CN110085841B - Preparation of Na from titanium dioxide carbon fiber 4 Ti 5 O 12 Method for preparing-C nano fiber negative electrode material - Google Patents

Preparation of Na from titanium dioxide carbon fiber 4 Ti 5 O 12 Method for preparing-C nano fiber negative electrode material Download PDF

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CN110085841B
CN110085841B CN201910379870.7A CN201910379870A CN110085841B CN 110085841 B CN110085841 B CN 110085841B CN 201910379870 A CN201910379870 A CN 201910379870A CN 110085841 B CN110085841 B CN 110085841B
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negative electrode
fiber
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titanium dioxide
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CN110085841A (en
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刘黎
苏蝶
聂苏
刘珺芳
王先友
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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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • 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
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    • 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 relates to a method for preparing Na from titanium dioxide carbon fibers 4 Ti 5 O 12 A preparation method of-C nanofiber negative electrode material. Firstly, uniformly mixing N, N-dimethylformamide, ethanol and acetic acid, then adding butyl titanate, and stirring until the butyl titanate is completely dissolved to obtain a light yellow transparent solution; and adding polyvinylpyrrolidone, continuously stirring to obtain an electrostatic spinning precursor solution, transferring the electrostatic spinning precursor solution into an electrostatic spinning medical injector, starting spinning on an electrostatic spinning device, and receiving the spun nano-fibers by using tin foil. Then the tin foil substrate carrying the nano-fiber is dried in vacuum, then the nano-fiber is collected by a corundum ark to be carbonized to obtain TiO2-C nano-fiber, and then the nano-fiber and sodium carbonate are sintered together to obtain Na 4 Ti 5 O 12 And the @ C negative electrode material. Na obtained by the invention 4 Ti 5 O 12 the-C nano fiber has uniform diameter of about 100-250 nm and excellent electrochemical performance.

Description

Preparation of Na from titanium dioxide carbon fiber 4 Ti 5 O 12 Method for preparing-C nanofiber negative electrode material
Technical Field
The invention relates to a sodium ion battery cathode material, in particular to a method for preparing Na from titanium dioxide carbon fibers 4 Ti 5 O 12 -a method of making a C nanofiber anode material.
Background
Under the background of global villages, human energy is gradually converted from fossil fuel to ecotype, and human faces an important period of energy conversion, and the development and utilization of renewable and clean new energy becomes the key of sustainable development of human society. New energy sources such as solar energy, wind energy, water energy and the like are still difficult to use due to the limitation of natural conditions, and are difficult to stably supply. Under the background, a large-scale energy storage system has great application prospect on meeting the living energy requirements of people. The lithium ion battery is an excellent energy storage material which is green and environment-friendly, light in weight, large in capacity and free of memory effect, and since the lithium ion battery is commercialized by Sony corporation in 1991, the novel energy storage material is widely applied to various fields all over the world. In the development of the automobile industry, countries and residents support new energy automobiles, and lithium ion batteries, which is the most core technology in power sources of automobiles, are always hot spots for research and development of students all over the world.
As one of novel battery negative electrode materials, titanium dioxide is widely studied in the field of lithium ion batteries due to the diversity of crystal forms and structures. However, the lithium content in the earth crust is low, and the research on the energy storage battery by using sodium with richer content is more practical. The volume expansion rate of the titanium dioxide is only 3% in the charging and discharging process, and the titanium dioxide has a high and stable discharging platform, small structural change and short sodium insertion and removal stroke, so that the titanium dioxide has good safety and long service life. The research on titanium dioxide as a substrate and titanium-based metal oxide as a negative electrode material is very hot at present. The most common of them is Na 2 Ti 3 O 7 Most notably, the theoretical reversible capacity of this material is close to 200mAh/g, primarily due to its lower redox couple Ti (III)/Ti (IV). However, it is noteworthy that Li 4 Ti 5 O 12 The spinel type can provide a good two-dimensional conduction path, so that sodium ions or lithium ions can smoothly pass through, and the theoretical reversible specific capacity of the spinel type lithium ion battery is also the highest in titanium-based lithium metal materials. Under such thinking, Na 4 Ti 5 O 12 Whether the sodium storage performance is better or not is provided, so that the current energy crisis is solved, and a thinking mode is provided for people.
However, Na has been reported 4 Ti 5 O 12 In the method for synthesizing the material, anatase and Na 16 Ti 10 O 28 After the synthesis of the molar ratio, the product can be obtained by reaction at 900 ℃. High energy consumption, rigorous synthesis conditions, expensive equipment and complex operation in the process cause the method to be limited in practical application. In recent years, electrospinningThe technology attracts extensive attention of scientific research personnel due to simple equipment and easy control of the preparation process, and is considered to be one of the simplest and most effective methods for preparing the nano-fibers. The electrostatic spinning is easy to prepare uniform composite materials, such as doping, functionalization and the like, and the prepared materials have high specific surface area and large length-diameter ratio. Due to these unique advantages, electrospinning technology can be applied in many fields such as energy, environment, biomedicine, etc. Therefore, if the electrospinning technique is introduced into Na 4 Ti 5 O 12 The preparation of the nano-fiber has very important significance.
Disclosure of Invention
The invention aims to provide simple Na synthesized by titanium dioxide carbon fiber by combining a solid phase method and an electrostatic spinning method 4 Ti 5 O 12 A method for preparing nano-fiber.
The technical scheme of the invention is as follows:
na synthesized by titanium dioxide and carbon fiber 4 Ti 5 O 12 The preparation method of the-C nanofiber negative electrode material comprises the following steps:
(1) uniformly mixing N, N-dimethylformamide, ethanol and acetic acid to obtain a mixed solvent, adding butyl titanate, and magnetically stirring until the butyl titanate is completely dissolved to obtain a light yellow transparent solution;
(2) adding polyvinylpyrrolidone into the solution obtained in the step (1), and continuing to perform magnetic stirring to obtain a light yellow transparent electrostatic spinning precursor solution;
(3) transferring the precursor solution obtained in the step (2) into a medical injector for electrostatic spinning, starting spinning on an electrostatic spinning device, and receiving the nanofiber obtained by spinning by using a tin foil;
(4) drying the baseplate tin foil loaded with the nano-fibers obtained in the step (3), collecting the nano-fibers by using a corundum ark, and putting the nano-fibers into a reactor filled with Ar and H 2 Carbonizing in a tube furnace of mixed gas to obtain a product TiO 2 -C nanofibers;
(5) TiO obtained in the step (4) 2 -C nanofibers andsodium carbonate is put into a tubular furnace together, and the temperature is raised and the calcination is carried out under the argon atmosphere, thus obtaining the Na synthesized by the titanium dioxide carbon fiber 4 Ti 5 O 12 -a C nanofiber negative electrode material.
Further, in the mixed solvent in the step (1), the volume ratio of the N, N-dimethylformamide to the ethanol to the acetic acid is 8-9: 12-13: 1 to 2.
Further, in the step (1), the volume ratio of the butyl titanate to the mixed solvent is 1-2: 9 to 11.
Further, the average molecular weight of polyvinylpyrrolidone in step (1) was 1300000.
Further, after polyvinylpyrrolidone is added in the step (2), the mass ratio of the polyvinylpyrrolidone to the mixed solvent is 9-11: 0.7-0.9, and the obtained TiO 2 The carbon content in the-C nanofibers is 33-46%.
Further, the electrostatic spinning parameters in the step (3) are as follows: the distance between the spinning needle head and the metal collecting substrate is 15-18 cm, the spinning voltage is 15-18 KV, the environmental temperature is 30-60 ℃, the humidity is 20-40%, and the liquid feeding speed is 0.2-0.5 mL/h.
Further, the drying in the step (4) is vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 4-6 hours.
Further, the carbonization treatment in the step (4) is to collect the nano-fiber by a corundum ark and put the nano-fiber into a reactor with Ar and H 2 And calcining the mixed gas in a tubular furnace, wherein the specific process comprises the steps of firstly heating to 150-250 ℃ from the room temperature at the heating rate of 2-5 ℃/min, preserving heat for 2-3 h, then continuously heating to 500-600 ℃, and preserving heat for 2-3 h.
Further, Ar and H in the step (4) 2 In the mixed gas, the volume fraction of Ar is 95 percent, and H 2 Is 5% by volume.
Further, in the step (5), TiO 2 The molar ratio of the-C nanofibers to the sodium carbonate is 4-6: 1.5-2.5.
Furthermore, the temperature rise rate of the calcination in the step (5) is 3-5 ℃/min, the calcination temperature is 500-600 ℃, and the calcination time is 9-11 h.
It is worth to be noted that experiments show that all factors in the process of the present invention act synergistically to finally obtain a product with excellent performance, all factors are indispensable, for example, the contribution of a specific mixed solvent is obvious, the types and combinations of solvents are very important, if a single solvent is used, a nanofiber-like product cannot be obtained, for example, a product obtained without adding acetic acid in the solvent is massive, and a nanofiber-like product cannot be obtained by using acetic acid only, and further, for example, if a carbon source is selected from other materials instead of polyvinylpyrrolidone of the present invention, the morphology of the obtained material can be influenced finally, even if the carbon source is nanofiber-like, the arrangement of fibers, the average diameter value and the like are obviously different, and the final morphology and the final application and performance are also obviously different.
The invention has the following technical effects:
(1) the invention adopts a solid phase method combined with an electrostatic spinning method to synthesize titanium dioxide carbon fiber and Na 4 Ti 5 O 12 the-C nanofiber has a uniform diameter of about 150-200 nm and excellent electrochemical performance.
(2) The preparation method has simple process and convenient operation, and the obtained Na 4 Ti 5 O 12 the-C nano fiber is a novel and simple battery negative electrode material.
Drawings
FIG. 1 shows Na prepared in example 5 of the present invention 4 Ti 5 O 12 -X-ray diffraction pattern of C nanofibers.
FIG. 2 shows TiO prepared in example 5 of the present invention 2 -scanning electron micrographs of C nanofibrous material.
FIG. 3 shows Na prepared in example 5 of the present invention 4 Ti 5 O 12 -scanning electron microscopy images of C nanofiber material.
FIG. 4 shows Na prepared in example 5 of the present invention 4 Ti 5 O 12 And (4) assembling the button cell by taking the-C nano fibers as a negative electrode material and a sodium sheet as a counter electrode. Charging and discharging at 20-25 deg.C and different current densities of 0.1C, 0.2C, 0.5C, 1C, 5C, 10C and 0.1C within a voltage range of 0.01-2.5VGraph of rate performance of the test.
FIG. 5 shows Na prepared in example 5 of the present invention 4 Ti 5 O 12 And (4) assembling the button cell by taking the-C nano fibers as a negative electrode material and a sodium sheet as a counter electrode. A cycle life chart for performing charge and discharge test at a voltage range of 0.01-2.5V and a current density of 0.5C at 20-25 ℃.
Detailed Description
The present invention will be described in further detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
The test methods in the following examples are conventional methods unless otherwise specified.
Example 1
Adding 0.5 mL of butyl titanate into a sealable glass bottle filled with 5 mL of N, N-dimethylformamide and 4mL of ethanol at the temperature of 15-25 ℃, and magnetically stirring at 300 rpm for 5 min to uniformly mix the solution to obtain a light yellow transparent solution; then 0.9 g of polyvinylpyrrolidone is added, and the mixture is stirred for 6 hours at the same rotating speed; the obtained light yellow transparent solution was transferred to a medical syringe for electrospinning, spinning was started on an electrospinning device, and the nanofibers obtained by spinning were received by a tin foil. The electrostatic spinning parameters are as follows: the distance between the spinning needle head and the metal collecting substrate is 15 cm, the spinning voltage is 15 KV, the environmental temperature is 30 ℃, the humidity is about 30%, and the liquid feeding speed is 0.18 mL/h. Vacuum drying the substrate tin foil loaded with the nano-fibers at 60 deg.C for 6H, collecting the nano-fibers on the substrate tin foil, transferring into a corundum ark, introducing Ar and H 2 Sintering and annealing in a mixed gas tube furnace, wherein the specific calcining process comprises the steps of heating from room temperature to 200 ℃, preserving heat for 2 hours, heating to 600 ℃, preserving heat for 3 hours, and then cooling to room temperature to obtain black TiO 2 -C bulk material. Weighing sodium carbonate 0.22g and TiO 2 0.46g of C block material, putting the C block material into a corundum ark, putting the corundum ark into an Ar tube furnace, and sintering and annealing, wherein the specific calcining process comprises the following steps: heating to 600 ℃, preserving heat for 10h, and cooling to obtain black Na 4 Ti 5 O 12 -C bulk material.
Example 2
Adding 1mL of butyl titanate into a sealable glass bottle filled with 5 mL of N, N-dimethylformamide, 4mL of ethanol and 1mL of glacial acetic acid at the temperature of 15-25 ℃, and magnetically stirring at 300 rpm for 5 min to uniformly mix the solution to obtain a light yellow transparent solution; then adding 1.0 g of polyvinylpyrrolidone, and stirring for 6h at the same rotating speed; the obtained light yellow transparent solution was transferred to a medical syringe for electrospinning, spinning was started on an electrospinning device, and the nanofibers obtained by spinning were received by a tin foil. The electrostatic spinning parameters are as follows: the distance between the spinning needle head and the metal collecting substrate is 15 cm, the spinning voltage is 15 KV, the environmental temperature is 30 ℃, the humidity is about 30%, and the liquid feeding speed is 0.18 mL/h. Vacuum drying the substrate tin foil loaded with the nano-fibers at 60 deg.C for 6H, collecting the nano-fibers on the substrate tin foil, transferring into a corundum ark, introducing Ar and H 2 Sintering and annealing in a mixed gas tube furnace, wherein the specific calcining process comprises heating from room temperature to 200 ℃, preserving heat for 2h, heating to 600 ℃, preserving heat for 3h, and cooling to room temperature to obtain black powdery TiO 2 -a C nanofiber material. Weighing sodium carbonate 0.22g and black powder TiO 2 0.46g of-C nanofiber material, putting the materials into a corundum ark, putting the corundum ark into an Ar-filled tube furnace, and sintering and annealing, wherein the specific calcining process comprises the following steps: heating to 600 deg.C, maintaining the temperature for 10h, and cooling to obtain black powdery Na 4 Ti 5 O 12 -a C nanofiber material.
Example 3
Adding 1.5 mL of butyl titanate into a sealable glass bottle filled with 5 mL of N, N-dimethylformamide, 4mL of ethanol and 1mL of glacial acetic acid at the temperature of 15-25 ℃, and magnetically stirring at 300 rpm for 5 min to uniformly mix the solution to obtain a light yellow transparent solution; then 0.7 g of polyvinylpyrrolidone is added, and the mixture is stirred for 6 hours at the same rotating speed; the obtained pale yellow transparent solution was transferred to a medical syringe for electrostatic spinning, and spinning was started on an electrostatic spinning device, and the nanofiber obtained by spinning was received by a tin foil. The electrostatic spinning parameters are as follows: the distance between the spinning needle head and the metal collecting substrate is 15 cm, the spinning voltage is 15 KV, the environmental temperature is 30 ℃, the humidity is about 30%, and the liquid feeding speed is 0.18 mL/h. Carrying the substrate tin foil of the nanometer fiber to dry in vacuum at 60 DEG CDrying for 6H, collecting the nano-fiber on the tin foil of the substrate, transferring into a corundum ark, introducing Ar and H 2 Sintering and annealing in a mixed gas tube furnace, wherein the specific calcining process comprises heating from room temperature to 200 ℃, preserving heat for 2h, heating to 600 ℃, preserving heat for 3h, and cooling to room temperature to obtain black powdery TiO 2 -a C nanofiber material. Weighing 0.22g of sodium carbonate and weighing black powdery TiO 2 0.46g of-C nanofiber material, putting the materials into a corundum ark, putting the corundum ark into an Ar-filled tube furnace, and sintering and annealing, wherein the specific calcining process comprises the following steps: heating to 600 deg.C, maintaining the temperature for 10h, and cooling to obtain black powdery Na 4 Ti 5 O 12 -a C nanofiber material.
Example 4
Adding 1.5 mL of butyl titanate into a sealable glass bottle filled with 5 mL of N, N-dimethylformamide, 4mL of ethanol and 1mL of glacial acetic acid at the temperature of 15-25 ℃, and magnetically stirring at 300 rpm for 5 min to uniformly mix the solution to obtain a light yellow transparent solution; then 0.8 g of polyvinylpyrrolidone is added, and the mixture is stirred for 6 hours at the same rotating speed; the obtained pale yellow transparent solution was transferred to a medical syringe for electrostatic spinning, and spinning was started on an electrostatic spinning device, and the nanofiber obtained by spinning was received by a tin foil. The electrostatic spinning parameters are as follows: the distance between the spinning needle head and the metal collecting substrate is 15 cm, the spinning voltage is 15 KV, the environmental temperature is 30 ℃, the humidity is about 30 percent, and the liquid feeding speed is 0.18 mL/h. Vacuum drying the substrate tin foil loaded with the nano-fiber at 60 deg.C for 6H, collecting the nano-fiber on the substrate tin foil, transferring into a corundum ark, introducing Ar and H 2 Sintering and annealing in a mixed gas tube furnace, wherein the specific calcining process comprises the steps of heating from room temperature to 200 ℃, preserving heat for 2 hours, heating to 600 ℃, preserving heat for 3 hours, and then cooling to room temperature to obtain black powdery TiO 2 -a C nanofiber material. Weighing sodium carbonate 0.22g and black powder TiO 2 0.46g of-C nanofiber material, putting the materials into a corundum ark, putting the corundum ark into an Ar-passing tube furnace, and sintering and annealing, wherein the specific calcining process comprises the following steps: heating to 600 deg.C, maintaining for 9 hr, and cooling to obtain black powdery Na 4 Ti 5 O 12 -a C nanofiber material.
Example 5
Adding 1.5 mL of butyl titanate into a sealable glass bottle filled with 5 mL of N, N-dimethylformamide, 4mL of ethanol and 1mL of glacial acetic acid at 15-25 ℃, and magnetically stirring at 300 rpm for 5 min to uniformly mix the solution to obtain a light yellow transparent solution; then 0.8 g of polyvinylpyrrolidone is added, and the mixture is stirred for 6 hours at the same rotating speed; the obtained light yellow transparent solution was transferred to a medical syringe for electrospinning, spinning was started on an electrospinning device, and the nanofibers obtained by spinning were received by a tin foil. The electrostatic spinning parameters are as follows: the distance between the spinning needle head and the metal collecting substrate is 15 cm, the spinning voltage is 15 KV, the environmental temperature is 30 ℃, the humidity is about 30%, and the liquid feeding speed is 0.2 mL/h. Vacuum drying the substrate tin foil loaded with the nano-fiber at 60 deg.C for 6H, collecting the nano-fiber on the substrate tin foil, transferring into a corundum ark, introducing Ar and H 2 Sintering and annealing in a mixed gas tube furnace, wherein the specific calcining process comprises the steps of heating from room temperature to 200 ℃, preserving heat for 2 hours, heating to 600 ℃, preserving heat for 3 hours, and then cooling to room temperature to obtain black powdery TiO 2 -a C nanofiber material. Weighing 0.22g of sodium carbonate and weighing black powdery TiO 2 0.46g of-C nanofiber material, putting the materials into a corundum ark, putting the corundum ark into an Ar-passing tube furnace, and sintering and annealing, wherein the specific calcining process comprises the following steps: heating to 600 deg.C, maintaining the temperature for 10h, and cooling to obtain black powdered Na 4 Ti 5 O 12 -a C nanofiber material.
The products obtained in examples 2 to 5 were used for various characterization results, and the obtained characterization results were substantially consistent, and the product obtained in example 5 is described below as an example.
As shown in FIG. 1, by reacting with Na 4 Ti 5 O 12 As can be seen from comparison of standard card PDF # 52-1814, Na is prepared 4 Ti 5 O 12 -C nanofiber material with Na 4 Ti 5 O 12 The characteristic diffraction peaks of (a) are well matched, wherein the carbon is amorphous.
As shown in FIGS. 2 and 3, it can be seen from FIG. 2 that TiO was produced 2 The diameter of the C nano fiber is very uniform and is about 150-200 nm; as can be seen from FIG. 3, Na was produced 4 Ti 5 O 12 The diameter of the-C nano fiber is relatively uniformAbout 150-200 nm, thereby being more beneficial to the embedding/releasing of Na +, and having good electrochemical performance.
As shown in FIG. 4, Na produced by the present invention 4 Ti 5 O 12 And (4) assembling the button cell by taking the-C nano fibers as a negative electrode material and a sodium sheet as a counter electrode. A multiplying power performance chart for performing charge and discharge tests at 20-25 ℃ and different current densities of 0.1C, 0.2C, 0.5C, 1C, 5C, 10C and 0.1C within a voltage range of 0.01-2.5V. Under the current density of 0.1C, the specific discharge capacity after 5 cycles of circulation is 76mAh g-1, when the current density is increased to 0.2C, 0.5C, 1C, 5C and 10C, the specific discharge capacity is 72, 64, 59, 49, 38 and 33 respectively, and when the current density returns to 0.1C after the high-current charge and discharge, the specific discharge capacity still has 58 mAh g-1 respectively, which indicates that Na 4 Ti 5 O 12 the-C nano fiber has good rate performance.
As shown in FIG. 5, Na produced by the present invention 4 Ti 5 O 12 and-C nano-fiber is used as a negative electrode material, and a sodium sheet is used as a counter electrode, so that the button cell is assembled. Performing charge-discharge cycle test at a voltage range of 0.01-2.5V and a current density of 0.5C at 20-25 ℃, wherein the first discharge specific capacity is 341 mAh g < -1 >, and the charge specific capacity is 138 mAh g < -1 >; the discharge specific capacity after 20 times of circulation is 117 mAh g < -1 >, and the charge specific capacity is 116 mAh g < -1 >; the specific discharge capacity after 100 times of circulation is 102 mAh g-1, the specific charge capacity is 102 mAh g-1, and the result shows that Na 4 Ti 5 O 12 the-C nanofiber material has stable cycle performance.

Claims (7)

1. Na synthesized by titanium dioxide and carbon fiber 4 Ti 5 O 12 The preparation method of the-C nanofiber negative electrode material is characterized by comprising the following steps of:
(1) uniformly mixing N, N-dimethylformamide, ethanol and acetic acid to obtain a mixed solvent, adding butyl titanate, and magnetically stirring until the butyl titanate is completely dissolved to obtain a light yellow transparent solution;
(2) adding polyvinylpyrrolidone into the solution obtained in the step (1), and continuing to perform magnetic stirring to obtain a light yellow transparent electrostatic spinning precursor solution;
(3) transferring the precursor solution obtained in the step (2) into a medical injector for electrostatic spinning, starting spinning on an electrostatic spinning device, and receiving the nanofiber obtained by spinning by using tin foil;
(4) drying the baseplate tin foil loaded with the nano-fibers obtained in the step (3), collecting the nano-fibers by using a corundum ark, and putting the nano-fibers into a reactor filled with Ar and H 2 Carbonizing the mixed gas in a tubular furnace to obtain a product TiO 2 The carbonization treatment is to collect the nano-fiber by a corundum ark and put the nano-fiber into a reactor with Ar and H 2 Calcining the mixed gas in a tubular furnace, wherein the specific process comprises the steps of firstly heating to 150-250 ℃ from room temperature at a heating rate of 2-5 ℃/min, preserving heat for 2-3 h, then continuously heating to 500-600 ℃, and preserving heat for 2-3 h;
(5) TiO obtained in the step (4) 2 Placing the-C nano-fiber and sodium carbonate together in a tubular furnace, and TiO 2 Heating and calcining the-C nanofiber and sodium carbonate at a molar ratio of 4-6: 1.5-2.5 in an argon atmosphere at a heating rate of 3-5 ℃/min at a calcining temperature of 500-600 ℃ for 9-11 h to obtain the Na synthesized from the titanium dioxide carbon fiber 4 Ti 5 O 12 -a C nanofiber negative electrode material.
2. The titanium dioxide carbon fiber synthesized Na according to claim 1 4 Ti 5 O 12 The preparation method of the-C nanofiber negative electrode material is characterized in that in the mixed solvent in the step (1), the volume ratio of N, N-dimethylformamide to ethanol to acetic acid is (8-9): 12-13: 1 to 2.
3. The titanium dioxide, carbon fiber, synthetic Na of claim 1 4 Ti 5 O 12 The preparation method of the-C nanofiber negative electrode material is characterized in that in the step (1), the volume ratio of butyl titanate to the mixed solvent is (1-2): 9 to 11.
4. The titania carbon fiber of claim 1, whereinSynthesis of Na 4 Ti 5 O 12 The preparation method of the-C nanofiber negative electrode material is characterized in that the average molecular weight of polyvinylpyrrolidone in the step (1) is 1300000.
5. The titanium dioxide carbon fiber synthesized Na according to claim 1 4 Ti 5 O 12 The preparation method of the-C nanofiber negative electrode material is characterized in that the mass ratio of polyvinylpyrrolidone to a mixed solvent added in the step (2) is 9-11: 0.7-0.9, and the obtained TiO 2 The carbon content of the-C nanofibers is 33-46%.
6. The titanium dioxide, carbon fiber, synthetic Na of claim 1 4 Ti 5 O 12 The preparation method of the-C nanofiber negative electrode material is characterized in that the electrostatic spinning parameters in the step (3) are as follows: the distance between the spinning needle head and the metal collecting substrate is 15-18 cm, the spinning voltage is 15-18 KV, the environmental temperature is 30-60 ℃, the humidity is 20-40%, and the liquid feeding speed is 0.2-0.5 mL/h.
7. The titanium dioxide, carbon fiber, synthetic Na of claim 1 4 Ti 5 O 12 The preparation method of the-C nanofiber negative electrode material is characterized in that the drying in the step (4) is vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 4-6 hours.
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