CN103966699A - Preparation method of graphene fibers - Google Patents
Preparation method of graphene fibers Download PDFInfo
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- CN103966699A CN103966699A CN201410016557.4A CN201410016557A CN103966699A CN 103966699 A CN103966699 A CN 103966699A CN 201410016557 A CN201410016557 A CN 201410016557A CN 103966699 A CN103966699 A CN 103966699A
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Abstract
The invention discloses a preparation method of graphene fibers. The preparation method comprises the following steps: (1), a mixture of a graphene oxide solution and a water-soluble reducing agent is added into a tubular reactor, wherein the water-soluble reducing agent is one or more of ascorbic acid, sodium ascorbate, sodium citrate, HI, HBr, NaHSO3, Na2S, ethylenediamine, p-phenylenediamine and hydroquinone; (2), the tubular reactor in the step (1) is heated, and graphene oxide is reduced and assembled to aqueous graphene gel fibers, and the heating temperature is 60-95 DEG C; and (3), the aqueous graphene gel fibers obtained in the step (2) is dried to obtain the graphene fibers. The preparation method is simple to operate, mild in conditions and low in raw material cost; and the graphene fibers obtained with the preparation method are uniform in structure, excellent in mechanical property and easiness in functionalization.
Description
Technical field
The present invention relates to a kind of preparation method of graphene fiber.
Background technology
Graphene, as the basic structural unit of all material with carbon elements, has real monoatomic layer thickness and strict two-dimensional structure, has very high mechanical strength, elasticity, thermal conductivity, electric conductivity and quantum hall effect etc.Since British scientist An Delie Jim in 2010 and Ke Siteyanuowosainuo have found Graphene and since obtaining the Nobel Prize, Graphene research reaches unprecedented research climax, increasing research discovery, it has huge application prospect at energy storage, electricity device, catalysis and biomedical special dimension.
From practical application angle, considering, is in macrostructure material, to be undoubtedly very valuable research direction by nano-graphene material transition.There is a large amount of research for research and the preparation of macroscopical graphene-structured material, comprised macroscopical three-dimensional grapheme matrix body gel rubber material, two-dimentional graphene film material.The fibre structure of one dimension was also foretold its feasibility by a lot of people, but this class trial is seldom successful.At present, only have minority seminar by diverse ways, to prepare graphene fiber respectively both at home and abroad.The people [patent of invention, application publication number CN102817111A] such as the high superfine people [patent of invention, application publication number CN102586946A] of Zhejiang University and Chinese University of Science and Technology's Yu's book are grand select different precipitating agents to obtain graphene fiber by wet spinning-reduction two-step method.The people [patent of invention, application publication number CN102583334A] such as the Qu Liangti of Beijing Institute of Technology have obtained graphene fiber by high-temperature water thermal response in glass tube.Therefore a kind of easy one-step method and low temperature, the method for leniently preparing graphene fiber have to be developed so that better large-scale application.
Summary of the invention
Technical problem to be solved by this invention is that preparation method's temperature of graphene fiber in prior art is high, the defect of complex process in order to have overcome, and a kind of preparation method of graphene fiber is provided.Preparation method of the present invention is simple to operate, mild condition, and the cost of raw material is low; The graphene fiber that utilizes method of the present invention to prepare, even structure, mechanical performance is excellent, easily functionalization.
The present invention solves the problems of the technologies described above by the following technical programs:
The preparation method who the invention provides a kind of graphene fiber, it comprises the steps:
(1) mixture of graphene oxide solution and water-soluble reductant is joined in tubular reactor; Described water-soluble reductant is ascorbic acid, sodium ascorbate, natrium citricum, HI, HBr, NaHSO
3, Na
2one or more in S, ethylenediamine, p-phenylenediamine (PPD) and hydroquinones;
(2) tubular reactor of heating steps (1), graphene oxide reduction is assembled into aqueous graphite feed alkene gelatinous fibre; The temperature of described heating is 60～95 ℃;
(3) aqueous graphite feed alkene gelatinous fibre step (2) being obtained is dry, obtains graphene fiber.
Wherein, in step (1), after mixture joins in tubular reactor, tubular reactor can seal, also can open-ended, and be preferably open-ended.
Wherein, described graphene oxide solution can be the graphene oxide solution that this area conventional method makes, preferably for adopting oxidation to peel off the graphene oxide solution that graphite method (being Hummers method) makes, more preferably for improved oxidation, peel off the graphene oxide solution that graphite method makes, by following step, make best: 1. pre-oxidation: graphite, the concentrated sulfuric acid and nitric acid are poured into water, filter, dry; Repeat above-mentioned preoxidation process 2～3 times, obtain pre-oxidation graphite; 2. thermal expansion: by step pre-oxidation graphite 1. thermal expansion 10～30s under 400～900 ℃ of conditions, obtain thermal expansion graphite oxide; 3. by thermal expansion graphite oxide 2. of step and the concentrated sulfuric acid, K
2s
2o
8heat under 80～90 ℃ of conditions with the mixture of phosphorus pentoxide, add water filtration washing, dry, obtain pre-oxidation thermal expansion graphite; 4. step pre-oxidation thermal expansion graphite is 3. mixed under 0～5 ℃ of condition with the concentrated sulfuric acid, add potassium permanganate, reaction, then adds hydrogen peroxide, standing, and centrifuge washing adds water to stir and obtains graphene oxide solution.
Wherein, in described mixture, the consumption of graphene oxide is preferably 1～10mg/mL mixture.
Wherein, described tubular reactor adopts general elongate reactor, and the diameter of described tubular reactor is preferably 2.5～18mm, and length is preferably 0.01～1m; Described tubular reactor is preferably pp pipeline, polyurethane plastics pipe or silica gel plastics pipe.
Wherein, the mass ratio of described graphene oxide and described water-soluble reductant is preferably (1:0.5)～(1:800), be more preferably (1:0.5)～(1:400).
In step (2), the time of described heating is preferably 0.5～100 hour.
In step (3), described dry temperature is preferably 10～100 ℃, and the described dry time is preferably 2～100 hours.
In the preparation method of described graphene fiber, the graphene fiber preferably further step (3) being obtained carries out post processing.Described post processing comprises the steps: graphene fiber vacuum heat in inert atmosphere that step (3) is obtained.Described inert atmosphere is preferably one or more in nitrogen, argon gas and helium, and described heat treated temperature is preferably 300～800 ℃, and the described heat treated time is preferably 2～3 hours.Described vacuum heat in inert atmosphere refers under inert atmosphere, then vacuumizes and heat-treat.After Overheating Treatment, the intensity of graphene fiber gets a promotion.
Meeting on the basis of this area general knowledge, above-mentioned each optimum condition, can be combined, and obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is:
(1) preparation method of graphene fiber of the present invention adopts graphene oxide solution a step reduction directly to obtain graphene fiber, and reaction temperature is low, and operation is succinct.
(2) raw material that the present invention utilizes, for graphene oxide and water-soluble reductant cheaply, are originated very extensive, and cost is low.
(3) reactor of utilization of the present invention can adopt plastic pipe PP(polypropylene) pipe, to originate very extensive, cost is low, flexible, and easily processing, can reuse, and comparing glass tubing has unique advantage.
(4) utilizing method of the present invention can prepare diameter is the graphene fiber that 100 μ m～1mm, fracture tensile strength are 100～280MPa, appearance and internal structure are even, satisfactory mechanical property, the intensity of the graphene fiber that step (3) obtains and the intensity of pure nano-carbon tube fiber approach, by the normalized intensity of density, higher than pure nano-carbon tube fiber, the graphene fiber intensity after heat treatment is higher; And pliability is good, can work out as graphene fiber net.
(5) diameter of the graphene fiber that method of the present invention prepares, density and fiber mesopore size are easily controlled by reactor diameter and reactant concentration and post-processing temperature.
Accompanying drawing explanation
Fig. 1 is the aqueous graphite feed alkene gelatinous fibre (a) and graphene fiber (b) photo obtaining in the embodiment of the present invention 1.
Fig. 2 is the graphene fiber stereoscan photograph obtaining in the embodiment of the present invention 1.
Fig. 3 is that the graphene fiber that obtains in the embodiment of the present invention 1 is around the photo of teflon rod.
Fig. 4 is the graphene fiber electrical conductance photo obtaining in the embodiment of the present invention 1.
Fig. 5 is the picture that the graphene fiber that obtains in the embodiment of the present invention 1 is woven into the SINAP on absorbent gauze.
Fig. 6 is the stitchability photo that the graphene fiber that obtains in the embodiment of the present invention 1 is woven into grid.
The specific embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to conventional method and condition, or selects according to catalogue.
Embodiment 1
(1) utilize improved oxidation to peel off graphite legal system for graphene oxide solution:
10g graphite, 98% sulfuric acid 150ml, nitric acid 30ml, joins stirring at room 24h in 500ml conical flask, slowly pours solid collected by filtration in 1L water into, washs 3 times, dries 4 hours for 80 ℃.Repeat twice of preoxidation process.Dried pre-oxidation graphite is put into 900 ℃ of thermal expansion 20s of batch-type furnace and obtain thermal expansion graphite oxide.In 500ml wide-mouth conical flask by 5g thermal expansion graphite oxide and 300ml sulfuric acid, 5g K
2s
2o
8, 7g phosphorus pentoxide mixes rear 80 ℃ of heating 4 hours, and with the dilution of 2L water, filtration washing, air drying obtains pre-oxidation thermal expansion graphite for 3 days.Dry pre-oxidation thermal expansion graphite is mixed at low temperature 0-5 ℃ with 200ml sulfuric acid, add 20g potassium permanganate, slowly add, 35 ℃ are stirred 1h, add 2L water and dilute the hydrogen peroxide that adds 10ml30% after standing 1h, standing 2 days, outwell supernatant, centrifuge washing, gentle agitation obtains disperseing good graphene oxide solution.
(2) graphene oxide solution step (1) being made and water-soluble reductant ascorbic acid are mixed with to obtain 4mg/ml graphene oxide mixed solution, and wherein the mass ratio of graphene oxide and water-soluble reductant is 1:100.
(3) graphene oxide mixed solution step (2) being obtained injects polypropylene (PP) plastic tube of diameter 4mm, and two ends are sealed.
(4) plastic tube of sealing is heated to 2h under 70 ℃ of conditions, in plastic tube, form aqueous graphite feed alkene gelatinous fibre.Aqueous graphite feed alkene gelatinous fibre outward appearance is continuous, and diameter is even.
(5) in convection oven, described aqueous graphite feed alkene gelatinous fibre is dry under 60 ℃ of conditions, and fibre diameter shrinks, and obtains the graphene fiber of dry state, and diameter is 150 μ m, and the graphene fiber contrast before and after shrinking as shown in Figure 1.Under scanning electron fibrescope, the graphene fiber structure of dry state as shown in Figure 2.Smooth from the graphene fiber close structure of the visible dry state of electron scanning micrograph.The graphene fiber very light in weight of dry state, and dry graphene fiber pliability is good, sub-thread graphene fiber can well be wrapped on teflon rod as shown in Figure 3.The fracture strength of measuring the graphene fiber of dry state in axial tension load test is 150MPa, and it has good electric conductivity as shown in Figure 4, with graphene fiber, can directly be woven into net as shown in Figure 6.
(6) the graphene fiber sample of described dry state is put into muffle furnace, 300 ℃ pass into argon gas, then vacuumize heat treatment 2h, and dry graphene fibre strength is improved, and in axial tension load test, recording its fracture strength is 250MPa.
Embodiment 2
Repeat embodiment 1, outside following difference, other conditions are all identical: the graphene oxide mixed solution that pure graphene oxide solution and water-soluble reductant hydroiodic acid (HI) is mixed with to the 2mg/ml obtaining packs in the PP plastic tube of 8mm diameter, sealing, wherein the mass ratio of graphene oxide and water-soluble reductant is 1:200.
The photo of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 3
Repeat embodiment 1, outside following difference, other conditions are all identical: by pure graphene oxide solution and water-soluble reductant NaHSO
3the graphene oxide mixed solution that is mixed with the 8mg/ml obtaining packs in the PP plastic tube of 2.5mm diameter, and wherein the mass ratio of graphene oxide and water-soluble reductant is 1:300; The plastic tube of sealing is heated to 3h under 70 ℃ of conditions.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 4
Repeat embodiment 1, outside following difference, other conditions are all identical: the graphene oxide liquid mixture that pure graphene oxide solution and water-soluble reductant ethylenediamine are mixed with to the 2mg/ml obtaining packs in the PP plastic tube of 6mm diameter, sealing, under 90 ℃ of conditions, react 24h, wherein the mass ratio of graphene oxide and water-soluble reductant is 1:50.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 5
Repeat embodiment 1, outside following difference, other conditions are all identical: the graphene oxide liquid mixture that pure graphene oxide solution and water-soluble reductant (mixture that p-phenylenediamine (PPD) and sodium ascorbate are 1:1 according to mass ratio) is mixed with to the 4mg/ml obtaining packs in the PP plastic tube of 5.5mm diameter, sealing, wherein the mass ratio of graphene oxide and water-soluble reductant is 1:1.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 6
Repeat embodiment 1, outside following difference, other conditions are all identical: the graphene oxide liquid mixture that pure graphene oxide solution and water-soluble reductant sodium ascorbate is mixed with to the 4mg/ml obtaining, pack in the PP plastic tube of 4mm diameter, wherein the mass ratio of graphene oxide and water-soluble reductant is 1:0.5; The plastic tube of sealing is heated to 96h under 90 ℃ of conditions.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 7
Repeat embodiment 1, outside following difference, other conditions are all identical: the graphene oxide liquid mixture that pure graphene oxide solution and water-soluble reductant ascorbic acid is mixed with to the 1.5mg/ml obtaining, pack in the PP plastic tube of 8mm diameter, wherein the mass ratio of graphene oxide and water-soluble reductant is 1:800; The plastic tube of sealing is heated to 0.5h under 70 ℃ of conditions.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 8
Repeat embodiment 1, outside following difference, other conditions are all identical: in convection oven, described aqueous graphite feed alkene gelatinous fibre is dry at 90 ℃, and fibre diameter shrinks, and obtains the graphene fiber of dry state.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 9
Repeat embodiment 1, outside following difference, other conditions are all identical: step (6) is put into muffle furnace by the graphene fiber sample of described dry state, 500 ℃ pass into nitrogen, vacuumize again heat treatment 2h, the graphene fiber intensity of dry state is improved, and in axial tension load test, recording its fracture strength is 270MPa.
Embodiment 10
Repeat embodiment 1, outside following difference, other conditions are all identical: step (6) is put into muffle furnace by the graphene fiber sample of described dry state, 300 ℃ pass into nitrogen, vacuumize again heat treatment 72h, the graphene fiber intensity of dry state is improved, and in axial tension load test, recording its fracture strength is 280MPa.
Embodiment 11
Repeat embodiment 1, outside following difference, other conditions are all identical: step (6) is put into muffle furnace by the graphene fiber sample of described dry state, 700 ℃ pass into nitrogen, vacuumize again heat treatment 2h, dry graphene fibre strength is improved, and in axial tension load test, recording its fracture strength is 250MPa.
Embodiment 12
Repeat embodiment 1, outside following difference, other conditions are all identical: the graphene oxide liquid mixture that pure graphene oxide solution and water-soluble reductant ascorbic acid is mixed with to the 2mg/ml obtaining, pack in the PP plastic tube of 4mm diameter, sealing, wherein the mass ratio of graphene oxide and water-soluble reductant is 1:0.1.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 13
Repeat embodiment 1, outside following difference, other conditions are all identical: the graphene oxide liquid mixture that pure graphene oxide solution and water-soluble reductant ascorbic acid is mixed with to the 4mg/ml obtaining, pack in the PP plastic tube of 4mm diameter, sealing, wherein the mass ratio of graphene oxide and water-soluble reductant is 1:900.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 14
Repeat embodiment 1, outside following difference, other conditions are all identical: step (6) is put into muffle furnace by the graphene fiber sample of described dry state, heat treatment 2h under 850 ℃ of vacuum conditions, and in axial tension load test, recording its fracture strength is 100MPa.
Embodiment 15
Repeat embodiment 1, outside following difference, other conditions are all identical: the graphene oxide liquid mixture that pure graphene oxide solution and water-soluble reductant ascorbic acid is mixed with to the 2mg/ml obtaining, pack open-ended in the polypropylene PP plastic tube of 8mm diameter into, wherein the mass ratio of graphene oxide and water-soluble reductant is 1:50.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 16
Repeat embodiment 1, outside following difference, other conditions are all identical: the graphene oxide liquid mixture that pure graphene oxide solution and water-soluble reductant ascorbic acid is mixed with to the 2mg/ml obtaining, pack open-ended in polyurethane (PU) plastic tube of 8mm diameter into, wherein the mass ratio of graphene oxide and water-soluble reductant is 1:50.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 17
Repeat embodiment 1, outside following difference, other conditions are all identical: the graphene oxide liquid mixture that pure graphene oxide solution and water-soluble reductant ascorbic acid is mixed with to the 2mg/ml obtaining, pack open-ended in the silica gel plastics pipe of 8mm diameter into, wherein the mass ratio of graphene oxide and water-soluble reductant is 1:50.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 18
Repeat embodiment 1, outside following difference, other conditions are all identical: the graphene oxide liquid mixture that pure graphene oxide solution and water-soluble reductant (mixture that ethylenediamine and natrium citricum are 1:1 according to mass ratio) are mixed with to the 2mg/ml obtaining packs open-ended in the PP plastic tube of 6mm diameter into, and wherein the mass ratio of graphene oxide and water-soluble reductant is 1:50.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Embodiment 19
Repeat embodiment 1, outside following difference, other conditions are all identical: by pure graphene oxide solution and water-soluble reductant (HBr, Na
2the mixture that S and hydroquinones are 1:1:1 according to mass ratio) graphene oxide liquid mixture that is mixed with the 2mg/ml obtaining packs in the PP plastic tube of 6.5mm diameter, and wherein the total mass ratio of graphene oxide and water-soluble reductant is 1:50.
The photo result of the graphene fiber obtaining is similar to Example 1, and its fibre diameter and TENSILE STRENGTH are as shown in table 1.
Comparative example 1
Repeat embodiment 1, outside following difference, other conditions are all identical: by pure graphene oxide solution and water-soluble reductant hydrazine hydrate (NH
2-NH
2(H
2o)) graphene oxide liquid mixture being mixed with, packs in the PP plastic tube of 4mm diameter, and wherein the mass ratio of graphene oxide and water-soluble reductant is 1:100.What its result obtained is the Graphene particle being deposited in pipe, can not get continuous hygrometric state graphene fiber, equally also can not get continuous dry graphene fiber.
Comparative example 2
Repeat embodiment 1, outside following difference, other conditions are all identical: pure graphene oxide solution is packed in the PP plastic tube of 4mm diameter and seal, wherein reaction temperature is 95 ℃, and the reaction time is 2h.Consequently can not get continuous hygrometric state graphene fiber, also can not get continuous dry graphene fiber.
Comparative example 3
Repeat embodiment 1, outside following difference, other conditions are all identical: pure graphene oxide solution is packed into open-ended in the PP plastic tube of 4mm diameter, wherein reaction temperature is 95 ℃, and the reaction time is 2h.Consequently can not get continuous hygrometric state graphene fiber, also can not get continuous dry graphene fiber.
The diameter of table 1 embodiment 1～19 and comparative example's 1～3 graphene fiber and fracture strength data
| Embodiment | Average fibre diameter (μ m) | Fibrous fracture intensity (MPa) |
| 1 | 170 | 250 |
| 2 | 160 | 230 |
| 3 | 178 | 190 |
| 4 | 150 | 200 |
| 5 | 180 | 270 |
| 6 | 160 | 210 |
| 7 | 146 | 240 |
| 8 | 200 | 180 |
| 9 | 160 | 270 |
| 10 | 165 | 280 |
| 11 | 165 | 250 |
| 12 | 100 | 80 |
| 13 | 180 | 160 |
| 14 | 160 | 100 |
| 15 | 220 | 265 |
| 16 | 210 | 275 |
| 17 | 225 | 260 |
| 18 | 180 | 285 |
| 19 | 195 | 270 |
| Comparative example 1 | 0 | 0 |
| Comparative example 2 | 0 | 0 |
| Comparative example 3 | 0 | 0 |
In prior art, reaction vessel adopts glass tube more, but glass tube cost is high, and processing difficulties is sold without longer glass tube in business now.Glass tube large-scale processing is more difficult, and cannot free bend, difficult industrialization, and a lot of swan-necks need customization.And the present invention selects, be commercial plastic pipe, can select on a large scale the commercially available plastic tube (such as PP pipe, polyurethane tube or silicone tube etc.) of different tube diameters, and cost be low.
Commodity price information for obtaining by open channel in table 2, usings that it is illustrated as graphene fiber preparation feedback device cost.
Wherein reactor caliber is 6mm, and wherein glass tube need have certain thickness (being greater than 10mm), to guarantee its use safety under high temperature and high pressure environment.
The estimation of table 2 reactor cost
Claims (10)
1. a preparation method for graphene fiber, it comprises the steps:
(1) mixture of graphene oxide solution and water-soluble reductant is joined in tubular reactor; Described water-soluble reductant is ascorbic acid, sodium ascorbate, natrium citricum, HI, HBr, NaHSO
3, Na
2one or more in S, ethylenediamine, p-phenylenediamine (PPD) and hydroquinones;
(2) tubular reactor of heating steps (1), graphene oxide reduction is assembled into aqueous graphite feed alkene gelatinous fibre; The temperature of described heating is 60～95 ℃;
(3) aqueous graphite feed alkene gelatinous fibre step (2) being obtained is dry, obtains graphene fiber.
2. preparation method as claimed in claim 1, is characterized in that, in step (1), and after mixture joins in tubular reactor, tubular reactor open-ended.
3. preparation method as claimed in claim 1, it is characterized in that, described graphene oxide solution is for adopting oxidation to peel off the graphene oxide solution that graphite method makes, preferably for improved oxidation, peel off the graphene oxide solution that graphite method makes, more preferably by following step, make: 1. pre-oxidation: graphite, the concentrated sulfuric acid and nitric acid are poured into water, filter, dry; Repeat above-mentioned preoxidation process 2～3 times, obtain pre-oxidation graphite; 2. thermal expansion: by step pre-oxidation graphite 1. thermal expansion 10～30s under 400～900 ℃ of conditions, obtain thermal expansion graphite oxide; 3. by thermal expansion graphite oxide 2. of step and the concentrated sulfuric acid, K
2s
2o
8heat under 80～90 ℃ of conditions with the mixture of phosphorus pentoxide, add water filtration washing, dry, obtain pre-oxidation thermal expansion graphite; 4. step pre-oxidation thermal expansion graphite is 3. mixed under 0～5 ℃ of condition with the concentrated sulfuric acid, add potassium permanganate, reaction, then adds hydrogen peroxide, standing, and centrifuge washing adds water to stir and obtains graphene oxide solution.
4. preparation method as claimed in claim 1, is characterized in that, in described mixture, the consumption of graphene oxide is 1～10mg/mL mixture.
5. preparation method as claimed in claim 1, is characterized in that, the diameter of described tubular reactor is 2.5～18mm, and length is 0.01～1m; Described tubular reactor is pp pipeline, polyurethane plastics pipe or silica gel plastics pipe.
6. preparation method as claimed in claim 1, is characterized in that, the mass ratio of described graphene oxide and described water-soluble reductant is (1:0.5)～(1:800).
7. preparation method as claimed in claim 1, is characterized in that, in step (2), the time of described heating is 0.5～100 hour.
8. preparation method as claimed in claim 1, is characterized in that, in step (3), described dry temperature is 10～100 ℃, and the described dry time is 2～100 hours.
9. preparation method as claimed in claim 1, is characterized in that, in the preparation method of described graphene fiber, the graphene fiber further step (3) being obtained carries out post processing; Described post processing comprises the steps: graphene fiber vacuum heat in inert atmosphere that step (3) is obtained.
10. preparation method as claimed in claim 9, is characterized in that, described inert atmosphere is one or more in nitrogen, argon gas and helium, and described heat treated temperature is 300～800 ℃, and the described heat treated time is 2～3 hours.
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| CN105803604A (en) * | 2015-01-02 | 2016-07-27 | 中原工学院 | Method for preparing graphene fibers through slitting of graphite oxide thin films |
| CN106032585A (en) * | 2015-03-13 | 2016-10-19 | 中国科学院上海应用物理研究所 | Graphene-inorganic nanometer particle composite fiber and preparing method thereof |
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| CN114348997A (en) * | 2021-12-29 | 2022-04-15 | 杭州嘉悦智能设备有限公司 | Nitrogen-doped graphene-metal nanoparticle film and preparation method thereof |
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