CN105088415A - Graphene oxide solution for wet spinning and preparation method thereof, graphene fiber and preparation method of graphene fiber - Google Patents
Graphene oxide solution for wet spinning and preparation method thereof, graphene fiber and preparation method of graphene fiber Download PDFInfo
- Publication number
- CN105088415A CN105088415A CN201510330999.0A CN201510330999A CN105088415A CN 105088415 A CN105088415 A CN 105088415A CN 201510330999 A CN201510330999 A CN 201510330999A CN 105088415 A CN105088415 A CN 105088415A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- preparation
- oxide solution
- wet spinning
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a preparation method of a graphene oxide solution for wet spinning; the preparation method includes the following steps: carrying out centrifugal concentration on a graphene oxide solution, to obtain the graphene oxide solution for wet spinning. The graphene oxide solution is subjected to centrifugal concentration so as to obtain the graphene oxide solution for wet spinning finally. The preparation method of the graphene oxide solution for wet spinning simplifies operation processes, and omits ultrasound, dialysis and pre-expansion processes and the like; the experimental preparation process is simple, the conditions are easy to control, and large-scale production can be realized. In addition, the graphene oxide solution used for wet spinning and prepared by the preparation method provided by the invention has the advantages of stable quality, good water solubility, controllable concentration, and easy adjustment of the size of obtained graphene fiber.
Description
Technical field
The invention belongs to graphene oxide technical field, be specifically related to a kind of wet spinning graphene oxide solution and preparation method thereof and a kind of graphene fiber and preparation method thereof.
Background technology
Graphene is a kind of new material of the individual layer laminated structure be made up of carbon atom, there is the thinnest in the world at present thickness, the hardest hardness, the highest electric conductivity, this is as the Two-dimensional Carbon atomic crystal of honeycomb, its excellent electric property had, thermal property, mechanical performance, and special quantum hall effect and quantum tunneling effect etc., be expected to be widely used in, in the materials such as inductor, nano composite material, battery, ultracapacitor, there is using value and application prospect extremely widely.
Along with the development of science and technology, possess wearable, can weave, the micro-nano device of the performance such as flexible, flexible, scalable, as micro-nano solar cell, ultracapacitor, sensor, display screen etc. have caused researcher's more and more keen interest.Go with the tide of historical development, the graphene fiber prepared in conjunction with the performance such as mechanics, electricity, calorifics of Graphene excellence, just obtains scientists once proposition and studies widely.
In graphene fiber preparation, wet spinning because its mild condition, technique are simple, be easy to large-scale production and cause it to become preparation technology the most common.In the wet spinning process of graphene fiber, spinning solution used is generally graphene oxide concentrated solution, current preparation-obtained graphene oxide solution, need through ultrasonic, dialysis or the process such as preexpanding, and then obtain wet spinning graphene oxide solution, then reduce after wet spinning graphene oxide solution being carried out wet spinning, just can obtain graphene fiber.But wet spinning graphene oxide solution complex steps prepared by this preparation method, complex process, cost are high, are therefore difficult to accomplish scale production.
Summary of the invention
In view of this; the technical problem to be solved in the present invention is to provide a kind of wet spinning graphene oxide solution and preparation method thereof; adopt preparation method's step of wet spinning graphene oxide solution provided by the invention simple, condition is easy to control, and can accomplish scale production.
The invention provides a kind of preparation method of wet spinning graphene oxide solution, comprise the following steps:
Graphene oxide solution is carried out centrifugal concentrating, obtains wet spinning graphene oxide solution.
Preferably, described graphene oxide solution is standby by improvement Hummers legal system.
Preferably, described improvement Hummers method is:
A) graphite and nitrate are dissolved in mix and blend in the concentrated sulfuric acid, add potassium permanganate, stir, leave standstill, obtain intermediate reaction liquid;
B) add in described intermediate reaction liquid deionized water and hydrogen peroxide react after centrifugal washing, obtain graphene oxide solution.
Preferably, described nitrate is potassium nitrate or sodium nitrate.
Preferably, centrifugal washing is carried out by the following method:
A) under the condition of 10000 ~ 14000 revs/min, centrifugal washing 8 ~ 10min is carried out by adding the end reaction liquid obtained after deionized water and hydrogen peroxide react in intermediate reaction liquid, until there is the brown layer of graphene oxide, remove supernatant and pipette collection graphene oxide layer;
B) bottom sediment is merged, a) continue centrifugal washing 3 ~ 5 times according to step, merge the graphene oxide layer after above-mentioned centrifugal washing, obtain graphene oxide solution.
Preferably, in step B) in described centrifugal water-washing process, also comprise concussion or stir.
Preferably, the rotating speed of described centrifugal concentrating is 12000 ~ 14000 revs/min, and the time is 30 ~ 40min, and the number of times of centrifugal concentrating is 2 ~ 3 times.
Present invention also offers one and prepare wet spinning graphene oxide solution by above-mentioned preparation method.
Present invention also offers a kind of preparation method of graphene fiber, comprise the following steps:
A) wet spinning graphene oxide solution will be prepared by above-mentioned preparation method and inject crosslinking agent coagulating bath solution, and carry out wet spinning, obtain graphene oxide fiber;
B) described graphene oxide fiber is reduced, obtain graphene fiber.
Preferably, described crosslinking agent coagulating bath solution is ethylenediamine/acetic acid/water/alcohol mixeding liquid, polyetheramine/acetic acid/water mixed liquor, polyamide-amide dendritic/water/alcohol mixeding liquid or 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride/I-hydroxybenzotriazole/water/alcohol mixeding liquid.
Preferably, the method for described reduction comprises the reduction of employing reductant or high temperature cabonization reduction, and described reductant is selected from hydroiodic acid or hydrazine hydrate.
Invention additionally provides a kind of graphene fiber prepared by above-mentioned preparation method.
Compared with prior art, the invention provides a kind of preparation method of wet spinning graphene oxide solution, comprise the following steps: graphene oxide solution is carried out centrifugal concentrating, obtain wet spinning graphene oxide solution.Graphene oxide solution is carried out centrifugal concentrating and is just obtained final wet spinning graphene oxide solution by the present invention.The preparation method of this wet spinning graphene oxide solution simplifies operating process, and eliminate ultrasonic, dialysis and the process such as preexpanding, experiment preparation process is simple, and condition is easy to control, and can accomplish scale production.In addition, preparation method provided by the invention prepares wet spinning dense graphene oxide solution steady quality, good water solubility, concentration graphene fiber size that is controlled, that obtain easily are adjusted.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the graphene oxide in the wet spinning graphene oxide solution of embodiment 1 preparation;
Fig. 2 is the atomic force microscopy of the graphene oxide in the wet spinning graphene oxide solution of embodiment 1 preparation;
Fig. 3 is the corresponding altitude curve figure of AFM Analysis of the graphene oxide in the wet spinning graphene oxide solution of embodiment 1 preparation;
Fig. 4 is the pictorial diagram of graphene oxide fiber prepared by embodiment 4;
Fig. 5 is the pictorial diagram of spirality graphene oxide fiber prepared by embodiment 4;
Fig. 6 is the stereoscan photograph of graphene oxide fiber prepared by embodiment 4;
Fig. 7 is the stereoscan photograph of graphene fiber prepared by embodiment 4;
Fig. 8 is graphene oxide fiber and the graphene fiber extension test figure of embodiment 4 preparation;
Fig. 9 is graphene oxide fiber and the graphene fiber X-ray diffractogram of embodiment 4 preparation;
Figure 10 is the stereoscan photograph of graphene oxide fiber prepared by embodiment 5;
Figure 11 is the stereoscan photograph of graphene oxide fiber prepared by embodiment 6;
Figure 12 is the stereoscan photograph of graphene oxide fiber prepared by embodiment 7.
Detailed description of the invention
The invention provides a kind of preparation method of wet spinning graphene oxide solution, comprise the following steps:
Graphene oxide solution is carried out centrifugal concentrating, obtains wet spinning graphene oxide solution.
The present invention, using graphene oxide solution as raw material, can obtain wet spinning graphene oxide solution by centrifugal concentrating.
In the present invention, described graphene oxide solution is standby preferably by the Hummers legal system of improvement.The Hummers method of described improvement is
A) graphite and nitrate are dissolved in mix and blend in the concentrated sulfuric acid, add potassium permanganate, stir, leave standstill, obtain intermediate reaction liquid;
B) add in described intermediate reaction liquid deionized water and hydrogen peroxide react after centrifugal washing, obtain graphene oxide solution.
First graphite and nitrate are dissolved in mix and blend in the concentrated sulfuric acid by the present invention, wherein, the mass ratio of described graphite and nitrate is (1 ~ 2): (1 ~ 3), in some embodiments of the invention, the mass ratio of described graphite and nitrate is 1:(0.5 ~ 3); The mass ratio of graphite and potassium permanganate is 1:(3 ~ 5), be preferably 1:(3.5 ~ 4.5); The mass ratio of graphite and the concentrated sulfuric acid is 1:(30 ~ 80), be preferably 1:(40 ~ 70).The concentration of the described concentrated sulfuric acid is 98wt%.Nitrate of the present invention is preferably potassium nitrate or sodium nitrate.The present invention is to the not special restriction of the method for described mix and blend, well known to a person skilled in the art the method for mix and blend, in the present invention, the rotating speed of described mix and blend is preferably 150 ~ 250 revs/min, and the time of mix and blend is preferably 20 ~ 40min.
After mix and blend terminates, then add potassium permanganate, stir, leave standstill, obtain intermediate reaction liquid.The mass ratio of described graphite and potassium permanganate is 1:(3 ~ 5), be preferably 1:(3.5 ~ 4.5).Described potassium permanganate is slowly progressively added into graphite and nitrate is dissolved in the mixed solution of the concentrated sulfuric acid, and the time of described interpolation is 40 ~ 60min, is preferably 45 ~ 55min.After adding potassium permanganate, continue agitating solution, the rotating speed of described stirring is preferably 150 ~ 250 revs/min, and the time of stirring is preferably 12 ~ 24 hours.After stirring terminates, left standstill by the mixed solution obtained, the described standing time is preferably 5 ~ 10 days, is more preferably 6 ~ 9 days.In the process left standstill, preferably described mixed solution is carried out artificial stirring 2 ~ 4 times.
After obtaining intermediate reaction liquid, in described reactant liquor, add deionized water and hydrogen peroxide reacts.Wherein, the mass ratio of described graphite and deionized water is 1:(40 ~ 200), be preferably 1:(50 ~ 180); The mass ratio of described graphite and hydrogen peroxide is 1:(6 ~ 10), be preferably 1:(7 ~ 9).The addition manner of deionized water of the present invention and hydrogen peroxide is preferably stirring reaction liquid limit, limit and adds deionized water and hydrogen peroxide.After reaction terminates, obtain end reaction liquid.
Described end reaction liquid is carried out centrifugal washing, obtains graphene oxide solution.In the present invention, described centrifugal washing is preferably carried out in the following manner:
Under the condition of 10000 ~ 14000 revs/min, carry out centrifugal washing 8 ~ 10min, until there is the brown layer of graphene oxide, remove supernatant and pipette collection graphene oxide layer, maintain overall solution volume in this process constant;
Merged by bottom sediment, continue centrifugal washing 3 ~ 5 times according to the method described above, merge the graphene oxide layer after above-mentioned centrifugal washing, obtain graphene oxide solution, described graphene oxide solution is graphene oxide solution of not dialysing.
In addition, the present invention is in centrifugal water-washing process, and the step also comprising concussion or stir, with the dispersion of accelerating oxidation Graphene.
Described graphene oxide solution is carried out centrifugal concentrating, goes supernatant and low viscosity upper strata small pieces graphene oxide solution, take out lower floor's high viscosity graphene oxide solution.The centrifugal rotational speed of described centrifugal concentrating is 12000 ~ 14000 revs/min, is preferably 12500 ~ 13500 revs/min; Time is 30 ~ 40min; Number of times is 2 ~ 3 times.Collect the high viscosity graphene oxide solution after centrifugal concentrating, obtain final wet spinning graphene oxide solution.
Present invention also offers a kind of wet spinning graphene oxide solution prepared by above-mentioned preparation method.
Present invention also offers a kind of preparation method of graphene fiber, it is characterized in that, comprise the following steps:
A) above-mentioned wet spinning graphene oxide solution is injected crosslinking agent coagulating bath solution, carry out wet spinning, obtain graphene oxide fiber;
B) described graphene oxide fiber is reduced, obtain graphene fiber.
Described wet spinning graphene oxide is carried out wet spinning by the present invention, obtains graphene oxide fiber.Concrete, described wet spinning graphene oxide solution is mixed with ion crosslinking agent, carries out wet spinning, obtain graphene oxide fiber.Described crosslinking agent coagulating bath solution is ethylenediamine/acetic acid/water/alcohol mixeding liquid, polyetheramine/acetic acid/water mixed liquor, polyamide-amide dendritic/water/alcohol mixeding liquid or 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride/I-hydroxybenzotriazole/water/alcohol mixeding liquid.In described ethylenediamine/acetic acid/water/alcohol mixeding liquid, the mass fraction of described ethylenediamine is 0.3wt% ~ 0.6wt%, and the mass fraction of described acetic acid is 0.08wt% ~ 0.12wt%, volume ratio 1:(3 ~ 5 of described second alcohol and water).In described polyamide-amide dendritic/water/alcohol mixeding liquid, the volume fraction of described polyamide-amide dendritic is 0.08% ~ 0.12%, volume ratio 1:(0.8 ~ 1.2 of described second alcohol and water).In described 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride/I-hydroxybenzotriazole/water/alcohol mixeding liquid, the mass fraction of described 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride is respectively the mass fraction 0.02wt% ~ 0.06wt% of 0.04wt% ~ 0.10wt%, described I-hydroxybenzotriazole, and described water and ethanol contend are than 1:(0.8 ~ 1.2).
The present invention, to the not special restriction of the method for described wet spinning, well known to a person skilled in the art the method for wet spinning.
After obtaining graphene oxide fiber, described graphene oxide fiber is reduced, obtains graphene fiber.The present invention, to the not special restriction of the method for described reduction, well known to a person skilled in the art the method for graphene oxide fiber reduction.In the present invention, the method for described reduction comprises the reduction of employing reductant or high temperature cabonization reduction, and described reductant is selected from hydroiodic acid or hydrazine hydrate, is preferably hydroiodic acid.The concentration of the hydroiodic acid reductant that described graphene oxide fiber is used is 20wt% ~ 60wt%, and be preferably 30wt%-40wt%, reduction temperature is 70 ~ 100 DEG C, is preferably 80 ~ 90 DEG C.
After being reduced by described graphene oxide fiber, also comprise the step that washing is dry.The present invention does not have special restriction to the method that described washing is dry, well known to a person skilled in the art the method that washing is dry.The present invention preferably adopts water to wash graphene oxide fiber.The temperature of described drying is 80 DEG C, and the time of described drying is 12h.
Present invention also offers the graphene fiber that a kind of above-mentioned preparation method prepares.
Graphene oxide solution is carried out centrifugal concentrating and is just obtained final wet spinning graphene oxide solution by the present invention.The preparation method of this wet spinning graphene oxide solution simplifies operating process, eliminates the processes such as ultrasonic, dialysis, preexpanding, and experiment preparation process is simple, and condition is easy to control, and can accomplish scale production.In addition, preparation method provided by the invention prepares wet spinning dense graphene oxide solution steady quality, good water solubility, concentration graphene fiber size that is controlled, that obtain easily are adjusted.
In order to understand the present invention further, be described wet spinning graphene oxide solution provided by the invention and preparation method thereof and a kind of graphene fiber and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
5g graphite and 3.75g sodium nitrate are dissolved in 160ml98% sulfuric acid solution, 200 revs/min of mechanical agitation 30min, slowly progressively add 20g potassium permanganate, the interpolation time is at about 40min, continue to stir 20h, static 7 days, slow interpolation 300ml deionized water and 20ml hydrogen peroxide (adding while stirring), centrifugal washing (10000 revs/min repeatedly, 10min) to occurring the brown layer of graphene oxide (it is constant that this process maintains overall solution volume), outwell supernatant and pipette brown oxidation graphene layer (without spar coloured particles) in the middle of collection, bottom sediment merges and continues centrifugal washing 3 times, and then graphene oxide solution of tentatively not dialysed, by further for this solution centrifugal concentrating (14000 revs/min, 30min, go supernatant and low viscosity upper strata small pieces graphene oxide solution, take out lower floor's high viscosity graphene oxide solution (note bottom is removed without spar coloured particles), collect and continue repeated centrifugation and concentrate 2-3 time), just wet spinning graphene oxide solution is obtained.
The wet spinning graphene oxide solution prepared by the present embodiment carries out transmission electron microscope observation, the results are shown in Figure 1, Fig. 1 is the transmission electron microscope photo of wet spinning graphene oxide solution prepared by embodiment 1, the smooth free from admixture of surface of graphene oxide as shown in Figure 1, is uniformly dispersed in the aqueous solution, piles up and manifest less and lamella is larger.
The wet spinning graphene oxide solution prepared by the present embodiment carries out atomic force microscope observation, the results are shown in Figure 2 and Fig. 3, Fig. 2 is the atomic force microscopy of wet spinning graphene oxide solution prepared by embodiment 1, and Fig. 3 is the corresponding altitude curve figure of AFM Analysis of the graphene oxide in the wet spinning graphene oxide solution of embodiment 1 preparation.From Fig. 2 and Fig. 3, in the wet spinning graphene oxide solution of preparation, the lamellar spacing of graphene oxide is about 1nm, is single-layer graphene oxide structure.
Embodiment 2
5g graphite and 4g potassium nitrate are dissolved in 180ml98% sulfuric acid solution, 200 revs/min of mechanical agitation 25min, slowly progressively add 20g potassium permanganate, the interpolation time is at about 40min, continue to stir 20h, static 5 days, slow interpolation 400ml deionized water and 30ml hydrogen peroxide (adding while stirring), centrifugal washing (8000 revs/min repeatedly, 10min) to occurring the brown layer of graphene oxide (it is constant that this process maintains overall solution volume), outwell supernatant and pipette brown oxidation graphene layer (without spar coloured particles) in the middle of collection, bottom sediment merges and continues centrifugal washing 3 times, and then graphene oxide solution of tentatively not dialysed, by further for this solution centrifugal concentrating (14000 revs/min, 30min, go supernatant and low viscosity upper strata small pieces graphene oxide solution, take out lower floor's high viscosity graphene oxide solution (note bottom is removed without spar coloured particles), collect and continue repeated centrifugation and concentrate 2-3 time), just wet spinning graphene oxide solution is obtained.
Embodiment 3
By 5g Graphene, 2g sodium nitrate and 2g potassium nitrate are dissolved in 160ml98% sulfuric acid solution, 200 revs/min of mechanical agitation 30min, slowly progressively add 20g potassium permanganate, the interpolation time is at about 40min, continue to stir 24h, static 6 days, slow interpolation 400ml deionized water and 30ml hydrogen peroxide (adding while stirring), centrifugal washing (8000 revs/min repeatedly, 15min) to occurring the brown layer of graphene oxide (it is constant that this process maintains overall solution volume), outwell supernatant and pipette brown oxidation graphene layer (without spar coloured particles) in the middle of collection, bottom sediment merges and continues centrifugal washing 3 times, and then graphene oxide solution of tentatively not dialysed, by further for this solution centrifugal concentrating (14000 revs/min, 30min, go supernatant and low viscosity upper strata small pieces graphene oxide solution, take out lower floor's high viscosity graphene oxide solution (note bottom is removed without spar coloured particles), collect and continue repeated centrifugation and concentrate 2-3 time), just wet spinning graphene oxide solution is obtained.
Embodiment 4
For verifying the feasibility of the wet spinning graphene oxide solution spinning of preparation further, wet spinning graphene oxide solution embodiment 1 prepared injects ethylenediamine/acetic acid/water/alcohol mixeding liquid, and wet spinning obtains graphene oxide fiber.Wherein, ethylenediamine/acetic acid/water/alcohol mixeding liquid comprises 5ml ethylenediamine, 1ml glacial acetic acid, 800ml water and 200ml ethanol.
Enter in 30%HI solution by the described graphene oxide fiber impregnation prepared, 90 DEG C, 12h reduction just obtains graphene fiber.Concrete pattern is shown in Fig. 4-7, Fig. 4 is the pictorial diagram of graphene oxide fiber prepared by embodiment 4, Fig. 5 is the pictorial diagram of spirality graphene oxide fiber prepared by embodiment 4, Fig. 6 is the stereoscan photograph of graphene oxide fiber prepared by embodiment 4, Fig. 7 is the stereoscan photograph of graphene fiber prepared by embodiment 4, graphene oxide fiber diminishes through HI reduction fibre diameter, Graphene is piled up more tight, the dense graphene oxide solution of the wet spinning prepared by the known the method for Fig. 4-7 can be directly used in wet spinning spinning to prepare graphene oxide fiber and then to obtain graphene fiber.Fig. 8 is the graphene oxide fiber prepared of embodiment 4 and graphene fiber extension test figure, and in Fig. 8,1 is the extension test curve of graphene fiber, and 2 is the extension test curve of graphene oxide fiber.The TENSILE STRENGTH of graphene oxide fiber and graphene fiber is respectively 123MPa, 384MPa as shown in Figure 8, and graphene fiber provided by the invention and graphene oxide fiber have good tensile property.Fig. 9 is the graphene oxide fiber prepared of embodiment 4 and graphene fiber X-ray diffractogram, and in Fig. 9,1 is the X-ray diffractogram of graphene fiber, and 2 is the X-ray diffractogram of graphene oxide fiber.Graphene oxide fiber and graphene fiber graphene oxide fiber reduce through HI as shown in Figure 9, graphene sheet layer interlamellar spacing reduces (calculate according to bragg's formula, interlamellar spacing by
(2 θ=9.43 °) reduce to
(2 θ=24.49 °)), echo mutually with scanning result.
Embodiment 5
Wet spinning graphene oxide solution embodiment 1 prepared injects polyetheramine/acetic acid/water mixed liquor, and wet spinning obtains graphene oxide fiber.
Wherein, polyetheramine (mean molecule quantity 2000) 5ml, glacial acetic acid 3ml in described polyetheramine/acetic acid/water mixed liquor, water volume is 400ml.Concrete bodily form looks are shown in Figure 10, and Figure 10 is the scanning electron microscope (SEM) photograph of graphene oxide fiber prepared by embodiment 5, and in the graphene oxide prepared as shown in Figure 10, graphene oxide axially-aligned obviously, smooth surface, arrangement be tight.
Embodiment 6
Wet spinning graphene oxide solution embodiment 1 prepared injects polyamide-amide dendritic/water/alcohol mixeding liquid, and wet spinning obtains graphene oxide fiber.
Wherein, polyamide-amide dendritic in described polyamide-amide dendritic/water/alcohol mixeding liquid (ethylenediamine core, 0.0 generation 20% methanol solution) 1ml, water and ethanol contend are 500ml.Figure 11 is the scanning electron microscope (SEM) photograph of graphene oxide fiber prepared by embodiment 11, and in the graphene oxide prepared as shown in Figure 11, graphene oxide axially-aligned is obvious.
Embodiment 7
Wet spinning graphene oxide solution embodiment 1 prepared injects 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride/I-hydroxybenzotriazole/water/alcohol mixeding liquid, and wet spinning obtains graphene oxide fiber.
Wherein, 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride 0.165g, I-hydroxybenzotriazole 0.101g in described 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride/I-hydroxybenzotriazole/water/alcohol mixeding liquid, water and ethanol contend are 500ml.Figure 12 is the scanning electron microscope (SEM) photograph of graphene oxide fiber prepared by embodiment 7, and in the graphene oxide prepared as shown in Figure 12, graphene oxide axially-aligned obviously, smooth surface, arrangement be tight.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (12)
1. a preparation method for wet spinning graphene oxide solution, is characterized in that, comprises the following steps: graphene oxide solution is carried out centrifugal concentrating, obtains wet spinning graphene oxide solution.
2. preparation method according to claim 1, is characterized in that, described graphene oxide solution is standby by the Hummers legal system of improvement.
3. preparation method according to claim 2, is characterized in that, the Hummers method of described improvement is:
A) graphite and nitrate are dissolved in mix and blend in the concentrated sulfuric acid, add potassium permanganate, stir, leave standstill, obtain intermediate reaction liquid;
B) add in described intermediate reaction liquid deionized water and hydrogen peroxide react after centrifugal washing, obtain graphene oxide solution.
4. preparation method according to claim 3, is characterized in that, described nitrate is potassium nitrate or sodium nitrate.
5. preparation method according to claim 3, is characterized in that, described centrifugal washing is carried out by the following method:
A) under the condition of 10000 ~ 14000 revs/min, centrifugal washing 8 ~ 10min is carried out by adding the end reaction liquid obtained after deionized water and hydrogen peroxide react in intermediate reaction liquid, until there is the brown layer of graphene oxide, remove supernatant and pipette collection graphene oxide layer;
B) bottom sediment is merged, a) continue centrifugal washing 3 ~ 5 times according to step, merge the graphene oxide layer after above-mentioned centrifugal washing, obtain graphene oxide solution.
6. preparation method according to claim 5, is characterized in that, in step B) in described centrifugal water-washing process, also comprise concussion or stir.
7. preparation method according to claim 1, is characterized in that, the rotating speed of described centrifugal concentrating is 12000 ~ 14000 revs/min, and the time is 30 ~ 40min, and the number of times of centrifugal concentrating is 2 ~ 3 times.
8. one kind prepares wet spinning graphene oxide solution by the preparation method of claim 1 ~ 7 any one claim.
9. a preparation method for graphene fiber, is characterized in that, comprises the following steps:
A) preparation method of claim 1 ~ 7 any one claim is prepared wet spinning graphene oxide solution and inject crosslinking agent coagulating bath solution, carry out wet spinning, obtain graphene oxide fiber;
B) described graphene oxide fiber is reduced, obtain graphene fiber.
10. preparation method according to claim 9, it is characterized in that, described crosslinking agent coagulating bath solution is ethylenediamine/acetic acid/water/alcohol mixeding liquid, polyetheramine/acetic acid/water mixed liquor, polyamide-amide dendritic/water/alcohol mixeding liquid or 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride/I-hydroxybenzotriazole/water/alcohol mixeding liquid.
11. preparation methods according to claim 9, is characterized in that, the method for described reduction comprises the reduction of employing reductant or high temperature cabonization reduction, and described reductant is selected from hydroiodic acid or hydrazine hydrate.
12. 1 kinds of graphene fibers prepared by the preparation method of claim 9 ~ 11 any one claim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510330999.0A CN105088415B (en) | 2015-06-15 | 2015-06-15 | A kind of wet spinning graphene oxide solution and preparation method thereof and a kind of graphene fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510330999.0A CN105088415B (en) | 2015-06-15 | 2015-06-15 | A kind of wet spinning graphene oxide solution and preparation method thereof and a kind of graphene fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105088415A true CN105088415A (en) | 2015-11-25 |
| CN105088415B CN105088415B (en) | 2018-01-05 |
Family
ID=54569707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510330999.0A Active CN105088415B (en) | 2015-06-15 | 2015-06-15 | A kind of wet spinning graphene oxide solution and preparation method thereof and a kind of graphene fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105088415B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105256408A (en) * | 2015-11-29 | 2016-01-20 | 南京新月材料科技有限公司 | Graphene oxide fibers and preparation method thereof |
| CN106087114A (en) * | 2016-06-27 | 2016-11-09 | 南京邮电大学 | A kind of graphene oxide fiber and preparation method thereof |
| CN107164817A (en) * | 2017-06-06 | 2017-09-15 | 烟台市烯能新材料股份有限公司 | A kind of preparation method of graphene graphene oxide composite nylon fiber |
| CN107893266A (en) * | 2017-11-20 | 2018-04-10 | 常宁市帝棉纺织制衣有限公司 | A kind of preparation method of High-performance graphene fiber |
| CN108070237A (en) * | 2016-11-15 | 2018-05-25 | 北京特生物化工有限公司 | A kind of graphene fiber composite material ultrahigh speed flywheel, its preparation method and its application |
| CN109137141A (en) * | 2018-07-30 | 2019-01-04 | 嘉兴学院 | A kind of graphene/fullerene hybridized fiber and preparation method thereof and application method |
| CN110115778A (en) * | 2019-06-10 | 2019-08-13 | 浙江德康医疗器械有限公司 | A kind of high-antiwear self-lubricating orthopaedics implant articular surface friction is secondary |
| CN110318112A (en) * | 2019-07-23 | 2019-10-11 | 东华大学 | A kind of high-strength graphene oxide composite fibre of anti-neutron irradiation and preparation method thereof |
| CN110629325A (en) * | 2019-09-30 | 2019-12-31 | 华中科技大学 | Multi-element doped graphene fiber, and preparation and application thereof |
| CN110699779A (en) * | 2019-11-01 | 2020-01-17 | 常州富烯科技股份有限公司 | Graphene oxide fiber cloth and preparation method thereof, and graphene gas diffusion film and preparation method thereof |
| CN111719212A (en) * | 2020-01-13 | 2020-09-29 | 中原工学院 | Preparation method of flexible graphene conductive yarn capable of being woven |
| CN112643036A (en) * | 2019-10-10 | 2021-04-13 | 中国科学技术大学 | Preparation method of graphene-based lithium metal composite material |
| CN112652741A (en) * | 2019-10-10 | 2021-04-13 | 中国科学技术大学 | Preparation method of graphene-based composite micron rod loaded with positive active material |
| CN113388905A (en) * | 2021-06-15 | 2021-09-14 | 广西大学 | Self-crimping preparation method and application of hollow graphene fiber |
| JP2022531167A (en) * | 2019-04-30 | 2022-07-06 | 青島大学 | Method for producing graphene oxide fiber and obtained fiber |
| CN114990734A (en) * | 2022-06-07 | 2022-09-02 | 苏州大学 | Graphene assembly fiber and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449460A (en) * | 2000-09-02 | 2003-10-15 | 纺织和塑料研究协会图林根研究院 | Method for producing cellulose fibers and cellulose filament yarns |
| CN102275908A (en) * | 2011-07-07 | 2011-12-14 | 中南大学 | Preparation method of graphene material |
| CN102534869A (en) * | 2012-01-05 | 2012-07-04 | 浙江大学 | Method for preparing high-strength conductive graphene fiber by large-size graphene oxide sheet |
| CN102534868A (en) * | 2011-12-26 | 2012-07-04 | 浙江大学 | Preparation method for high strength macro graphene conductive fiber |
| KR101193970B1 (en) * | 2011-03-15 | 2012-10-24 | 한양대학교 산학협력단 | Graphene fiber and method for preparing the same |
| CN102817111A (en) * | 2012-08-02 | 2012-12-12 | 中国科学技术大学 | Preparation method and product of one-dimensional macroscopic graphene fibers |
| CN103806128A (en) * | 2014-01-15 | 2014-05-21 | 北京理工大学 | Graphene oxide fiber and preparation method and application thereof |
-
2015
- 2015-06-15 CN CN201510330999.0A patent/CN105088415B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449460A (en) * | 2000-09-02 | 2003-10-15 | 纺织和塑料研究协会图林根研究院 | Method for producing cellulose fibers and cellulose filament yarns |
| KR101193970B1 (en) * | 2011-03-15 | 2012-10-24 | 한양대학교 산학협력단 | Graphene fiber and method for preparing the same |
| EP2687626A2 (en) * | 2011-03-15 | 2014-01-22 | IUCF-HYU (Industry-University Cooperation Foundation Hanyang University) | Graphene fiber and method for manufacturing same |
| CN102275908A (en) * | 2011-07-07 | 2011-12-14 | 中南大学 | Preparation method of graphene material |
| CN102534868A (en) * | 2011-12-26 | 2012-07-04 | 浙江大学 | Preparation method for high strength macro graphene conductive fiber |
| CN102534869A (en) * | 2012-01-05 | 2012-07-04 | 浙江大学 | Method for preparing high-strength conductive graphene fiber by large-size graphene oxide sheet |
| CN102817111A (en) * | 2012-08-02 | 2012-12-12 | 中国科学技术大学 | Preparation method and product of one-dimensional macroscopic graphene fibers |
| CN103806128A (en) * | 2014-01-15 | 2014-05-21 | 北京理工大学 | Graphene oxide fiber and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 梨花犹殇: ""氧化石墨烯还原的评价标准"", 《百度文库》 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105256408A (en) * | 2015-11-29 | 2016-01-20 | 南京新月材料科技有限公司 | Graphene oxide fibers and preparation method thereof |
| CN106087114A (en) * | 2016-06-27 | 2016-11-09 | 南京邮电大学 | A kind of graphene oxide fiber and preparation method thereof |
| CN108070237A (en) * | 2016-11-15 | 2018-05-25 | 北京特生物化工有限公司 | A kind of graphene fiber composite material ultrahigh speed flywheel, its preparation method and its application |
| CN107164817A (en) * | 2017-06-06 | 2017-09-15 | 烟台市烯能新材料股份有限公司 | A kind of preparation method of graphene graphene oxide composite nylon fiber |
| CN107893266A (en) * | 2017-11-20 | 2018-04-10 | 常宁市帝棉纺织制衣有限公司 | A kind of preparation method of High-performance graphene fiber |
| CN109137141A (en) * | 2018-07-30 | 2019-01-04 | 嘉兴学院 | A kind of graphene/fullerene hybridized fiber and preparation method thereof and application method |
| JP2022531167A (en) * | 2019-04-30 | 2022-07-06 | 青島大学 | Method for producing graphene oxide fiber and obtained fiber |
| JP7377564B2 (en) | 2019-04-30 | 2023-11-10 | 青島大学 | Method for producing graphene oxide fiber and obtained fiber |
| CN110115778A (en) * | 2019-06-10 | 2019-08-13 | 浙江德康医疗器械有限公司 | A kind of high-antiwear self-lubricating orthopaedics implant articular surface friction is secondary |
| CN110318112B (en) * | 2019-07-23 | 2022-04-29 | 东华大学 | Neutron radiation prevention high-strength graphene oxide composite fiber and preparation method thereof |
| CN110318112A (en) * | 2019-07-23 | 2019-10-11 | 东华大学 | A kind of high-strength graphene oxide composite fibre of anti-neutron irradiation and preparation method thereof |
| CN110629325A (en) * | 2019-09-30 | 2019-12-31 | 华中科技大学 | Multi-element doped graphene fiber, and preparation and application thereof |
| CN112652741A (en) * | 2019-10-10 | 2021-04-13 | 中国科学技术大学 | Preparation method of graphene-based composite micron rod loaded with positive active material |
| CN112652741B (en) * | 2019-10-10 | 2022-09-06 | 中国科学技术大学 | Preparation method of graphene-based composite micron rod loaded with positive active material |
| CN112643036A (en) * | 2019-10-10 | 2021-04-13 | 中国科学技术大学 | Preparation method of graphene-based lithium metal composite material |
| CN112643036B (en) * | 2019-10-10 | 2024-02-23 | 中国科学技术大学 | Preparation method of graphene-based lithium metal composite material |
| CN110699779B (en) * | 2019-11-01 | 2022-05-13 | 常州富烯科技股份有限公司 | Graphene oxide fiber cloth and preparation method thereof, and graphene gas diffusion film and preparation method thereof |
| CN110699779A (en) * | 2019-11-01 | 2020-01-17 | 常州富烯科技股份有限公司 | Graphene oxide fiber cloth and preparation method thereof, and graphene gas diffusion film and preparation method thereof |
| CN111719212A (en) * | 2020-01-13 | 2020-09-29 | 中原工学院 | Preparation method of flexible graphene conductive yarn capable of being woven |
| CN113388905A (en) * | 2021-06-15 | 2021-09-14 | 广西大学 | Self-crimping preparation method and application of hollow graphene fiber |
| CN114990734A (en) * | 2022-06-07 | 2022-09-02 | 苏州大学 | Graphene assembly fiber and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105088415B (en) | 2018-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105088415A (en) | Graphene oxide solution for wet spinning and preparation method thereof, graphene fiber and preparation method of graphene fiber | |
| CN106410223B (en) | N doping carbonization bacteria cellulose/graphene/platinum composite nano materials and preparation method thereof | |
| Dai et al. | Boosting the electrochemical performance of nitrogen-oxygen co-doped carbon nanofibers based supercapacitors through esterification of lignin precursor | |
| CN104264260B (en) | A kind of graphene/nanometer cellulose composite fiber and preparation method thereof | |
| Wang et al. | Honeycomb-structured carbon aerogels from nanocellulose and skin secretion of Andrias davidianus for highly compressible binder-free supercapacitors | |
| CN102974838B (en) | Method for preparing graphene loaded nano nickel composite powder material by hydrothermal method | |
| CN109244484A (en) | A kind of preparation method of porous graphene/carbon nano tube flexible self-supported membrane material | |
| Wang et al. | Anatase titania coated CNTs and sodium lignin sulfonate doped chitosan proton exchange membrane for DMFC application | |
| CN104692368B (en) | A kind of Graphene prepared as raw material with cellulose and preparation method thereof | |
| CN105439133B (en) | A kind of preparation method of elecrtonegativity single-layer graphene | |
| CN107032343A (en) | The preparation method of wet spinning graphene oxide solution and graphene fiber | |
| CN106046404B (en) | NafionTMModifiedTwo-dimensional layered material nanosheet-polymer hybrid proton exchange membrane and preparation method thereof | |
| CN104021948B (en) | Nanofiber-shaped three-dimensional nickel hydroxide/carbon nanotube composite material as well as preparation method and application thereof | |
| CN110289173A (en) | A kind of bacteria cellulose-base flexibility nitrogen-doped graphene electrode material for super capacitor of high specific capacitance and its preparation method and application | |
| CN104947227A (en) | Polyvinylpyrrolidone/graphene composite nanofiber material and preparation method thereof | |
| CN103966644A (en) | Preparation method for graphene/macromolecule emulsion composite film material | |
| CN105810455A (en) | Method for preparing graphene/polyaniline composite film electrode | |
| Hou et al. | Preparation of flexible composite electrode with bacterial cellulose (BC)-derived carbon aerogel supported low loaded NiS for methanol electrocatalytic oxidation | |
| CN111925776B (en) | Preparation method of polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite photo-thermal material | |
| CN102145283A (en) | Supported platinum catalyst for fuel cell and preparation method thereof | |
| CN106898435A (en) | A kind of preparation method of high-bulk-density flexible electrode material | |
| CN102974341A (en) | Method for preparing proton exchange membrane fuel cell catalyst with nanocrystalline structure | |
| CN107104005B (en) | A kind of preparation method of NiO@graphene fiber super capacitor electrode material | |
| CN106876155A (en) | A kind of preparation method of the conductive bafta based on CNT | |
| CN113083272A (en) | FeNxPreparation method of nano-particle doped bamboo-like carbon nano-tube |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |