CN106222799B - A kind of double-layer nested nanofiber and preparation method thereof - Google Patents
A kind of double-layer nested nanofiber and preparation method thereof Download PDFInfo
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- CN106222799B CN106222799B CN201610628911.8A CN201610628911A CN106222799B CN 106222799 B CN106222799 B CN 106222799B CN 201610628911 A CN201610628911 A CN 201610628911A CN 106222799 B CN106222799 B CN 106222799B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- 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
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
Abstract
The present invention is configured to uniform precursor sol liquid by the polymer and metal salt of different molecular weight, nanofiber is obtained using high-voltage electrostatic spinning technology, in conjunction with gradient heat treatment process, obtain the nano material of the adjustable interior structure of the contraction of high quality, the decomposable process of the ingenious heating rate control composite fibre different using two stages, accurate and convenient control form nested structure and the double-deck inside pattern.
Description
Technical field
The invention belongs to technical field of nanometer material preparation.
Background technology
With the reach of science, great research finds that the structure of microcosmic multistage can make material possess many excellent property
Matter.Due to the development of modern synthetic technology and analysis test, microcosmic nano material also undergoes this and is drilled from simple to complicated structure
Become.In turn, many science greatly be have stimulated in the third generation micrometer/nanometer material for possessing more complicated interior structure in recent years
The research interest of family, because these structures possess more excellent performance.In addition, one-dimensional nano structure, because of its unique property
Cause the broad interest of researcher, and achieves very excellent chemical property.Electrostatic spinning has in all preparation methods
It has a clear superiority.Electrostatic spinning is simple with its manufacturing device, cost of spinning is cheap, it is various to spin substance classes, technique is controllable etc.
Advantage, it has also become effectively prepare one of main path of nano-fiber material.It is abundant that electrostatic spinning technique has been prepared for type
Nanofiber, including organic, organic/inorganic is compound and inorganic nano-fiber.For example, Xiang et al. is also with the technology
CuO doughnuts have been synthesized, and have further obtained porous hollow Cu fibers by hydrogen reduction process on this basis
（CrystEngComm, 2011, 13(15): 4856-4860）.In addition, beading chain nanofiber, loose porous Nanowire
Dimension and tasselled shape nanofiber also have been reported.It is needed however, preparing nanofiber using electrostatic spinning technique and being also faced with some
It solves the problems, such as.First, in terms of preparing organic nanofibers, the natural polymer kind for electrostatic spinning also extremely has
Limit, incomplete to the research of structure of title compound and performance, the application of final products is mostly only at the experimental stage, especially
There is also larger problems for the industrialization production of these products.Secondly, the performance of Static Spinning organic/inorganic composite nano fiber is not
It is only related with the structure of nano-particle, also with the clustered pattern of nano-particle and synergisticing performance, polymeric matrix structural behaviour,
The interfacial structure performance and processing combination process of particle and matrix etc. are related.How to prepare and is suitble to needs, high-performance, more work(
The composite nano fiber of energy is the key that research.In addition, the research of Static Spinning inorganic nano-fiber is substantially at initial period, nothing
Machine nanofiber has latent in multiple fields such as high temperature filtration, efficient catalytic, bioengineered tissue, photoelectric device, space flight equipment
Purposes, still, the larger brittleness of Static Spinning inorganic nano-fiber limits its application performance and range, therefore, exploitation tool
Simple production process, flexibility, continuity, the nano material of structural integrity are a technological difficulties.
Invention content
To solve the above-mentioned problems, technical scheme is as follows：
The present invention is configured to uniform precursor sol liquid, high-voltage electrostatic spinning by the polymer and metal salt of different molecular weight
Nanofiber is obtained, is heat-treated (gradient increased temperature rate and gradient temperature) process in conjunction with gradient, obtain the contraction of high quality can
The inorganic nano material of structure in adjusting, the decomposable process of the ingenious heating rate control composite fibre different using two stages,
Accurate and convenient control forms nested structure and the double-deck inside pattern.
The preparation method of the fiber, it is characterised in that：
1) weigh respectively the polyacrylamide of the high molecular weight of 0.3 ~ 1.5g, the middle-molecular-weihydroxyethyl of 0.78 ~ 1g polyacrylamide
The polyacrylamide of the low molecular weight of amine, 0.4 ~ 0.8g and the precipitating reagent of the metal salt of 2 ~ 3mmol and 4 ~ 7mmol are added simultaneously
To 28 ~ 39mL deionized waters, putting it to magnetic agitation 6h in 70 ~ 88 DEG C of thermostat water bath makes it all dissolve, and is formed saturating
Bright solution；In nitrate, sulfate, acetate, chloride and oxalates of the metal salt selected from Mg, Al, Zn, Zr and Fe
It is one or more；Selected from phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hydroxide, ammonium fluoride, carbon in the precipitating reagent
It is one or more in sour ammonium, ammonium hydrogen carbonate and oxalic acid；
2) step 1) precursor solution is added in injection, in 17 ~ 20kV of positive high voltage, negative high voltage -1.1 ~ 1.9kV's
Under the conditions of carry out electrostatic spinning, receive nanofiber with aluminium foil, syringe needle is adjusted to 13 ~ 18 cm, spinning solution at a distance from receiver board
1 ~ 1.5mL/h of fltting speed；
3) nanofiber obtained to step 2) is positioned in 120 DEG C of baking ovens dry 5h；
4) the compound nanofiber for obtaining electrostatic spinning in step 3), under inert gas atmosphere first with 20 DEG C of min-1
Fast heating rate keeps the temperature 1.5h, then with 2 DEG C of min to 380 DEG C-1Slow heating rate is to 550 DEG C and keeps the temperature 4h, you can obtains
The nested nanofiber being made of small nano particle；
A length of 5~15 μm of obtained nanofiber is formed by inside and outside two layer nestings, is between layers hollow-core construction,
A diameter of 200~400 nm of outer layer, a diameter of 80~120nm of internal layer, inside and outside interlamellar spacing is 40~70 nm, layer wall thickness 20
~30 nm.With more than or equal to 130m2The specific surface area of/g.
Inert gas is preferably nitrogen.Metal salt is preferably selected from one in the nitrate, sulfate and oxalates of Mg, Fe
Kind is a variety of；Selected from phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate in the precipitating reagent.
The Molecular Weight for Polyacrylamide of high molecular weight is 300-2,200 ten thousand, the Molecular Weight for Polyacrylamide of middle-molecular-weihydroxyethyl is
100-200 ten thousand, low molecular weight polyacrylamide molecular weight be less than 1,000,000.
Since high, medium and low molecular weight polyisoprene propylene milling amine has different viscosity and surface tension, in the work of high-pressure electrostatic
Under, three nano wire in the radial direction be in layered distribution, formed three coaxial configurations (i.e. high molecular weight outermost layer, low point
Son amount center, middle-molecular-weihydroxyethyl therebetween).However inorganic salts are uniformly distributed in nanofiber.First, electrospun nanofiber is fine
Dimension is with 20 DEG C of min-1Fast heating rate is to 380 DEG C, and the crystalline rate Vc of inorganic salts is less than Polymer-pyrolysis rate Vp, this will lead
It causes moving direction by internal layer outer layers, is formed hollow.Then, 1.5h is kept the temperature at 380 DEG C, because capillary force and polymer pipe are soft
Essence will cause outer polymeric layer to shrink.Finally with 2 DEG C of min-1Heating rate be heated to 550 DEG C, keep the temperature 4h.Because low
Heating rate under Vp be more than Vc, moving direction forms bivalve from centre to both sides.Finally, at high temperature, inorganic matter is further
Crystallization, forms the nanostructure of contraction.
Nanofiber and preparation method thereof in the present invention has following advantageous effect compared with the prior art：
（1）The present invention has prepared the metal composite oxide nanofiber with double-layer nested structure, inside and outside wall to
Contract can integrally improve the tap density of nanofiber, and diameter is distributed in relatively narrow region, have preferable structural integrity
With certain magnetism；
（2）The present invention is configured to uniform precursor sol liquid, high-pressure electrostatic by the polymer and metal salt of different molecular weight
Spinning obtains nanofiber, is heat-treated (gradient increased temperature rate and gradient temperature) process in conjunction with gradient, obtains the contraction of high quality
Adjustable interior structure inorganic nano material, it is ingenious using two stages it is different heating rate control composite fibre decomposition
Journey, accurate and convenient control form the pattern of nested structure.
Description of the drawings
Fig. 1 is nanofiber stereoscan photograph of the present invention
Specific implementation mode
Embodiment 1
1) weigh respectively the polyacrylamide of the high molecular weight of 1.1g, the middle-molecular-weihydroxyethyl of 0.8g polyacrylamide, 0.8g
The polyacrylamide of low molecular weight and the precipitating reagent of the metal salt of 2.3mmol and 4.7mmol simultaneously be added to 2.9mL go from
Sub- water, putting it to magnetic agitation 6h in 70 ~ 88 DEG C of thermostat water bath makes it all dissolve, and forms transparent solution；Metal
Salt is selected from ferric nitrate；Phosphoric acid is selected from the precipitating reagent；
2) step 1) precursor solution is added in injection, under conditions of positive high voltage 18kV, negative high voltage -1.8kV
Electrostatic spinning is carried out, receives nanofiber with aluminium foil, syringe needle is adjusted to 18 cm, spinning solution fltting speed at a distance from receiver board
1.4mL/h；
3) nanofiber obtained to step 2) is positioned in 120 DEG C of baking ovens dry 5h；
4) the compound nanofiber for obtaining electrostatic spinning in step 3), under inert gas atmosphere first with 20 DEG C of min-1
Fast heating rate keeps the temperature 1.5h, then with 2 DEG C of min to 380 DEG C-1Slow heating rate is to 550 DEG C and keeps the temperature 4h, you can obtains
The nested nanofiber being made of small nano particle；
A length of 13 μm of obtained nanofiber is formed by inside and outside two layer nestings, is between layers hollow-core construction, outer layer
A diameter of 300nm, a diameter of 100nm of internal layer, inside and outside interlamellar spacing are 55 nm, 21 nm of layer wall thickness.
Embodiment 2
1) weigh respectively the polyacrylamide of the high molecular weight of 1g, the polyacrylamide of the middle-molecular-weihydroxyethyl of 1g, 0.8g it is low
The polyacrylamide of molecular weight and the precipitating reagent of the metal salt of 2mmol and 5mmol are added to 30mL deionized waters simultaneously, by it
Being put into magnetic agitation 6h in 70 DEG C of thermostat water bath makes it all dissolve, and forms transparent solution；Metal salt is selected from magnesium chloride；
Diammonium hydrogen phosphate is selected from the precipitating reagent；
2) step 1) precursor solution is added in injection, under conditions of positive high voltage 18kV, negative high voltage -1.4kV
Electrostatic spinning is carried out, receives nanofiber with aluminium foil, syringe needle is adjusted to 15 cm, spinning solution fltting speed at a distance from receiver board
1mL/h；
3) nanofiber obtained to step 2) is positioned in 120 DEG C of baking ovens dry 5h；
4) the compound nanofiber for obtaining electrostatic spinning in step 3), under inert gas atmosphere first with 20 DEG C of min-1
Fast heating rate keeps the temperature 1.5h, then with 2 DEG C of min to 380 DEG C-1Slow heating rate is to 550 DEG C and keeps the temperature 4h, you can obtains
The nested nanofiber being made of small nano particle；
A length of 11 μm of obtained nanofiber is formed by inside and outside two layer nestings, is between layers hollow-core construction, outer layer
A diameter of 255 nm, a diameter of 85nm of internal layer, inside and outside interlamellar spacing are 48nm, layer wall thickness 25nm.
Comparative example 1
1) weigh respectively the polyvinyl alcohol of the high molecular weight of 1g, the polyvinyl alcohol of the middle-molecular-weihydroxyethyl of 0.75g, 0.35g it is low
The polyvinyl alcohol molecule amount of molecular weight and the four water manganese acetates of the four water cobalt acetates of 1.5mmol and 3mmol are added to simultaneously
20mL deionized waters, putting it to magnetic agitation 6h in 80 DEG C of thermostat water bath makes its all dissolve, and is formed transparent molten
Liquid；
2) step 1) precursor solution is added in injection, under conditions of positive high voltage 15kV, negative high voltage -2kV into
Row electrostatic spinning receives nanofiber with aluminium foil；
3) nanofiber obtained to step 2) is positioned in 120 DEG C of baking ovens dry 5h；
4) the compound nanofiber for obtaining electrostatic spinning in step 3), in air atmosphere first with 1 DEG C of min-1Slow
Heating rate keeps the temperature 1h, then with 10 DEG C of min to 280 DEG C-1Fast heating rate is to 500 DEG C and keeps the temperature 3h, you can obtains by micro-
The nanofiber of the contraction of small nano particle composition.
Comparative example 2
（1）2 solution of Mn (NO3) addition for weighing 0.4000g Fe2 (SO4) 3 and 0.36g 50wt% respectively fills 6 mL
In the beaker of DMF, stirring obtains the solution of clear homogeneous until all dissolving, and adds 1g PVP, is mixed evenly, obtains
The spinning solution of clear viscous；
（2）By step（1）The spinning solution of preparation pours into the syringe with the stainless steel syringe needle that outer diameter is 0.8 mm
Electrostatic spinning is carried out, indoor temperature and relative humidity are controlled respectively in 15 DEG C and 35% or so, syringe needle tune at a distance from receiver board
Whole is 20 cm, and spinning solution fltting speed is 0.9 mL/h, and the voltage of electrostatic spinning process is 16 kV, is collected using receiver board
To the composite nano fiber of ferrimanganic metal salt and polyvinylpyrrolidone；
（3）By step（2）The composite fibre of preparation carries out calcine by steps, and the first stage with the heating rate of 1 DEG C/min, rises
For temperature to 250 DEG C, second stage is warming up to 600 DEG C from 250 DEG C, and using the heating rate of 10 DEG C/min, soaking time is 4 h, so
After cool to room temperature with the furnace to get to iron-manganese metal composite oxide magnetic Nano fiber.
Material prepared by the present invention is as active material, according to active material：Acetylene black：Graphene oxide (binder)
Mass ratio be 7:2.5:0.5.In view of electrode reaction binary channels process (ion and electronics) and preferably play its structure
Advantage, graphene oxide are used to the adhesive instead of insulation, and the conductivity of electrode can but be increased by only accounting for the 5% of entire electrode.
Active material and acetylene black are sufficiently mixed first, while suitable isopropanol grinding is added uniformly, is eventually adding graphite oxide
Alkene makes active material be bonded together with acetylene black.Then mixture is pressed into diaphragm in homogeneous thickness on twin rollers, then cut
It is about 0.8cm to be cut into the same size, area2Small pieces, be put into 70 DEG C of baking oven it is dry for 24 hours.It is just with the diaphragm after tabletting
Pole, metal lithium sheet are cathode, stainless (steel) wire is collector, and shell is CR2016 type battery cases, and diaphragm paper is that Celgard2400 is micro-
Hole polypropylene screen, electrolyte are ethylene carbonate (EC)/dimethyl carbonate (DMC) (VEC of 1.0mol/LLiPF6:VDMC=
1:1) solution assembles lithium ion battery in the glove box (moisture is controlled in 8ppm or less) full of argon gas and seals, will be made
Standby battery standing can carry out electrochemical property test after one day.
Average size under the different current densities of table 1
The experimental results showed that the present invention has excellent high rate performance.
Cycle performance under the current density of 2 200mA g-1 of table, after 140 cycles, discharge capacity 200mA g-1's
Cycle performance under current density
| Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | |
| Discharge capacity（mAh/g） | 938 | 940 | 924 | 925 |
Claims (1)
1. a kind of double-layer nanometer fiber, it is characterised in that：Fiber has inside and outside two layers, and the preparation method of the fiber is：
1) weigh respectively the high molecular weight polyacrylamide of 0.3 ~ 1.5g, the middle-molecular-weihydroxyethyl polyacrylamide of 0.78 ~ 1g, 0.4 ~
The low molecular weight polyacrylamide of 0.8g and the precipitating reagent of the metal salt of 2 ~ 3mmol and 4 ~ 7mmol are added 28 ~ 39mL and go simultaneously
Ionized water, being then put into magnetic agitation 6h in 70 ~ 88 DEG C of thermostat water bath makes it all dissolve, and forms transparent solution；Gold
Belong to one or more in nitrate, sulfate, acetate, chloride and oxalates of the salt selected from Mg, Al, Zn, Zr and Fe；Institute
State in precipitating reagent selected from phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hydroxide, ammonium fluoride, ammonium carbonate, ammonium hydrogen carbonate and
It is one or more in oxalic acid；
2) step 1) precursor solution is added in injection, in 17 ~ 20kV of positive high voltage, the item of negative high voltage -1.1 ~ 1.9kV
Electrostatic spinning is carried out under part, receives nanofiber with aluminium foil, syringe needle is adjusted to 13 ~ 18 cm at a distance from receiver board, and spinning solution pushes away
Into 1 ~ 1.5mL/h of speed；
3) nanofiber obtained to step 2) is positioned in 120 DEG C of baking ovens dry 5h；
4) the compound nanofiber for obtaining electrostatic spinning in step 3), under inert gas atmosphere first with 20 DEG C of min-1Liter
Warm rate is warming up to 380 DEG C, keeps the temperature 1.5h, then with 2 DEG C of min-1Heating rate be warming up to 550 DEG C and keep the temperature 4h, you can obtain
The nested nanofiber being made of small nano particle；
A length of 5~15 μm of obtained nanofiber is formed by inside and outside two layer nestings, is between layers hollow-core construction, outer layer
A diameter of 200~400 nm, a diameter of 80~120nm of internal layer, inside and outside interlamellar spacing are 40~70 nm, layer wall thickness 20~30
nm。
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| CN201610628911.8A CN106222799B (en) | 2016-08-03 | 2016-08-03 | A kind of double-layer nested nanofiber and preparation method thereof |
| CN201810594833.3A CN108728935A (en) | 2016-08-03 | 2016-08-03 | A kind of metal composite oxide nanofiber |
| CN201810284958.6A CN108301070A (en) | 2016-08-03 | 2016-08-03 | A kind of preparation method of double-layer nested nanofiber |
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| CN201810284958.6A Division CN108301070A (en) | 2016-08-03 | 2016-08-03 | A kind of preparation method of double-layer nested nanofiber |
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| EP2204480B1 (en) * | 2008-12-25 | 2013-03-20 | Shinshu University | Process of manufacturing inorganic nanofibers |
| KR20110099475A (en) * | 2010-03-02 | 2011-09-08 | 건국대학교 산학협력단 | Manufacturing method of gradient nanofiber materials using coaxial multinozzle and the gradient nanofiber materials thereof |
| CN101787580B (en) * | 2010-03-12 | 2011-08-17 | 浙江大学 | Method for preparing coaxial micrometer fibers by utilizing combined drawing and filament forming device |
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