CN112186161B - Semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material and preparation method thereof - Google Patents

Semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material and preparation method thereof Download PDF

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CN112186161B
CN112186161B CN202011060902.6A CN202011060902A CN112186161B CN 112186161 B CN112186161 B CN 112186161B CN 202011060902 A CN202011060902 A CN 202011060902A CN 112186161 B CN112186161 B CN 112186161B
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electrode material
semi
filled
longitudinal hole
flexible electrode
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CN112186161A (en
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刘治明
王晓君
孙洪冉
徐常蒙
魏晴
李海昌
李慧芳
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Qingdao University of Science and Technology
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    • 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
    • H01M4/366—Composites as layered products
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 belongs to the technical field of electrode material preparation, and particularly relates to a semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material and a preparation method thereof. Synthesis of Sb by hydrothermal method2S3Or Bi2S3Nanorod, and then Sb is subjected to electrostatic spinning2S3Nanorod or Bi2S3Spinning the uniform mixture of the nanorods and the PAN spinning solution, and finally firing the electrostatic spinning product to respectively obtain the antimony carbon or bismuth carbon composite nanofiber membrane flexible electrode material with semi-filled one-dimensional nano longitudinal holes. The composite structure of the invention fully exerts the characteristics of high specific capacity of the metal antimony/bismuth and the characteristics of stable structure, good flexibility and high conductivity of the carbon material formed by PAN high-temperature treatment, and in addition, the volume expansion effect of the metal antimony/bismuth in the circulation process can be buffered by the semi-filling type longitudinal hole structure formed by partial volatilization of the antimony/bismuth.

Description

Semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material and preparation method thereof
The technical field is as follows:
the invention belongs to the technical field of electrode material preparation, and particularly relates to a semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material and a preparation method thereof.
Background art:
the development of sodium ion batteries is faced with problems mainly of low energy density, low power density, short cycle life. The development of large-capacity, long-cycle, high-rate sodium storage materials is a major challenge in the development of sodium ion batteries. The negative electrode material is one of the main factors influencing the performance of the sodium ion battery, so that the development of the negative electrode material with high specific capacity and long cycle life is very important. The negative electrode material with alloy or conversion reaction has higher theoretical specific capacity due to multi-electron reaction in the process of energy storage, and has been widely concerned by people in recent years. The metal antimony and the metal bismuth have simple synthesis methods and moderate voltage platforms due to high specific capacity, and are widely concerned by researchers. However, antimony/bismuth undergoes large volume expansion during sodium intercalation, and a pulverization phenomenon occurs under the action of stress, so that the antimony/bismuth falls off from a current collector, loss of active substances and structural damage of an electrode material are caused, and the cycle life and the actual specific capacity of the antimony/bismuth are affected. In addition, the side reaction of antimony/bismuth in direct contact with the electrolyte is another drawback that limits its development. In recent years, researchers have attempted to solve the above-mentioned problems by means of a strategy of making structures nano-sized and combining the structures with carbon materials. However, other work is to attach the antimony/bismuth to the surface of the carbon material, so that the antimony/bismuth is directly exposed in the electrolyte, side reactions in the charging and discharging process are increased, and the coulombic efficiency and the actual specific capacity are reduced; or the carbon material is attached to the surface of the metal antimony/bismuth, so that the metal antimony/bismuth is prevented from being directly exposed in the electrolyte, but the antimony/bismuth in the carbon material is subjected to large volume change in the charging and discharging process, the carbon material can continuously fall off under the action of cyclic stress, the loss of the active substances caused by the loss of restrained antimony powder is avoided, the cyclic performance is further influenced, and the problem cannot be fundamentally solved.
The invention content is as follows:
the invention aims to solve the technical problems that antimony/bismuth can generate large volume expansion in the process of sodium intercalation, and can generate pulverization phenomenon to fall off from a current collector under the action of stress, so that the loss of active substances and the damage of an electrode material structure are caused, and the cycle life and the actual specific capacity of the electrode material are influenced; and the side reaction of antimony/bismuth in direct contact with the electrolyte is another drawback that limits its development.
In order to solve the problems, the invention obtains the antimony carbon or bismuth carbon composite nanofiber membrane flexible electrode material with the semi-filled one-dimensional nano longitudinal hole, the composite structure fully exerts the characteristics of high specific capacity of metal antimony/bismuth and the characteristics of stable structure, good flexibility and high conductivity of a carbon material formed by PAN high-temperature treatment, and in addition, the semi-filled longitudinal hole structure formed by partial volatilization of antimony/bismuth can buffer the volume expansion effect of the metal antimony/bismuth in the circulation process.
In order to achieve the purpose, the invention is realized by the following technical scheme that the preparation method of the semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material is characterized in that Sb is synthesized by a hydrothermal method2S3(antimony trisulfide) or Bi2S3(bismuth trisulfide) nano-rod, then Sb is spun by electrostatic spinning method2S3Nanorod or Bi2S3Spinning the uniform mixture of the nanorods and the PAN spinning solution, and finally firing the electrostatic spinning product to respectively obtain the antimony carbon or bismuth carbon composite nanofiber membrane flexible electrode material with semi-filled one-dimensional nano longitudinal holes.
Further, the method comprises the following steps:
(1)Sb2S3the preparation of (1): reacting SbCl3L-cysteine and Na2S·9H2Dissolving O in deionized water in sequence, and stirring; transferring the product to heating equipment for hydrothermal treatment, and centrifugally washing the product with deionized water and alcohol to obtain Sb2S3A nanorod; SbCl3First hydrolyzed to produce Sb3+After dissolvingS in the sulfur source of (1)2-And Sb3+And (4) reacting. Sb2S3Nanorod main edge [001 ]]Directional growth of cysteine and Na2S·9H2O as a double sulfur source to Sb2S3The formation of nanorods has an important synergistic effect.
Or Bi2S3The preparation of (1): adding BiCl3·9H2Dissolving O in deionized water, adding HCl, and stirring until the solution is clear to obtain a solution A; mixing Na2S·9H2Dissolving O in deionized water, and stirring until the O is dissolved to obtain a solution B; mixing the solution A and the solution B, transferring the mixture into heating equipment for hydrothermal treatment, and centrifugally washing the mixture by using deionized water and alcohol to obtain Bi2S3A nanorod; HCl BiCl avoidance3Hydrolysis produced a white precipitate (BiOCl) in which Na is present2S·9H2The O dissolution provides a sulfur source. Bi in the synthesis process2S3Along [001 ]]The crystal face grows directly.
(2) Dissolving PAN into DMF under the condition of heating and stirring; then, stirring and fully dissolving PAN-DMF under the heating condition to form a spinning solution; sb prepared in the step (1)2S3Or Bi2S3Adding the nano-rods into the spinning solution, and continuously stirring for electrostatic spinning; after the electrostatic spinning is finished, carrying out vacuum drying on the fiber cloth obtained by electrostatic spinning; PAN is a solid powder which gradually dissolves at 70 ℃ to form a viscous liquid after adding DMF liquid. Adding the nano-rods and stirring to form a spinning solution precursor with uniformly dispersed nano-rods. And (3) dragging the precursor liquid into one-dimensional nano fibers under the action of high-voltage electrostatic force, and finally obtaining the fiber cloth formed by the one-dimensional nano wires.
(3) Heating the dried spun yarn in a tubular furnace at 250 ℃ for 1 hour under the flowing argon atmosphere, and then heating the spun yarn to 500-700 ℃ for 1 hour; carbonizing the PAN spinning main body and simultaneously utilizing carbon formed by carbonizing PAN to obtain Sb2S3Reduction to Sb or Bi2S3Reducing the carbon nano-fiber into Bi, forming longitudinal hole spaces on the carbon nano-fiber framework by the two methods respectively, and leaving Sb or Bi with different carrying amounts in the spaces; namely, Sb or Bi can be continuously volatilized in the subsequent heat treatment process, and the productThe volume is reduced, cavities can be formed around Sb or Bi in the process, the problem of active substance pulverization caused by large volume expansion of Sb or Bi in the charging and discharging process can be well buffered by the longitudinal hole space, the active substance Sb or Bi can be reserved in the longitudinal holes of the carbon fibers, the loss of the active substance is avoided, and the high capacity and the cycle performance of the composite material in the energy storage element are ensured.
Further, in step (1), 2mmol of SbCl was added34mmol of L-cysteine, 4mmol of Na2S·9H2O was sequentially dissolved in 40ml of deionized water and magnetically stirred.
Further, in the step (1), 12mmol of BiCl is added3·9H2Dissolving O in 16ml of deionized water, adding 4ml of HCl, and stirring until the solution is clear; 20mmol of Na2S·9H2O was dissolved in 20ml of deionized water and stirred magnetically.
Further, Sb in the step (1)2S3Or Bi2S3The hydrothermal treatment conditions of (2) were 180 ℃ for 12 hours.
Further, in the step (2), 0.2g of PAN is dissolved in 1.2g of DMF under the condition of heating and stirring; the condition for forming the spinning solution is to stir for 8 hours under the heating condition of 70 ℃; the spinning conditions are that the voltage is 15-20kv and the glue pushing speed is 0.5-2 ml/h; the vacuum drying condition is drying for 6h at 60-80 ℃.
Further, the temperature rise rate in the step (3) is 2 ℃/min.
The semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material prepared by the method adopts a one-dimensional nano structure as an active material precursor, and simultaneously plays the roles of a template and the precursor; the carbon nano-wire wraps antimony/bismuth in different longitudinal hole micro-cavities, and charge-discharge reactions in each micro-cavity are independent. The volume expansion of the antimony/bismuth also occurs in the micro-cavity, and each carbon nano-wire as a whole basically has no obvious volume expansion to the outside, so that the cycling stability of the electrode material is further improved.
The invention has the following beneficial effects:
(1) according to the invention, the carbon nanowires wrap antimony/bismuth in different longitudinal hole micro-cavities, so that charge and discharge reactions in each micro-cavity are independent, volume expansion of the antimony/bismuth also occurs in the micro-cavity, and each carbon nanowire as a whole basically has no obvious volume expansion to the outside, so that the cycle stability of the electrode material is further improved. The existing method is that a carbon material is directly coated on the surface of metal antimony or metal bismuth, and a space for the metal antimony/bismuth to expand in volume is not reserved in the charging and discharging process of the metal antimony/bismuth, so that the antimony/bismuth is greatly changed in volume in the charging and discharging process, a coated carbon shell is dropped under the action of cyclic stress, the antimony/bismuth is directly exposed in electrolyte, the metal antimony/bismuth is pulverized to cause the loss of active substances, and the cyclic performance is further influenced; or the antimony/bismuth is attached to the surface of the carbon material, so that the structural stability of the antimony/bismuth and the carbon material is reduced, the antimony/bismuth is directly exposed in the electrolyte, the side reaction in the charge-discharge process is increased, and the coulombic efficiency and the actual specific capacity are reduced. The composite structure of the invention fully exerts the characteristic of high specific capacity of the metal antimony/bismuth, the mesopore space around the antimony/bismuth can well buffer the problem of large volume expansion of the antimony in the charging and discharging processes, and the carbon nanowire main body has a directional electron ion conduction direction, strong stress bearing capacity and a short axial electron ion transmission path, and the advantages can effectively improve the cycle performance and the rate capability of the electrode material. In addition, the coated carbon shell has a stable structure, so that the overall conductivity can be improved, and the overall stability of the structure can be improved.
(2) Interconnected PAN forms a carbon nanowire body with a directional electron-ion conduction direction. In addition, the strong stress bearing capacity and the short axial electron ion transmission path can effectively improve the cycle performance and the rate capability of the electrode material. In addition, the coated carbon nanowire shell can not only improve the overall conductivity, but also improve the overall stability of the structure. The carbon nanowire shell wraps antimony/bismuth in different micro-cavities, so that charging and discharging reactions in each micro-cavity are independent, volume expansion of the antimony/bismuth also occurs in the micro-cavity, and the wrapped carbon nanowire framework does not have obvious volume expansion to the outside basically as a whole, so that the circulation stability of the electrode material is further improved.
(3) The composite electrode material finished product has extremely high flexibility, can be bent or even folded at will, can keep the structural integrity after being unfolded, can still keep the shape of the one-dimensional nano longitudinal hole composite nanofiber membrane after charge-discharge circulation, and can still be bent or folded at will. Due to the macroscopic structural stability and the special high conductivity, the self-supporting membrane electrode material can be used as a self-supporting electrode material without an adhesive or a conductive agent, and the mode of using the self-supporting membrane electrode material avoids using the adhesive and the conductive agent which do not contribute to the capacity, and improves the specific capacity of the quality. The composite material can be combined with a proper flexible positive electrode material to be developed into a flexible battery, and has wide application in wearable equipment, flexible special equipment and the like. The existing preparation method adopts a method of adding a binder and a conductive agent, so that the mass specific capacity of the electrode material is reduced, the preparation is complex, the preparation process of the electrode material is time-consuming, the electrode material has no flexible characteristic, and the electrode material cannot be developed in the direction of a flexible electrode.
(4) The method can control the size of the cavity around the antimony/bismuth in the finished carbon fiber and the content of the antimony/bismuth in the carbon fiber by controlling the high-temperature treatment time, and can reasonably optimize the electrochemical performance of the antimony-carbon/bismuth-carbon composite fiber membrane flexible electrode material (the Sb volume ratio in the cavity is smaller as the heating time is longer) by reasonably optimizing the proportion of antimony sulfide to PAN or the proportion of bismuth sulfide to PAN, the heating condition and other parameters in the electrostatic spinning process. When the heat treatment time is long enough, antimony/bismuth can be completely volatilized, only independent longitudinal holes are left in the carbon fibers, PAN can be used for preparing the carbon fibers with porous interiors, and the method has certain guiding significance in carbon fiber morphology engineering.
(5) The method is also suitable for preparing the composite nanofiber membrane flexible electrode material semi-filled with the one-dimensional nano longitudinal holes by other one-dimensional precursors such as tin sulfide and the like through an electrostatic spinning method.
Drawings
FIG. 1 shows Sb according to the invention2S3Scanning electron microscope images after spinning with PAN mixed spinning solution;
FIG. 2 is an electron microscope image I of the one-dimensional antimony sulfide nanorod template removed to different degrees at different firing times;
FIG. 3 is an electron microscope image II of the one-dimensional antimony sulfide nanorod template removed to different degrees at different firing times;
FIG. 4 shows Bi of the present invention2S3Scanning electron microscope images after spinning with PAN mixed spinning solution;
FIG. 5 is an electron microscope image I of the one-dimensional bismuth sulfide nanorod template removed to different degrees at different firing times;
FIG. 6 is an electron microscope image II of the one-dimensional bismuth sulfide nanorod template removed to different degrees at different firing times.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of a semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material comprises the following steps:
(1)Sb2S3the preparation of (1):
40ml of deionized water were placed in a 50ml Teflon bottle, and 2mmol of SbCl was added34mmol of L-cysteine, 4mmol of Na2S·9H2O was dissolved in the above deionized water sequentially and magnetically stirred for 3 hours. And sealing the stirred polytetrafluoroethylene bottle filled with the homogeneous suspension into a stainless steel shell matched with the polytetrafluoroethylene bottle, transferring the polytetrafluoroethylene bottle to heating equipment, and carrying out hydrothermal treatment at 180 ℃ for 12 hours. After the water heating is finished, centrifugal washing is carried out by deionized water and alcohol to obtain Sb2S3And (4) nanorods.
(2) 0.2g of PAN was dissolved in 1.2g of DMF under stirring with heating. PAN-DMF is fully dissolved by stirring for 8h under the heating condition of 70 DEG CThen forming a spinning solution by mixing 0.1-0.5g of Sb2S3Adding the mixture into the spinning solution, and continuously heating and stirring for 3 hours to form mixed spinning solution for electrostatic spinning. The spinning conditions are that the voltage is 15-20kv and the glue pushing speed is 0.5-2 ml/h. And after spinning is finished, the spun yarn is dried for 6 hours in vacuum at the temperature of 60-80 ℃.
(3) The dried spun yarn was heated at 250 ℃ for 1 hour (heating rate 2 ℃/min) in a flowing argon atmosphere in a tube furnace, and then heated at 500 ℃ to 700 ℃ for 1 hour (heating rate 2 ℃/min) in order to carbonize the main body of PAN spun yarn and simultaneously carbonize Sb with carbon formed by PAN carbonization2S3The two methods respectively form longitudinal hole spaces on the carbon nanofiber framework and leave Sb with different loading amounts in the spaces.
Example 2:
a preparation method of a semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material comprises the following steps:
(1)Bi2S3the preparation of (1):
16ml of deionized water was added to a 50ml Teflon bottle, and 12mmol of BiCl was added3·9H2O, dissolved in the above deionized water, 4ml HCl was added and stirred until clear. 20mmol of Na2S·9H2O was dissolved in another beaker of deionized water and magnetically stirred until completely dissolved. Mixing the two well-stirred homogeneous suspensions, transferring the mixed homogeneous suspensions to a polytetrafluoroethylene bottle, sealing the polytetrafluoroethylene bottle in a stainless steel shell matched with the polytetrafluoroethylene bottle, transferring the polytetrafluoroethylene bottle to heating equipment, and carrying out hydrothermal treatment at 180 ℃ for 12 hours. After the hydrothermal reaction is finished, the solution is centrifugally washed by deionized water and alcohol to obtain Bi2S3And (4) nanorods.
(2) 0.2g of PAN was dissolved in 1.2g of DMF under stirring with heating. PAN-DMF is stirred for 8 hours under the heating condition of 70 ℃ to be fully dissolved to form spinning solution, and 0.1 to 0.5g of Bi2S3Adding the mixture into the spinning solution, and continuously heating and stirring for 3 hours to form mixed spinning solution for electrostatic spinning. The spinning conditions are that the voltage is 15-20kv and the glue pushing speed is 0.5-2 ml/h. Vacuum drying the spun yarn at 60-80 deg.C for 6h after spinning, and during the above synthesis process, PAN and Bi2S3、Sb2S3The proportion of DMF and DMF can be adjusted.
(3) The dried spun yarn was heated at 250 ℃ for 1 hour (heating rate 2 ℃/min) in a flowing argon atmosphere in a tube furnace, and then heated at 500 ℃ to 700 ℃ for 1 hour (heating rate 2 ℃/min) in order to carbonize the main body of PAN spun yarn and simultaneously to carbonize Bi by the carbon formed by PAN carbonization2S3The two methods respectively form longitudinal hole spaces on the carbon nanofiber framework and leave Sb or Bi with different loading amounts in the spaces, and parameters such as temperature, heating rate, heating time and the like in the synthesis process are adjustable.

Claims (8)

1. A preparation method of a semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material is characterized by comprising the following steps: synthesis of Sb by hydrothermal method2S3Or Bi2S3Nanorod, and then Sb is subjected to electrostatic spinning2S3Nanorod or Bi2S3Spinning the uniform mixture of the nanorods and the PAN spinning solution, and finally firing the electrostatic spinning product to respectively obtain the antimony carbon or bismuth carbon composite nanofiber membrane flexible electrode material with semi-filled one-dimensional nano longitudinal holes.
2. The preparation method of the semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material as claimed in claim 1, characterized by comprising the following steps:
(1)Sb2S3the preparation of (1): reacting SbCl3L-cysteine and Na2S·9H2Dissolving O in deionized water in sequence, and stirring; transferring the product to heating equipment for hydrothermal treatment, and centrifugally washing the product with deionized water and alcohol to obtain Sb2S3A nanorod;
or Bi2S3The preparation of (1): adding BiCl3·9H2Dissolving O in deionized water, adding HCl, and stirring until the solution is clear to obtain a solution A; mixing Na2S·9H2Dissolving O in deionized water, and stirring until the O is dissolved to obtain a solution B; mixing the solution A and the solution B, transferring the mixture into heating equipment for hydrothermal treatment, and centrifugally washing the mixture by using deionized water and alcohol to obtain Bi2S3A nanorod;
(2) dissolving PAN into DMF under the condition of heating and stirring; then, stirring and fully dissolving PAN-DMF under the heating condition to form a spinning solution; sb prepared in the step (1)2S3Or Bi2S3Adding the nano-rods into the spinning solution, and continuously stirring for electrostatic spinning; after finishing, carrying out vacuum drying on the spinning;
(3) the dried spun yarn was heated in a tube furnace under flowing argon atmosphere at 250 ℃ for 1 hour and then heated to 500 ℃ and 700 ℃ for 1 hour.
3. The method for preparing the semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material as claimed in claim 2, wherein the method comprises the following steps: in step (1), 2mmol of SbCl34mmol of L-cysteine, 4mmol of Na2S·9H2O was sequentially dissolved in 40ml of deionized water and magnetically stirred.
4. The method for preparing the semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material as claimed in claim 2, wherein the method comprises the following steps: in the step (1), 12mmol of BiCl is added3·9H2Dissolving O in 16ml of deionized water, adding 4ml of HCl, and stirring until the solution is clear; 20mmol Na2S·9H2O was dissolved in 20ml of deionized water and stirred magnetically.
5. The method for preparing the semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material as claimed in claim 2, wherein the method comprises the following steps: sb in step (1)2S3Or Bi2S3The hydrothermal treatment conditions of (2) were 180 ℃ for 12 hours.
6. The method for preparing the semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material as claimed in claim 2, wherein the method comprises the following steps: dissolving 0.2g of PAN into 1.2g of DMF under the condition of heating and stirring in the step (2); the condition for forming the spinning solution is to stir for 8 hours under the heating condition of 70 ℃; the spinning conditions are that the voltage is 15-20kv and the glue pushing speed is 0.5-2 ml/h; the vacuum drying condition is drying for 6h at 60-80 ℃.
7. The method for preparing the semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material as claimed in claim 2, wherein the method comprises the following steps: the temperature rise rate in the step (3) is 2 ℃/min.
8. A semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material prepared by any one of the methods of claims 1 to 7, which is characterized in that: a one-dimensional nanostructure is adopted as an active material precursor, and the active material precursor plays the roles of a template and the precursor at the same time; the carbon nano-wire wraps antimony/bismuth in different longitudinal hole micro-cavities, and charge-discharge reactions in each micro-cavity are independent.
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