CN111600032A - SnSb alloy-carbon nanofiber sodium ion battery negative electrode material and preparation method thereof - Google Patents

SnSb alloy-carbon nanofiber sodium ion battery negative electrode material and preparation method thereof Download PDF

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CN111600032A
CN111600032A CN202010463970.0A CN202010463970A CN111600032A CN 111600032 A CN111600032 A CN 111600032A CN 202010463970 A CN202010463970 A CN 202010463970A CN 111600032 A CN111600032 A CN 111600032A
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ion battery
parts
snsb alloy
carbon nanofiber
sodium
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许东
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Xinchang Pinhong Technology Co ltd
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Xinchang Pinhong Technology Co ltd
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • 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 relates to the technical field of sodium ion battery cathode materials, and discloses a sodium ion battery cathode material of SnSb alloy-carbon nanofiber, which comprises the following formula raw materials and components: polyacrylonitrile, porous N-S doped carbon nano-microsphere, SnCl2、SbCl3And a dispersant. According to the sodium ion battery cathode material of the SnSb alloy-carbon nanofiber, the porous N-S doped carbon nanospheres have a huge specific surface area and a developed pore structure, the electronegativity of nitrogen is stronger than that of carbon, the conductivity of the carbon nanospheres is enhanced through nitrogen atom doping, and the nano-structure is preparedThe SnSb alloy is uniformly loaded on the surface of the carbon nano-microsphere, so that the agglomeration and caking phenomena of the nano-SnSb alloy are reduced, more electrochemical active sites are exposed out of the negative electrode material, the conductivity of the negative electrode material is improved by the carbon nano-microsphere, the transmission of ions and charges is promoted, the transmission path of the ions is shortened by the abundant pore structure, and the specific capacity of the negative electrode material is improved.

Description

SnSb alloy-carbon nanofiber sodium ion battery negative electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of sodium ion battery cathode materials, in particular to a sodium ion battery cathode material of SnSb alloy-carbon nanofiber and a preparation method thereof.
Background
With the increasing severity of energy crisis and environmental problems, the development of a novel green and efficient energy storage battery system becomes a research hotspot, and a sodium ion battery has the advantages of abundant sodium resources, low cost, excellent stability, good safety performance, no pollution and the like, is an energy storage battery with huge potential, and has the following advantages compared with a commercial lithium ion battery: the conductivity of the sodium salt is high, and low-concentration electrolyte can be selected to reduce the production cost; the sodium resource has wide distribution range, rich reserves and low price; the sodium ion battery has no over-discharge characteristic and can discharge to zero V; sodium ions are difficult to react with the alloy, and the aluminum foil can be used as a current collector of the negative electrode, so that the cost can be reduced, and the quality of electrode materials can be reduced.
The sodium ion battery mainly comprises a positive electrode material, a negative electrode material, an electrolyte, a diaphragm and the like, wherein the negative electrode material has a great influence on the performance of the sodium ion battery and mainly provides an active site capable of storing ions and a lower-potential redox couple for the sodium ion battery in the charging and discharging processes.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the SnSb alloy-carbon nanofiber sodium ion battery cathode material and the preparation method thereof, and solves the problem that the volume expansion is easy to occur in the process of charging and discharging of the SnSb alloy cathode material, so that the matrix of the cathode material is lost and even decomposed.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the SnSb alloy-carbon nanofiber sodium ion battery negative electrode material comprises the following formula raw materials in parts by weight: 18-22Polyacrylonitrile, 17-32 parts of porous N-S doped carbon nano-microspheres and 20-23 parts of SnCl224-28 parts of SbCl36-10 parts of a dispersing agent.
Preferably, the dispersant is polyvinylpyrrolidone.
Preferably, the preparation method of the porous N-S doped carbon nano microsphere comprises the following steps:
(1) adding sodium hydroxide solution with the mass concentration of 0.1-0.15mol/L into a reaction bottle, adding phenol and formaldehyde aqueous solution, placing the reaction bottle in a constant-temperature water bath, heating to 75-85 deg.C, stirring at uniform speed for 1-3h, adding poloxamer as surfactant, stirring at uniform speed for 5-8h, adding distilled water to adjust the concentration of sodium hydroxide substance to 0.02-0.03mol/L, stirring at uniform speed for 3-5h, transferring the solution into hydrothermal synthesis reaction kettle, distilled water is added to adjust the amount concentration of sodium hydroxide substances to be 0.003 to 0.045mol/L, placing the mixture in a heating box of a reaction kettle, heating the mixture to the temperature of 140 ℃ and 150 ℃, reacting for 10-15h, cooling the solution to room temperature, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying the solid product.
(2) Placing the solid product, potassium hydroxide and thiourea in a planetary ball mill, ball-milling for 20-30h until the solid product passes through a 1000-plus 1500-mesh sieve, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 5-10 ℃/min, carrying out heat preservation calcination for 3-5h at the temperature of 720-plus 750 ℃, washing the calcination product with distilled water, and fully drying to prepare the porous N-S doped carbon nano microsphere.
Preferably, the mass ratio of the phenol to the formaldehyde to the poloxamer is 1:1.2-1.5: 1.6-2.
Preferably, the mass ratio of the solid product to the potassium hydroxide to the thiourea is 1:1.8-2.2: 2-2.5.
Preferably, the preparation method of the sodium ion battery anode material of the SnSb alloy-carbon nanofiber comprises the following steps:
(1) adding N, N-dimethylformamide solvent, 17-32 parts of porous N-S doped carbon nano microspheres and 20-23 parts of SnCl into a reaction bottle224-28 parts of SbCl36-10 parts of dispersant, and placing the reaction bottle in ultrasonic after stirring uniformlyHeating to 60-80 deg.C in a treating instrument, and performing ultrasonic dispersion treatment at 30-40KHz for 2-4 h.
(2) Adding 18-22 parts of polyacrylonitrile into the solution, stirring uniformly, pouring the solution into a miniature injector, and carrying out electrostatic spinning, wherein the voltage of an electrostatic spinning machine is 19-22kV, the distance between a syringe needle and a receiver is 12-16cm, and the flow rate of the electrostatic spinning solution is 0.6-0.8 mL/h.
(3) And (2) placing the nanofiber prepared by electrostatic spinning in an atmosphere resistance furnace, introducing nitrogen, heating to 200-10 ℃/min at the heating rate of 5-10 ℃/min, carrying out heat preservation preactivation treatment for 2-3h, heating to 720-750 ℃, carrying out heat preservation calcination for 2-3h, wherein the calcination product is the sodium ion battery cathode material of the SnSb alloy-carbon nanofiber.
Preferably, the ultrasonic treatment appearance includes the host computer, fixed mounting has ultrasonic generrator on the interior roof of host computer, ultrasonic probe is installed to ultrasonic generrator's bottom, fixed mounting has flexible seat on the interior diapire of host computer, the container has been placed at the top of flexible seat, movable mounting has the carousel on the host computer, evenly distributed's the thing groove of putting is seted up to the inside of carousel, the spare part has been placed to the inside of putting the thing groove, the inside of putting the thing groove and the back activity that is located the spare part is pegged graft and is had the slide, the back fixedly connected with magnetic path of slide, be provided with the iron sheet on the tank bottom of putting the thing groove, the inside of host computer and the back mounting who is located the top.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the SnSb alloy-carbon nanofiber sodium ion battery cathode material has the advantages that the interlayer spacing of carbon nano microspheres is enlarged by doping the carbon nano microspheres with sulfur atoms, a mesoporous structure is formed on the surfaces of the carbon microspheres, so that the carbon nano microspheres form a huge specific surface area and a developed pore structure, the electronegativity of nitrogen is stronger than that of carbon, the conductivity of the carbon nano microspheres is enhanced by doping nitrogen atoms, the porous N-S doped carbon nano microspheres are used as carriers, the nano SnSb alloy is uniformly loaded on the surfaces of the carbon nano microspheres by an electrostatic spinning method, the agglomeration and agglomeration of the nano SnSb alloy are greatly reduced, more electrochemical active sites are exposed out of the nano fiber cathode material, the conductivity of the cathode material is improved by the carbon nano microspheres, the transmission of ions and charges is promoted, and the transmission path of the ions is shortened by the rich pore structure, thereby improving the specific capacity and the coulombic efficiency of the cathode material.
According to the sodium ion battery cathode material of the SnSb alloy-carbon nanofiber, the nanofiber prepared by an electrostatic spinning method has high mechanical strength and excellent electrochemical stability, and the SnSb alloy is coated by the carbon nanofiber, so that elastic expansion buffering is provided for mechanical stress generated in the process of sodium desorption of the SnSb alloy during charging and discharging, the volume expansion phenomenon of the SnSb alloy is effectively relieved, and the reduction of the cycle stability and the rate capability of the sodium ion battery due to the loss and decomposition of a cathode material matrix is avoided.
Drawings
FIG. 1 is a schematic front view of the present invention;
FIG. 2 is a schematic front view of the turntable configuration of the present invention;
FIG. 3 is a side view of the turntable and mainframe mounting structure of the present invention.
In the figure: 1. a host; 2. an ultrasonic generator; 3. an ultrasonic probe; 4. a telescopic base; 5. a container; 6. a turntable; 7. a storage groove; 8. a spare part; 9. a slide plate; 10. a magnetic block; 11. iron sheets; 12. a magnet; 13. a handle.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the SnSb alloy-carbon nanofiber sodium ion battery negative electrode material comprises the following formula raw materials in parts by weight: 18-22 parts of polyacrylonitrile, 17-32 parts of porous N-S doped carbon nano-microspheres and 20-23 parts of SnCl224-28 parts of SbCl36-10 parts of a dispersing agent, wherein the dispersing agent is polyvinylpyrrolidone.
The preparation method of the porous N-S doped carbon nano microsphere comprises the following steps:
(1) adding a sodium hydroxide solution with the mass concentration of 0.1-0.15mol/L into a reaction bottle, adding phenol and a formaldehyde aqueous solution, placing the reaction bottle in a constant-temperature water bath, heating to 75-85 ℃, uniformly stirring for reaction for 1-3h, adding a surfactant poloxamer, wherein the mass ratio of phenol to formaldehyde to poloxamer is 1:1.2-1.5:1.6-2, uniformly stirring for 5-8h, adding distilled water to adjust the mass concentration of the sodium hydroxide substance to be 0.02-0.03mol/L, uniformly stirring for reaction for 3-5h, transferring the solution into a hydrothermal synthesis reaction kettle, adding distilled water to adjust the mass concentration of the sodium hydroxide substance to be 0.003-0.045mol/L, placing the solution into a reaction kettle heating box, heating to 140-150 ℃, reacting for 10-15h, cooling the solution to room temperature, the solvent was removed by filtration, and the solid product was washed with distilled water and ethanol and dried thoroughly.
(2) Placing the solid product, potassium hydroxide and thiourea in a planetary ball mill with the mass ratio of 1:1.8-2.2:2-2.5, ball milling for 20-30h until the solid product passes through a 1500-mesh screen with 1000-plus-material, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 5-10 ℃/min, carrying out heat preservation and calcination for 3-5h at the temperature of 720-plus-material and 750 ℃, washing the calcined product with distilled water, and fully drying to prepare the porous N-S doped carbon nano microsphere.
The preparation method of the sodium ion battery anode material of the SnSb alloy-carbon nanofiber comprises the following steps:
(1) adding N, N-dimethylformamide solvent, 17-32 parts of porous N-S doped carbon nano microspheres and 20-23 parts of SnCl into a reaction bottle224-28 parts of SbCl36-10 parts of dispersing agent, the reaction bottle is placed in the ultrasonic treatment instrument after being uniformly stirred, the ultrasonic treatment instrument comprises a host, an ultrasonic generator is fixedly mounted on the inner top wall of the host, an ultrasonic probe is mounted at the bottom of the ultrasonic generator, a telescopic seat is fixedly mounted on the inner bottom wall of the host, a container is placed at the top of the telescopic seat, a turntable is movably mounted on the host, uniformly distributed storage grooves are formed in the turntable, spare parts are placed in the storage grooves, sliding plates are movably inserted in the storage grooves and positioned on the back of the spare parts, magnetic blocks are fixedly connected to the back of the sliding plates, iron sheets are arranged on the bottom of the storage grooves, magnets are mounted in the storage grooves and positioned on the top of the host, a handle is arranged on the turntable, the heating is carried out to 60-80 ℃, and the ultrasonic frequency is 30Carrying out ultrasonic dispersion treatment for 2-4h at-40 KHz.
(2) Adding 18-22 parts of polyacrylonitrile into the solution, stirring uniformly, pouring the solution into a miniature injector, and carrying out electrostatic spinning, wherein the voltage of an electrostatic spinning machine is 19-22kV, the distance between a syringe needle and a receiver is 12-16cm, and the flow rate of the electrostatic spinning solution is 0.6-0.8 mL/h.
(3) And (2) placing the nanofiber prepared by electrostatic spinning in an atmosphere resistance furnace, introducing nitrogen, heating to 200-10 ℃/min at the heating rate of 5-10 ℃/min, carrying out heat preservation preactivation treatment for 2-3h, heating to 720-750 ℃, carrying out heat preservation calcination for 2-3h, wherein the calcination product is the sodium ion battery cathode material of the SnSb alloy-carbon nanofiber.
(4) The method comprises the steps of dispersing a sodium ion battery negative electrode material 1 of SnSb alloy-carbon nanofiber, conductive carbon black and a polyvinylidene fluoride adhesive in an N-methyl pyrrolidone solvent to form slurry according to a mass ratio of 8:1:1, uniformly coating the slurry on a copper foil, and drying to obtain the electrode material.
Example 1
(1) Preparing a porous N-S doped carbon nano microsphere component 1: adding a sodium hydroxide solution with the mass concentration of 0.1mol/L into a reaction bottle, adding phenol and a formaldehyde aqueous solution, placing the reaction bottle into a constant-temperature water bath, heating to 75 ℃, stirring at a constant speed for reaction for 1h, adding a surfactant poloxamer, wherein the mass ratio of phenol to formaldehyde to poloxamer is 1:1.2:1.6, stirring at a constant speed for 5h, adding distilled water to adjust the mass concentration of the sodium hydroxide substance to be 0.02mol/L, stirring at a constant speed for reaction for 3h, transferring the solution into a hydrothermal synthesis reaction kettle, adding distilled water to adjust the mass concentration of the sodium hydroxide substance to be 0.003mol/L, placing the solution into a reaction kettle heating box, heating to 140 ℃, reacting for 10h, cooling the solution to room temperature, filtering to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product, potassium hydroxide and thiourea into a planetary ball mill, ball-milling the three components for 20 hours until the solid product passes through a 1000-mesh screen sieve, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 5 ℃/min, keeping the temperature and calcining for 3 hours at 720 ℃, washing the calcined product with distilled water, and fully drying to obtain the porous N-S doped carbon nanosphere component 1.
(2) Preparing a sodium ion battery anode material of SnSb alloy-carbon nanofiber 1: adding N, N-dimethylformamide solvent, 32 parts of porous N-S doped carbon nano microsphere component 1 and 20 parts of SnCl into a reaction bottle224 parts of SbCl 36 parts of dispersing agent, the reaction bottle is placed in an ultrasonic treatment instrument after being uniformly stirred, the ultrasonic treatment instrument comprises a host machine, an ultrasonic generator is fixedly arranged on the inner top wall of the host machine, an ultrasonic probe is arranged at the bottom of the ultrasonic generator, a telescopic seat is fixedly arranged on the inner bottom wall of the host machine, a container is placed at the top of the telescopic seat, a turntable is movably arranged on the host machine, storage grooves which are uniformly distributed are formed in the turntable, spare parts are placed in the storage grooves, sliding plates are movably inserted in the storage grooves and positioned on the back of the spare parts, magnetic blocks are fixedly connected to the back of the sliding plates, iron sheets are arranged on the bottom of the storage grooves, magnets are arranged in the host machine and positioned on the back of the storage grooves at the top, a handle is arranged on the turntable, the turntable is heated to 60 ℃, the ultrasonic frequency is 30KHz, ultrasonic dispersion treatment is carried out for, after the solution is uniformly stirred, pouring the solution into a micro injector, carrying out an electrostatic spinning process, wherein the voltage of an electrostatic spinning machine is 19kV, the distance between a syringe needle and a receiver is 12cm, the flow rate of the electrostatic spinning solution is 0.6mL/h, placing the nanofiber prepared by electrostatic spinning into an atmosphere resistance furnace, introducing nitrogen, heating up at the rate of 5 ℃/min to 200 ℃, carrying out heat preservation and pre-activation treatment for 2h, heating up to 720 ℃, carrying out heat preservation and calcination for 2h, and obtaining a calcined product, namely the SnSb alloy-carbon nanofiber sodium ion battery cathode material 1.
(3) Preparation of electrode material 1: the method comprises the steps of dispersing a sodium ion battery negative electrode material 1 of SnSb alloy-carbon nanofiber, conductive carbon black and a polyvinylidene fluoride adhesive in an N-methyl pyrrolidone solvent to form slurry according to a mass ratio of 8:1:1, uniformly coating the slurry on a copper foil, and drying to obtain the electrode material 1.
Example 2
(1) Preparing a porous N-S doped carbon nano microsphere component 2: adding a sodium hydroxide solution with the mass concentration of 0.15mol/L into a reaction bottle, adding phenol and a formaldehyde aqueous solution, placing the reaction bottle into a constant-temperature water bath, heating to 75 ℃, uniformly stirring for reaction for 3 hours, adding a surfactant poloxamer, wherein the mass ratio of phenol to formaldehyde to poloxamer is 1:1.5:2, uniformly stirring for 5 hours, adding distilled water to adjust the mass concentration of the sodium hydroxide substance to be 0.03mol/L, uniformly stirring for reaction for 3 hours, transferring the solution into a hydrothermal synthesis reaction kettle, adding distilled water to adjust the mass concentration of the sodium hydroxide substance to be 0.003mol/L, placing the solution into a reaction kettle heating box, heating to 150 ℃, reacting for 10 hours, cooling the solution to room temperature, filtering to remove the solvent, washing a solid product with distilled water and ethanol, fully drying, placing the solid product, potassium hydroxide and thiourea into a planetary ball mill, ball-milling the three components for 30 hours until the solid product passes through a 1500-mesh screen, putting the solid mixture into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 5 ℃/min, keeping the temperature and calcining for 5 hours at 720 ℃, washing the calcined product with distilled water, and fully drying to obtain the porous N-S doped carbon nanosphere component 2.
(2) Preparing a sodium ion battery cathode material of SnSb alloy-carbon nanofiber 2: adding N, N-dimethylformamide solvent, 28 parts of porous N-S doped carbon nano microsphere component 2 and 21 parts of SnCl into a reaction bottle225 parts of SbCl 37 parts of dispersing agent, the reaction bottle is placed in an ultrasonic treatment instrument after being uniformly stirred, the ultrasonic treatment instrument comprises a host machine, an ultrasonic generator is fixedly arranged on the inner top wall of the host machine, an ultrasonic probe is arranged at the bottom of the ultrasonic generator, a telescopic seat is fixedly arranged on the inner bottom wall of the host machine, a container is placed at the top of the telescopic seat, a turntable is movably arranged on the host machine, storage grooves which are uniformly distributed are formed in the turntable, spare parts are placed in the storage grooves, sliding plates are movably inserted in the storage grooves and positioned on the back of the spare parts, magnetic blocks are fixedly connected to the back of the sliding plates, iron sheets are arranged on the bottom of the storage grooves, magnets are arranged in the host machine and positioned on the back of the storage grooves at the top, a handle is arranged on the turntable, the turntable is heated to 80 ℃, the ultrasonic frequency is 30KHz, ultrasonic dispersion treatment is carried out for, after stirring uniformly, pouring the solution into a micro-injector for electrostatic spinningThe voltage of an electrostatic spinning machine is 19kV, the distance between a syringe needle and a receiver is 12cm, the flow rate of an electrostatic spinning solution is 0.8mL/h, the nanofiber prepared by electrostatic spinning is placed in an atmosphere resistance furnace, nitrogen is introduced, the temperature rise rate is 5 ℃/min, the temperature is raised to 240 ℃, the heat preservation preactivation treatment is carried out for 2h, the temperature is raised to 750 ℃, the heat preservation calcination is carried out for 2h, and the calcination product is the sodium ion battery cathode material 2 of the SnSb alloy-carbon nanofiber.
(3) Preparing an electrode material 2: the method comprises the steps of dispersing a sodium ion battery negative electrode material 2 of SnSb alloy-carbon nanofiber, conductive carbon black and a polyvinylidene fluoride adhesive in an N-methyl pyrrolidone solvent to form slurry according to a mass ratio of 8:1:1, uniformly coating the slurry on a copper foil, and drying to obtain an electrode material 2.
Example 3
(1) Preparing a porous N-S doped carbon nano microsphere component 3: adding a sodium hydroxide solution with the mass concentration of 0.12mol/L into a reaction bottle, adding phenol and a formaldehyde aqueous solution, placing the reaction bottle into a constant-temperature water bath, heating to 80 ℃, uniformly stirring for reaction for 2 hours, adding a surfactant poloxamer, wherein the mass ratio of phenol to formaldehyde to poloxamer is 1:1.3:1.8, uniformly stirring for 6.5 hours, adding distilled water to adjust the mass concentration of the sodium hydroxide substance to be 0.025mol/L, uniformly stirring for reaction for 4 hours, transferring the solution into a hydrothermal synthesis reaction kettle, adding distilled water to adjust the mass concentration of the sodium hydroxide substance to be 0.0038mol/L, placing the solution into a reaction kettle heating box, heating to 145 ℃, reacting for 12 hours, cooling the solution to room temperature, filtering to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product, potassium hydroxide and thiourea into a planetary ball mill, ball-milling the three components for 25 hours until the solid product passes through a 1200-mesh screen sieve, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 7 ℃/min, keeping the temperature and calcining at 735 ℃ for 4 hours, washing the calcined product with distilled water, and fully drying to obtain the porous N-S doped carbon nanosphere component 3.
(2) Preparing a sodium ion battery anode material 3 of SnSb alloy-carbon nanofiber: adding N, N-dimethylformamide solvent and 22 parts of porous N-S doping into a reaction bottleCarbon nano microsphere component 3, 22 portions SnCl226.5 parts of SbCl38.5 parts of dispersing agent, after being uniformly stirred, the reaction bottle is placed in an ultrasonic treatment instrument, the ultrasonic treatment instrument comprises a host, an ultrasonic generator is fixedly arranged on the inner top wall of the host, an ultrasonic probe is arranged at the bottom of the ultrasonic generator, a telescopic seat is fixedly arranged on the inner bottom wall of the host, a container is placed at the top of the telescopic seat, a turntable is movably arranged on the host, evenly distributed storage grooves are formed in the turntable, spare parts are placed in the storage grooves, sliding plates are movably inserted in the storage grooves and positioned on the back of the spare parts, magnetic blocks are fixedly connected to the back of the sliding plates, iron sheets are arranged on the bottom of the storage grooves, magnets are installed in the storage grooves and positioned on the top of the host, a handle is arranged on the turntable, the turntable is heated to 70 ℃, the ultrasonic frequency is 35KHz, ultrasonic dispersion treatment is carried out for 3 hours, 21 parts of polyacrylonitrile are added, and after uniformly stirring, pouring the solution into a micro injector, and carrying out an electrostatic spinning process, wherein the voltage of an electrostatic spinning machine is 20kV, the distance between a syringe needle and a receiver is 14cm, the flow rate of the electrostatic spinning solution is 0.7mL/h, placing the nanofiber prepared by electrostatic spinning in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 8 ℃/min to 220 ℃, carrying out heat preservation and pre-activation treatment for 2.5h, heating to 735 ℃, carrying out heat preservation and calcination for 2.5h, and obtaining a calcination product, namely the SnSb alloy-carbon nanofiber sodium ion battery negative electrode material 3.
(3) Preparing an electrode material 3: the method comprises the steps of dispersing a sodium ion battery negative electrode material 3 of SnSb alloy-carbon nanofiber, conductive carbon black and a polyvinylidene fluoride adhesive in an N-methyl pyrrolidone solvent to form slurry according to a mass ratio of 8:1:1, uniformly coating the slurry on a copper foil, and drying to obtain the electrode material 3.
Example 4
(1) Preparing a porous N-S doped carbon nano microsphere component 4: adding a sodium hydroxide solution with the mass concentration of 0.15mol/L into a reaction bottle, adding phenol and a formaldehyde aqueous solution, placing the reaction bottle into a constant-temperature water bath, heating to 85 ℃, uniformly stirring for reaction for 3 hours, adding a surfactant poloxamer, wherein the mass ratio of phenol to formaldehyde to poloxamer is 1:1.5:2, uniformly stirring for 8 hours, adding distilled water to adjust the mass concentration of the sodium hydroxide substance to be 0.03mol/L, uniformly stirring for reaction for 5 hours, transferring the solution into a hydrothermal synthesis reaction kettle, adding distilled water to adjust the mass concentration of the sodium hydroxide substance to be 0.045mol/L, placing the solution into a reaction kettle heating box, heating to 150 ℃, reacting for 15 hours, cooling the solution to room temperature, filtering to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product, potassium hydroxide and thiourea into a planetary ball mill, ball-milling the three components for 30 hours until the solid product passes through a 1500-mesh screen, putting the solid mixture into an atmosphere resistance furnace, introducing nitrogen, heating at a rate of 10 ℃/min, keeping the temperature and calcining for 5 hours at 750 ℃, washing the calcined product with distilled water, and fully drying to obtain the porous N-S doped carbon nanosphere component 4.
(2) Preparing a sodium ion battery negative electrode material of SnSb alloy-carbon nanofiber 4: adding N, N-dimethylformamide solvent, 17 parts of porous N-S doped carbon nano microsphere component 4 and 23 parts of SnCl into a reaction bottle228 parts of SbCl310 parts of dispersing agent, after being uniformly stirred, the reaction bottle is placed in an ultrasonic treatment instrument, the ultrasonic treatment instrument comprises a host machine, an ultrasonic generator is fixedly arranged on the inner top wall of the host machine, an ultrasonic probe is arranged at the bottom of the ultrasonic generator, a telescopic seat is fixedly arranged on the inner bottom wall of the host machine, a container is placed at the top of the telescopic seat, a turntable is movably arranged on the host machine, storage grooves which are uniformly distributed are formed in the turntable, spare parts are placed in the storage grooves, sliding plates are movably inserted in the storage grooves and positioned on the back of the spare parts, magnetic blocks are fixedly connected to the back of the sliding plates, iron sheets are arranged on the bottom of the storage grooves, magnets are arranged in the host machine and positioned on the back of the storage grooves at the top, a handle is arranged on the turntable, the turntable is heated to 80 ℃, the ultrasonic frequency is 40KHz, ultrasonic dispersion treatment is carried out, after stirring evenly, pouring the solution into a micro injector, carrying out electrostatic spinning process, wherein the voltage of an electrostatic spinning machine is 22kV, the distance between the injector needle and a receiver is 16cm, the flow rate of the electrostatic spinning solution is 0.8mL/h, placing the nanofiber prepared by electrostatic spinning into an atmosphere resistance furnace, introducing nitrogen, the heating rate is 10 ℃/min,and heating to 240 ℃, carrying out heat preservation preactivation treatment for 3h, heating to 750 ℃, carrying out heat preservation calcination for 3h, wherein the calcination product is the SnSb alloy-carbon nanofiber sodium ion battery negative electrode material 4.
(3) Preparation of electrode material 4: the method comprises the steps of dispersing a sodium ion battery negative electrode material 4 of SnSb alloy-carbon nanofiber, conductive carbon black and a polyvinylidene fluoride adhesive in an N-methyl pyrrolidone solvent to form slurry according to the mass ratio of 8:1:1, uniformly coating the slurry on a copper foil, and drying to obtain the electrode material 4.
Comparative example 1
(1) Preparing a porous N-S doped carbon nano microsphere component 1: adding a sodium hydroxide solution with the mass concentration of 0.15mol/L into a reaction bottle, adding a phenol and formaldehyde aqueous solution, placing the reaction bottle into a constant-temperature water bath, heating to 75 ℃, stirring at a constant speed for reaction for 3 hours, adding a surfactant poloxamer, wherein the mass ratio of the phenol to the formaldehyde to the poloxamer is 1:1.6:2.2, stirring at a constant speed for 6 hours, adding distilled water to adjust the mass concentration of the sodium hydroxide to be 0.02mol/L, stirring at a constant speed for reaction for 5 hours, transferring the solution into a hydrothermal synthesis reaction kettle, adding distilled water to adjust the mass concentration of the sodium hydroxide to be 0.045mol/L, placing the solution into a reaction kettle heating box, heating to 140 ℃, reacting for 15 hours, cooling the solution to room temperature, filtering to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product, potassium hydroxide and thiourea into a planetary ball mill, ball-milling the three components for 20 hours until the solid product passes through a 1500-mesh screen, putting the solid mixture into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 5 ℃/min, keeping the temperature and calcining for 5 hours at 750 ℃, washing the calcined product with distilled water, and fully drying to obtain the porous N-S doped carbon nanosphere component 1.
(2) Preparing a sodium ion battery anode material of SnSb alloy-carbon nanofiber 1: adding N, N-dimethylformamide solvent and 36 parts of porous N-S doped carbon nano microsphere component 1 and 19 parts of SnCl into a reaction bottle223 parts of SbCl35 parts of dispersing agent, the reaction bottle is arranged in the ultrasonic treatment instrument after being uniformly stirred, the ultrasonic treatment instrument comprises a host, and the inner top wall of the host is fixedly provided with an ultrasonic generatorThe ultrasonic spinning device comprises a generator, an ultrasonic probe is installed at the bottom of an ultrasonic generator, a telescopic seat is fixedly installed on the inner bottom wall of a main machine, a container is placed at the top of the telescopic seat, a rotary table is movably installed on the main machine, evenly-distributed storage grooves are formed in the rotary table, spare parts are placed in the storage grooves, sliding plates are movably inserted in the storage grooves and located on the back of the spare parts, magnetic blocks are fixedly connected to the back of the sliding plates, iron sheets are arranged on the bottom of the storage grooves, magnets are installed in the main machine and located on the back of the top storage grooves, a handle is arranged on the rotary table, the rotary table is heated to 60-80 ℃, the ultrasonic frequency is 40KHz, ultrasonic dispersion treatment is carried out for 4 hours, 17 parts of polyacrylonitrile are added into a solution, after the solution is uniformly stirred, the solution is poured into a micro-injector, the electrostatic spinning process is carried out, and (3) putting the nanofiber prepared by electrostatic spinning in an atmosphere resistance furnace at the flow rate of 0.8mL/h, introducing nitrogen at the heating rate of 10 ℃/min, heating to 200 ℃, carrying out heat preservation pre-activation treatment for 2h, heating to 720 ℃, carrying out heat preservation calcination for 3h, wherein the calcination product is the SnSb alloy-carbon nanofiber sodium ion battery cathode material 1.
(3) Preparation of electrode material 1: the method comprises the steps of dispersing a sodium ion battery negative electrode material 1 of SnSb alloy-carbon nanofiber, conductive carbon black and a polyvinylidene fluoride adhesive in an N-methyl pyrrolidone solvent to form slurry according to a mass ratio of 8:1:1, uniformly coating the slurry on a copper foil, and drying to obtain the electrode material 1.
Comparative example 2
(1) Preparing a porous N-S doped carbon nano microsphere component 2: adding a sodium hydroxide solution with the mass concentration of 0.1mol/L into a reaction bottle, adding phenol and a formaldehyde aqueous solution, placing the reaction bottle into a constant-temperature water bath, heating to 85 ℃, uniformly stirring for reaction for 1h, adding a surfactant poloxamer, wherein the mass ratio of phenol to formaldehyde to poloxamer is 1:1.2:2, uniformly stirring for 8h, adding distilled water to adjust the mass concentration of the sodium hydroxide substance to be 0.03mol/L, uniformly stirring for reaction for 3h, transferring the solution into a hydrothermal synthesis reaction kettle, adding distilled water to adjust the mass concentration of the sodium hydroxide substance to be 0.045mol/L, placing the solution into a reaction kettle heating box, heating to 140 ℃, reacting for 15h, cooling the solution to room temperature, filtering to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product, potassium hydroxide and thiourea into a planetary ball mill, ball-milling the three components for 30 hours until the solid product passes through a 1000-mesh screen sieve, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 10 ℃/min, keeping the temperature and calcining for 3 hours at 750 ℃, washing the calcined product with distilled water, and fully drying to obtain the porous N-S doped carbon nanosphere component 2.
(2) Preparing a sodium ion battery cathode material of SnSb alloy-carbon nanofiber 2: adding N, N-dimethylformamide solvent, 12 parts of porous N-S doped carbon nano microsphere component 2 and 24.5 parts of SnCl into a reaction bottle229.5 parts of SbCl312 parts of dispersing agent, after being uniformly stirred, the reaction bottle is placed in an ultrasonic treatment instrument, the ultrasonic treatment instrument comprises a host machine, an ultrasonic generator is fixedly arranged on the inner top wall of the host machine, an ultrasonic probe is arranged at the bottom of the ultrasonic generator, a telescopic seat is fixedly arranged on the inner bottom wall of the host machine, a container is placed at the top of the telescopic seat, a turntable is movably arranged on the host machine, storage grooves which are uniformly distributed are formed in the turntable, spare parts are placed in the storage grooves, sliding plates are movably inserted in the storage grooves and positioned on the back of the spare parts, magnetic blocks are fixedly connected to the back of the sliding plates, iron sheets are arranged on the bottom of the storage grooves, magnets are arranged in the host machine and positioned on the back of the storage grooves at the top, a handle is arranged on the turntable, the turntable is heated to 90 ℃, the ultrasonic frequency is 30KHz, ultrasonic dispersion treatment is carried out, after the solution is uniformly stirred, pouring the solution into a micro injector, carrying out an electrostatic spinning process, wherein the voltage of an electrostatic spinning machine is 22kV, the distance between a syringe needle and a receiver is 18cm, the flow rate of the electrostatic spinning solution is 0.5mL/h, placing the nanofiber prepared by electrostatic spinning into an atmosphere resistance furnace, introducing nitrogen, heating up to 250 ℃ at the heating rate of 12 ℃/min, carrying out heat preservation and pre-activation treatment for 3h, heating up to 760 ℃ again, carrying out heat preservation and calcination for 4h, and obtaining a calcination product, namely the SnSb alloy-carbon nanofiber sodium ion battery negative electrode material 2.
(3) Preparing an electrode material 2: the method comprises the steps of dispersing a sodium ion battery negative electrode material 2 of SnSb alloy-carbon nanofiber, conductive carbon black and a polyvinylidene fluoride adhesive in an N-methyl pyrrolidone solvent to form slurry according to a mass ratio of 8:1:1, uniformly coating the slurry on a copper foil, and drying to obtain an electrode material 2.
The electrode materials prepared in examples 1-4 and comparative examples 1-2 were used as a negative electrode, sodium metal as a counter electrode, a glass fiber membrane as a separator, and a 5% fluoroethylene carbonate +1mol/L mixed solution of sodium perchlorate-ethylene carbonate + diethyl carbonate as an electrolyte, and assembled into a CR2032 button cell in an argon atmosphere, and electrochemical performance tests were performed in a LAND-CT2001A cell test system.
Figure BDA0002511946170000131
Figure BDA0002511946170000141
In summary, the SnSb alloy-carbon nanofiber sodium ion battery cathode material expands the interlayer spacing of the carbon nanospheres by doping the carbon nanospheres with sulfur atoms, and forms a mesoporous structure on the surface of the carbon nanospheres, so that the carbon nanospheres form a huge specific surface area and a developed pore structure, the electronegativity of nitrogen is stronger than that of carbon, the conductivity of the carbon nanospheres is enhanced by doping nitrogen atoms, the nano SnSb alloy is prepared and uniformly loaded on the surface of the carbon nanospheres by taking the porous N-S doped carbon nanospheres as a carrier through an electrostatic spinning method, the agglomeration and agglomeration of the nano SnSb alloy are greatly reduced, more electrochemical active sites are exposed from the nanofiber cathode material, the conductivity of the cathode material is improved by the carbon nanospheres, the transmission of ions and charges is promoted, and the transmission path of the ions is shortened by the abundant pore structure, thereby improving the specific capacity and the coulombic efficiency of the cathode material.
According to the sodium ion battery cathode material of the SnSb alloy-carbon nanofiber, the nanofiber prepared by an electrostatic spinning method has high mechanical strength and excellent electrochemical stability, and the SnSb alloy is coated by the carbon nanofiber, so that elastic expansion buffering is provided for mechanical stress generated in the process of sodium desorption of the SnSb alloy during charging and discharging, the volume expansion phenomenon of the SnSb alloy is effectively relieved, and the reduction of the cycle stability and the rate capability of the sodium ion battery due to the loss and decomposition of a cathode material matrix is avoided.

Claims (7)

1. The SnSb alloy-carbon nanofiber sodium ion battery negative electrode material comprises the following formula raw materials in parts by weight: 18-22 parts of polyacrylonitrile, 17-32 parts of porous N-S doped carbon nano-microspheres and 20-23 parts of SnCl224-28 parts of SbCl36-10 parts of a dispersing agent.
2. The SnSb alloy-carbon nanofiber sodium-ion battery anode material as set forth in claim 1, wherein: the dispersing agent is polyvinylpyrrolidone.
3. The SnSb alloy-carbon nanofiber sodium-ion battery anode material as set forth in claim 1, wherein: the preparation method of the porous N-S doped carbon nano microsphere comprises the following steps:
(1) adding phenol and formaldehyde aqueous solution into sodium hydroxide solution with the mass concentration of 0.1-0.15mol/L, heating the solution to 75-85 ℃, reacting for 1-3h, adding poloxamer as a surfactant, stirring at a constant speed for 5-8h, adding distilled water to adjust the mass concentration of the sodium hydroxide to 0.02-0.03mol/L, reacting for 3-5h, transferring the solution into a reaction kettle, adding distilled water to adjust the mass concentration of the sodium hydroxide to 0.003-0.045mol/L, heating to 140-.
(2) And (2) placing the solid product, potassium hydroxide and thiourea in a planetary ball mill, ball-milling for 20-30h until the solid product passes through a 1000-ion 1500-mesh sieve, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 5-10 ℃/min, carrying out heat preservation calcination for 3-5h at the temperature of 720-750 ℃, washing and drying the calcined product, and thus obtaining the porous N-S doped carbon nano microsphere.
4. The SnSb alloy-carbon nanofiber sodium-ion battery anode material as set forth in claim 3, wherein: the mass ratio of the phenol to the formaldehyde to the poloxamer is 1:1.2-1.5: 1.6-2.
5. The SnSb alloy-carbon nanofiber sodium-ion battery anode material as set forth in claim 3, wherein: the mass ratio of the solid product to the potassium hydroxide to the thiourea is 1:1.8-2.2: 2-2.5.
6. The SnSb alloy-carbon nanofiber sodium-ion battery anode material as set forth in claim 1, wherein: the preparation method of the sodium ion battery anode material of the SnSb alloy-carbon nanofiber comprises the following steps:
(1) adding 17-32 parts of porous N-S doped carbon nano-microspheres and 20-23 parts of SnCl into an N, N-dimethylformamide solvent224-28 parts of SbCl36-10 parts of dispersing agent, and placing the mixture in an ultrasonic treatment instrument for ultrasonic dispersion treatment for 2-4h at the temperature of 60-80 ℃, wherein the ultrasonic frequency is 30-40 KHz.
(2) Adding 18-22 parts of polyacrylonitrile into the solution, pouring the solution into a miniature injector, and carrying out electrostatic spinning, wherein the voltage of an electrostatic spinning machine is 19-22kV, the distance between a syringe needle and a receiver is 12-16cm, and the flow rate of the electrostatic spinning solution is 0.6-0.8 mL/h.
(3) And (2) placing the nanofiber prepared by electrostatic spinning in an atmosphere resistance furnace, introducing nitrogen, heating to 200-10 ℃/min at the heating rate of 5-10 ℃/min, carrying out heat preservation preactivation treatment for 2-3h, heating to 720-750 ℃, carrying out heat preservation calcination for 2-3h, wherein the calcination product is the sodium ion battery cathode material of the SnSb alloy-carbon nanofiber.
7. The SnSb alloy-carbon nanofiber sodium-ion battery anode material as set forth in claim 6, wherein: the ultrasonic treatment instrument comprises a host (1), an ultrasonic generator (2) is fixedly installed on the inner top wall of the host (1), an ultrasonic probe (3) is installed at the bottom of the ultrasonic generator (2), a telescopic seat (4) is fixedly installed on the inner bottom wall of the host (1), a container (5) is placed at the top of the telescopic seat (4), a turntable (6) is movably installed on the host (1), storage grooves (7) which are uniformly distributed are formed in the turntable (6), spare parts (8) are placed in the storage grooves (7), a sliding plate (9) is movably inserted in the storage grooves (7) and positioned at the back of the spare parts (8), magnetic blocks (10) are fixedly connected to the back of the sliding plate (9), iron sheets (11) are arranged on the bottom of the storage grooves (7), a magnet (12) is installed in the host (1) and positioned at the back of the storage grooves (7) at the top, a handle (13) is arranged on the rotating disc (6).
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