CN105839203A - Three-dimensional porous yarn prepared through electro-spinning technology and preparation method of three-dimensional porous yarn - Google Patents
Three-dimensional porous yarn prepared through electro-spinning technology and preparation method of three-dimensional porous yarn Download PDFInfo
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- CN105839203A CN105839203A CN201610273756.2A CN201610273756A CN105839203A CN 105839203 A CN105839203 A CN 105839203A CN 201610273756 A CN201610273756 A CN 201610273756A CN 105839203 A CN105839203 A CN 105839203A
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- Prior art keywords
- dimensional porous
- yarn
- porous yarn
- preparation
- fiber
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- 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
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
Abstract
The invention discloses three-dimensional porous yarn prepared through an electro-spinning technology and a preparation method of the three-dimensional porous yarn. The method includes the steps of collecting polymer or polymer composite fiber prepared through electro-spinning with rotary fiber as the supporting object, and preparing the three-dimensional porous yarn through subsequent processing. By means of the preparation method, yarn forming can be rapid and direct; the method is suitable for forming all cell phones of nanometer materials capable of being prepared through high-voltage electrostatic spinning; the prepared yarn has an interconnected network structure, and high conductivity can be easily achieved. The spaces between the nanometer fibers can be filled with lots of interconnected pores, and liquid like electrolyte can be easily diffused in electrodes.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, be specifically related to a kind of utilize Electrospinning to prepare
Three-dimensional porous yarn and preparation method thereof.
Background technology
As far back as the sixties in 20th century, thought and the blank of wearable smart machine occur the most.In recent years,
Along with the fast development of information technology, nanotechnology, material science, energy storage technology etc., wearable device is opened
Beginning to enter the stage of fast development, its form and function start to become variation, gradually industry, medical treatment,
Military, educate, the numerous areas such as amusement shows important researching value and application potential.Wearable device
The energy resource supply device that develops into propose more requirement: can weave, lighting, Large Copacity, high magnification,
High stability etc..
The method currently preparing wire electrode includes the technology such as wet spinning technology, dry spinning, confinement hydro-thermal.
Prepare yarn by wet spinning or dry spinning technology the physicochemical properties of material be there are certain requirements, some
The material of function admirable is often unsatisfactory for the condition of dry spinning and wet spinning.As dry spinning needs material
For polymer and have certain viscosity, molecular weight electric conductivity sufficiently large, suitable and surface tension etc.；Wet
Method spinning then utilizes material curing properties under some chemical reaction to prepare yarn, is only applicable to meet
The material of specific chemical reaction.And confinement hydro-thermal method is except being required to meet specific chemical reaction, also needing to
Product generates continuous print colloidal sol or gel yarn.It addition, confinement hydro-thermal method is limited by confinement container,
Yarn cannot be produced continuously.
As can be seen from the above analysis, the method currently preparing yarn has its limitation, and explores new
Yarn technology of preparing replaces or makes up current techniques becoming a key technology of current field of nanometer material technology
Problem.The solution of this problem will for ultracapacitor, lithium ion battery, lithium-sulfur cell, photoelectric chemical electrode,
The fields such as photocatalysis, pollutant absorption provide new material preparation technology.
Summary of the invention
[solving the technical problem that]
Present invention aim to address above-mentioned prior art problem, it is provided that a kind of utilize Electrospinning to prepare
Three-dimensional porous yarn and preparation method thereof.
[technical scheme]
In order to reach above-mentioned technique effect, the present invention takes techniques below scheme:
The present invention, by high-voltage electrostatic spinning technology, uses special Electrospun wire drawing device to rotate fiber
The straight forming realizing yarn electrode is collected.
A kind of preparation method utilizing Electrospinning to prepare three-dimensional porous yarn, the method is to use to rotate fibre
Tie up and collect polymer or polymer composite fibrous prepared by Electrospun as supporter, and by subsequent treatment system
For obtaining three-dimensional porous yarn.
According to the present invention further technical scheme, described rotation fiber be diameter ＜ 1cm tinsel,
Cotton thread, chemical fibre or glass fibre.
According to the present invention further technical scheme, the preferred carbon fiber of described chemical fibre；Described metal
Silk is titanium silk, steel wire, tantalum wire, copper wire or nickel wire.
According to the present invention further technical scheme, the rotary rpm of described rotation fiber be 0～
20000rpm。
According to the present invention further technical scheme, described polymer or polymer composite fibrous include poly-third
Alkene nitrile PAN, polyvinylpyrrolidone PVP, PVAC polyvinylalcohol, polyoxyethylene PEO, polyvinyl acetate
One or more in ester PVAc, poly-3,4-ethylenedioxy thiophene PEDOT, polyaniline.
According to the present invention further technical scheme, described subsequent treatment is for removal or does not remove rotation fiber,
Its subsequent treatment includes carbonization technique, in-situ polymerization, acid-alkali treatment, photocuring, electronics or ion beam irradiation
Or radioactivity irradiation.
The above-mentioned preparation method utilizing Electrospinning to prepare three-dimensional porous yarn is by Electrospun precursor solution
Electrostatic pressure be 5～50kV, under conditions of conductive capillary needle pore footpath is 0.5～0.8nm, with 0.02～
The flow velocity of 0.5mL/h flows out from conductive capillary needle tubing and carries out Electrospun operation.
A kind of three-dimensional porous yarn, this three-dimensional porous yarn is to be prepared by above-mentioned preparation method.Gained yarn
Line is made up of nanofiber, and described nanofiber structurally forms the network structure of mutual UNICOM, is conducive to real
The biggest electrical conductivity.Between described nanofiber by the pore filling communicated with one another in a large number, beneficially liquid such as
Electrolyte diffusion in the electrodes.
Described three-dimensional porous yarn is made up of the nanofiber of diameter ＜ 1 μm, between described nanofiber by
The pore filling of the aperture ＞ 10nm communicated with one another.
A kind of application of the three-dimensional porous yarn prepared according to above-mentioned preparation method, this three-dimensional porous yarn
Can be applicable to ultracapacitor, lithium ion battery, lithium-sulfur cell, photoelectric chemical electrode, photocatalysis or pollution
Thing adsorbing domain.
The electric spinning device that a kind of above-mentioned preparation method uses, it includes high voltage power supply, conductive capillary needle
Pipe and metal collection flat board, the both positive and negative polarity of described high voltage power supply is received with conductive capillary needle tubing, metal respectively
Collection flat board connects, and it also includes rotating fiber, and described rotation fiber is placed in conductive capillary needle tubing and metal
Collect between flat board, and the axle of described rotation fiber and metal collection platen parallel；Described rotation fiber is put
Below conductive capillary needle tubing at 1～100cm, on metal collection flat board at 0.1～100cm, and
And described rotation fiber is shorter with the distance of conductive capillary needle tubing than it with the distance of metal collection flat board；Institute
State rotation fiber to be connected with metal collection flat board or be not attached to.
Will be described in detail the present invention below.
The present invention uses the wire drawing device that the fiber of rotation is equipped as high-voltage electrostatic spinning, then passes through Electrospun
The molding that the fiber of preparation realizes yarn in the winding rotated on fiber is collected.The high pressure that the present invention uses is quiet
Electrospinning is prior art, and the device of use can also be existing apparatus, however it is necessary that at existing apparatus
In between conductive capillary needle tubing and metal collection flat board, rotation fiber is set.Concrete preparation method is as follows:
Electrospun precursor solution is gone out by conductive capillary needle pipe flow, in high-voltage electrostatic field, solution viscous force,
It is drawn into nanofiber under the comprehensive function such as solution surface tension, gravity.Described high voltage electric field is by high-tension electricity
Source is applied on conductive capillary needle tubing and metal collection flat board by wire.Described rotation fiber conduct
The supporter of Electrospun product, can be removed after being successfully prepared and prepare hollow three-dimensional porous electrode, it is possible to
Do not remove the part as electrode, play carrier collection or increase the effect of mechanical performance.
[beneficial effect]
The present invention compared with prior art, has a following beneficial effect:
The preparation method of the present invention can make yarn molding quickly direct, and the method to be suitable for all high pressure quiet
The collection molding of the nano material that Electrospun can be prepared；And the yarn that the present invention prepares is by nanofiber
Composition, described nanofiber structurally forms the network structure of mutual UNICOM, is advantageously implemented big electrical conductivity.
Between described nanofiber by the pore filling communicated with one another in a large number, beneficially liquid such as electrolyte in the electrodes
Diffusion.
Accompanying drawing explanation
Fig. 1 is the structural representation of electric spinning device of the present invention；
Fig. 2 is the electron scanning micrograph of the three-dimensional porous yarn of the embodiment of the present invention 1 preparation.
Detailed description of the invention
Below in conjunction with embodiments of the invention, the invention will be further elaborated.
A kind of electric spinning device as shown in Figure 1, it includes high voltage power supply 4, conductive capillary needle tubing 2 and
Metal collection flat board 6, the both positive and negative polarity of described high voltage power supply 4 is received with conductive capillary needle tubing 2, metal respectively
Collection flat board 6 connects, and it also includes rotating fiber 7, and described rotation fiber 7 is placed in conductive capillary needle tubing 2
And between metal collection flat board 6, and the axle of described rotation fiber and metal collection platen parallel；Described rotation
Turn fiber and be placed in below conductive capillary needle tubing at 1～100cm, on metal collection flat board 0.1～100cm
Place, and described rotation fiber and the distance of metal collection flat board are than itself and the distance of conductive capillary needle tubing
Short；Described rotation fiber can be connected with metal collection flat board or be not attached to.
Utilize that this electric spinning device is prepared specifically comprises the following steps that Electrospun precursor solution 1 is by can
The capillary needle tubing 2 of conduction flows out, in high-voltage electrostatic field, solution viscous force, solution surface tension, gravity etc.
Nanofiber 3 it is drawn under comprehensive function.Described high voltage electric field is applied to by wire 5 by high voltage power supply 4
On conductive capillary needle tubing 2 and metal collection flat board 6；Nanofiber 3 prepared by Electrospun is made at electric field
Assemble on metal collection flat board 6 with lower, the rotation fiber 7 being placed in accumulation process on metal collection plate
It is wound around and collects and form yarn.
Following example are prepared from by above-mentioned electric spinning device.
Embodiment 1:
0.5g PAN is dissolved in 5mL dimethylformamide (DMF) as Electrospun solution.So
After go out from conductive capillary needle pipe flow with the flow velocity of 0.2mL/h, conductive capillary needle tubing and a diameter of 300
The distance rotated between titanium silk of micron is 15cm, between conductive capillary needle tubing to metal collection flat board away from
From for 18cm, rotate fiber and be placed in 3cm source on metal collection flat board, rotate the axle of titanium silk and collect flat
Plate is parallel, and described conductive capillary needle tubing is extremely connected with just (bearing) of high voltage power supply, metal collection plate and
Negative (just) is connected.The high pressure of 15kV is applied between conductive capillary needle tubing and metal plate.Control rotation
The rotating speed turning Ti silk is 3000rpm.
Nanometer PAN nanofiber prepared by the present embodiment Electrospun is fallen on rotation titanium silk and is wound and is rolled in
Titanium silk surface forms PAN yarn.Obtain after the PAN yarn of prepared titaniferous silk is carried out carbonization treatment
Ti/ carbon nano-fiber yarn as shown in Figure 2.
This product Ti/ carbon nano-fiber yarn can be applicable to yarn ultracapacitor field, due to this structure simultaneously
There is conductive network and the electrolyte proliferation network of mutual UNICOM, active material utilization can be significantly improved, carry
The specific capacity of high device, energy density, power density.
Embodiment 2
0.5g PAN is dissolved in 5mL dimethylformamide (DMF) as Electrospun solution.So
After go out from conductive capillary needle pipe flow with the flow velocity of 0.2mL/h, conductive capillary needle tubing and a diameter of 300
The distance rotated between copper wire of micron is 15cm, between conductive capillary needle tubing to metal collection flat board away from
From for 18cm, rotate fiber and be placed in 3cm source on metal collection flat board, rotate the axle of copper wire and collect flat
Plate is parallel, and described conductive capillary needle tubing is extremely connected with just (bearing) of high voltage power supply, metal collection plate and
Negative (just) is connected.The high pressure of 15kV is applied between conductive capillary needle tubing and metal plate.Control rotation
The rotating speed turning copper wire is 3000r/min.
Nanometer PAN nanofiber prepared by the present embodiment Electrospun is fallen on rotation copper wire and is wound and is rolled in
Copper wire surface forms PAN yarn.Obtain after the prepared PAN yarn containing copper wire is carried out carbonization treatment
Cu/ carbon nano-fiber yarn.Carbon nano-fiber yarn is obtained after eroding copper wire with nitric acid.
This hollow carbon nano-fibre yams can be applicable to the field such as electro-catalysis, ultracapacitor, due to this structure
There is conductive network and the electrolyte proliferation network of mutual UNICOM simultaneously, active material utilization can be significantly improved,
Improve electrocatalysis characteristic (to the electro-catalysis) specific capacity of device, energy density, power density (super capacitor
Device).
Embodiment 3
0.5g PAN is dissolved in 5mL dimethylformamide (DMF) as Electrospun solution.So
After go out from conductive capillary needle pipe flow with the flow velocity of 0.2mL/h, conductive capillary needle tubing and a diameter of 400
The distance rotated between copper wire of micron is 15cm, between conductive capillary needle tubing to metal collection flat board away from
From for 18cm, rotate fiber and be placed in 3cm source on metal collection flat board, rotate the axle of copper wire and collect flat
Plate is parallel, and described conductive capillary needle tubing is extremely connected with just (bearing) of high voltage power supply, metal collection plate and
Negative (just) is connected.The high pressure of 15kV is applied between conductive capillary needle tubing and metal plate.Control rotation
The rotating speed turning copper wire is 3000r/min.
It is (micro-by diameter 7 that nanometer PAN nanofiber prepared by the present embodiment Electrospun falls rotation carbon fiber bundle
The carbon fiber composition of rice, diameter about 100 microns) go up and be wound and be rolled in carbon fiber bundle surface and form PAN
Yarn.Obtain carbon fiber bundle/carbon after the PAN yarn of prepared carbon fiber-containing bundle is carried out carbonization treatment to receive
Rice fiber yarn.
This hollow carbon nano-fibre yams can be applicable to ultracapacitor field, owing to this structure has mutually simultaneously
The conductive network of UNICOM and electrolyte proliferation network, can significantly improve active material utilization, improves device
Specific capacity, energy density, power density (ultracapacitor).
Although reference be made herein to invention has been described for the explanatory embodiment of the present invention, and above-described embodiment is only
For the present invention preferably embodiment, embodiments of the present invention are also not restricted to the described embodiments, it should
Understanding, those skilled in the art can be designed that a lot of other amendments and embodiment, and these are revised and real
The mode of executing will fall within spirit disclosed in the present application and spirit.
Claims (7)
1. one kind utilizes the preparation method that Electrospinning prepares three-dimensional porous yarn, it is characterised in that the method is
Use and rotate the polymer or polymer composite fibrous that fiber is prepared as supporter collection Electrospun, and
Three-dimensional porous yarn is obtained by subsequent treatment.
The preparation method utilizing Electrospinning to prepare three-dimensional porous yarn the most according to claim 1, its
It is characterised by that described rotation fiber is the tinsel of diameter ＜ 1cm, cotton thread, chemical fibre or glass fibers
Dimension.
The preparation method utilizing Electrospinning to prepare three-dimensional porous yarn the most according to claim 1, its
The rotary rpm being characterised by described rotation fiber is 0～20000rpm.
The preparation method utilizing Electrospinning to prepare three-dimensional porous yarn the most according to claim 1, its
Be characterised by described polymer or polymer composite fibrous include polyacrylonitrile, polyvinylpyrrolidone,
In polyvinyl alcohol, polyoxyethylene, polyvinyl acetate, poly-3,4-ethylenedioxy thiophene, polyaniline
One or more.
The preparation method utilizing Electrospinning to prepare three-dimensional porous yarn the most according to claim 1, its
Being characterised by that described subsequent treatment for removal or does not remove rotation fiber, its subsequent treatment includes carbonizer
Skill, in-situ polymerization, acid-alkali treatment, photocuring, electronics or ion beam irradiation or radioactivity irradiation.
6. a three-dimensional porous yarn, it is characterised in that this three-dimensional porous yarn is any one by Claims 1 to 5
Item preparation method prepares.
Three-dimensional porous yarn the most according to claim 6, it is characterised in that described three-dimensional porous yarn be by
The nanofiber composition of diameter ＜ 1 μm, by the aperture ＞ 10nm communicated with one another between described nanofiber
Pore filling.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610273756.2A CN105839203B (en) | 2016-04-28 | 2016-04-28 | Utilize the three-dimensional porous yarn and preparation method thereof of Electrospinning preparation |
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| CN201610273756.2A CN105839203B (en) | 2016-04-28 | 2016-04-28 | Utilize the three-dimensional porous yarn and preparation method thereof of Electrospinning preparation |
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| CN105839203B CN105839203B (en) | 2019-02-12 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106299286A (en) * | 2016-09-08 | 2017-01-04 | 天津大学 | A kind of lithium-sulfur cell macromolecule composite positive pole and preparation method |
| CN106531474A (en) * | 2016-12-14 | 2017-03-22 | 中国工程物理研究院化工材料研究所 | Linear electrode and preparation method therefor by adopting electrospinning technique |
| CN109253740A (en) * | 2018-09-10 | 2019-01-22 | 中原工学院 | A kind of capacitance type sensor and preparation method thereof based on nanofiber covering yarn |
| CN109273273A (en) * | 2018-09-10 | 2019-01-25 | 中原工学院 | PAN-GO/PEDOT:PSS electrode material for super capacitor based on nano fibre yarn and preparation method thereof |
| CN112376118A (en) * | 2020-04-13 | 2021-02-19 | 广东三水合肥工业大学研究院 | Electrostatic spinning equipment |
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| CN102912456A (en) * | 2011-08-04 | 2013-02-06 | 中国人民解放军装甲兵工程学院 | Method and system for preparing nanofiber coating on surface of yarn or fiber bundle |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106299286A (en) * | 2016-09-08 | 2017-01-04 | 天津大学 | A kind of lithium-sulfur cell macromolecule composite positive pole and preparation method |
| CN106299286B (en) * | 2016-09-08 | 2018-11-30 | 天津大学 | A kind of lithium-sulfur cell macromolecule composite positive pole and preparation method |
| CN106531474A (en) * | 2016-12-14 | 2017-03-22 | 中国工程物理研究院化工材料研究所 | Linear electrode and preparation method therefor by adopting electrospinning technique |
| CN109253740A (en) * | 2018-09-10 | 2019-01-22 | 中原工学院 | A kind of capacitance type sensor and preparation method thereof based on nanofiber covering yarn |
| CN109273273A (en) * | 2018-09-10 | 2019-01-25 | 中原工学院 | PAN-GO/PEDOT:PSS electrode material for super capacitor based on nano fibre yarn and preparation method thereof |
| CN109253740B (en) * | 2018-09-10 | 2021-02-12 | 中原工学院 | Capacitive sensor based on nanofiber core-spun yarn and preparation method thereof |
| CN112376118A (en) * | 2020-04-13 | 2021-02-19 | 广东三水合肥工业大学研究院 | Electrostatic spinning equipment |
| CN112376118B (en) * | 2020-04-13 | 2022-05-10 | 广东三水合肥工业大学研究院 | Electrostatic spinning equipment |
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