CN111485296B - Preparation method and application of bionic multi-component fiber - Google Patents
Preparation method and application of bionic multi-component fiber Download PDFInfo
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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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/06—Feeding liquid to the spinning head
- D01D1/09—Control of pressure, temperature or feeding rate
-
- 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
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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
- 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
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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
- 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
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention relates to a preparation method and application of a bionic multi-component fiber, which comprises an outer shell layer and a multi-inner core layer, wherein the outer shell layer is made of a biological material with excellent mechanical properties, the multi-inner core layer is made of a biological material with excellent electrical properties so as to ensure the tensile property and the electrical properties of the bionic multi-component fiber, and the tensile property and the electrical properties of the fiber are accurately adjusted by controlling the number of inner cores and the thickness ratio of the outer shell to the inner cores; the outer shell layer and the multi-core layer are prepared by a multi-component microfluidic technology. The multi-component fiber provided by the invention has good mechanical properties and electrical properties, and the preparation method of the microfluidic spinning has the advantages of low cost, convenience in assembly and control, safety, reliability and capability of accurately controlling the shape of the fiber. The invention provides application of the prepared bionic multi-component fiber in flexible electronics, which has good flexibility and cyclicity in good electrical properties and strong applicability.
Description
Technical Field
The invention relates to the field of biological materials, in particular to a preparation method and application of a bionic multi-component fiber.
Background
As an emerging technology, flexible electronics, which is characterized by wearability and portability, has been applied to various aspects of human society. In order to accommodate the rapid development of flexible electronics, a variety of energy storage devices such as supercapacitors with sufficient energy density and long cycle life are being extensively studied and developed. Currently, fiber-like flexible electronics is considered as the most promising trend due to its advantages of light weight, good flexibility, low cost, etc. However, current manufacturing strategies for these fibrous flexible electronics are mainly based on multi-step coating or manual twisting, and the manufacturing process is often complicated, time-consuming, labor-consuming, and incapable of precise control. Therefore, a simple and precisely controlled generation of fibrous flexible electrons is still desirable.
The current simple and convenient controllable fiber preparation methods include direct drawing method, wet spinning, electrospinning, micro-spinning and the like. The micro-fluidic spinning technology can accurately and systematically control the fluid in the set micro-fluidic channel, so that the micro-fluidic spinning technology becomes the optimal choice for continuously preparing the fibrous functional material. By adjusting the rheological parameters such as the concentration, the flow speed, the viscosity and the like of the fluid in the microfluidic spinning process, the flowing state of the fluid in the microfluidic channel can be correspondingly changed, thereby generating certain influence on the performance and the structure of the fiber. Meanwhile, the microfluidic spinning technology has the advantages of simple and convenient operation, low cost, safety, reliability and the like, and shows great potential in biomedical engineering applications such as cell culture, drug sustained release and the like. However, the preparation of fibrous flexible electrons by the microfluidic spinning technology still remains to be developed.
Therefore, the invention is inspired by the silkworm spinning process and the silk hierarchical structure in nature, and based on the microfluidic spinning technology, the multi-component fiber is prepared and applied to flexible electronic systems such as flexible supercapacitors and the like.
Disclosure of Invention
The invention aims to overcome the defect of the existing research on simply and controllably preparing fibrous flexible electrons, and provides a method for simply and controllably preparing multi-component fibers based on a microfluidic spinning technology, and the method is applied to flexible electronic systems such as supercapacitors.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a bionic multi-component fiber comprises an outer shell layer and a multi-core layer, wherein the outer shell layer is made of a biological material with excellent mechanical properties, the multi-core layer is made of a biological material with excellent electrical properties, so that the tensile property and the electrical properties of the bionic multi-component fiber are ensured, and the tensile property and the electrical properties of the fiber are accurately adjusted by controlling the number of cores and the thickness ratio of the outer shell to the cores; the outer shell layer and the multi-core layer are prepared by a multi-component microfluidic technology.
The preparation method of the bionic multi-component fiber comprises the following steps:
(1) preparing a multi-component microfluidic device: a plurality of capillary tubes which are stretched into cones are taken as inner core fluid channels and coaxially assembled into an intermediate phase capillary tube which is taken as a shell layer precursor solution channel, and then all the capillary tubes are coaxially inserted into an outer phase collecting capillary tube which is used for solidifying the shell layer precursor solution channel;
(2) preparing an inner core solution with good electrical property for preparing an inner core layer, a shell layer precursor solution with good mechanical property for preparing an outer shell layer and a curing solution for curing the shell precursor solution; respectively introducing the capillary core fluid channels, the intermediate phase capillary fluid channels and the external phase collection capillary fluid channels in the step (1), and enabling all fluids to flow in the same direction;
(3) the core-shell ratio of the multi-component fiber is accurately controlled by adjusting the flow rate of each phase of solution; the number of the inner core fluid channels of the microfluidic device is adjusted to realize the accurate control of the number of the inner cores of the multicomponent fibers; thereby realizing the regulation and control of the mechanical property and the electrical property of the multi-component fiber.
In step (1), transparent epoxy resin is used to seal at the necessary capillary interface.
The multi-component fiber corresponding to the capillary cross-sectional structure is formed by utilizing the property that the phase solutions present a laminar flow state.
The solution with good electrical property of the inner core is a carbon nano tube solution, a conductive polymer solution or an MXene solution
The inner core solution with good electrical property for preparing the inner core layer is a carbon nano tube solution, a conductive polymer solution or an MXene solution.
The shell layer precursor solution with good mechanical property for preparing the outer shell layer is a polyurethane solution PU, a polyvinylidene fluoride solution PVDF or a sodium alginate solution Na-Alg.
The curing solution for curing the shell precursor solution is an alcohol solution, a deionized water solution or a calcium chloride solution.
The bionic multi-component fiber can be continuously generated, the diameter is 400-550 mu m, and the shell thickness is 350-550 mu m. The capacitance value of the prepared bionic multi-component fiber can reach 250 ℃ per meter2And exhibits better cycle performance.
The invention also protects the application of the bionic multi-component fiber as flexible electronics, and the prepared bionic multi-component fiber has excellent tensile property and electrical property and can be applied to manufacturing super capacitors and the like.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a bionic multi-component fiber, wherein the multi-component fiber has good mechanical property and electrical property, and the preparation method of the microfluidic spinning has the advantages of low cost, convenience in assembly and control, safety, reliability and capability of accurately controlling the shape of the fiber. The invention provides application of the prepared bionic multi-component fiber in flexible electronics, which has good flexibility and cyclicity in good electrical properties and strong applicability.
Drawings
FIG. 1 is a schematic structural diagram of a biomimetic multicomponent fiber according to the present invention.
Fig. 2 is a schematic structural diagram of a microfluidic device for preparing a biomimetic multicomponent fiber according to the present invention.
FIG. 3 is a schematic representation of the structure of a multicomponent fiber obtained in one embodiment of the present invention.
FIG. 4 is a graph of profile control of a multicomponent fiber obtained in accordance with an embodiment of the present invention.
FIG. 5 is a graph of electrical properties of a multicomponent fiber obtained in one example of the invention.
FIG. 6 is a graph of tensile properties and tensile-electrical response of a multicomponent fiber obtained in an example of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
A bionic multi-component fiber comprises an outer shell layer and a multi-core layer, wherein the outer shell layer is made of a biological material with excellent mechanical properties, the multi-core layer is made of a biological material with excellent electrical properties, so that the tensile property and the electrical properties of the bionic multi-component fiber are ensured, and the tensile property and the electrical properties of the fiber are accurately adjusted by controlling the number of cores and the thickness ratio of the outer shell to the cores; the outer shell layer and the multi-core layer are prepared by a multi-component microfluidic technology.
The preparation method of the bionic multi-component fiber comprises the following steps:
(1) preparing a multi-component microfluidic device: a plurality of capillary tubes which are stretched into cones are taken as inner core fluid channels and coaxially assembled into an intermediate phase capillary tube which is taken as a shell layer precursor solution channel, and then all the capillary tubes are coaxially inserted into an outer phase collecting capillary tube which is used for solidifying the shell layer precursor solution channel;
(2) preparing an inner core solution with good electrical property for preparing an inner core layer, a shell layer precursor solution with good mechanical property for preparing an outer shell layer and a curing solution for curing the shell precursor solution; respectively introducing the capillary core fluid channels, the intermediate phase capillary fluid channels and the external phase collection capillary fluid channels in the step (1), and enabling all fluids to flow in the same direction;
(3) the core-shell ratio of the multi-component fiber is accurately controlled by adjusting the flow rate of each phase of solution; the number of the inner core fluid channels of the microfluidic device is adjusted to realize the accurate control of the number of the inner cores of the multicomponent fibers; thereby realizing the regulation and control of the mechanical property and the electrical property of the multi-component fiber.
In step (1), transparent epoxy resin is used to seal at the necessary capillary interface.
The multi-component fiber corresponding to the capillary cross-sectional structure is formed by utilizing the property that the phase solutions present a laminar flow state.
The solution with good electrical property of the inner core is a carbon nano tube solution, a conductive polymer solution or an MXene solution
The inner core solution with good electrical property for preparing the inner core layer is a carbon nano tube solution, a conductive polymer solution or an MXene solution.
The shell layer precursor solution with good mechanical property for preparing the outer shell layer is a polyurethane solution PU, a polyvinylidene fluoride solution PVDF or a sodium alginate solution Na-Alg.
The curing solution for curing the shell precursor solution is an alcohol solution, a deionized water solution or a calcium chloride solution.
The bionic multi-component fiber can be continuously generated, the diameter is 400-550 mu m, and the shell thickness is 350-550 mu m. The capacitance value of the prepared bionic multi-component fiber can reach 250 ℃ per meter2And exhibits better cycle performance.
Fig. 1 shows a schematic structural diagram of a bionic multicomponent fiber, which specifically comprises an outer shell made of a biomaterial with good mechanical properties and a plurality of inner cores made of a biomaterial with excellent electrical properties. The multi-component structure is inspired by the silk structure in nature.
Fig. 2 shows a schematic structural diagram of a microfluidic device of a bionic multicomponent fiber, which specifically comprises a plurality of conical internal phase capillary channels, a conical intermediate phase capillary channel and an external phase collecting channel. The outer sides of the plurality of internal phase capillary channels are coaxially sleeved with intermediate phase capillary channels, and the outer phase collecting channel channels are coaxially sleeved outside the intermediate phase capillary channels. And the plurality of internal phase capillary channels, the plurality of intermediate phase capillary channels and the plurality of external phase capillary channels are respectively connected with the internal phase liquid inlet device, the intermediate phase liquid inlet device and the external phase liquid inlet device. Each phase liquid inlet device comprises a syringe pump and a syringe (comprising a syringe needle); the injection pump is connected with the injector, and the injection needle of the injector is connected with the plurality of internal phase capillaries, the intermediate phase capillaries and the external phase capillaries through the conduits.
Example 1 preparation of biomimetic multicomponent fibers
(1) Preparing a multi-component microfluidic spinning device:
according to the schematic structural diagram of the microfluidic device shown in fig. 2, a plurality of internal phase capillary channels, intermediate phase capillary channels and external phase collecting channel channels are coaxially assembled and connected with each phase liquid inlet device.
(2) Preparing the relevant solution
Selecting a 0.15 wt% single-walled carbon nanotube aqueous dispersion liquid mixed with 10% polyvinyl alcohol (PVA) in an internal phase solution of 1:1, a polyurethane/dimethylformamide (PU/DMF) solution with a mass volume ratio of 1:5 in an intermediate phase, and an alcohol solution in an external phase collection liquid.
(3) The prepared internal phase solution, intermediate phase solution and external phase solution are connected with each phase injector and injection pump through pipes, and are injected into each phase channel through the injection pump, the flow velocity of each phase is adjusted, the PU fiber of the stable continuous multi-Carbon Nano Tube (CNTs) core is prepared and collected in large quantity, as shown in figure 3.
Example 2 morphology modulation of biomimetic multicomponent fibers
And selecting a microfluidic device of the double internal phase capillary, and determining the internal diameters of the internal phase capillary to be 100 mu m and 140 mu m. In the preparation process of the fiber, the change of the fiber wall thickness is obtained by real-time measurement in an online observation device by adjusting the flow rate of the inner phase CNTs solution or the flow rate of the intermediate phase PU solution, and the accurate control of the fiber wall thickness can be realized, as shown in FIG. 4.
Example 3 Electrical Performance testing of biomimetic multicomponent fibers
Taking the PU fiber with double CNTs as an example, the scanning rate of 10mV/s was determined, the fiber was subjected to cyclic voltammetry testing for 50 times at 0 to 1V, and the corresponding capacitance value was calculated, so that it was clear that the obtained multicomponent PU fiber had stable and good electrical properties, as shown in fig. 5. In the aspect of flexibility, the PU fiber of the CNTs core is subjected to a tensile test, and the capacitance change of the PU fiber of the double CNTs core under the tensile condition is tested, as shown in figure 6, the obtained multi-component PU fiber has excellent tensile property and tensile-response property. On the basis, the bionic multi-component PU fiber can be predicted to play a great advantage in other flexible electronic applications.
Example 4 preparation of biomimetic multicomponent MXene fibers
(1) Preparing a multi-component microfluidic spinning device:
according to the schematic structural diagram of the microfluidic device shown in fig. 2, a plurality of internal phase capillary channels, intermediate phase capillary channels and external phase collecting channel channels are coaxially assembled and connected with each phase liquid inlet device.
(2) Preparing the relevant solution
Selecting MXene aqueous dispersion with 5mg/mL internal phase solution, sodium alginate aqueous solution with 2 wt% intermediate phase, and calcium chloride (CaCl) with 2 wt% external phase collection solution2) And (3) solution.
(3) And connecting the prepared inner phase solution, intermediate phase solution and outer phase solution with injectors and injection pumps of all phases through pipes, injecting the solutions into channels of all phases through the injection pumps, adjusting the flow velocity of all phases, preparing the stable continuous calcium alginate fibers with MXene cores, and collecting a large amount of the stable continuous calcium alginate fibers.
Example 5 preparation of a biomimetic multicomponent conductive Polymer fiber
(1) Preparing a multi-component microfluidic spinning device:
according to the schematic structural diagram of the microfluidic device shown in fig. 2, a plurality of internal phase capillary channels, intermediate phase capillary channels and external phase collecting channel channels are coaxially assembled and connected with each phase liquid inlet device.
(2) Preparing the relevant solution
Selecting a conductive polymer PEDOT: PSS dispersion liquid with 10.5mg/mL of internal phase solution, a polyvinylidene fluoride/dimethylformamide (PVDF/DMF) solution with the mass volume ratio of 1:10 as an intermediate phase, and a deionized water solution as an external phase collecting liquid.
(3) And connecting the prepared internal phase solution, intermediate phase solution and external phase solution with each phase injector and injection pump through pipes, injecting the solutions into each phase channel through the injection pump, adjusting the flow velocity of each phase, preparing and obtaining stable continuous PVDF fibers of PEDOT (Poly ethylene propylene diene monomer) PSS cores, and collecting a large amount of the PVDF fibers.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (1)
1. A preparation method of bionic multi-component fibers for manufacturing a supercapacitor is characterized by comprising the following steps: the bionic multi-component fiber comprises an outer shell layer and a multi-inner core layer, wherein the outer shell layer is made of a biological material with excellent mechanical properties, the multi-inner core layer is made of a biological material with excellent electrical properties, so that the tensile property and the electrical properties of the bionic multi-component fiber are guaranteed, and the tensile property and the electrical properties of the fiber are accurately adjusted by controlling the number of inner cores and the thickness ratio of the outer shell to the inner cores; the outer shell layer and the multi-core layer are prepared by a multi-component microfluidic technology;
the inner core solution with good electrical property for preparing the inner core layer is a carbon nano tube solution, a conductive polymer solution or an MXene solution; the shell layer precursor solution with good mechanical property for preparing the outer shell layer is a polyurethane solution PU, a polyvinylidene fluoride solution PVDF or a sodium alginate solution Na-Alg; the curing solution for curing the shell precursor solution is an alcohol solution, a deionized water solution or a calcium chloride solution;
the bionic multi-component fiber can be continuously generated, the diameter is 400-550 mu m, and the thickness of the shell can be controlled to be 350-550 mu m; the tensile property and the electrical property are excellent;
the preparation method comprises the following steps:
(1) preparing a multi-component microfluidic device: a plurality of capillary tubes which are stretched into cones are taken as inner core fluid channels and coaxially assembled into an intermediate phase capillary tube which is taken as a shell layer precursor solution channel, and then all the capillary tubes are coaxially inserted into an outer phase collecting capillary tube which is used for solidifying the shell layer precursor solution channel;
(2) preparing an inner core solution with good electrical property for preparing an inner core layer, a shell layer precursor solution with good mechanical property for preparing an outer shell layer and a curing solution for curing the shell precursor solution; respectively introducing the capillary core fluid channels, the intermediate phase capillary fluid channels and the external phase collection capillary fluid channels in the step (1), and enabling all fluids to flow in the same direction;
(3) the core-shell ratio of the multi-component fiber is accurately controlled by adjusting the flow rate of each phase of solution; the number of the inner core fluid channels of the microfluidic device is adjusted to realize the accurate control of the number of the inner cores of the multicomponent fibers; thereby realizing the regulation and control of the mechanical property and the electrical property of the multi-component fiber;
in the step (1), transparent epoxy resin is used for sealing at a necessary capillary tube interface;
the multi-component fiber corresponding to the capillary cross-sectional structure is formed by utilizing the property that the phase solutions present a laminar flow state.
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CN112481721A (en) * | 2020-12-28 | 2021-03-12 | 南京鼓楼医院 | Microfluidic spinning device, linear type core-shell structure conductive fiber, and preparation method and application thereof |
CN112593302A (en) * | 2020-12-28 | 2021-04-02 | 南京鼓楼医院 | Microfluidic spinning device, spiral core-shell structure conductive fiber, and preparation method and application thereof |
CN112921436B (en) * | 2021-03-08 | 2023-04-07 | 南京鼓楼医院 | Fiber wrapping perovskite quantum dots, preparation method and device |
CN113350562A (en) * | 2021-06-04 | 2021-09-07 | 南京鼓楼医院 | Preparation method and application of gellan gum bionic microfiber doped with antibacterial peptide |
CN113737512B (en) * | 2021-09-15 | 2023-08-08 | 武汉纺织大学 | Method for preparing elastic conductive fiber by micro-fluid coating technology and elastic conductive fiber |
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