CN103966699B - A kind of preparation method of graphene fiber - Google Patents
A kind of preparation method of graphene fiber Download PDFInfo
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- CN103966699B CN103966699B CN201410016557.4A CN201410016557A CN103966699B CN 103966699 B CN103966699 B CN 103966699B CN 201410016557 A CN201410016557 A CN 201410016557A CN 103966699 B CN103966699 B CN 103966699B
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Abstract
The preparation method that the invention discloses a kind of graphene fiber.This preparation method comprises the steps: that the mixture of graphene oxide solution Yu water-soluble reducing agent is joined in tubular reactor by (1)；Described water-soluble reducing agent is ascorbic acid, sodium ascorbate, sodium citrate, HI, HBr, NaHSO3、Na2One or more in S, ethylenediamine, p-phenylenediamine and hydroquinone；(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 DEG C；(3) the aqueous graphite feed alkene gelatinous fibre that step (2) obtains is dried, obtain graphene fiber.The preparation method of the present invention is simple to operate, mild condition, and the cost of raw material is low；Utilizing the graphene fiber that method of the present invention prepares, even structure, mechanical performance is excellent, easy functionalization.
Description
Technical field
The preparation method that the present invention relates to a kind of graphene fiber.
Background technology
Graphene, as the most basic construction unit of all material with carbon elements, has real monoatomic layer thickness and strict two-dimensional structure, has significantly high mechanical strength, elasticity, heat conductivity, electric conductivity and quantum hall effect etc..Since British scientist An Delie Jim in 2010 and Ke Siteyanuowosainuo find that Graphene obtains Nobel Prize, Graphene research reaches unprecedented research climax, more and more studying discovery, it has huge application prospect at energy storage, electricity device, catalysis and biomedical special dimension.
Consider from practical application angle, nano-graphene material is changed in macrostructure material and is undoubtedly very valuable research direction.There is substantial amounts of research for the macroscopic view research of graphene-structured material and preparation, including the graphene-based block gel rubber material of macroscopic three dimensional, two-dimensional graphene thin-film material.One-dimensional fibre structure was also foretold its feasibility by a lot of people, but this kind of trial is seldom successful.At present, only minority seminar has prepared graphene fiber respectively through diverse ways both at home and abroad.[patent of invention that Zhejiang University is superb et al., application publication number CN102586946A] and Chinese University of Science and Technology's Yu's book grand et al. [patent of invention, application publication number CN102817111A] select different precipitant to obtain graphene fiber by wet spinning-reduction two-step method.Beijing Institute of Technology Qu Liangti et al. [patent of invention, application publication number CN102583334A] obtains graphene fiber by high-temperature water thermal response in glass tubing.Therefore the one-step method of a kind of simplicity and low temperature, the method for leniently preparing graphene fiber have to be developed, in order to better large-scale application.
Summary of the invention
The technical problem to be solved is in that the defect of the preparation method temperature height in order to overcome graphene fiber in prior art, complex process, it is provided that the preparation method of a kind of graphene fiber.The preparation method of the present invention is simple to operate, mild condition, and the cost of raw material is low；Utilizing the graphene fiber that method of the present invention prepares, even structure, mechanical performance is excellent, easy functionalization.
The present invention solves above-mentioned technical problem by the following technical programs:
The preparation method that the invention provides a kind of graphene fiber, it comprises the steps:
(1) mixture of graphene oxide solution Yu water-soluble reducing agent is joined in tubular reactor；Described water-soluble reducing agent is ascorbic acid, sodium ascorbate, sodium citrate, HI, HBr, NaHSO3、Na2One or more in S, ethylenediamine, p-phenylenediamine and hydroquinone；
(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 DEG C；
(3) the aqueous graphite feed alkene gelatinous fibre that step (2) obtains is dried, obtain graphene fiber.
Wherein, in step (1), mixture joins after in tubular reactor, and tubular reactor can seal, it is also possible to open-ended, it is preferred that for open-ended.
Wherein, the graphene oxide solution that described graphene oxide solution can prepare for this area conventional method, it is preferably and adopts oxidation to peel off the graphene oxide solution that graphite method (i.e. Hummers method) is prepared, more preferably the graphene oxide solution that graphite method prepares is peeled off in the oxidation for improving, prepared by following step best: 1. pre-oxidation: graphite, concentrated sulphuric 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 thermal expansion 10～30s under 400～900 DEG C of conditions 1., obtain thermal expansion graphite oxide；3. by step thermal expansion graphite oxide 2. and concentrated sulphuric acid, K2S2O8Heat under 80～90 DEG C 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 3. is mixed with concentrated sulphuric acid under 0～5 DEG C of condition, add potassium permanganate, reaction, add hydrogen peroxide, stand, centrifuge washing, add water and stir and obtain 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 reducing agent is preferably (1:0.5)～(1:800), is 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 DEG C, and the described dry time is preferably 2～100 hours.
In the preparation method of described graphene fiber, it is preferable that the graphene fiber further step (3) obtained carries out post processing.Described post processing comprises the steps: the graphene fiber vacuum heat in an inert atmosphere step (3) obtained.Described inert atmosphere is preferably one or more in nitrogen, argon and helium, and described heat treated temperature is preferably 300～800 DEG C, and the described heat treated time is preferably 2～3 hours.Described vacuum heat in an inert atmosphere refers under an inert atmosphere, then evacuation carries out heat treatment.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 combination in any, obtain the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
The actively progressive effect of the present invention is in that:
(1) preparation method of the graphene fiber of the present invention adopts graphene oxide solution a step reduction can directly obtain graphene fiber, and reaction temperature is low, and operation is succinct.
(2) water-soluble reducing agent that the raw material that the present invention utilizes is graphene oxide and low cost, widely, cost is low in source.
(3) reactor that the present invention utilizes can adopt plastic pipe PP(polypropylene) pipe, widely, cost is low, flexible, easily processes, repeatable utilization in source, and comparing glass tubing has the advantage of uniqueness.
(4) it be 100 μm～1mm, fracture tensile strength is the graphene fiber of 100～280MPa that the method utilizing the present invention can prepare diameter, appearance and consistent internal structure, satisfactory mechanical property, the intensity of the graphene fiber that step (3) obtains is close with the intensity of pure nano-carbon tube fiber, by the normalized intensity of density then 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 the method for the present invention prepares, density and fiber mesopore size control easily by reactor diameter and reactant concentration and post-processing temperature.
Accompanying drawing explanation
Fig. 1 is aqueous graphite feed alkene gelatinous fibre (a) and graphene fiber (b) photo that obtain in the embodiment of the present invention 1.
Fig. 2 is the graphene fiber stereoscan photograph obtained in the embodiment of the present invention 1.
Fig. 3 is the photo that the graphene fiber obtained in the embodiment of the present invention 1 is wound on teflon rod.
Fig. 4 is the graphene fiber electrical conductance photo obtained in the embodiment of the present invention 1.
Fig. 5 is the picture of the SINAP that the graphene fiber obtained in the embodiment of the present invention 1 is woven on absorbent gauze.
Fig. 6 is the stitchability photo that the graphene fiber obtained in the embodiment of the present invention 1 is woven into grid.
Detailed description of the invention
Mode by the examples below 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, conventionally and condition, or selects according to catalogue.
Embodiment 1
(1) utilize the oxidation improved to peel off graphite method and prepare graphene oxide solution:
10g graphite, 98% sulphuric acid 150ml, nitric acid 30ml, join in 500ml conical flask and 24h is stirred at room temperature, slowly pour solid collected by filtration in 1L water into, wash 3 times, dry 4 hours for 80 DEG C.Repeat preoxidation process twice.Dried pre-oxidation graphite is put into 900 DEG C of thermal expansion 20s in batch-type furnace and obtains thermal expansion graphite oxide.By 5g thermal expansion graphite oxide and 300ml sulphuric acid, 5gK in 500ml wide mouthed Erlenmeyer bottle2S2O8, latter 80 DEG C of 7g phosphorus pentoxide mixing is heated 4 hours, dilutes with 2L water, and 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 DEG C with 200ml sulphuric acid, add 20g potassium permanganate, it is slowly added into, 35 DEG C of stirring 1h, add the hydrogen peroxide adding 10ml30% after the dilution of 2L water stands 1h, stand 2 days, outwell supernatant, centrifuge washing, gentle agitation obtains disperseing good graphene oxide solution.
(2) with water-soluble reducing agent ascorbic acid, the graphene oxide solution that step (1) prepares being mixed with to obtain 4mg/ml graphene oxide mixed solution, wherein graphene oxide is 1:100 with the mass ratio of water-soluble reducing agent.
(3) graphene oxide mixed solution step (2) obtained injects in polypropylene (PP) plastic tube of diameter 4mm, is sealed at two ends.
(4) plastic tube sealed is heated 2h under 70 DEG C of conditions, plastic tube is formed aqueous graphite feed alkene gelatinous fibre.Aqueous graphite feed alkene gelatinous fibre outward appearance is continuous, uniform diameter.
(5) in convection oven, being dried by described aqueous graphite feed alkene gelatinous fibre under 60 DEG C of conditions, fibre diameter shrinks, and obtains the graphene fiber of dry state, and diameter is 150 μm, and the graphene fiber before and after shrinking contrasts as shown in Figure 1.Under scanning electron fibrescope, the graphene fiber structure of dry state is 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 the graphene fiber measuring dry state in axial tensile loads is tested is 150MPa, and it has good electric conductivity as shown in Figure 4, can directly be woven into net as shown in Figure 6 with graphene fiber.
(6) the graphene fiber sample of described dry state being put into muffle furnace, 300 DEG C pass into argon then evacuation heat treatment 2h so that dry graphene fibre strength improves, and recording its fracture strength in axial tensile loads is tested is 250MPa.
Embodiment 2
Repeat embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution and water-soluble reducing agent hydroiodic acid (HI) are mixed with in the PP plastic tube of graphene oxide mixed solution loading 8mm diameter of the 2mg/ml obtained, sealing, wherein graphene oxide is 1:200 with the mass ratio of water-soluble reducing agent.
The photo of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 3
Repeating embodiment 1, except having following difference, other conditions are all identical: by pure graphene oxide solution and water-soluble reducing agent NaHSO3Being mixed with in the PP plastic tube of graphene oxide mixed solution loading 2.5mm diameter of the 8mg/ml obtained, wherein graphene oxide is 1:300 with the mass ratio of water-soluble reducing agent；The plastic tube sealed is heated 3h under 70 DEG C of conditions.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 4
Repeat embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution and water-soluble reducing agent ethylenediamine are mixed with in the PP plastic tube of graphene oxide liquid mixture loading 6mm diameter of the 2mg/ml obtained, sealing, reacting 24h under 90 DEG C of conditions, wherein graphene oxide is 1:50 with the mass ratio of water-soluble reducing agent.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 5
Repeat embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution and water-soluble reducing agent (p-phenylenediamine and sodium ascorbate are the mixture of 1:1 according to mass ratio) are mixed with in the PP plastic tube of graphene oxide liquid mixture loading 5.5mm diameter of the 4mg/ml obtained, sealing, wherein graphene oxide is 1:1 with the mass ratio of water-soluble reducing agent.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 6
Repeat embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution and water-soluble reducing agent sodium ascorbate are mixed with the graphene oxide liquid mixture of the 4mg/ml obtained, loading in the PP plastic tube of 4mm diameter, wherein graphene oxide is 1:0.5 with the mass ratio of water-soluble reducing agent；The plastic tube sealed is heated 96h under 90 DEG C of conditions.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 7
Repeat embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution and water-soluble reducing agent ascorbic acid are mixed with the graphene oxide liquid mixture of the 1.5mg/ml obtained, loading in the PP plastic tube of 8mm diameter, wherein graphene oxide is 1:800 with the mass ratio of water-soluble reducing agent；The plastic tube sealed is heated 0.5h under 70 DEG C of conditions.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 8
Repeating embodiment 1, except having following difference, other conditions are all identical: in convection oven, dried by described aqueous graphite feed alkene gelatinous fibre at 90 DEG C, and fibre diameter shrinks, and obtains the graphene fiber of dry state.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 9
Repeat embodiment 1, except having following difference, other conditions are all identical: the graphene fiber sample of described dry state is put into muffle furnace by step (6), 500 DEG C pass into nitrogen, evacuation heat treatment 2h again, the graphene fiber intensity making dry state improves, and recording its fracture strength in axial tensile loads is tested is 270MPa.
Embodiment 10
Repeat embodiment 1, except having following difference, other conditions are all identical: the graphene fiber sample of described dry state is put into muffle furnace by step (6), 300 DEG C pass into nitrogen, evacuation heat treatment 72h again, the graphene fiber intensity making dry state improves, and recording its fracture strength in axial tensile loads is tested is 280MPa.
Embodiment 11
Repeat embodiment 1, except having following difference, other conditions are all identical: the graphene fiber sample of described dry state is put into muffle furnace by step (6), 700 DEG C pass into nitrogen, evacuation heat treatment 2h again, dry graphene fibre strength is improved, and recording its fracture strength in axial tensile loads is tested is 250MPa.
Embodiment 12
Repeat embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution and water-soluble reducing agent ascorbic acid are mixed with the graphene oxide liquid mixture of the 2mg/ml obtained, load in the PP plastic tube of 4mm diameter, sealing, wherein graphene oxide is 1:0.1 with the mass ratio of water-soluble reducing agent.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 13
Repeat embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution and water-soluble reducing agent ascorbic acid are mixed with the graphene oxide liquid mixture of the 4mg/ml obtained, load in the PP plastic tube of 4mm diameter, sealing, wherein graphene oxide is 1:900 with the mass ratio of water-soluble reducing agent.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 14
Repeating embodiment 1, except having following difference, other conditions are all identical: the graphene fiber sample of described dry state is put into muffle furnace by step (6), heat treatment 2h under 850 DEG C of vacuum conditions, and recording its fracture strength in axial tensile loads is tested is 100MPa.
Embodiment 15
Repeat embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution and water-soluble reducing agent ascorbic acid are mixed with the graphene oxide liquid mixture of the 2mg/ml obtained, loading open-ended in the polypropylene PP plastic tube of 8mm diameter, wherein graphene oxide is 1:50 with the mass ratio of water-soluble reducing agent.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 16
Repeat embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution and water-soluble reducing agent ascorbic acid are mixed with the graphene oxide liquid mixture of the 2mg/ml obtained, loading open-ended in polyurethane (PU) plastic tube of 8mm diameter, wherein graphene oxide is 1:50 with the mass ratio of water-soluble reducing agent.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 17
Repeat embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution and water-soluble reducing agent ascorbic acid are mixed with the graphene oxide liquid mixture of the 2mg/ml obtained, loading open-ended in the silica gel plastics pipe of 8mm diameter, wherein graphene oxide is 1:50 with the mass ratio of water-soluble reducing agent.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 18
Repeat embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution and water-soluble reducing agent (ethylenediamine and sodium citrate are the mixture of 1:1 according to mass ratio) being mixed with the graphene oxide liquid mixture of the 2mg/ml obtained and loads open-ended in the PP plastic tube of 6mm diameter, wherein graphene oxide is 1:50 with the mass ratio of water-soluble reducing agent.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Embodiment 19
Repeating embodiment 1, except having following difference, other conditions are all identical: by pure graphene oxide solution and water-soluble reducing agent (HBr, Na2S and hydroquinone are the mixture of 1:1:1 according to mass ratio) it is mixed with in the PP plastic tube of graphene oxide liquid mixture loading 6.5mm diameter of the 2mg/ml obtained, wherein graphene oxide is 1:50 with the total mass ratio of water-soluble reducing agent.
The photographic result of the graphene fiber obtained is similar to Example 1, and its fibre diameter and hot strength are as shown in table 1.
Comparative example 1
Repeating embodiment 1, except having following difference, other conditions are all identical: by pure graphene oxide solution and water-soluble reducing agent hydrazine hydrate (NH2-NH2(H2O) graphene oxide liquid mixture) being mixed with, loads in the PP plastic tube of 4mm diameter, and wherein graphene oxide is 1:100 with the mass ratio of water-soluble reducing agent.What its result obtained is the Graphene granule being deposited in pipe, can not get continuous print hygrometric state graphene fiber, equally also can not get continuous print dry graphene fiber.
Comparative example 2
Repeating embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution loads sealing in the PP plastic tube of 4mm diameter, and wherein reaction temperature is 95 DEG C, and the response time is 2h.Its result is to can not get continuous print hygrometric state graphene fiber, also can not get continuous print dry graphene fiber.
Comparative example 3
Repeating embodiment 1, except having following difference, other conditions are all identical: pure graphene oxide solution loads open-ended in the PP plastic tube of 4mm diameter, and wherein reaction temperature is 95 DEG C, and the response time is 2h.Its result is to can not get continuous print hygrometric state graphene fiber, also can not get continuous print dry graphene fiber.
The diameter of the graphene fiber of table 1 embodiment 1～19 and comparative example 1～3 and fracture strength data
| Embodiment | Average fibre diameter (μm) | Fibrous fracture intensity (MPa) 6--> |
| 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 many employings glass tubing, but glass tubing cost is high, processing difficulties, sells without longer glass tubing in present business.Glass tubing large-scale processing is more difficult, and cannot free bend, difficult industrialization, a lot of swan-necks need customization.And present invention selection is commercial plastic tubing, it is possible to the extensive commercially available plastic tube (such as PP pipe, polyurethane tube or silica gel tube etc.) selecting different tube diameters, and cost is low.
Table 2 is the commodity price information obtained by open channel, prepares reactor cost signal using it as graphene fiber.
Wherein reactor caliber is 6mm, and wherein glass tubing need to have certain thickness (more than 10mm), to ensure its use safety under high temperature and high pressure environment.
Table 2 reactor cost is estimated
Claims (9)
1. a preparation method for graphene fiber, it comprises the steps:
(1) mixture of graphene oxide solution Yu water-soluble reducing agent is joined in tubular reactor；Described water-soluble reducing agent is ascorbic acid, sodium ascorbate, sodium citrate, HI, HBr, NaHSO3、Na2One or more in S, ethylenediamine, p-phenylenediamine and hydroquinone；Described graphene oxide solution is prepared by following step: 1. pre-oxidation: graphite, concentrated sulphuric acid and nitric acid are poured into water, and filters, and dries；Repeat above-mentioned preoxidation process 2～3 times, obtain pre-oxidation graphite；2. thermal expansion: by step pre-oxidation graphite thermal expansion 10～30s under 400～900 DEG C of conditions 1., obtain thermal expansion graphite oxide；3. by step thermal expansion graphite oxide 2. and concentrated sulphuric acid, K2S2O8Heat under 80～90 DEG C 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 3. is mixed with concentrated sulphuric acid under 0～5 DEG C of condition, add potassium permanganate, reaction, add hydrogen peroxide, stand, centrifuge washing, add water and stir and obtain graphene oxide solution；
(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 DEG C；
(3) the aqueous graphite feed alkene gelatinous fibre that step (2) obtains is dried, obtain graphene fiber.
2. preparation method as claimed in claim 1, it is characterised in that in step (1), mixture joins after in tubular reactor, tubular reactor open-ended.
3. preparation method as claimed in claim 1, it is characterised in that in described mixture, the consumption of graphene oxide is 1～10mg/mL mixture.
4. preparation method as claimed in claim 1, it is characterised 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.
5. preparation method as claimed in claim 1, it is characterised in that the mass ratio of described graphene oxide and described water-soluble reducing agent is (1:0.5)～(1:800).
6. preparation method as claimed in claim 1, it is characterised in that in step (2), the time of described heating is 0.5～100 hour.
7. preparation method as claimed in claim 1, it is characterised in that in step (3), described dry temperature is 10～100 DEG C, and the described dry time is 2～100 hours.
8. preparation method as claimed in claim 1, it is characterised in that in the preparation method of described graphene fiber, the graphene fiber further step (3) obtained carries out post processing；Described post processing comprises the steps: the graphene fiber vacuum heat in an inert atmosphere step (3) obtained.
9. preparation method as claimed in claim 8, it is characterised in that described inert atmosphere is one or more in nitrogen, argon and helium, and described heat treated temperature is 300～800 DEG C, and the described heat treated time is 2～3 hours.
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| CN110203911A (en) * | 2019-07-10 | 2019-09-06 | 吉林大学 | A kind of graphene fiber and preparation method |
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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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