add the graphite oxide ene product of gained in 1g step (b) in reaction bulb in 10g water, with the ultrasonic processing of 50KHz 1 hour, obtain graphene oxide spinning solution colloidal sol;
Step (d): get the graphene oxide spinning solution colloidal sol of gained in step (c), take the extruded velocity of 30 mL/h by diameter the spinning capillary as 20 μ m, in liquid nitrogen, solidify 1s postlyophilization 3h, obtain the ordered porous fiber of high strength graphene oxide;
Step (e): the ordered porous fiber of graphene oxide of gained in step (d) is placed in to hydrobromic acid, is heated to 80 ℃ of reaction 10h, through washing the dry high-strength graphene ordered porous fibers that obtains reduction.
Through above step, the graphene oxide obtaining has good dissolubility in water, forms stable liquid crystal gel under high concentration.In liquid crystal gel, graphene oxide sheet is layer structure and arranges.The diameter of the ordered porous fiber of graphene oxide of gained is 20 microns, and density is 0.1g/cm
3, TENSILE STRENGTH is 8-10MPa, and compressive strength is 1-2MPa, and elongation at break is 5-10%.High-strength graphene ordered porous fibers, graphene film is arranged vertically and is piled into along fiber axially extending bore, and density is 0.5-0.8g/cm
3, TENSILE STRENGTH is 15-20MPa, and compressive strength is 4-5MPa, and the diameter of fiber is 15-20 micron, and elongation at break is 8-10%, conductance is greater than 1000S/m.
embodiment 2:
Step (a): add 10g graphite in reaction bulb, 90% sulfuric acid of 100 g, 50 g potassium peroxydisulfates and 50 g phosphorus pentoxides, at 80 ℃, stirring reaction is 5 hours, after cool to room temperature, with deionized water dilution, with filter membrane suction filtration, with deionized water cyclic washing filter cake, repeatedly to neutral, air dry obtains intercalated graphite for 10 hours;
Step (b): the intercalated graphite product that adds gained in 5g step (a) in reaction bulb, 90% sulfuric acid of 300g and 50g potassium permanganate, at 50 ℃, stirring reaction is after 2 hours, add 30% hydrogen peroxide of 1kg deionized water and 30g to stir 10 hours, with membrane filtration, with deionized water cyclic washing filter cake, to neutral, air dry obtains graphite oxide;
Step (c): add the graphite oxide ene product of gained in 1g step (b) in reaction bulb in 20g water, with the ultrasonic processing of 50KHz 1 hour, obtain graphene oxide spinning solution colloidal sol;
Step (d): the graphene oxide spinning solution colloidal sol of getting gained in step (c), take the extruded velocity of 20 mL/h by diameter the spinning capillary as 100 μ m, in liquid nitrogen, solidify 1s postlyophilization 10h, obtain the ordered porous fiber of high strength graphene oxide;
Step (e): the ordered porous fiber of graphene oxide of gained in step (d) is placed in to acetic acid and hydrobromic mixed acid, is heated to 80 ℃ of reaction 10h, through washing the dry high-strength graphene ordered porous fibers that obtains reduction.
Through above step, the graphene oxide obtaining has good dissolubility in water, forms stable liquid crystal gel under high concentration.In liquid crystal gel, graphene oxide sheet is layer structure and arranges.The diameter of the ordered porous fiber of graphene oxide of gained is 100 microns, and density is 0.05g/cm
3, TENSILE STRENGTH is 5-8MPa, and compressive strength is 0.5-1MPa, and elongation at break is 5-10%.High-strength graphene ordered porous fibers, graphene film is arranged vertically and is piled into along fiber axially extending bore, and density is 0.03-0.04g/cm
3, TENSILE STRENGTH is 10-15MPa, and compressive strength is 2-4MPa, and the diameter of fiber is 80-100 micron, and elongation at break is 8-10%, conductance is greater than 1000S/m.
Above-described embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change that the present invention is made, all fall into protection scope of the present invention.
Claims (3)
1. a preparation method for the ordered porous fiber of Graphene, is characterized in that, comprises the following steps:
(1) graphite raw material of 1 weight portion, 1 ~ 100 weight portion sulfuric acid, 0.5 ~ 5 weight portion potassium peroxydisulfate and 0.5 ~ 5 weight portion phosphorus pentoxide are mixed, at 25 ~ 100 ℃, stirring reaction is 1 ~ 10 hour, after cool to room temperature, with deionized water, dilute, with filter membrane suction filtration, with deionized water washing, to neutral, air dry obtains intercalated graphite for 10 ~ 50 hours;
(2) intercalated graphite of gained in 1 weight portion step (1), 1 ~ 100 weight portion sulfuric acid and 0.5 ~ 10 weight portion potassium permanganate are mixed, at-10 ~ 50 ℃, stirring reaction is after 0.1 ~ 10 hour, add deionized water and 0.1 ~ 10 weight portion hydrogen peroxide of 10 ~ 2000 weight portions to stir 0.1 ~ 10 hour, with membrane filtration, with deionized water cyclic washing, to neutral, air dry obtains graphite oxide;
(3) graphite oxide of gained in 1 weight portion step (2) is dissolved in the water of 5 ~ 100 weight portions, with the ultrasonic processing of 50KHz 1 hour, obtains graphene oxide spinning solution colloidal sol;
(4) get the graphene oxide spinning solution colloidal sol of step (3) gained, extruded velocity with 1 ~ 100 mL/h, it by diameter, is the spinning capillary of 50 ~ 500 μ m, colloidal sol is clamp-oned and in liquid nitrogen, stopped 1 ~ 50s and condense, further freeze drying or critical freeze drying 2-40h, finally obtain ordered porous graphene oxide fiber again;
(5) the graphene oxide fiber of gained in step (4) is placed in to reductant and reduces 0.1 ~ 100h, washing is dry, obtain the ordered porous fiber of Graphene, one or more the mixing of described reductant in hydrazine hydrate, sodium borohydride, hydrobromic acid, hydroiodic acid, acetic acid forms.
2. the preparation method of the ordered porous fiber of Graphene according to claim 1, is characterized in that, in described step (1), described graphite is native graphite or pyrolytic graphite.
3. the preparation method of the ordered porous fiber of Graphene according to claim 1, is characterized in that, in described step (1) and step (2), described sulfuric acid is the sulfuric acid that mass concentration is greater than 80%.
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| CN102225330B (en) * | 2011-04-20 | 2013-04-03 | 东南大学 | Method for preparing photochemical catalyst/graphene one-dimensional nuclear shell compound structure by using photochemical catalysis method |
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