CN109468686A - Electrostatic spinning apparatus, the porous Gr/PAN composite nano fiber of orientation and preparation method thereof - Google Patents
Electrostatic spinning apparatus, the porous Gr/PAN composite nano fiber of orientation and preparation method thereof Download PDFInfo
- Publication number
- CN109468686A CN109468686A CN201811221658.XA CN201811221658A CN109468686A CN 109468686 A CN109468686 A CN 109468686A CN 201811221658 A CN201811221658 A CN 201811221658A CN 109468686 A CN109468686 A CN 109468686A
- Authority
- CN
- China
- Prior art keywords
- porous
- preparation
- pan
- composite nano
- nano fiber
- 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.)
- Pending
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Nonwoven Fabrics (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The present invention relates to a kind of electrostatic spinning apparatus, the porous Gr/PAN composite nano fiber of orientation and preparation method thereof, the conductive copper wire that the electrostatic spinning apparatus is placed in parallel using two is as reception device, and at it between the syringe needle of syringe additional jet flow control device, keep spinning engineering continuously smooth, a large amount of highly oriented porous composite fibres can be prepared；The preparation method uses above-mentioned electrostatic spinning apparatus, using polyacrylonitrile (PAN) as carbon-based material, the porous compound Gr/PAN nanofiber of orientation is prepared using two kinds of dicyandiamide solutions of N-N dimethylformamide (DMF) and deionized water (H2O).The preparation method is easy to operate, control is easy, process flow is short, and the porous Gr/PAN composite nano fiber of orientation can largely be prepared at lower cost, compared to unordered conductive-nano-fibers, being orientated conductive-nano-fibers has better electric conductivity and physical mechanical property, is conducive to the application field for widening electrospinning conductive-nano-fibers.
Description
Technical field
The present invention relates to a kind of electrostatic spinning apparatus, the porous Gr/PAN composite nano fiber of orientation and preparation method thereof.
Background technique
With the development of nanosecond science and technology, requirement of the people for fibrous material is higher and higher, and it is attached how to obtain high-performance, height
Value added fibrous material product is one of important directions of Recent study.In fibrous material system, porous material is due to tool
Have outstanding advantages of ultra-high surface energy, ultra-high surface activity, excellent wave absorbtion, by scientists extensive concern and answered
For electronic device, chemical engineering and biomedicine field etc..
Nano magnetic material is as a kind of emerging functional material, due to its unique physicochemical properties, make its physics,
Chemistry etc. shows the specific use different from conventional magnetic material.Traditional electrostatic spinning is usually miscellaneous because of the fiber of preparation
The performances such as filamentary conductive, mechanics, magnetism are disorderly influenced without chapter, compare unordered conductive-nano-fibers, are orientated conductive-nano-fibers
With better electric conductivity and physical mechanical property, be conducive to the application field for widening electrospinning conductive-nano-fibers.Graphene
It (Gr) is a kind of single layer sp separated from graphite material2The carbon atom material of hydridization, the pi-electron that there is conjugation to stack are
The two-dimensional structure of carbon, due to have many advantages, such as significant mechanics, electricity and become the nanofiber reinforcing material welcome very much.
Electrostatic spinning is to prepare one of effective ways of porous nano-fibre, have many scholars be prepared for using this method it is more
Hole nanofiber.The polymer nanofiber production technology being most simple and efficient, electrostatic spinning have been acknowledged as one kind
It is to overcome the surface tension of the taylor cone of solution or melt under high voltage electric field environment using electric field force and turn to charge occurs
The spinning liquid of shifting carries out slenderizing and forms the technology of nanofiber.The nanofiber as prepared by electrostatic spinning process
Film/beam is with performances such as its high surface area, high surface energy and high surfaces in various fields all by joyous
It meets.However, traditional electrospinning process and electrostatic spinning apparatus influence fiber and lead because the fiber of preparation is usually disorderly and unsystematic
Electrically.Also, the unordered porous nano-fibre of neat polymer causes to answer since the performances such as its electric conductivity, mechanics are relatively poor
It is limited with by various aspects, biological medicine, microwave absorption, optics, the numerous areas such as electrochemistry can not be applied to.Wherein, it applies
Energy-storage property, the gas adsorption desorption performance of material are improved in the material requirements of electrochemical field specific surface area with higher
Deng.
Based on the above situation, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide a kind of electrostatic spinning apparatus, the porous Gr/PAN composite nano fiber of orientation and its systems
Preparation Method, by the electrostatic spinning apparatus and preparation method using polyacrylonitrile (PAN) as carbon-based material, with graphene (Gr) work
For conducting particles, and use N-N dimethylformamide (DMF) and deionized water (H2O) two kinds of dicyandiamide solutions, by being equipped with jet stream
The electrostatic spinning apparatus of control device carries out electrostatic spinning, to obtain the porous Gr/PAN composite conducting nanometer with orientation
Fiber.
In order to achieve the above objectives, the invention provides the following technical scheme: a kind of electrostatic spinning apparatus, including liquid feed device,
Syringe, at least two high voltage power supplies, jet vectoring device and reception device, the syringe are connect with liquid feed device, institute
It states syringe and is separately connected the positive and negative of one of them high voltage power supply equipped with syringe needle, the syringe needle and receiving device
Pole, the reception device are two conductive copper wires being placed in parallel, jet vectoring device setting in the reception device and
Between syringe needle, and the jet vectoring device is connect with the anode of high voltage power supply described at least one.
Further, the jet vectoring device is conductive copper.
The present invention also provides a kind of preparation methods for being orientated porous Gr/PAN composite nano fiber, using the Static Spinning
Silk device, the preparation method of the porous Gr/PAN composite nano fiber of the orientation the following steps are included:
S1, DMF solution, polyacrylonitrile and graphene are provided, the graphene are added into DMF solution and are stirred,
Subsequent ultrasonic vibration is stirred for that the polyacrylonitrile is added, obtains spinning solution；
S2, by the spinning solution as in the electrostatic spinning apparatus, be 15-20kV, receive distance in spinning voltage
To carry out electrostatic spinning under conditions of 15-20cm, and controlled during the electrostatic spinning by the jet vectoring device
Jet stability processed obtains the porous Gr/PAN composite nano fiber of orientation.
Further, in the spinning solution, the concentration of deionized water is 1-10wt%.
Further, in the spinning solution, the concentration of the graphene is 0.1-3wt%.
Further, in the spinning solution, the concentration of the polyacrylonitrile is 5-15wt%.
Further, in step S1, further includes: the polyacrylonitrile is dried, poly- third after drying is added in stirring
Alkene nitrile obtains the spinning solution.
Further, in step S2, during the electrostatic spinning, spinning temperature is 23-27 DEG C, humidity 45-
55%.
Further, in step S2, during the electrostatic spinning, the additional annulus voltage of the conductive copper is 1-
10kV。
The present invention is provided again obtained by a kind of preparation method of porous Gr/PAN composite nano fiber of orientation according to
The porous Gr/PAN composite nano fiber of orientation.
Compared with prior art, the beneficial effects of the present invention are: electrostatic spinning apparatus of the invention is put in parallel with two
The conductive copper wire set as reception device, and at it between the syringe needle of syringe additional jet flow control device, make spinning engineering
It is continuous smooth, a large amount of highly oriented porous composite fibres can be prepared.By from jet vectoring after spinning jet injection
The constraint of the regular electric field of device, whip dynamic stability increase, so that fiber orientation degree increases.And the conductive copper being placed in parallel with two
Silk makes the fiber orientation degree obtained improve a lot as reception device, and the fiber being collected into is easy to shift and facilitates progress
Further processing, application.The raising of the degree of orientation of fiber is made, the electric conductivity of fiber can be made to greatly enhance.
Also, graphene (Gr) grain added by the preparation method of the porous Gr/PAN composite nano fiber of orientation of this patent
Son is the material with superelevation conductivity, excellent mechanics and thermal property.After adding Gr particle, it can greatly improve compound
The electric conductivity of nanofiber, and there was only simple physical bond between Gr particle and PAN, and between will not be formed it is new
Crystal structure will not have an impact PAN structure, to will not change the characteristic of PAN.The addition of Gr and fiber surface are more simultaneously
The appearance of pore structure makes the aperture size reduction of composite cellulosic membrane substantially and quantity increases, and further promotes the electric conductivity of fiber
Energy.Since the addition of Gr and the appearance of fiber surface porous structure make the surface of composite cellulosic membrane roughening, Gr's
It is added and the appearance of fiber surface porous structure makes the contact angle of composite cellulosic membrane become larger, thus the face for contacting it with water
Product is fewer, and hydrophobicity is stronger.For the Gr/PAN fiber of porous structure, the more non-porous Gr/PAN of the contact area of surface and water is fine
Dimension is few, therefore its water contact angle increases, hydrophobicity enhancing.Therefore the preparation method is easy to operate, control is easy, process flow is short, and
The porous Gr/PAN composite nano fiber of orientation can largely be prepared at lower cost, compare unordered conductive-nano-fibers, take
There is better electric conductivity and physical mechanical property to conductive-nano-fibers, be conducive to widen answering for electrospinning conductive-nano-fibers
Use field.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of electrostatic spinning apparatus of the invention；
Fig. 2 a to 2c is the SEM electromicroscopic photograph of the porous Gr/PAN composite nano fiber of orientation in the embodiment of the present invention four；
Fig. 3 a to 3f is the TEM electromicroscopic photograph of the porous Gr/PAN composite nano fiber of orientation in the embodiment of the present invention four；
Fig. 4 a to 4c is that the SEM Electronic Speculum of the unordered composite conducting GR/PAN nanofiber in comparative example of the present invention is shone
Piece.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
It should be understood that the terms such as "upper" of the invention, "lower", "left", "right", "inner", "outside" only refer to attached drawing
The present invention will be described, not as restriction term.
Referring to Figure 1, electrostatic spinning apparatus of the invention includes that liquid feed device (not shown), syringe 1, at least two are high
Voltage source 2, jet vectoring device 3 and reception device 4, the syringe 1 are connect with liquid feed device, are set on the syringe 1
There are 11, needle, the syringe needle 11 and receiving device 4 are separately connected the anode 22 and cathode 21 of one of them high voltage power supply 2,
The reception device 4 is two conductive copper wires being placed in parallel, and the jet vectoring device 3 is arranged in 4 He of reception device
Between syringe needle 11, and the jet vectoring device 3 is connect with the anode 22 of high voltage power supply 2 described at least one.In the present invention,
The jet vectoring device 3 is conductive copper.
The preparation method of the porous Gr/PAN composite nano fiber of orientation of the invention, is filled using electrostatic spinning shown in FIG. 1
Set, the preparation method of the porous Gr/PAN composite nano fiber of the orientation the following steps are included:
S1, DMF solution, polyacrylonitrile and graphene are provided, the graphene are added into DMF solution and are stirred,
Subsequent ultrasonic vibration is stirred for that the polyacrylonitrile is added, obtains spinning solution；
S2, by the spinning solution as in the electrostatic spinning apparatus, be 15-20kV, receive distance in spinning voltage
To carry out electrostatic spinning under conditions of 15-20cm, and controlled during the electrostatic spinning by the jet vectoring device
Jet stability processed obtains the porous Gr/PAN composite nano fiber of orientation.
Specifically, the concentration of deionized water is 1-10wt%, and the concentration of the graphene is in the spinning solution
0.1-3wt%, the concentration of the polyacrylonitrile are 5-15wt%.Preferably, PAN concentration is 12wt%, and Gr concentration is
0.5wt%, the concentration of water are 2wt%.
In the preparation method, step S1 further include: the polyacrylonitrile is dried, it is poly- after stirring addition is dry
Acrylonitrile obtains the spinning solution.In step S2, during the electrostatic spinning, spinning temperature is 23-27 DEG C, humidity
For 45-55%, the additional annulus voltage of conductive copper is 1-10kV, it is preferred that spinning voltage 18kV, additional annulus voltage are
5kV, the reception distance of spinning are 18cm, and the spacing of parallel pole is 5cm.
Below in conjunction with specific embodiment, invention is further explained.
Embodiment one
0.3g Gr is weighed before the experiments, the H for being 0.4g by load weighted quality2O is poured into the DMF of 16.9g.Then
Using magnetic stirring apparatus stirring at normal temperature 1h, then ultrasonic vibration 0.5h is to prevent Gr from reuniting.The solution shaken is taken out, 2.4g is added
The PAN powder of 2h is dried in Constant Temp. Oven, is continued at the uniform velocity stirring 6h under room temperature and is placed in after solution stable homogeneous
Electrostatic spinning is carried out in electrostatic spinning apparatus of the invention, wherein spinning voltage 18kV, adding annulus voltage is 5kV, spinning
Receiving distance is 18cm, and parallel pole spacing is 5cm, and during the electrostatic spinning, spinning environment requires room temperature to be maintained at
25 ± 2 DEG C, humidity requires control in 50 ± 5% ranges.
Embodiment two
0.5g Gr is weighed before the experiments, the H for being 0.4g by load weighted quality2O is poured into the DMF of 16.7g.Then
Using magnetic stirring apparatus stirring at normal temperature 1h, then ultrasonic vibration 0.5h is to prevent Gr from reuniting.The solution shaken is taken out, 2.4g is added
The PAN powder of 2h is dried in Constant Temp. Oven, is continued at the uniform velocity to stir 6h under room temperature, be started after solution stable homogeneous quiet
Electrospun, wherein spinning voltage 18kV, adding annulus voltage is 5kV, and it is 18cm, parallel pole spacing that spinning, which receives distance,
For 5cm, and during the electrostatic spinning, spinning environment requires room temperature to be maintained at 25 ± 2 DEG C, humidity require control 50 ±
In 5% range.
Embodiment three
0.1g Gr is weighed before the experiments, the H for being 0.4g by load weighted quality2O is poured into the DMF of 17.5g.Then
Using magnetic stirring apparatus stirring at normal temperature 1h, then ultrasonic vibration 0.5h is to prevent Gr from reuniting.The solution shaken is taken out, 2.0g is added
The PAN powder of 2h is dried in Constant Temp. Oven, is continued at the uniform velocity to stir 6h under room temperature, be started after solution stable homogeneous quiet
Electrospun, wherein spinning voltage 18kV, adding annulus voltage is 5kV, and it is 18cm, parallel pole spacing that spinning, which receives distance,
For 5cm, and during the electrostatic spinning, spinning environment requires room temperature to be maintained at 25 ± 2 DEG C, humidity require control 50 ±
In 5% range.
Example IV
0.1g Gr is weighed before the experiments, the H for being 0.4g by load weighted quality2O is poured into the DMF of 17.1g.Then
Using magnetic stirring apparatus stirring at normal temperature 1h, then ultrasonic vibration 0.5h is to prevent Gr from reuniting.The solution shaken is taken out, 2.4g is added
The PAN powder of 2h is dried in Constant Temp. Oven, is continued at the uniform velocity to stir 6h under room temperature, be started after solution stable homogeneous quiet
Electrospun, wherein spinning voltage 18kV, adding annulus voltage is 5kV, and it is 18cm, parallel pole spacing that spinning, which receives distance,
For 5cm, and during the electrostatic spinning, spinning environment requires room temperature to be maintained at 25 ± 2 DEG C, humidity require control 50 ±
In 5% range.
Fig. 2 a to 2c is referred to, Fig. 3 a to 3f, as seen from the figure, nanofiber obtained by preparation method of the invention have
The higher degree of orientation, surface are in porous structure, and in fibrous inside graphene particles along fiber axial alignment.High-orientation can make
The electric conductivity for obtaining fiber greatly improves, and the porous structure of fiber surface, then the hydrophobic properties of the surface of fiber can be made to obtain
To reinforcement.
Embodiment five
The present embodiment is basically the same as the first embodiment, and difference place is: Gr 0.1g, DMF 17.9g,.PAN is
1.6g。
Embodiment six
The present embodiment is basically the same as the first embodiment, and difference place is: Gr 0.1g, H2O is 1.0g, and DMF is
16.5g。
Embodiment seven
The present embodiment is basically the same as the first embodiment, and difference place is: Gr 0.1g, H2O is 1.6g, and DMF is
15.9g。
Comparative example
Unordered composite conducting GR/ is prepared using conventional electrostatic spinning apparatus and electrospinning process in the present embodiment
PAN nanofiber refers to Fig. 4 a to 4c, and compared with example IV, nanofiber obtained by traditional preparation method is nothing
Sequence state, and fibre diameter is thicker.
The orientation composite conducting GR/PAN of unordered composite conducting GR/PAN nanofiber and example IV to the present embodiment
The tunica fibrosa that nanofiber and the two are formed is tested to obtain following data:
The test data of 1 tunica fibrosa porous structure of table
From table 1 it follows that the addition of Gr and the appearance of fiber surface porous structure make composite cellulosic membrane substantially
Aperture size reduces and quantity increases；Meanwhile preparation method of the invention but also the ordered composite tunica fibrosa obtained aperture
It is smaller and more.
The contact angle of 2 PAN, Gr/PAN tunica fibrosa of table
| Tunica fibrosa | ES(°) | MPEM(°) |
| Porous PAN | 119.1+1.1 | 133.7+0.8 |
| Porous Gr/PAN | 134.9+0.9 | 132.6+4.1 |
| Non-porous Gr/PAN | 132.2+0.5 | 119.6+5.0 |
From Table 2, it can be seen that the addition of Gr and the appearance of fiber surface porous structure make connecing for composite cellulosic membrane
Feeler becomes larger, and hydrophobicity is stronger.This is because the addition of Gr and the appearance of fiber surface porous structure make composite cellulosic membrane
Surface it is roughening, so that the area for contacting it with water is fewer.Cassie and Baxter law points out what material was contacted with water
The more few then water contact angle of area is bigger, and material hydrophobic is stronger.For the Gr/PAN fiber of porous structure, surface and water are connect
Contacting surface product is few compared with non-porous Gr/PAN fiber, therefore its water contact angle increases, hydrophobicity enhancing.In addition, using preparation side of the invention
Method can make hydrophobic fiber more hydrophobic.
The sheet resistance of 3 different type Gr/PAN tunica fibrosa of table
The sheet resistance of Gr/PAN tunica fibrosa is measured using megger, the results are shown in Table 3.As shown in Table 3, orientation is fine
The sheet resistance of dimension is less than the resistance of the Random fiber under the conditions of, illustrates that the electric conductivity of fiber can be improved by being orientated fiber, also be proved
The electric conductivity of fiber can be improved using preparation method of the invention.
As known from the above, by improving electrostatic spinning apparatus, using preparation method of the invention, in certain experiment parameter
Under, the Gr/PAN fiber prepared has high-orientation and surface porosity.For the Gr/PAN fiber of porous structure,
The contact area of surface and water is few compared with non-porous Gr/PAN fiber, therefore its water contact angle increases, hydrophobicity enhancing, so using this hair
Bright preparation method can make hydrophobic fiber more hydrophobic.And the high-orientation of fiber, then the electric conductivity of fiber can be made substantially to mention
It rises.
In summary: the conductive copper wire that electrostatic spinning apparatus of the invention is placed in parallel using two as reception device, and
At it between the syringe needle of syringe additional jet flow control device, keep spinning engineering continuously smooth, a large amount of height can be prepared and taken
To porous composite fibre.Constraint after spinning jet injection by the regular electric field from jet vectoring device, whip are dynamic steady
Qualitative increase, so that fiber orientation degree increases.And the conductive copper wire being placed in parallel using two makes the fibre obtained as reception device
The dimension degree of orientation improves a lot, and the fiber being collected into is easy to shift and is conveniently further processed, applies.Fiber is made
The raising of the degree of orientation can be such that the electric conductivity of fiber greatly enhances.
Also, graphene (Gr) grain added by the preparation method of the porous Gr/PAN composite nano fiber of orientation of this patent
Son is the material with superelevation conductivity, excellent mechanics and thermal property.After adding Gr particle, it can greatly improve compound
The electric conductivity of nanofiber, and there was only simple physical bond between Gr particle and PAN, and between will not be formed it is new
Crystal structure will not have an impact PAN structure, to will not change the characteristic of PAN.The addition of Gr and fiber surface are more simultaneously
The appearance of pore structure makes the aperture size reduction of composite cellulosic membrane substantially and quantity increases, and further promotes the electric conductivity of fiber
Energy.Since the addition of Gr and the appearance of fiber surface porous structure make the surface of composite cellulosic membrane roughening, Gr's
It is added and the appearance of fiber surface porous structure makes the contact angle of composite cellulosic membrane become larger, thus the face for contacting it with water
Product is fewer, and hydrophobicity is stronger.For the Gr/PAN fiber of porous structure, the more non-porous Gr/PAN of the contact area of surface and water is fine
Dimension is few, therefore its water contact angle increases, hydrophobicity enhancing.Therefore the preparation method is easy to operate, control is easy, process flow is short, and
The porous Gr/PAN composite nano fiber of orientation can largely be prepared at lower cost, compare unordered conductive-nano-fibers, take
There is better electric conductivity and physical mechanical property to conductive-nano-fibers, be conducive to widen answering for electrospinning conductive-nano-fibers
Use field.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of electrostatic spinning apparatus, which is characterized in that including liquid feed device, syringe, at least two high voltage power supplies, jet stream control
Device processed and reception device, the syringe are connect with liquid feed device, and the syringe is equipped with syringe needle, the syringe needle and are connect
The anode and cathode of one of them high voltage power supply are separately connected by device, the reception device is that two be placed in parallel lead
Electrolytic copper silk, the jet vectoring device are arranged between the reception device and syringe needle, and the jet vectoring device at least
The anode connection of one high voltage power supply.
2. electrostatic spinning apparatus as described in claim 1, which is characterized in that the jet vectoring device is conductive copper.
3. a kind of preparation method for being orientated porous Gr/PAN composite nano fiber, which is characterized in that using as claimed in claim 2
Electrostatic spinning apparatus, the preparation method of the porous Gr/PAN composite nano fiber of the orientation the following steps are included:
S1, DMF solution, polyacrylonitrile and graphene are provided, the graphene is added into DMF solution and is stirred, then
Ultrasonic vibration is stirred for that the polyacrylonitrile is added, obtains spinning solution；
S2, by the spinning solution as in the electrostatic spinning apparatus, spinning voltage is 15-20kV, to receive distance be 15-
Electrostatic spinning is carried out under conditions of 20cm, and jet stream is controlled by the jet vectoring device during electrostatic spinning
Stability obtains the porous Gr/PAN composite nano fiber of orientation.
4. being orientated the preparation method of porous Gr/PAN composite nano fiber as claimed in claim 3, which is characterized in that described
In spinning solution, the concentration of deionized water is 1-10wt%.
5. being orientated the preparation method of porous Gr/PAN composite nano fiber as claimed in claim 3, which is characterized in that described
In spinning solution, the concentration of the graphene is 0.1-3wt%.
6. being orientated the preparation method of porous Gr/PAN composite nano fiber as claimed in claim 3, which is characterized in that described
In spinning solution, the concentration of the polyacrylonitrile is 5-15wt%.
7. being orientated the preparation method of porous Gr/PAN composite nano fiber as claimed in claim 3, which is characterized in that step S1
In, further includes: the polyacrylonitrile is dried, the polyacrylonitrile after drying is added in stirring, obtains the spinning solution.
8. being orientated the preparation method of porous Gr/PAN composite nano fiber as claimed in claim 3, which is characterized in that step S2
In, during the electrostatic spinning, spinning temperature is 23-27 DEG C, humidity 45-55%.
9. being orientated the preparation method of porous Gr/PAN composite nano fiber as claimed in claim 3, which is characterized in that step S2
In, during the electrostatic spinning, the additional annulus voltage of the conductive copper is 1-10kV.
10. a kind of preparation method of the porous Gr/PAN composite nano fiber of orientation according to any one of claim 3 to 9
The porous Gr/PAN composite nano fiber of obtained orientation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811221658.XA CN109468686A (en) | 2018-10-19 | 2018-10-19 | Electrostatic spinning apparatus, the porous Gr/PAN composite nano fiber of orientation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811221658.XA CN109468686A (en) | 2018-10-19 | 2018-10-19 | Electrostatic spinning apparatus, the porous Gr/PAN composite nano fiber of orientation and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109468686A true CN109468686A (en) | 2019-03-15 |
Family
ID=65665728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811221658.XA Pending CN109468686A (en) | 2018-10-19 | 2018-10-19 | Electrostatic spinning apparatus, the porous Gr/PAN composite nano fiber of orientation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109468686A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109881302A (en) * | 2019-03-19 | 2019-06-14 | 嘉兴学院 | A kind of composite nano fiber and preparation method thereof with porous surface structure |
| CN110067035A (en) * | 2019-05-14 | 2019-07-30 | 中国科学院沈阳应用生态研究所 | A kind of electrostatic spinning and preparation method thereof of hydrophobic graphene composite high-molecular fiber |
| CN111996666A (en) * | 2020-09-08 | 2020-11-27 | 北京康烯科技创新研究有限公司 | Titanium nanosheet/graphene-based fiber membrane and preparation method thereof |
| CN111991137A (en) * | 2020-09-08 | 2020-11-27 | 北京康烯科技创新研究有限公司 | Titanium nano sheet/graphene-based hot compress medicine pillow |
| CN112030349A (en) * | 2020-09-08 | 2020-12-04 | 北京康烯科技创新研究有限公司 | Non-layered molybdenum nanosheet/graphene-based fiber membrane and preparation method thereof |
| CN112021893A (en) * | 2020-09-08 | 2020-12-04 | 北京康烯科技创新研究有限公司 | Palladium nanosheet/graphene-based hot compress medicine pillow |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110062216A (en) * | 2009-12-03 | 2011-06-10 | 한국전자통신연구원 | A electrospinning apparatus and a method for preparing well aligned nanofibers using the same |
| US8608992B2 (en) * | 2010-09-24 | 2013-12-17 | The Board Of Trustees Of The University Of Illinois | Carbon nanofibers derived from polymer nanofibers and method of producing the nanofibers |
| CN203715801U (en) * | 2014-01-16 | 2014-07-16 | 苏州大学 | Electrostatic spinning device |
| CN105483939A (en) * | 2016-01-12 | 2016-04-13 | 山东佳星环保科技有限公司 | Preparation method of porous graphene nanofiber membrane |
| CN106898731A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of composite membrane and its preparation and application |
| CN107137753A (en) * | 2017-05-09 | 2017-09-08 | 重庆大学 | A kind of preparation method of graphene/carbon nanofiber bio-medical external application non-woven fabrics |
-
2018
- 2018-10-19 CN CN201811221658.XA patent/CN109468686A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110062216A (en) * | 2009-12-03 | 2011-06-10 | 한국전자통신연구원 | A electrospinning apparatus and a method for preparing well aligned nanofibers using the same |
| US8608992B2 (en) * | 2010-09-24 | 2013-12-17 | The Board Of Trustees Of The University Of Illinois | Carbon nanofibers derived from polymer nanofibers and method of producing the nanofibers |
| CN203715801U (en) * | 2014-01-16 | 2014-07-16 | 苏州大学 | Electrostatic spinning device |
| CN106898731A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of composite membrane and its preparation and application |
| CN105483939A (en) * | 2016-01-12 | 2016-04-13 | 山东佳星环保科技有限公司 | Preparation method of porous graphene nanofiber membrane |
| CN107137753A (en) * | 2017-05-09 | 2017-09-08 | 重庆大学 | A kind of preparation method of graphene/carbon nanofiber bio-medical external application non-woven fabrics |
Non-Patent Citations (4)
| Title |
|---|
| XIAOLAN YU ET AL: "Preparation of porous polyacrylonitrile fibers by electrospinning a ternary system of PAN/DMF/H2O", 《MATERIALS LETTERS》 * |
| 刘洪莹: "静电纺有序纳米纤维的制备及其性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 周文英 等: "《聚合物基导热复合材料》", 30 June 2017, 北京：国防工业出版社 * |
| 谢凯 等: "《新一代锂二次电池技术》", 31 August 2013, 北京：国防工业出版社 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109881302A (en) * | 2019-03-19 | 2019-06-14 | 嘉兴学院 | A kind of composite nano fiber and preparation method thereof with porous surface structure |
| CN109881302B (en) * | 2019-03-19 | 2022-03-01 | 嘉兴学院 | Composite nanofiber with porous surface structure and preparation method thereof |
| CN110067035A (en) * | 2019-05-14 | 2019-07-30 | 中国科学院沈阳应用生态研究所 | A kind of electrostatic spinning and preparation method thereof of hydrophobic graphene composite high-molecular fiber |
| CN111996666A (en) * | 2020-09-08 | 2020-11-27 | 北京康烯科技创新研究有限公司 | Titanium nanosheet/graphene-based fiber membrane and preparation method thereof |
| CN111991137A (en) * | 2020-09-08 | 2020-11-27 | 北京康烯科技创新研究有限公司 | Titanium nano sheet/graphene-based hot compress medicine pillow |
| CN112030349A (en) * | 2020-09-08 | 2020-12-04 | 北京康烯科技创新研究有限公司 | Non-layered molybdenum nanosheet/graphene-based fiber membrane and preparation method thereof |
| CN112021893A (en) * | 2020-09-08 | 2020-12-04 | 北京康烯科技创新研究有限公司 | Palladium nanosheet/graphene-based hot compress medicine pillow |
| CN111996666B (en) * | 2020-09-08 | 2021-11-30 | 北京康烯科技创新研究有限公司 | Titanium nanosheet/graphene-based fiber membrane and preparation method thereof |
| CN112030349B (en) * | 2020-09-08 | 2022-02-15 | 北京康烯科技创新研究有限公司 | Non-layered molybdenum nanosheet/graphene-based fiber membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109468686A (en) | Electrostatic spinning apparatus, the porous Gr/PAN composite nano fiber of orientation and preparation method thereof | |
| Bavatharani et al. | Electrospinning technique for production of polyaniline nanocomposites/nanofibres for multi-functional applications: A review | |
| CN107478360B (en) | Capacitive flexible pressure sensor and preparation method thereof | |
| Abd Razak et al. | A review of electrospun conductive polyaniline based nanofiber composites and blends: processing features, applications, and future directions | |
| Sun et al. | Carbonized cotton fabric in-situ electrodeposition polypyrrole as high-performance flexible electrode for wearable supercapacitor | |
| Joshi et al. | Progress and potential of electrospinning-derived substrate-free and binder-free lithium-ion battery electrodes | |
| Wang et al. | Polymorphous supercapacitors constructed from flexible three-dimensional carbon network/polyaniline/MnO2 composite textiles | |
| Zhang et al. | A review: carbon nanofibers from electrospun polyacrylonitrile and their applications | |
| Chen et al. | Fabrication and characterization of magnetic cobalt ferrite/polyacrylonitrile and cobalt ferrite/carbon nanofibers by electrospinning | |
| CN109468701A (en) | Electrostatic spinning apparatus, orientation Fe3O4/ Gr/PAN composite conducting nanofiber and preparation method thereof | |
| CN110136998B (en) | Preparation method and application of metal organic framework carbon fiber composite film | |
| CN106784856A (en) | A kind of carbon nano-fiber/metal foil double-layer composite material and preparation method thereof | |
| Raza et al. | Ultrathin honeycomb-like MnO2 on hollow carbon nanofiber networks as binder-free electrode for flexible symmetric all-solid-state supercapacitors | |
| Kim et al. | Hierarchical porous MnO2/carbon nanofiber composites with hollow cores for high-performance supercapacitor electrodes: Effect of poly (methyl methacrylate) concentration | |
| Zhao et al. | Solution blown silicon carbide porous nanofiber membrane as electrode materials for supercapacitors | |
| Zhang et al. | Polypyrrole/nylon membrane composite film for ultra-flexible all-solid supercapacitor | |
| CN106848314A (en) | The method that lithium-sulfur cell prepares positive electrode with the preparation method of double-layer porous carbon nano-fiber and using it | |
| CN110379642B (en) | Stretchable nanofiber, application thereof, stretchable capacitor electrode comprising stretchable nanofiber and preparation method | |
| CN108335917A (en) | A kind of preparation method of carbon nanofibers load ordered arrangement redox graphene electrode material | |
| CN108149343A (en) | The composite nano fiber of N doping porous carbon cladding nano silicon particles and preparation | |
| Ning et al. | Tailoring the morphologies of PVDF nanofibers by interfacial diffusion during coaxial electrospinning | |
| Tagsin et al. | Electrochemical mechanisms of activated carbon, α-MnO2 and composited activated carbon-α-MnO2 films in supercapacitor applications | |
| CN109859954A (en) | A kind of nanofiber-based flexible array structure electrode and preparation method thereof | |
| CN112981725A (en) | Nanofiber membrane, thermosensitive Janus composite membrane and preparation method of nanofiber membrane and thermosensitive Janus composite membrane | |
| CN105040409A (en) | Preparation method for magnetic nanocomposite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190315 |