CN107881600B - Preparation method and application of nano carbon fiber for lithium ion battery cathode - Google Patents

Preparation method and application of nano carbon fiber for lithium ion battery cathode Download PDF

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CN107881600B
CN107881600B CN201710838111.3A CN201710838111A CN107881600B CN 107881600 B CN107881600 B CN 107881600B CN 201710838111 A CN201710838111 A CN 201710838111A CN 107881600 B CN107881600 B CN 107881600B
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nano
nitrogen
temperature
quinoline
lithium ion
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CN107881600A (en
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邱介山
肖南
刘畅
王玉伟
李宏强
纪勇强
宋军伟
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Dalian University of Technology
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21Carbon 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
    • D01F9/22Carbon 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 from polyacrylonitriles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to the technical field of preparation and application of new energy materials, in particular to a preparation method and application of nano carbon fibers for a lithium ion battery cathode, wherein the preparation method comprises the following steps: nitrogen-rich quinoline oligomers are prepared from quinoline and used as nitrogen-rich soft carbon precursors. Polyacrylonitrile is used as a hard carbon precursor and a spinning aid, and the nano-fiber is prepared by an electrostatic spinning technology. Then heating the carbon nano-fiber to 250-300 ℃ in the air atmosphere for pre-oxidation, and heating the carbon nano-fiber to 600-1200 ℃ in the nitrogen atmosphere for carbonization to obtain the target material carbon nano-fiber. The nano carbon fiber provided by the invention has higher nitrogen content and good conductivity, and has excellent rate performance and cycling stability when being used as a lithium ion battery cathode material.

Description

Preparation method and application of nano carbon fiber for lithium ion battery cathode
Technical Field
The invention relates to a preparation method and application of nano carbon fibers for a lithium ion battery cathode, and belongs to the technical field of preparation and application of new energy materials.
Background
The lithium ion battery is used as a new generation of energy storage device, has the advantages of high energy density, good cycle stability, environmental friendliness, no memory effect and the like, and is widely applied to energy storage power supplies of portable equipment such as mobile phones, intelligent wearable equipment and notebooks. The traditional commercialized lithium ion battery cathode graphite material has lower price and better cycling stability, but the graphite electrode is used as the lithium ion battery cathode, the theoretical capacity of the graphite electrode is only 372mAh/g, the rate capability is poorer, and the use requirement of electronic equipment cannot be met more and more.
Nitrogen-doped carbon materials are gradually a research hotspot in recent years, and nitrogen doping not only has stronger lithium ion adsorption capacity, but also can reduce the diffusion resistance of lithium ions by introducing defect sites, so that higher specific mass capacity, more excellent multiplying power and more excellent cycling stability are obtained. The graphitization process of the nitrogen-doped hard carbon material is generally low, which provides an ideal active site for the storage of lithium ions, but the conductivity of the nitrogen-doped hard carbon material is generally poor, which is not favorable for the rapid transmission of electrons, and further the rate capability of the nitrogen-doped hard carbon material is poor. In addition, during the first charge and discharge process, excessive defect sites inside the material can cause larger irreversible capacity loss and lower first coulombic efficiency. In comparison, the soft carbon material has a lower specific surface area and fewer defect sites, can effectively reduce the generation of irreversible capacity, and also has better rate and cycling stability, but the further application of the soft carbon material is limited due to the lower specific mass capacity. The patent 201510581382.6 discloses that pitch-based carbon nanofibers are prepared by using medium-temperature coal pitch as a soft carbon source and polyacrylonitrile as a hard carbon source, but the nitrogen content of the medium-temperature coal pitch adopted in the patent is extremely low, the nitrogen content of the carbon fibers prepared by introducing the medium-temperature coal pitch is obviously reduced compared with that of the polyacrylonitrile-based carbon fibers, the capacity is obviously reduced, and the specific mass capacity under the current density of 100mA/g is only 490.2 mAh/g.
Disclosure of Invention
Aiming at overcoming the defects in the prior art, the invention aims to provide a preparation method of nano carbon fiber for a lithium ion battery cathode and application thereof, aiming at the phenomena that the multiplying power and the cycling stability of a nitrogen-doped hard carbon material are poor and the mass specific capacity of the nitrogen-doped hard carbon material is obviously reduced after the nitrogen-doped hard carbon material is compounded with soft carbon. The invention uses nitrogen-rich quinoline oligomer as soft carbon precursor, uses high molecular polymer polyacrylonitrile as hard carbon precursor, and adopts electrostatic spinning technology and heat treatment method to prepare the nano carbon fiber for the cathode of lithium ion battery. The nano carbon fiber prepared by the method has higher nitrogen content and higher conductivity, and has the advantages of high specific capacity, good rate capability, excellent cycling stability and the like when being used as a lithium ion battery cathode material.
In order to achieve the above purpose and solve the problems existing in the prior art, the invention adopts the technical scheme that: a preparation method of nano carbon fiber for a lithium ion battery cathode comprises the following steps:
step 1, firstly, quinoline is added into a round-bottom flask, aluminum trichloride powder is added under the protection of nitrogen atmosphere, heating is carried out for 6-12 hours, the temperature is controlled to be 250-320 ℃, natural cooling is carried out to room temperature, black solid particles are obtained, then 1mol/L diluted hydrochloric acid and deionized water are used for washing in sequence, aluminum trichloride is removed, the washed solid particles are dried in vacuum for 8-14 hours, the temperature is controlled to be 50-80 ℃, and nitrogen-enriched quinoline oligomer is obtained, wherein the mass ratio of aluminum trichloride to quinoline is 1.0: 1.0-5.0;
step 2, smashing the nitrogen-rich quinoline oligomer particles obtained in the step 1 to 5-10 microns, adding a part of the nitrogen-rich quinoline oligomer particles into a polar organic solvent, stirring for 2-5 hours to obtain a first stirring liquid, then adding polyacrylonitrile into the first stirring liquid, heating to 40-80 ℃, and stirring for 2-5 hours to obtain a second stirring liquid, wherein the mass ratio of the polyacrylonitrile to the nitrogen-rich quinoline oligomer is 1.0: 0.25-4.0, wherein the polar organic solvent is selected from one of N, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide, and the mass of the polar organic solvent is 15-25 g;
step 3, taking the second stirring liquid obtained in the step 2 as a spinning liquid, and preparing the nano fibers by adopting an electrostatic spinning technology, wherein the inner diameter of a needle head of the electrostatic spinning is 0.58-1.04mm, a metal cylinder is a collecting device, the distance between the needle head and the metal cylinder is 10-20cm, the voltage applied to the needle head is 14-20kV, and the rotating speed of the metal cylinder is controlled at 50-300 r/min;
and 4, putting the nano-fiber obtained in the step 3 into a tubular furnace, introducing air at the air speed of 0.5-1L/min, raising the temperature to 250-300 ℃ at the heating rate of 0.5-3 ℃/min, pre-oxidizing at constant temperature for 1-5h, continuing to raise the temperature to 600-1200 ℃ at the heating rate of 1-5 ℃/min under the protection of nitrogen atmosphere, carbonizing at constant temperature for 1-5h, and naturally cooling to room temperature to obtain the target material nano-carbon fiber.
The carbon nanofiber prepared by the method is applied to a lithium ion battery cathode.
The invention has the beneficial effects that: a preparation method of nano carbon fiber for a lithium ion battery cathode comprises the following steps: (1) firstly, quinoline is added into a round-bottom flask, aluminum trichloride powder is added under the protection of nitrogen atmosphere for heating, the mixture is naturally cooled to room temperature to obtain black solid particles, then diluted hydrochloric acid and deionized water are used for washing in sequence to remove aluminum trichloride, and the washed solid particles are dried in vacuum to obtain nitrogen-rich quinoline oligomer; (2) pulverizing the nitrogen-rich quinoline oligomer particles obtained in the step (1) to 5-10 microns, adding a part of the nitrogen-rich quinoline oligomer particles into a polar organic solvent, stirring to obtain a first stirring liquid, adding polyacrylonitrile into the first stirring liquid, heating and stirring to obtain a second stirring liquid; (3) preparing the nanofibers by using the second stirring liquid obtained in the step (2) as a spinning solution and adopting an electrostatic spinning technology; (4) and (4) putting the nano-fiber obtained in the step (3) into a tubular furnace, introducing air for constant-temperature pre-oxidation, carbonizing at constant temperature under the protection of nitrogen atmosphere, and naturally cooling to room temperature to obtain the target material nano-carbon fiber. Compared with the prior art, the method has the advantages of simple process, convenient operation and easy realization of large-scale industrial production. The carbon nanofiber prepared by the method has the diameter of 200-300nm, has high nitrogen content, is used as a lithium ion battery cathode material, has higher specific mass capacity, and has good rate performance and stable cycle performance.
Drawings
FIG. 1 is a scanning electron micrograph of the filamentous nanocarbon prepared in example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of the filamentous nanocarbon prepared in example 1 of the present invention.
Fig. 3 is a first charge-discharge curve diagram of the lithium ion battery in example 1 of the present invention.
Fig. 4 is a graph of rate performance of the lithium ion battery of example 1 of the present invention during charging and discharging under different current densities.
Fig. 5 is a graph of the cycle performance of the lithium ion battery of example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Weighing 150g of quinoline, adding the quinoline into a 500mL round-bottom flask, adding 50g of aluminum trichloride powder under the protection of nitrogen atmosphere, heating for 10h, controlling the temperature at 300 ℃, naturally cooling to room temperature, then sequentially washing by using 1mol/L dilute hydrochloric acid and deionized water to remove aluminum trichloride, and then carrying out vacuum drying on the washed solid particles for 12h, controlling the temperature at 60 ℃ to obtain nitrogen-rich quinoline oligomer; crushing the nitrogen-rich quinoline oligomer particles to 8 microns, adding 3g of the powder into 18g N, N-dimethylformamide, stirring for 4 hours to obtain a first stirring liquid, adding 3g of polyacrylonitrile into the first stirring liquid, heating to 60 ℃, and stirring for 4 hours to obtain a second stirring liquid; preparing nano-fibers by using the obtained second stirring solution as a spinning solution and adopting an electrostatic spinning technology, wherein the inner diameter of an electrostatic spinning needle is 0.84mm, a metal cylinder is a collecting device, the distance between the needle and the metal cylinder is 15cm, the voltage applied to the needle is 18kV, and the rotating speed of the metal cylinder is controlled at 200 r/min; and then putting the obtained nano-fiber into a tubular furnace, introducing air at the air speed of 0.5L/min, raising the temperature to 280 ℃ at the heating rate of 1 ℃/min, carrying out constant-temperature pre-oxidation for 2h, continuing raising the temperature to 700 ℃ at the heating rate of 3 ℃/min under the protection of nitrogen atmosphere, carrying out constant-temperature carbonization for 2h, and naturally cooling to room temperature to obtain the target material nano-carbon fiber.
The prepared nano carbon fiber is used as an integral electrode, and 1mol/L LiPF6The two-component mixed solvent is an electrolyte mixed according to the volume ratio of EC/DEC to 1:1, a polypropylene film is a diaphragm, and the diaphragm is assembled into a CR2016 button cell in a glove box filled with argon. The charge and discharge test is carried out on a Wuhan Land CT2001A type battery test system, and the charge and discharge voltage range is 0.01-3V.
FIG. 1 is a scanning electron micrograph of the carbon nanofiber prepared by the invention, which shows that the prepared fiber has a complete shape and a diameter of 200-300nm, and the fibers are interwoven to form a three-dimensional network shape, thereby providing a channel for the rapid transmission of electrons. FIG. 2 is an X-ray diffraction diagram of the nano carbon fiber prepared by the present invention, wherein the nitrogen content of the prepared nano carbon fiber is 12.1 wt%. FIG. 3 is a first charge-discharge curve of the nano carbon fiber prepared by the invention under the current density of 0.1A/g, wherein the first charge mass-to-capacity ratio is 764.9 mAh/g. FIG. 4 shows the rate capability of the nano carbon fiber prepared by the invention under different current densities for the lithium ion battery cathode material, the reversible discharge capacity under the current density of 0.1A/g can reach 748.3mAh/g, the reversible discharge capacity under the current density of 10A/g can still reach 340.2mAh/g, the capacity retention rate is 45.5%, and the conductivity is 0.47S/m. FIG. 5 shows the cycle performance of the carbon nanofiber prepared by the invention under the current density of 2A/g for the negative electrode material of the lithium ion battery, and the cycle retention rate is 91.7%.
Example 2
Weighing 50g of quinoline, adding the quinoline into a 500mL round-bottom flask, adding 50g of aluminum trichloride powder under the protection of nitrogen atmosphere, heating for 6h, controlling the temperature at 250 ℃, naturally cooling to room temperature, then sequentially washing by using 1mol/L dilute hydrochloric acid and deionized water to remove aluminum trichloride, and then drying the washed solid particles in vacuum for 8h, controlling the temperature at 50 ℃ to obtain nitrogen-rich quinoline oligomer; crushing the nitrogen-rich quinoline oligomer particles to 5 microns, adding 1g of the powder into 15g N, N-dimethylacetamide, stirring for 2 hours to obtain first stirring liquid, adding 4g of polyacrylonitrile into the first stirring liquid, heating to 40 ℃, and stirring for 2 hours to obtain second stirring liquid; preparing nano-fibers by using the obtained second stirring solution as a spinning solution and adopting an electrostatic spinning technology, wherein the inner diameter of an electrostatic spinning needle is 0.58mm, a metal cylinder is a collecting device, the distance between the needle and the metal cylinder is 10cm, the voltage applied to the needle is 14kV, and the rotating speed of the metal cylinder is controlled at 50 r/min; and then putting the obtained nano-fiber into a tubular furnace, introducing air at the air speed of 0.5L/min, raising the temperature to 250 ℃ at the heating rate of 0.5 ℃/min, carrying out constant-temperature pre-oxidation for 1h, continuing raising the temperature to 600 ℃ at the heating rate of 1 ℃/min under the protection of nitrogen atmosphere, carrying out constant-temperature carbonization for 1h, and naturally cooling to room temperature to obtain the target material nano-carbon fiber.
The prepared nano carbon fiber is used as an integral electrode, and 1mol/L LiPF6The two-component mixed solvent is an electrolyte mixed according to the volume ratio of EC/DEC to 1:1, a polypropylene film is a diaphragm, the two-component mixed solvent is assembled into a CR2016 button cell in an argon-filled glove box, and the charge and discharge test is performed in Wuhan Land CT2001A type battery test system, charge and discharge voltage range was 0.01-3V.
The nitrogen content of the prepared carbon nanofiber negative electrode material is 14.8 wt%, the reversible discharge capacity under the current density of 0.1A/g reaches 608.6mAh/g, the reversible discharge capacity under the current density of 10A/g is 240.7mAh/g, the capacity retention rate is 39.5%, and the cycle retention rate under the current density of 2A/g is 87.5%.
Example 3
Weighing 250g of quinoline, adding the quinoline into a 500mL round-bottom flask, adding 50g of aluminum trichloride powder under the protection of nitrogen atmosphere, heating for 12h, controlling the temperature at 300 ℃, naturally cooling to room temperature, then sequentially washing by using 1mol/L dilute hydrochloric acid and deionized water to remove aluminum trichloride, and then carrying out vacuum drying on the washed solid particles for 14h, controlling the temperature at 80 ℃ to obtain nitrogen-rich quinoline oligomer; crushing the nitrogen-rich quinoline oligomer particles to 10 microns, adding 8g of the powder into 25g of dimethyl sulfoxide, stirring for 5 hours to obtain first stirring liquid, adding 2g of polyacrylonitrile into the first stirring liquid, heating to 80 ℃, and stirring for 5 hours to obtain second stirring liquid; preparing nano-fibers by using the obtained second stirring solution as a spinning solution and adopting an electrostatic spinning technology, wherein the inner diameter of an electrostatic spinning needle is 1.04mm, a metal cylinder is a collecting device, the distance between the needle and the metal cylinder is 20cm, the voltage applied to the needle is 20kV, and the rotating speed of the metal cylinder is controlled at 300 r/min; and then putting the obtained nano-fiber into a tubular furnace, introducing air at the air speed of 1L/min, raising the temperature to 300 ℃ at the heating rate of 3 ℃/min, carrying out constant-temperature pre-oxidation for 5h, continuing raising the temperature to 1200 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen atmosphere, carrying out constant-temperature carbonization for 5h, and naturally cooling to room temperature to obtain the target material nano-carbon fiber.
The prepared nano carbon fiber is used as an integral electrode, and 1mol/L LiPF6The two-component mixed solvent is an electrolyte mixed according to the volume ratio of EC/DEC to 1:1, a polypropylene film is a diaphragm, and the diaphragm is assembled into a CR2016 button cell in a glove box filled with argon. The charge and discharge test is carried out on a Wuhan Land CT2001A type battery test system, and the charge and discharge voltage range is 0.01-3V.
The nitrogen content of the prepared carbon nanofiber negative electrode material is 10.4 wt%, the reversible discharge capacity under the current density of 0.1A/g is 627.1mAh/g, the reversible discharge capacity under the current density of 10A/g is 254.6mAh/g, the capacity retention rate is 40.6%, and the cycle retention rate under the current density of 2A/g is 86.3%.
Comparative example 1
Weighing 3g of polyacrylonitrile powder, adding the polyacrylonitrile powder into 18g N, N-dimethylformamide, heating to 60 ℃, stirring for 4 hours, taking the obtained stirring liquid as spinning solution, preparing polyacrylonitrile nano-fiber by adopting an electrostatic spinning technology, wherein the inner diameter of an electrostatic spinning needle head is 0.84mm, a metal cylinder is a collecting device, the distance from the needle head to the metal cylinder is 15cm, and the voltage applied to the needle head is 20 kV; and then putting the obtained polyacrylonitrile nano-fiber into a tubular furnace, introducing air at the air speed of 0.5L/min, raising the temperature to 280 ℃ at the heating rate of 1 ℃/min, carrying out constant-temperature pre-oxidation for 2h, continuing raising the temperature to 700 ℃ at the heating rate of 3 ℃/min under the protection of nitrogen atmosphere, carrying out constant-temperature carbonization for 2h, and naturally cooling to room temperature to obtain the polyacrylonitrile nano-carbon fiber.
The prepared polyacrylonitrile-based carbon nanofiber is used as an integral electrode, and 1mol/L LiPF6The two-component mixed solvent is an electrolyte mixed according to the volume ratio of EC/DEC to 1:1, a polypropylene film is a diaphragm, and the diaphragm is assembled into a CR2016 button cell in a glove box filled with argon. The charge and discharge test is carried out on a Wuhan Land CT2001A type battery test system, and the charge and discharge voltage range is 0.01-3V.
The nitrogen content of the prepared polyacrylonitrile-based carbon nanofiber negative electrode material is 18.2 wt%, the reversible discharge capacity under the current density of 0.1A/g reaches 639.7mAh/g, the reversible discharge capacity under the current density of 10A/g is only 119.7mAh/g, the capacity retention rate is only 18.7%, the rate capability is poor, the conductivity is 0.098S/m, and the cycle retention rate under the current density of 2A/g is only 61.5%.
Comparative example 2
Crushing the medium-temperature coal pitch to 8 microns, adding 3g of medium-temperature coal pitch powder into 18g N, N-dimethylformamide, stirring for 4 hours to obtain a first stirring solution, adding 3g of polyacrylonitrile into the first stirring solution, heating to 60 ℃, and stirring for 4 hours to obtain a second stirring solution; preparing the nano-fiber by using the obtained second stirring liquid as a spinning solution and adopting an electrostatic spinning technology, wherein the inner diameter of an electrostatic spinning needle is 0.84mm, a metal cylinder is a collecting device, the distance from the needle to the metal cylinder is 15cm, and the voltage applied to the needle is 20 kV;
and then putting the obtained nano-fiber into a tubular furnace, introducing air at the air speed of 0.5L/min, raising the temperature to 280 ℃ at the heating rate of 1 ℃/min, carrying out constant-temperature pre-oxidation for 2h, continuing raising the temperature to 700 ℃ at the heating rate of 3 ℃/min under the protection of nitrogen atmosphere, carrying out constant-temperature carbonization for 2h, and naturally cooling to room temperature to obtain the nano-carbon fiber.
The prepared nano carbon fiber is used as an integral electrode, and 1mol/L LiPF6The two-component mixed solvent is an electrolyte mixed according to the volume ratio of EC/DEC to 1:1, a polypropylene film is a diaphragm, and the diaphragm is assembled into a CR2016 button cell in a glove box filled with argon. The charge and discharge test is carried out on a Wuhan Land CT2001A type battery test system, and the charge and discharge voltage range is 0.01-3V.
The nitrogen content of the prepared carbon nanofiber is 7.1 wt%, the reversible discharge capacity under the current density of 0.1A/g is only 482.5mAh/g, the reversible discharge capacity under the current density of 10A/g is only 150.7mAh/g, and the capacity retention rate is 31.2%. The cycle retention at a current density of 2A/g was 74.5%.

Claims (2)

1. A preparation method of nano carbon fiber for a lithium ion battery cathode is characterized by comprising the following steps:
step 1, firstly, quinoline is added into a round-bottom flask, aluminum trichloride powder is added under the protection of nitrogen atmosphere, heating is carried out for 6-12 hours, the temperature is controlled to be 250-320 ℃, natural cooling is carried out to room temperature, black solid particles are obtained, then 1mol/L diluted hydrochloric acid and deionized water are used for washing in sequence, aluminum trichloride is removed, the washed solid particles are dried in vacuum for 8-14 hours, the temperature is controlled to be 50-80 ℃, and nitrogen-enriched quinoline oligomer is obtained, wherein the mass ratio of aluminum trichloride to quinoline is 1.0: 1.0-5.0;
step 2, smashing the nitrogen-rich quinoline oligomer particles obtained in the step 1 to 5-10 microns, adding a part of the nitrogen-rich quinoline oligomer particles into a polar organic solvent, stirring for 2-5 hours to obtain a first stirring liquid, then adding polyacrylonitrile into the first stirring liquid, heating to 40-80 ℃, and stirring for 2-5 hours to obtain a second stirring liquid, wherein the mass ratio of the polyacrylonitrile to the nitrogen-rich quinoline oligomer is 1.0: 0.25-4.0, wherein the polar organic solvent is selected from one of N, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide, and the mass of the polar organic solvent is 15-25 g;
step 3, taking the second stirring liquid obtained in the step 2 as a spinning liquid, and preparing the nano fibers by adopting an electrostatic spinning technology, wherein the inner diameter of a needle head of the electrostatic spinning is 0.58-1.04mm, a metal cylinder is a collecting device, the distance between the needle head and the metal cylinder is 10-20cm, the voltage applied to the needle head is 14-20kV, and the rotating speed of the metal cylinder is controlled at 50-300 r/min;
and 4, putting the nano-fiber obtained in the step 3 into a tubular furnace, introducing air at the air speed of 0.5-1L/min, raising the temperature to 250-300 ℃ at the heating rate of 0.5-3 ℃/min, pre-oxidizing at constant temperature for 1-5h, continuing to raise the temperature to 600-1200 ℃ at the heating rate of 1-5 ℃/min under the protection of nitrogen atmosphere, carbonizing at constant temperature for 1-5h, and naturally cooling to room temperature to obtain the target material nano-carbon fiber.
2. The application of the nano carbon fiber prepared by the method of claim 1 in the negative electrode of a lithium ion battery.
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CN105845441B (en) * 2016-03-29 2018-04-27 大连理工大学 A kind of preparation method of dye-sensitized solar cells based on N doping porous carbon material to electrode

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