CN107032343A - The preparation method of wet spinning graphene oxide solution and graphene fiber - Google Patents
The preparation method of wet spinning graphene oxide solution and graphene fiber Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The present invention relates to can wet spinning graphene oxide solution and graphene fiber preparation method, can wet spinning graphene oxide solution preparation method, comprise the following steps：(1) persulfate and phosphorus pentoxide are dissolved in the concentrated sulfuric acid and mixed, then added graphite and heated, stirred, stood, centrifuged, dried, obtain initial reactant；(2) described initial reactant is dissolved in the concentrated sulfuric acid and is slowly added to potassium permanganate and carry out ice-water bath, stirring, standing, centrifugation, obtain intermediate reaction liquid；(3) added into described intermediate reaction liquid and pickling, centrifugation washing are carried out after deionized water and hydrogen peroxide, obtain end reaction liquid.(4) the end reaction liquid is subjected to high speed centrifugation concentration, obtaining can wet spinning graphene oxide solution.This method is simple to operate, and condition is controllable, it is easy to large-scale production, and obtained graphene oxide degree of oxidation is high, good water solubility, steady quality.The preparation method of graphene fiber, including step：A) by above-mentioned preparation method obtain can wet spinning be injected into graphene oxide solution in coagulating bath, carry out wet spinning, obtain graphene oxide fiber；B) the graphene oxide fiber is reduced and post-processed, obtains being provided simultaneously with excellent tensile strength and high conduction performance graphene fiber.
Description
Technical field
The invention belongs to graphene oxide technical field, and in particular to one kind can wet spinning graphene oxide solution and
The preparation method of its preparation method and graphene fiber.
Technical background
Graphene is a kind of only single layer of carbon atom thickness, two-dimensional material in honeycomb lattice shape, its basic structural unit
It can be regarded as organic compound benzene hexatomic ring.Graphene possesses in white spectrum 2.3% absorptivity, high-specific surface area,
High carrier mobility, excellent electric conductivity, thermal property and mechanical performance.Due to the property that graphene is excellent, graphene
There are application, including electronics and optical field, production energy and storage energy, hybrid material, electricity in one very wide field
Catalytic applications, chemical sensor and DNA gene Electronic Testing Technologies etc..
With continuing to develop for electronic science and technology, people are also gradually stepped up to healthy living demand, and skill is innovated accordingly
Art emerges in an endless stream, and flexible wearable electronics is exactly one of them.The energy storage device such as ultracapacitor and lithium ion battery to it is light,
High-energy, high-flexibility and miniaturization development, especially ultracapacitor gradually show different macroshapes, and such as flat board is passed
System capacitor, wearable fibrous type capacitor etc..Stone with reference to prepared by the performances such as the excellent electricity of graphene, mechanics and calorifics
Black alkene fiber, has triggered scientists extensive concern and research after proposition.
In numerous preparation methods of graphene fiber, wet spinning is simple to operate because of its mild condition, it is easy to scale
Produce as most common preparation method.During wet spinning, spinning solution used is usually graphene oxide solution.
During graphene oxide solution is prepared, it is not necessary to by the complex process such as ultrasound and dialysis, prepare that degree of oxidation is higher, water
Dissolubility preferably can wet spinning graphene oxide solution, then graphene oxide fiber is obtained by wet spinning process, passed through
Graphene fiber is just obtained after crossing reduction.The graphene fiber reported at present still has very in terms of mechanical strength and electric conductivity
Big room for promotion, can be made by the method such as spinning solution and spinning technique optimization, post processing and be provided simultaneously with high tensile, height
The graphene fiber of electric conductivity.
The content of the invention
In consideration of it, the technical problem to be solved in the present invention be provide one kind can wet spinning graphene oxide solution and
Its preparation method, this method is simple to operate, and condition is easy to control, and degree of oxidation is high, good water solubility, is easy to large-scale production.
The invention provides it is a kind of can wet spinning graphene oxide solution preparation method, mainly including following step
Suddenly：
(1) by persulfate and phosphorus pentoxide be dissolved in the concentrated sulfuric acid mix, then add graphite heated,
Stir, stand, centrifuge, dry, obtain initial reactant；
(2) by described initial reactant be dissolved in the concentrated sulfuric acid and be slowly added to potassium permanganate carry out ice-water bath, it is stirring, quiet
Put, centrifuge, obtain intermediate reaction liquid；
(3) added into described intermediate reaction liquid and pickling, centrifugation washing are carried out after deionized water and hydrogen peroxide, obtained most
End reaction liquid.
(4) the end reaction liquid is subjected to high speed centrifugation concentration, obtaining can wet spinning graphene oxide solution.
The mass ratio of the graphite and persulfate is 1：The mass ratio of (0.25~2), preferably graphite and persulfate is
1：(0.5~1.5)；
The mass ratio of the graphite and phosphorus pentoxide is 1：(0.25~2)；The matter of preferable graphite and phosphorus pentoxide
Amount is than being 1：(1~2), more preferably 1：(1~1.5)；
The mass ratio of the graphite and the concentrated sulfuric acid is 1：(30~80), preferably 1：(40~60), the concentrated sulfuric acid it is dense
Spend for 98wt%；
The mass ratio of the graphite and potassium permanganate is 1：(3~7), preferably 1：(4~6).The potassium permanganate is slow
Progressively add, 1-2 spoons per minute.The addition time is 30~60min, preferably 40~50min.Add after potassium permanganate
Continue agitating solution, the speed of agitator is preferably 150~250 revs/min, and mixing time is preferably 1~3h.
Persulfate of the present invention is preferably potassium peroxydisulfate.
The method of the mixing is not specifically limited, is well known to a person skilled in the art the method for mixing
Can.In the present invention, the rotating speed of the mixing is preferably 150~250 revs/min, and time of mixing is preferably 30~
40min。
The graphite and the mass ratio of deionized water are 1：(20~60), preferably 1：(30~50).The addition time
For 100~200min, preferably 100~150min.
The mass ratio of the graphite and hydrogen peroxide is 1：(3~10), preferably 1：(4~8).The concentration of the hydrogen peroxide is
30wt%, the addition manner of hydrogen peroxide of the present invention is preferably side stirring reaction liquid while adding hydrogen peroxide.
Specifically, the pickling in described (3) step is to carry out pickling twice with 5% hydrochloric acid.
Specifically, the centrifugation washing in described (3) step is carried out by the following method：
A) reaction solution through pickling is carried out to 20~40min centrifugation washing under conditions of 8000~10000 revs/min,
Until brown occurs in graphene oxide, supernatant collection lower floor graphene oxide is removed.
B) sediment for being centrifuged out bottom merges, and continues to centrifuge washed several times with water according to step a), obtains graphene oxide
Solution.
In addition, the present invention is in centrifugation water-washing process, in addition to the step such as vibration or stirring, to promote graphene oxide
It is scattered.
Specifically, in described (4) step, end reaction liquid, which carries out high speed centrifugation concentration, to be included：Go supernatant and on
Layer low concentration, small pieces graphene oxide solution, take out lower floor's high concentration graphene oxide solution, and the centrifugal concentrating rotating speed is
8000~12000 revs/min, the time is 30~40min, and number of times is 2~3 times.Collect the high concentration oxygen graphite after centrifugal concentrating
Alkene solution, obtain it is final can wet spinning graphene oxide solution.It is preferred that, described centrifugal rotational speed is 10000-
12000 revs/min, the time is 30min, and number of times is 2 times, and time of repose is 2-3 days.
Present invention also offers the preparation method of graphene fiber, mainly include the following steps that：
A) by above-mentioned preparation method obtain can wet spinning be injected into graphene oxide solution in coagulating bath, carry out it is wet
Method spinning, obtains graphene oxide fiber；
B) the graphene oxide fiber is reduced, graphene fiber is obtained.
It is preferred that, described coagulating bath is anhydrous calcium chloride/water/alcohol mixeding liquid, sodium hydroxide/water/methyl alcohol mixed liquor
Any of with potassium hydroxide/water/methyl alcohol mixed liquor.
It is preferred that, described reducing agent is hydroiodic acid.The concentration of the hydroiodic acid is 20wt%~60wt%, is preferably
30wt%~45wt%.Reduction temperature is 80~120 DEG C, preferably 90~110 DEG C.
In the anhydrous calcium chloride/water/alcohol mixeding liquid, the mass fraction of the anhydrous calcium chloride is 5%~20%, institute
State the volume ratio 1 of second alcohol and water：(2~5).
In the sodium hydroxide/water/methyl alcohol mixed liquor, the mass fraction of the sodium hydroxide is 3%~8%, the first
The volume ratio of alcohol and water is 1:(0.3~0.8).
In the potassium hydroxide/water/methyl alcohol mixed liquor, the mass fraction of described potassium hydroxide is 3%~10%, described
The volume ratio of first alcohol and water is 1：(0.3~0.8).
The present invention is not specifically limited to the method for described wet spinning, and wet spinning process well known in the art is
Can.The restoring method of described graphene oxide fiber is as follows：Under the conditions of certain temperature, the electronation carried out in the solution
Method, is not particularly limited to reducing agent, and reducing agent preferably is hydroiodic acid.
After the present invention is reduced the graphene oxide fiber, in addition to the dry step of washing.The present invention is to institute
State the dry method of washing not specifically limited, it is well known in the art to wash dry method.Currently preferred water
Graphene fiber is washed with ethanol.The drying temperature is 30 DEG C, and the drying time is 12h.
Present invention also offers the graphene fiber obtained by above-mentioned preparation method.
Compared with prior art, the present invention provide can wet spinning graphene oxide solution degree of oxidation it is high, can
To be better dispersed in water, with good water solubility, concentration is controllable and steady quality.Meanwhile, graphene oxide solution
Synthesis technique is simply time saving, without processes such as complicated dialysis.Experimentation conditional is easily controllable, and scale metaplasia can be achieved
Production.Meanwhile, in graphene fiber preparation process, pass through the side such as spinning solution and spinning technique optimization, electronation and post processing
Method, enhances the interaction force between graphene sheet layer, is made and is provided simultaneously with excellent tensile strength, the graphite of high conduction performance
Alkene fiber.
Brief description of the drawings
Fig. 1 be embodiment 1 prepare can in wet spinning graphene oxide solution graphene oxide infrared spectrum.
Fig. 2 be embodiment 1 prepare can in wet spinning graphene oxide solution graphene oxide x-ray photoelectron
Spectrogram.
Fig. 3 be embodiment 1 prepare can in wet spinning graphene oxide solution graphene oxide transmission electron microscope picture.
Fig. 4 is graphene fiber pictorial diagram prepared by embodiment 2.
Fig. 5 is the field emission scanning electron microscope figure of graphene fiber prepared by embodiment 2.
Fig. 6 is graphene fiber cross section field emission scanning electron microscope figure prepared by embodiment 2.
Fig. 7 is the electric conductivity of graphene fiber prepared by embodiment 2.
Fig. 8 is graphene fiber extension test curve prepared by embodiment 2.
Fig. 9 is graphene fiber pictorial diagram prepared by embodiment 3.
Figure 10 is the field emission scanning electron microscope figure of graphene fiber prepared by embodiment 3.
Figure 11 is graphene oxide fiber pictorial diagram prepared by embodiment 4.
Figure 12 is graphene fiber field emission scanning electron microscope figure prepared by embodiment 4.
Embodiment
To further understand the present invention, with reference to embodiment, the present invention is described in detail, protection model of the invention
Enclose and be not limited by the following examples.
Embodiment 1
8g potassium peroxydisulfates and 8g phosphorus pentoxides are dissolved in the concentrated sulfuric acids of 40ml 98%, in 200 revs/min of mechanical agitations
30min, then adds 8g native graphites, continues to stir 5h under 80 DEG C of water-baths, after standing, centrifugation, drying, obtains pre- oxygen
Graphite.Pre-oxidation graphite is dissolved in the concentrated sulfuric acids of 200ml 98%, 30min is stirred under the conditions of ice-water bath, is slowly added to
40g potassium permanganate, the addition time is 40min or so, continues to stir 2h under the conditions of 35 DEG C, be then slowly added into 320ml go from
Sub- water and 40ml hydrogen peroxide (stirring while adding).It is that 5% hydrochloric acid carries out pickling twice to add concentration, and upper strata is poured out after standing 2 days
Clear liquid, collects lower floor and is centrifuged repeatedly washing (8000 revs/min, 10min, 20min, 30min respectively twice) to graphene oxide in brown
Color, outwells supernatant and pipettes merging bottom brown oxidation graphene, continue to centrifuge washing 3 times, and then tentatively obtain graphite oxide
Alkene solution.By the further centrifugal concentrating of this solution, (10000 revs/min, 30min goes the oxidation of supernatant and upper strata low concentration
Graphene, takes out lower floor's high concentration graphene oxide solution, collects and repeats centrifugal concentrating 2-3 times), obtaining can wet spinning use
Graphene oxide solution.
By embodiment 1 prepare can wet spinning with graphene oxide solution carry out examination of infrared spectrum, as a result see Fig. 1.
Native graphite is successfully aoxidized by oxidants such as the concentrated sulfuric acid and potassium permanganate as shown in Figure 1, in 1059cm-1And 1225cm-1Left and right has
Strong absworption peak, represents there are substantial amounts of C-O keys in product.In 1403cm-1There is strong absworption peak vicinity, it was demonstrated that product
In contain C-OH keys.In 1736cm-1Nearby there is obvious absworption peak, illustrate the presence containing C=O in product.
By embodiment 1 prepare can wet spinning x-ray photoelectron spectroscopy test is carried out with graphene oxide solution, tie
Fruit sees Fig. 2.Native graphite is successfully aoxidized by oxidants such as the concentrated sulfuric acid and potassium permanganate as shown in Figure 2, in 284.7eV, 286.0eV
There is obvious characteristic peak with 287.0eV positions, C=C or C-C, C-O, C=O or O-C=O are represented respectively.In graphene oxide
Middle C:O content ratio about 1:1, further prove that graphite is oxidized to graphene oxide, and degree of oxidation is higher, the result
Result with infrared spectrum is corresponding.
By embodiment 1 prepare can wet spinning with graphene oxide solution carry out transmission electron microscope sign, as a result see Fig. 3.
Graphite is oxidized to after graphene oxide as shown in Figure 3, shows stacking, fold and tangled structure, the lamella in oxidizing process
Peel off and the formation of stacking process again.Meanwhile, graphene oxide layer is frivolous, shows the good single dispersing shape of graphene oxide
State.
Embodiment 2
For further checking prepare can wet spinning graphene oxide spinning feasibility.It is prepared by embodiment 1
Can wet spinning graphene oxide solution injection anhydrous calcium chloride/water/alcohol mixeding liquid in, wet spinning obtains graphite oxide
Alkene fiber.Wherein anhydrous calcium chloride/water/alcohol mixeding liquid includes 40g anhydrous calcium chlorides, 160ml deionized waters and 40ml second
Alcohol.
By in the graphene oxide fiber immersion 45%HI solution of above-mentioned preparation, 8h is kept under 100 DEG C of temperature conditionss, also
Original obtains graphene fiber, and specific pattern is shown in Fig. 4-7.Fig. 4 is graphene fiber pictorial diagram prepared by embodiment 2.Fig. 5 is implementation
The field emission scanning electron microscope figure of graphene fiber prepared by example 2, the diameter of graphene fiber respectively may be about 200 μm (Fig. 5 a-b) and
50 μm (Fig. 5 c-d), fiber axial surface shows the fold lamella of graphene, stacks pattern again.Fig. 6 is graphene fiber
The field emission scanning electron microscope figure of cross section.The cross section of graphene fiber is coarse, irregular, with certain toughness, and certain
Orderly, loose structure is shown in degree.Fig. 7 is the conducting performance test of graphene fiber prepared by embodiment 2, and diameter is about
200 μm of graphene fiber shows good electric conductivity, and the average conductivity that test is three times is 5.35 × 104Sm-1.Fig. 8 is
Graphene fiber extension test curve prepared by embodiment 2, the tensile strength of a diameter of 140 μm of graphene fiber reaches
1040MPa, elongation at break is 2.3%, illustrates that graphene fiber has good tensile property and mechanical flexibility.
Embodiment 3
By embodiment 1 prepare can wet spinning graphene oxide solution injection potassium hydroxide/water/methyl alcohol mixed liquor
In, obtain graphene oxide fiber.Fig. 9 is graphene oxide fiber pictorial diagram prepared by embodiment 3.
Wherein, methanol 100ml, the water 50ml in the potassium hydroxide/water/methyl alcohol mixed liquor, potassium hydroxide 15g.
By in the graphene oxide fiber immersion 45%HI solution of above-mentioned preparation, 4h is kept under 100 DEG C of temperature conditionss, also
Original obtains graphene fiber.Specific pattern is shown in Figure 10.Figure 10 is the field emission scanning electron microscope of graphene fiber prepared by embodiment 3
Figure, the diameter of graphene fiber respectively may be about 200 μm (Figure 10 a) and 100 μm (Figure 10 b), and graphene fiber surface topography is in pleat
Wrinkle, stacking pattern, also show good pliability；Graphene fiber cross section shows relatively tidily and orderly, porous knot
Configuration looks, show the orientation texture of graphene sheet layer in graphene fiber.
Embodiment 4
By embodiment 1 prepare can wet spinning graphene oxide solution injection sodium hydroxide/water/methyl alcohol mixed liquor
In, obtain graphene oxide fiber.
Wherein, methanol 100ml, the water 50ml in the sodium hydroxide/water/methyl alcohol mixed liquor, sodium hydroxide 7.5g.
By in the graphene oxide fiber immersion 45%HI solution of above-mentioned preparation, 4h is kept under 100 DEG C of temperature conditionss, also
Original obtains graphene fiber.Specific pattern is shown in that Figure 11-12, Figure 11 is graphene fiber pictorial diagram prepared by embodiment 4, Tu12Wei
The field emission scanning electron microscope figure of graphene fiber prepared by embodiment 4, the diameter of graphene fiber respectively may be about 200 μm of (figures
12a) with 100 μm (Figure 12 b), graphene fiber also shows good pliability, can knotted such as Figure 12 b.
Described above is only the preferred embodiment of the present invention, it is noted that to those skilled in the art, not
On the premise of departing from the principle of the invention, some improvement and modification can also be made, these are improved and modification also should be regarded as the present invention
Protection domain.
Claims (10)
1. it is a kind of can wet spinning graphene oxide solution preparation method, mainly include the following steps that：
(1) persulfate and phosphorus pentoxide are dissolved in the concentrated sulfuric acid and mixed, then added graphite and heated, stirred
Mix, stand, centrifuge, obtain initial reactant；
(2) by described initial reactant be dissolved in the concentrated sulfuric acid and be slowly added to potassium permanganate carry out ice-water bath, stirring, standing,
Centrifugation, obtains intermediate reaction liquid；
(3) added into described intermediate reaction liquid and pickling, centrifugation washing are carried out after deionized water and hydrogen peroxide, obtain final anti-
Answer liquid；
(4) the end reaction liquid is subjected to high speed centrifugation concentration, obtaining can wet spinning graphene oxide solution.
2. it is according to claim 1 can wet spinning graphene oxide solution preparation method, it is characterised in that it is described
The mass ratio of graphite and persulfate is 1：The mass ratio of (0.25~2), preferably graphite and persulfate is 1：(0.5-1.5)；
The mass ratio of the graphite and phosphorus pentoxide is 1：(0.25~2)；The mass ratio of preferable graphite and phosphorus pentoxide
For 1：(1~2)；
The mass ratio of the graphite and the concentrated sulfuric acid is 1：(30~80), the concentration of the concentrated sulfuric acid is 98wt%,
The mass ratio of the graphite and potassium permanganate is 1：(3~7).
3. it is according to claim 1 can wet spinning graphene oxide solution preparation method, it is characterised in that it is described
Potassium permanganate is slowly progressively added, and the addition time is 30~60min, adds potassium permanganate lasting agitating solution simultaneously, described to stir
Mix rotating speed is 150~250 revs/min, and mixing time is 1~3 hour.
4. it is according to claim 1 can wet spinning graphene oxide solution preparation method, it is characterised in that it is described
Persulfate be potassium peroxydisulfate.
5. it is according to claim 1 can wet spinning graphene oxide solution preparation method, it is characterised in that it is described
Graphite and the mass ratio of deionized water are 1：(20~60), the deionized water addition time is 100~200min, the time of repose
For 4~8 hours；The mass ratio of the graphite and hydrogen peroxide is 1：(3~10), the concentration of the hydrogen peroxide is 30wt%.
6. it is according to claim 1 can wet spinning graphene oxide solution preparation method, it is characterised in that it is described
Pickling in (3) step is to carry out pickling twice with 5% hydrochloric acid；Described centrifugation washing is carried out by the following method：
A) reaction solution through pickling is carried out to 20~40min centrifugation washing under conditions of 8000~10000 revs/min, until
There is brown in graphene oxide, removes supernatant collection graphene oxide；
B) sediment for being centrifuged out bottom merges, and continues to centrifuge washed several times with water according to step a), obtains graphene oxide solution.
7. it is according to claim 1 can wet spinning graphene oxide solution preparation method, it is characterised in that it is described
In (4) step, end reaction liquid, which carries out high speed centrifugation concentration, to be included：Remove supernatant and low concentration upper strata small pieces graphite oxide
Alkene solution, takes out lower floor high concentration graphene oxide solution, and the centrifugal concentrating rotating speed is 8000~12000 revs/min, and the time is
30~40min, number of times is 2~3 times.
8. the preparation method of graphene fiber, comprises the following steps：
A) by claim 1 prepare can wet spinning be injected into graphene oxide solution in coagulating bath, carry out wet method
Spinning, obtains graphene oxide fiber；
B) the graphene oxide fiber is reduced, graphene fiber is obtained；
Described coagulating bath be anhydrous calcium chloride/water/alcohol mixeding liquid, sodium hydroxide/water/methyl alcohol mixed liquor and potassium hydroxide/
Any of water/methyl alcohol mixed liquor；
Described reducing agent is hydroiodic acid.
9. the preparation method of graphene fiber according to claim 8, the concentration of the hydroiodic acid for 20wt%~
60wt%, reduction temperature is 80~120 DEG C.
10. the preparation method of graphene fiber according to claim 8, the anhydrous calcium chloride/water/alcohol mixeding liquid
In, the mass fraction of the anhydrous calcium chloride is 5%~20%, the volume ratio 1 of the second alcohol and water：(2~5)；
In the sodium hydroxide/water/methyl alcohol mixed liquor, the mass fraction of the sodium hydroxide is 3%~8%, the methanol and
The volume ratio of water is 1:(0.3~0.8)；
In the potassium hydroxide/water/methyl alcohol mixed liquor, the mass fraction of described potassium hydroxide is 3%~10%, the methanol
Volume ratio with water is 1：(0.3~0.8).
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