CN110042506A - A kind of flexibility Sb2Se3The electrostatic spinning preparation method of/C nano fiber - Google Patents

A kind of flexibility Sb2Se3The electrostatic spinning preparation method of/C nano fiber Download PDF

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Publication number
CN110042506A
CN110042506A CN201910359015.XA CN201910359015A CN110042506A CN 110042506 A CN110042506 A CN 110042506A CN 201910359015 A CN201910359015 A CN 201910359015A CN 110042506 A CN110042506 A CN 110042506A
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electrostatic spinning
nano fiber
flexibility
solution
spinning
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刘黎
袁依婷
夏靖
王先友
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Xiangtan University
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Xiangtan University
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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
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of flexibility Sb2Se3The electrostatic spinning preparation method of/C nano fiber.N,N-Dimethylformamide solvent is heated first, SbCl is added into hot solution3, magnetic agitation to dissolve, obtain colourless transparent solution；Then Se powder is added in colourless transparent solution, stirs evenly, obtains dark solution；Polyvinylpyrrolidone is added, continues to stir to get sticky electrostatic spinning precursor solution, then transfer them in injector for medical purpose, the spinning on electrostatic spinning apparatus, gained nano-fiber material is received with glass plate, and rear high temperature cabonization is dried to material, obtains final product Sb2Se3/ C nano fiber.Gained Sb of the invention2Se3/ C is uniform nanofiber, and diameter is about 200 ~ 400 nm, and has excellent chemical property.

Description

A kind of flexibility Sb2Se3The electrostatic spinning preparation method of/C nano fiber
Technical field
The present invention relates to the preparation of electrode material, in particular to a kind of flexibility Sb2Se3The electrostatic spinning system of/C nano fiber Preparation Method.
Background technique
Demand of the mankind to the energy increasingly increases, and oil production rate but reduces increasingly, oil combustion pollution on the environment The worry of people is also resulted in, so the energy-storage system for seeking clean and effective becomes the topic that researchers are concerned about very much.Currently, For lithium ion battery since its is environmental-friendly, it is at this stage that the advantages of high-energy density and long circulation life, which has been widely used, Using a kind of very high energy-storage system of degree.Lithium ion battery is in portable electronic product and electric car and hybrid electric vapour Commercialization in terms of the power of vehicle has numerous successful cases, is concerned.But since the resources reserve of elemental lithium is limited, excessively Exploitation can similarly face the even exhausted problem of resource scarcity, and sodium-ion battery reacts machine with similar with lithium ion battery Reason, and sodium element resources reserve is abundant, therefore can become the preferred substitute of lithium ion battery.
Negative electrode material is most important for the high-energy density for realizing sodium-ion battery.Two-dimensional material is received since its is lesser Rice structure and there is unique property, typical two-dimensional material includes Transition Metal Sulfur, selenides, the graphene etc. of layering.Its In, laminated metal selenides is very suitable to use because there is relatively weak M-Se ionic bond to have outstanding performance in material kinetics Make the negative electrode material of sodium-ion battery.Wherein, the stratiform antimony selenide with adjustable interval structure is due to its high theoretical capacity and height Electric conductivity and cause extensive concern.
Present invention uses electrospinning process, this method is a kind of special fiber fabrication process, in forceful electric power is had a meeting, an audience, etc. well under one's control By conducting polymer fluid atomizing at the thread with nanostructure, nanofiber is solidified into longer injection route. This method is lower to environmental requirement, easy to operate, and gained nanofibers of dimensions becomes uniformly and with biggish specific surface area A kind of effective ways preparing basic material in new energy field.The present invention is once added all required during electrostatic spinning Reagent, spinning gained nano-fiber material obtain final product through one-step calcination, and process is simple and environmentally-friendly, and product safely cleaning is A kind of excellent spinning mode of innovative energy-saving.
Summary of the invention
The purpose of the present invention is to provide a kind of flexibility Sb2Se3The electrostatic spinning preparation method of/C nano fiber, utilization are quiet Prepared by the method for Electrospun, resulting materials have nanofibrous structures, can effectively inhibit antimony base negative electrode material in charge and discharge Volume expansion in the process；Its speciality flexible makes it possible application of the material in flexible battery, be it is a kind of it is great before The sodium ion negative electrode material of scape.
The technical solution of the present invention is as follows:
A kind of flexibility Sb2Se3The electrostatic spinning preparation method of/C nano fiber, includes the following steps:
(1) N,N-dimethylformamide solvent is heated to 50 ~ 80 DEG C；
(2) SbCl is added in the N,N-dimethylformamide solvent after step (1) heating3, magnetic agitation to dissolve, obtain nothing Color clear solution；
(3) Se powder is added into step (2) colourless transparent solution, stirs evenly, obtains dark solution；
(4) polyvinylpyrrolidone is added in dark solution obtained by step (3), is sufficiently dissolved, continuous heating stirring, until solution It is sticky and uniform, obtain electrostatic spinning presoma；
(5) electrostatic spinning presoma liquid relief obtained by step (4) is subjected to spinning with electrostatic spinning machine into flat needle applicator, Gained nanofiber is collected with glass plate；
(6) after the nanofiber drying collected to step (5), high temperature cabonization is carried out, flexible Sb is obtained2Se3/ C nano fiber.
Further, in step (2), SbCl3Mass fraction in the solution is 13.89 ~ 24.57%.
Further, in step (3), the Se powder of addition and the amount ratio of n,N-Dimethylformamide are 4 ~ 8 mmol: 5mL。
Further, in step (4), the polyvinylpyrrolidone average molecular weight of addition is 1300000.
Further, SbCl3, Se powder, polyvinylpyrrolidone mass ratio be 3 ~ 6:1 ~ 2:16.
Further, in step (5), spinning parameter are as follows: voltage in 12 ~ 18 kV, the setting of micro-injection flow rate pump 0.3 ~ 0.6 mL/h, for syringe needle internal diameter in 0.8 ~ 1.2 mm, receiving the distance i.e. spacing of spinning nozzle and receiver board is 12 ~ 25 cm, spinning Instrument internal temperature is 20 ~ 40 DEG C.
Further, in step (6), drying temperature is 60 ~ 110 DEG C.
Further, in step (6), high temperature cabonization carries out under an ar atmosphere, detailed process are as follows: with the liter of 3 ~ 4 DEG C/min Warm rate is raised to 550 ~ 750 DEG C from room temperature, keeps the temperature 4 ~ 8 h, be then cooled to room temperature with the rate of temperature fall of 3 ~ 4 DEG C/min.
The present invention has following technical effect that
The present invention is prepared for a kind of Sb flexible using electrospinning process easy to operate2Se3/ C-material, during the spinning process SbCl is added3With the common spinning of Se powder, solid-state Se powder and SbCl in tube furnace inert atmosphere3Directly react, by one-step calcination, Resulting materials are uniform nano-fiber material, and distribution of fiber diameters has good flexibility and excellent in 200 ~ 500 nm Different chemical property, can be used for flexible battery, be a kind of negative electrode material of great prospect of sodium-ion battery.
Detailed description of the invention
Fig. 1 is Sb prepared by the embodiment of the present invention 32Se3The x-ray diffraction pattern of/C.
Fig. 2 is the Sb that the embodiment of the present invention 3 is prepared in 650 DEG C of high temperature cabonizations2Se3/ C flexible nano fiber is as cathode material Material, sodium piece are to be assembled into button cell to electrode.At 20 ~ 25 DEG C, in the voltage range of 0.01 ~ 2.5 V, 50 mA g-1 Current density under carry out charge-discharge test cycle performance and coulombic efficiency figure.
Fig. 3 is the Sb that the embodiment of the present invention 3 is prepared in 650 DEG C of high temperature cabonizations2Se3/ C flexible nano fiber is as cathode material Material, sodium piece are to be assembled into button cell to electrode.At 20 ~ 25 DEG C, in the voltage range of 0.01 ~ 2.5 V, 50, 100,200,500,1000,2000 and 50 mA g-1The high rate performance figure of charge-discharge test is carried out under current density.
Fig. 4 is flexible Sb prepared by the embodiment of the present invention 32Se3(amplification factor is the scanning electron microscope (SEM) photograph of/C nano fiber 10000 times).
Fig. 5 is flexible Sb prepared by the embodiment of the present invention 32Se3/ C nano fiber is as sodium-ion battery flexible electrode Photo.
Specific embodiment
The present invention will be further described combined with specific embodiments below, but the present invention is not limited thereto.
Embodiment 1
The N,N-dimethylformamide solution of 5 mL is placed in the salable vial of 10 mL heating stirring to 50 at room temperature DEG C, 0.912 g SbCl is added in hot solution3It is sufficiently stirred to obtain colourless transparent solution；0.473 g Se powder is added, after It is continuous to stir to get dark solution；0.5 g polyvinylpyrrolidone is added into dark solution, 6 h of magnetic agitation is sticky to solution Uniformly, electrostatic spinning presoma is obtained；The electrostatic spinning presoma of brand-new is injected in flat needle applicator, electrostatic spinning machine is used Spinning is carried out, nanofiber obtained by spinning is collected with glass plate, spinning parameter are as follows: voltage is 12 kV, and micro-injection flow rate pump is 0.3 mL/h, syringe needle internal diameter are 1.2 mm, and receiving distance (spacing of spinning nozzle and receiver board) is 15 cm, temperature inside spinning instrument Degree is 25 DEG C.By collecting nanofibers obtained by spinning in porcelain boat, it is placed in 60 DEG C of 6 h of drying of vacuum oven；After drying Nanofiber carries out high temperature cabonization, specifically: with the heating rate of 3 DEG C/min, 500 DEG C are raised to from room temperature, keeps the temperature 4 h, later It is cooled to room temperature with the rate of temperature fall of 4 DEG C/min, obtains the incomplete Sb that is carbonized2Se3/ C, because carburizing temperature is lower and other Process conditions such as are not enough suitable at the reasons, are carbonized not complete enough, resulting materials electric conductivity is poor.
Embodiment 2
The N,N-dimethylformamide solution of 5 mL is placed in the salable vial of 10 mL heating stirring to 70 at room temperature DEG C, 0.912 g SbCl is added in hot solution3It is sufficiently stirred to obtain colourless transparent solution；0.632 g Se powder is added, after It is continuous to stir to get dark solution；0.5 g polyvinylpyrrolidone is added into dark solution, 6 h of magnetic agitation is sticky to solution Uniformly, electrostatic spinning presoma is obtained；The electrostatic spinning presoma of brand-new is injected in flat needle applicator, electrostatic spinning machine is used Spinning is carried out, nanofiber obtained by spinning is collected with glass plate, spinning parameter are as follows: voltage is 15 kV, and micro-injection flow rate pump is 0.4 mL/h, syringe needle internal diameter are 1.0 mm, and receiving distance (spacing of spinning nozzle and receiver board) is 15 cm, temperature inside spinning instrument Degree is 25 DEG C.By collecting nanofibers obtained by spinning in porcelain boat, it is placed in 60 DEG C of 6 h of drying of vacuum oven；After drying Nanofiber carries out high temperature cabonization, specifically: with the heating rate of 3 DEG C/min, 600 DEG C are raised to from room temperature, keeps the temperature 3 h, later It is cooled to room temperature with the rate of temperature fall of 4 DEG C/min, obtains the incomplete Sb that is carbonized2Se3/ C, because carbonization time is shorter and other Process conditions such as are not enough suitable at the reasons, are carbonized not complete enough, resulting materials electric conductivity is poor.
Embodiment 3
The N,N-dimethylformamide solution of 5 mL is placed in the salable vial of 10 mL heating stirring to 50 at room temperature DEG C, 1.369 g SbCl are added in hot solution3It is sufficiently stirred to obtain colourless transparent solution；0.632 g Se powder is added, after It is continuous to stir to get dark solution；0.5 g polyvinylpyrrolidone is added into dark solution, 6 h of magnetic agitation is sticky to solution Uniformly, electrostatic spinning presoma is obtained；The electrostatic spinning presoma of brand-new is injected in flat needle applicator, electrostatic spinning machine is used Spinning is carried out, nanofiber obtained by spinning is collected with glass plate, spinning parameter are as follows: voltage is 16 kV, and micro-injection flow rate pump is 0.3 mL/h, syringe needle internal diameter are 1.0 mm, and receiving distance (spacing of spinning nozzle and receiver board) is 15 cm, temperature inside spinning instrument Degree is 25 DEG C.By collecting nanofibers obtained by spinning in porcelain boat, it is placed in 60 DEG C of 6 h of drying of vacuum oven；After drying Nanofiber carries out high temperature cabonization, specifically: with the heating rate of 3 DEG C/min, 650 DEG C are raised to from room temperature, keeps the temperature 4 h, later It is cooled to room temperature with the rate of temperature fall of 4 DEG C/min up to final product Sb2Se3/C。
Embodiment 4
The N,N-dimethylformamide solution of 5 mL is placed in the salable vial of 10 mL heating stirring to 70 at room temperature DEG C, 1.141 g SbCl are added in hot solution3It is sufficiently stirred to obtain colourless transparent solution；0.473 g Se powder is added, after It is continuous to stir to get dark solution；0.5 g polyvinylpyrrolidone is added into dark solution, 6 h of magnetic agitation is sticky to solution Uniformly, electrostatic spinning presoma is obtained；The electrostatic spinning presoma of brand-new is injected in flat needle applicator, electrostatic spinning machine is used Spinning is carried out, nanofiber obtained by spinning is collected with glass plate, spinning parameter are as follows: voltage is 16 kV, and micro-injection flow rate pump is 0.3 mL/h, syringe needle internal diameter are 1.0 mm, and receiving distance (spacing of spinning nozzle and receiver board) is 15 cm, temperature inside spinning instrument Degree is 25 DEG C.By collecting nanofibers obtained by spinning in porcelain boat, it is placed in 60 DEG C of 6 h of drying of vacuum oven；After drying Nanofiber carries out high temperature cabonization, specifically: with the heating rate of 3 DEG C/min, 700 DEG C are raised to from room temperature, keeps the temperature 4 h, later It is cooled to room temperature with the rate of temperature fall of 4 DEG C/min up to final product Sb2Se3/C。
Embodiment 5
The N,N-dimethylformamide solution of 5 mL is placed in the salable vial of 10 mL heating stirring to 50 at room temperature DEG C, 1.369 g SbCl are added in hot solution3It is sufficiently stirred to obtain colourless transparent solution；0.632 g Se powder is added, after It is continuous to stir to get dark solution；0.5 g polyvinylpyrrolidone is added into dark solution, 6 h of magnetic agitation is sticky to solution Uniformly, electrostatic spinning presoma is obtained；The electrostatic spinning presoma of brand-new is injected in flat needle applicator, electrostatic spinning machine is used Spinning is carried out, nanofiber obtained by spinning is collected with glass plate, spinning parameter are as follows: voltage is 18 kV, and micro-injection flow rate pump is 0.3 mL/h, syringe needle internal diameter are 1.2 mm, and receiving distance (spacing of spinning nozzle and receiver board) is 15 cm, temperature inside spinning instrument Degree is 25 DEG C.By collecting nanofibers obtained by spinning in porcelain boat, it is placed in 60 DEG C of 6 h of drying of vacuum oven；After drying Nanofiber carries out high temperature cabonization, specifically: with the heating rate of 3 DEG C/min, 800 DEG C are raised to from room temperature, keeps the temperature 8 h, later It is cooled to room temperature with the rate of temperature fall of 4 DEG C/min, obtains the complete Sb that is carbonized2Se3/ C, but cause to receive since carburizing temperature is excessively high Rice fibre structure is destroyed, and the flexibility of resulting materials is poor.
3 to 4 products obtained therefrom of embodiment is used for all kinds of characterizations, gained characterization result is almost the same, below with 3 institute of embodiment Be illustrated for product.
Shown in Fig. 1, by with Sb2Se3Standard card PDF 15-0861 comparison as can be seen that embodiment 3 prepare Sb2Se3/ C and Sb2Se3Characteristic diffraction peak it is very identical, and crystallinity is high, substantially free of impurities peak, it was demonstrated that the material it is main Ingredient is Sb2Se3。
Shown in Fig. 2, the Sb of the preparation of embodiment 32Se3For/C flexible nano fiber as negative electrode material, sodium piece is to electrode, group Dress up button cell.At 20 ~ 25 DEG C, in the voltage range of 0.01 ~ 2.5 V, 50 mA g-1Current density under carry out The cycle performance and coulombic efficiency figure of charge-discharge test.First discharge specific capacity is 623.6 mAh g-1, charge specific capacity is 253.6 mAh g-1, coulombic efficiency is 55.8 % for the first time, and specific discharge capacity still has 211 mAh g after 100 circle of circulation-1.This table Bright, flexible material of the invention has preferable electrochemistry cycle performance, to provide more fully possibility for its application.
Shown in Fig. 3, with the Sb of the preparation of embodiment 32Se3/ C flexible nano fiber as negative electrode material, sodium piece be to electrode, It is assembled into button cell.At 20 ~ 25 DEG C, in the voltage range of 0.01 ~ 2.5 V, 50,100,200,500,1000, 2000 and 50 mA g-1The high rate performance figure of charge-discharge test is carried out under current density.In 50 mA g-1Current density under, Specific discharge capacity is about 326 mAh g after 5 circle of circulation-1, when current density rises to 100,200,500,1000,2000, put Electric specific capacity is respectively 306,288,266,241,213 mAh g-1, current density returns to 50 mA after the charge and discharge of high current g-1And after recycling ten circles, still there are 307 mAh g-1Specific discharge capacity, show flexibility Sb2Se3/ C nano fiber has more excellent Different high rate performance.
Shown in Fig. 4, the flexible Sb of the preparation of embodiment 32Se3Scanning electron microscope (SEM) photograph (the amplification factor 10000 of/C nano fiber Times), nanofiber diameter is uniform in figure, about between 200 ~ 400 nanometers, fiber surface is smooth, completely without obvious burr, lack It falls into, there is more completely classical spinning fibre structure.
Shown in Fig. 5, the flexible Sb of the preparation of embodiment 32Se3Photograph of/C nano the fiber as sodium-ion battery flexible electrode Piece.The electrode thickness is uniform, and surfacing has preferable flexibility, can larger angle bending, restore rebound after electrode without obvious Damage, can bear repeatedly to crimp.Prove that the electrode material has a possibility that realizing flexible battery.

Claims (8)

1. a kind of flexibility Sb2Se3The electrostatic spinning preparation method of/C nano fiber, which comprises the steps of:
(1) N,N-dimethylformamide solvent is heated to 50 ~ 80 DEG C；
(2) SbCl is added in the N,N-dimethylformamide solvent after step (1) heating3, magnetic agitation to dissolve, obtain nothing Color clear solution；
(3) Se powder is added into step (2) colourless transparent solution, stirs evenly, obtains dark solution；
(4) polyvinylpyrrolidone is added in dark solution obtained by step (3), is sufficiently dissolved, continuous heating stirring, until solution It is sticky and uniform, obtain electrostatic spinning presoma；
(5) electrostatic spinning presoma liquid relief obtained by step (4) is subjected to spinning with electrostatic spinning machine into flat needle applicator, Gained nanofiber is collected with glass plate；
(6) after the nanofiber drying collected to step (5), high temperature cabonization is carried out, flexible Sb is obtained2Se3/ C nano fiber.
2. flexibility Sb according to claim 12Se3The electrostatic spinning preparation method of/C nano fiber, which is characterized in that step Suddenly in (2), SbCl3Mass fraction in the solution is 13.89 ~ 24.57%.
3. flexibility Sb according to claim 12Se3The electrostatic spinning preparation method of/C nano fiber, which is characterized in that step Suddenly in (3), the Se powder of addition and the amount ratio of n,N-Dimethylformamide are 4 ~ 8 mmol: 5 mL.
4. flexibility Sb according to claim 12Se3The electrostatic spinning preparation method of/C nano fiber, which is characterized in that step Suddenly in (4), the polyvinylpyrrolidone average molecular weight of addition is 1300000.
5. flexibility Sb according to claim 12Se3The electrostatic spinning preparation method of/C nano fiber, which is characterized in that SbCl3, Se powder, polyvinylpyrrolidone mass ratio be 3 ~ 6: 1 ~ 2: 16.
6. flexibility Sb according to claim 12Se3The electrostatic spinning preparation method of/C nano fiber, which is characterized in that step Suddenly in (5), spinning parameter are as follows: voltage is arranged in 12 ~ 18 kV, micro-injection flow rate pump in 0.3 ~ 0.6 mL/h, syringe needle internal diameter In 0.8 ~ 1.2 mm, receiving the spacing that distance is spinning nozzle and receiver board is 12 ~ 25 cm, spinning instrument internal temperature is 20 ~ 40℃。
7. flexibility Sb according to claim 12Se3The electrostatic spinning preparation method of/C nano fiber, which is characterized in that step Suddenly in (6), drying temperature is 60 ~ 110 DEG C.
8. flexibility Sb according to claim 12Se3The electrostatic spinning preparation method of/C nano fiber, which is characterized in that step Suddenly in (6), high temperature cabonization carries out under an ar atmosphere, detailed process are as follows: with the heating rate of 3 ~ 4 DEG C/min, is raised to 550 from room temperature ~ 750 DEG C, 4 ~ 8 h are kept the temperature, are then cooled to room temperature with the rate of temperature fall of 3 ~ 4 DEG C/min.
CN201910359015.XA 2019-04-30 2019-04-30 A kind of flexibility Sb2Se3The electrostatic spinning preparation method of/C nano fiber Pending CN110042506A (en)

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Application publication date: 20190723