CN111977699A - Ultrathin nanometer SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery and the preparation method thereof - Google Patents

Ultrathin nanometer SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery and the preparation method thereof Download PDF

Info

Publication number
CN111977699A
CN111977699A CN202010887248.XA CN202010887248A CN111977699A CN 111977699 A CN111977699 A CN 111977699A CN 202010887248 A CN202010887248 A CN 202010887248A CN 111977699 A CN111977699 A CN 111977699A
Authority
CN
China
Prior art keywords
electrode material
petal
negative electrode
ion battery
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202010887248.XA
Other languages
Chinese (zh)
Inventor
杨永凤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guigang Yile Technology Development Co ltd
Original Assignee
Guigang Yile Technology Development Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guigang Yile Technology Development Co ltd filed Critical Guigang Yile Technology Development Co ltd
Priority to CN202010887248.XA priority Critical patent/CN111977699A/en
Publication of CN111977699A publication Critical patent/CN111977699A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 field of sodium ion batteries and discloses ultrathin nanometer SiO2Coated with Fe2O3The negative electrode material of sodium ion battery is nano Fe2O3Self-assembly to form porous Fe2O3The nanometer flower has a unique petal-shaped structure and a porous structure, has an ultra-high specific surface area and rich sodium storage active sites, provides a transmission channel for sodium ions, promotes the process of sodium ions extraction and insertion, hydrolyzes ethyl orthosilicate at a low temperature, and forms petal-shaped porous Fe2O3Depositing a layer to form ultrathin SiO2Layer of p-Fe2O3Has good functions of coating and supporting structure, and buffers Fe2O3The stress generated by the negative electrode material in the sodium removal/sodium insertion process improves the phenomenon of volume expansion, and inhibits the pulverization and the falling of the electrode material matrix into the electrolyte, thereby avoiding the rapid attenuation of the capacity of the negative electrode material and enhancing the electrochemical cycle stability.

Description

Ultrathin nanometer SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery and the preparation method thereof
Technical Field
The invention relates to the field of sodium ion batteries, in particular to ultrathin nanometer SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery and the preparation method thereof.
Background
The sodium ion battery is a rechargeable secondary battery, compared with a lithium ion battery, the sodium salt raw material of the sodium ion battery is rich in reserve and low in price, the sodium ion battery can use low-concentration electrolyte, the cost is further reduced, and meanwhile, the sodium ion battery has no over-discharge characteristic and allows the sodium ion battery to discharge to zero volts, so that the sodium ion battery has the advantages of high energy density, good cycle performance, low cost and the like.
The sodium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm and the like, wherein the negative electrode material has great influence on the sodium ion battery, the specific capacity and the cycling stability of the negative electrode material are improved, and the negative electrode material is an effective way for improving the electrochemical performance of the sodium ion battery2O3The theoretical capacity is higher and reaches more than 1000mAh/g, and the material has rich reserves, low price, safety and no toxicity, is a sodium ion battery cathode material with great development potential, but Fe2O3During the charging and discharging process, Fe is continuously removed/inserted due to sodium removal2O3The matrix generates serious volume expansion change, which causes the active matrix of the electrode material to be pulverized and fall into the electrolyte, and the specific capacity and the cycling stability of the electrode material are seriously influenced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides high-efficiency ultrathin nanometer SiO2Coated with Fe2O3The sodium ion battery cathode material and the preparation method thereof solve the problem of Fe2O3The specific capacity of the negative electrode material is seriously attenuated, and the cycling stability is poor.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: ultrathin nanometer SiO2Coated with Fe2O3The sodium ion battery cathode material is the ultrathin nanometer SiO2Coated with Fe2O3The preparation method of the sodium-ion battery negative electrode material comprises the following steps:
(1) adding an ethylene glycol solvent and sodium acetate into a reaction bottle, placing the reaction bottle in a magnetic stirring reaction device, stirring uniformly, adding an ethylene glycol solution of polyethylene glycol and ferric nitrate into a nitrogen atmosphere, heating to the temperature of 140 ℃ and 160 ℃, stirring at a constant speed for reaction for 48-72h, performing centrifugal separation to remove the solvent, washing a precipitate by using distilled water and ethanol, and drying to prepare the petal-shaped porous iron alkoxide precursor.
(2) Placing the petal-shaped porous iron alkoxide precursor in a resistance furnace, and carrying out a heat treatment process to prepare the petal-shaped porous Fe2O3。
(3) Adding ethanol solvent and petal-shaped porous Fe into a reaction bottle2O3Adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 8-10, adding hexadecyl trimethyl ammonium bromide, stirring uniformly, slowly dropwise adding an ethanol solution of ethyl orthosilicate, stirring at a constant speed at 0-5 ℃ for reacting for 18-36h, centrifugally separating to remove the solvent, washing a solid mixed product by using distilled water and ethanol, and drying to prepare the ultrathin silicon precursor coated petal-shaped porous Fe2O3。
(4) Coating the ultrathin silicon precursor with petal-shaped porous Fe2O3Placing the mixture in a resistance furnace, and carrying out calcination process to prepare the ultrathin nano SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery.
Preferably, the mass ratio of the sodium acetate, the polyethylene glycol and the ferric nitrate in the step (1) is 250-350:75-95: 100.
Preferably, the magnetic stirring reaction device in the step (1) comprises a motor, the motor is movably connected with a rotating shaft, a large guide wheel rotating disc is fixedly connected above the rotating shaft, a large rotating magnet is fixedly connected with the large guide wheel rotating disc, a small gear disc is movably connected with the large guide wheel rotating disc, a small magnet is fixedly connected with the small gear disc, and a reaction bottle is arranged above the magnetic stirring reaction device.
Preferably, the heating rate of the resistance furnace heat treatment process in the step (2) is 1-3 ℃/min, the heat treatment temperature is 480-520 ℃, and the heat treatment time is 45-90 min.
Preferably, the petal-shaped porous Fe in the step (3)2O3The mass ratio of the hexadecyl trimethyl ammonium bromide to the tetraethoxysilane is 100:14-20: 25-35.
Preferably, the temperature rise rate of the calcination process in the step (4) is 3-8 ℃/min, the calcination temperature is 420-460 ℃, and the calcination time is 3-4 h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
the ultrathin nanometer SiO2Coated with Fe2O3The sodium ion battery cathode material is prepared by taking polyethylene glycol as a template agent in a hot solvent system of ethylene glycol to obtain a petal-shaped porous iron alkoxide precursor, and then carrying out high-temperature heat treatment to obtain petal-shaped porous Fe2O3From nano Fe2O3Self-assembly to form porous Fe2O3The nanometer flower has the appearance, unique petal-shaped structure and porous structure, has ultrahigh specific surface area and abundant sodium storage active sites, provides a transmission channel for sodium ions, and promotes the process of sodium ions extraction and insertion, thereby improving the actual specific capacity of the cathode material.
The ultrathin nanometer SiO2Coated with Fe2O3In the sodium ion battery cathode material, cetyl trimethyl ammonium bromide is used as a structure guiding agent in the atmosphere of ethanol-ammonia water, ethyl orthosilicate is hydrolyzed at low temperature, and petal-shaped porous Fe is formed2O3Depositing a layer to form ultrathin SiO2Layer of p-Fe2O3Has good functions of coating and supporting structure, and obviously buffers Fe2O3The stress generated by the negative electrode material in the sodium removal/sodium insertion process improves the phenomenon of volume expansion, and inhibits the pulverization and the falling of the electrode material matrix into the electrolyte, thereby avoiding the rapid attenuation of the capacity of the negative electrode material and enhancing the electrochemical cycle stability.
Drawings
FIG. 1 is a schematic front view of a magnetic stirring reaction apparatus;
FIG. 2 is a schematic top view of a large idler turntable.
1-magnetic stirring reaction device; 2, a motor; 3-a rotating shaft; 4-large guide wheel turntable; 5-rotating the magnet; 6-pinion disc; 7-small magnet; 8-reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: ultrathin nanometer SiO2Coated with Fe2O3The preparation method of the sodium ion battery negative electrode material comprises the following steps:
(1) adding glycol solvent and sodium acetate into a reaction bottle, placing the reaction bottle in a magnetic stirring reaction device, the magnetic stirring reaction device comprises a motor, the motor is movably connected with a rotating shaft, a large guide wheel rotating disc is fixedly connected above the rotating shaft, a large rotating magnet is fixedly connected with the large guide wheel rotating disc, a small gear disc is movably connected with the large guide wheel rotating disc, a small magnet is fixedly connected with the small gear disc, a reaction bottle is arranged above the magnetic stirring reaction device, after being uniformly stirred, glycol solution of polyethylene glycol and ferric nitrate is added into a nitrogen atmosphere, wherein the mass ratio of sodium acetate, polyethylene glycol and ferric nitrate is 250-350:75-95:100, the mixture is heated to 140-160 ℃, the mixture is stirred at a constant speed for reaction for 48-72h, the solvent is removed by centrifugal separation, and the precipitate product is washed by distilled water and ethanol and dried to prepare the petal-shaped porous iron alkoxide precursor.
(2) Placing the petal-shaped porous iron alkoxide precursor in a resistance furnace, heating to 480-520 ℃ at the heating rate of 1-3 ℃/min, and carrying out heat treatment for 45-90min to obtain the petal-shaped porous Fe2O3。
(3) Adding ethanol solvent and petal-shaped porous Fe into a reaction bottle2O3Adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 8-10, adding hexadecyl trimethyl ammonium bromide, stirring uniformly, and slowly dropwise adding an ethanol solution of ethyl orthosilicate, wherein petal-shaped porous Fe2O3Cetyl trimethyl ammonium bromide and ethyl orthosilicate in a mass ratio of 100:14-20:25-35, uniformly stirring and reacting at 0-5 ℃ for 18-36h, and removing by centrifugal separationSolvent, washing the solid mixed product by using distilled water and ethanol and drying to prepare the ultrathin silicon precursor coated petal-shaped porous Fe2O3。
(4) Coating the ultrathin silicon precursor with petal-shaped porous Fe2O3Placing the mixture in a resistance furnace, heating the mixture to 420-460 ℃ at the heating rate of 3-8 ℃/min, and carrying out the calcination process for 3-4h to obtain the ultrathin nano SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery.
Example 1
(1) Adding a glycol solvent and sodium acetate into a reaction bottle, placing the reaction bottle in a magnetic stirring reaction device, wherein the magnetic stirring reaction device comprises a motor, the motor is movably connected with a rotating shaft, a large guide wheel rotating disc is fixedly connected above the rotating shaft, a large rotating magnet is fixedly connected with the large guide wheel rotating disc, a small gear disc is movably connected with the large guide wheel rotating disc, a small magnet is fixedly connected with the small gear disc, the reaction bottle is arranged above the magnetic stirring reaction device, stirring uniformly, adding a glycol solution of polyethylene glycol and ferric nitrate into a nitrogen atmosphere, the mass ratio of the sodium acetate, the polyethylene glycol and the ferric nitrate is 250:75:100, heating to 140 ℃, stirring at a constant speed for reaction for 48-72 hours, centrifugally separating to remove the solvent, washing a precipitation product by using distilled water and ethanol, and drying to prepare the petal-shaped porous iron alkoxide precursor.
(2) Placing the petal-shaped porous iron alkoxide precursor in a resistance furnace, heating to 480 ℃ at the heating rate of 1 ℃/min, and carrying out heat treatment for 45min to obtain the petal-shaped porous Fe2O3。
(3) Adding ethanol solvent and petal-shaped porous Fe into a reaction bottle2O3Adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 8, adding hexadecyl trimethyl ammonium bromide, stirring uniformly, and slowly dropwise adding an ethanol solution of ethyl orthosilicate, wherein petal-shaped porous Fe2O3The mass ratio of the hexadecyl trimethyl ammonium bromide to the ethyl orthosilicate is 100:14:25, the mixture is stirred at a constant speed at 0 ℃ for reaction for 18 hours, the solvent is removed by centrifugal separation, the solid mixed product is washed by distilled water and ethanol and dried, and the ultrathin silicon precursor package is preparedPetal-shaped porous Fe2O3。
(4) Coating the ultrathin silicon precursor with petal-shaped porous Fe2O3Placing in a resistance furnace, heating to 420 ℃ at a heating rate of 3 ℃/min, and calcining for 3h to obtain the ultrathin nanometer SiO2Coated with Fe2O3The negative electrode material 1 for a sodium-ion battery of (1).
Example 2
(1) Adding a glycol solvent and sodium acetate into a reaction bottle, placing the reaction bottle in a magnetic stirring reaction device, wherein the magnetic stirring reaction device comprises a motor, the motor is movably connected with a rotating shaft, a large guide wheel rotating disc is fixedly connected above the rotating shaft, a large rotating magnet is fixedly connected with the large guide wheel rotating disc, a small gear disc is movably connected with the large guide wheel rotating disc, a small magnet is fixedly connected with the small gear disc, the reaction bottle is arranged above the magnetic stirring reaction device, stirring uniformly, adding a glycol solution of polyethylene glycol and ferric nitrate into a nitrogen atmosphere, heating to 160 ℃, stirring at a constant speed for reaction for 48-72 hours, centrifugally separating to remove the solvent, washing a precipitation product by using distilled water and ethanol, and drying to prepare the petal-shaped porous iron alkoxide precursor.
(2) Placing the petal-shaped porous iron alkoxide precursor in a resistance furnace, heating to 480 ℃ at the heating rate of 3 ℃/min, and carrying out heat treatment for 90min to obtain the petal-shaped porous Fe2O3。
(3) Adding ethanol solvent and petal-shaped porous Fe into a reaction bottle2O3Adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 10, adding hexadecyl trimethyl ammonium bromide, stirring uniformly, and slowly dropwise adding an ethanol solution of ethyl orthosilicate, wherein petal-shaped porous Fe2O3Cetyl trimethyl ammonium bromide and ethyl orthosilicate in a mass ratio of 100:16:27, uniformly stirring and reacting at 5 ℃ for 36 hours, centrifugally separating to remove the solvent, washing a solid mixed product by using distilled water and ethanol, and drying to prepare the ultrathin silicon precursor coated petal-shaped porous Fe2O3。
(4) Ultra-thin silicon precursorCoated petal-shaped porous Fe2O3Placing in a resistance furnace, heating to 460 ℃ at a heating rate of 3 ℃/min, and calcining for 4h to obtain the ultrathin nanometer SiO2Coated with Fe2O3The sodium ion battery negative electrode material 2.
Example 3
(1) Adding a glycol solvent and sodium acetate into a reaction bottle, placing the reaction bottle in a magnetic stirring reaction device, wherein the magnetic stirring reaction device comprises a motor, the motor is movably connected with a rotating shaft, a large guide wheel rotating disc is fixedly connected above the rotating shaft, a large rotating magnet is fixedly connected with the large guide wheel rotating disc, a small gear disc is movably connected with the large guide wheel rotating disc, a small magnet is fixedly connected with the small gear disc, the reaction bottle is arranged above the magnetic stirring reaction device, stirring uniformly, adding a glycol solution of polyethylene glycol and ferric nitrate into a nitrogen atmosphere, the mass ratio of the sodium acetate, the polyethylene glycol and the ferric nitrate is 320:87:100, heating to 150 ℃, stirring at a constant speed for reaction for 48-72 hours, centrifugally separating to remove the solvent, washing a precipitation product by using distilled water and ethanol, and drying to prepare the petal-shaped porous iron alkoxide precursor.
(2) Placing the petal-shaped porous iron alkoxide precursor in a resistance furnace, heating to 500 ℃ at the heating rate of 2 ℃/min, and carrying out heat treatment for 60min to obtain the petal-shaped porous Fe2O3。
(3) Adding ethanol solvent and petal-shaped porous Fe into a reaction bottle2O3Adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 9, adding hexadecyl trimethyl ammonium bromide, stirring uniformly, and slowly dropwise adding an ethanol solution of ethyl orthosilicate, wherein petal-shaped porous Fe2O3Cetyl trimethyl ammonium bromide and ethyl orthosilicate in a mass ratio of 100:18:32, uniformly stirring and reacting for 24 hours at the temperature of 2 ℃, centrifugally separating to remove the solvent, washing a solid mixed product by using distilled water and ethanol, and drying to prepare the ultrathin silicon precursor coated petal-shaped porous Fe2O3。
(4) Coating the ultrathin silicon precursor with petal-shaped porous Fe2O3Placing in a resistance furnace, heating at a rate of 5 deg.C/min to 440 deg.CCalcining for 3.5h to obtain the ultrathin nano SiO2Coated with Fe2O3The negative electrode material 3 for a sodium ion battery of (1).
Example 4
(1) Adding an ethylene glycol solvent and sodium acetate into a reaction bottle, placing the reaction bottle in a magnetic stirring reaction device, wherein the magnetic stirring reaction device comprises a motor, the motor is movably connected with a rotating shaft, a large guide wheel rotating disc is fixedly connected above the rotating shaft, a large rotating magnet is fixedly connected with the large guide wheel rotating disc, a small gear disc is movably connected with the large guide wheel rotating disc, a small magnet is fixedly connected with the small gear disc, the reaction bottle is arranged above the magnetic stirring reaction device, stirring uniformly, adding an ethylene glycol solution of polyethylene glycol and ferric nitrate into a nitrogen atmosphere, the mass ratio of the sodium acetate, the polyethylene glycol and the ferric nitrate is 350:95:100, heating to 160 ℃, stirring at a constant speed for reaction for 72 hours, centrifugally separating to remove the solvent, washing a precipitation product by using distilled water and ethanol, and drying to prepare the petal-shaped porous iron.
(2) Placing the petal-shaped porous iron alkoxide precursor in a resistance furnace, heating to 520 ℃ at the heating rate of 3 ℃/min, and carrying out heat treatment for 90min to obtain the petal-shaped porous Fe2O3。
(3) Adding ethanol solvent and petal-shaped porous Fe into a reaction bottle2O3Adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 10, adding hexadecyl trimethyl ammonium bromide, stirring uniformly, and slowly dropwise adding an ethanol solution of ethyl orthosilicate, wherein petal-shaped porous Fe2O3Cetyl trimethyl ammonium bromide and ethyl orthosilicate in a mass ratio of 100:20:35, uniformly stirring and reacting at 5 ℃ for 36 hours, centrifugally separating to remove the solvent, washing a solid mixed product by using distilled water and ethanol, and drying to prepare the ultrathin silicon precursor coated petal-shaped porous Fe2O3。
(4) Coating the ultrathin silicon precursor with petal-shaped porous Fe2O3Placing in a resistance furnace, heating to 460 ℃ at a heating rate of 8 ℃/min, and calcining for 4h to obtain the ultrathin nanometer SiO2Coated with Fe2O3Sodium (II) ofAnd an ion battery negative electrode material 4.
Comparative example 1
(1) Adding an ethylene glycol solvent and sodium acetate into a reaction bottle, placing the reaction bottle in a magnetic stirring reaction device, wherein the magnetic stirring reaction device comprises a motor, the motor is movably connected with a rotating shaft, a large guide wheel rotating disc is fixedly connected above the rotating shaft, a large rotating magnet is fixedly connected with the large guide wheel rotating disc, a small gear disc is movably connected with the large guide wheel rotating disc, a small magnet is fixedly connected with the small gear disc, the reaction bottle is arranged above the magnetic stirring reaction device, stirring uniformly, adding an ethylene glycol solution of polyethylene glycol and ferric nitrate into a nitrogen atmosphere, the mass ratio of the sodium acetate, the polyethylene glycol and the ferric nitrate is 220:70:100, heating to 160 ℃, stirring at a constant speed for reaction for 48 hours, centrifugally separating to remove the solvent, washing a precipitation product by using distilled water and ethanol, and drying to prepare the petal-shaped porous iron.
(2) Placing the petal-shaped porous iron alkoxide precursor in a resistance furnace, heating to 480 ℃ at the heating rate of 2 ℃/min, and carrying out heat treatment for 90min to obtain the petal-shaped porous Fe2O3。
(3) Adding ethanol solvent and petal-shaped porous Fe into a reaction bottle2O3Adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 10, adding hexadecyl trimethyl ammonium bromide, stirring uniformly, and slowly dropwise adding an ethanol solution of ethyl orthosilicate, wherein petal-shaped porous Fe2O3Cetyl trimethyl ammonium bromide and ethyl orthosilicate in a mass ratio of 100:12:20, uniformly stirring and reacting at 5 ℃ for 36 hours, centrifugally separating to remove the solvent, washing a solid mixed product by using distilled water and ethanol, and drying to prepare the ultrathin silicon precursor coated petal-shaped porous Fe2O3。
(4) Coating the ultrathin silicon precursor with petal-shaped porous Fe2O3Placing in a resistance furnace, heating to 460 ℃ at a heating rate of 5 ℃/min, and calcining for 3h to obtain the ultrathin nanometer SiO2Coated with Fe2O3Comparative example 1.
The superadditions in the examples and comparative examples are respectivelyThin nano SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery is placed in an N-methyl pyrrolidone solvent, acetylene black and polyvinylidene fluoride are added and uniformly mixed, then the mixture is coated on the surface of copper foil, dried and punched to form a negative working electrode, a sodium sheet is used as a positive working electrode, a Celgard2300 membrane is used as a diaphragm, a mixed solution of 1mol/L sodium hexafluorophosphate, dimethyl carbonate and dimethyl carbonate is used as an electrolyte to assemble a CR2032 button battery, and the electrochemical cycle performance of the battery is tested in a BTS4000 battery test system.
Figure BDA0002655940050000091

Claims (6)

1. Ultrathin nanometer SiO2Coated with Fe2O3The sodium ion battery negative electrode material is characterized in that: the ultrathin nanometer SiO2Coated with Fe2O3The preparation method of the sodium-ion battery negative electrode material comprises the following steps:
(1) adding sodium acetate into an ethylene glycol solvent, placing the mixture into a magnetic stirring reaction device, adding an ethylene glycol solution of polyethylene glycol and ferric nitrate in a nitrogen atmosphere, heating the mixture to the temperature of 140 ℃ and 160 ℃, reacting for 48 to 72 hours, and performing centrifugal separation, washing and drying to prepare a petal-shaped porous iron alkoxide precursor;
(2) placing the petal-shaped porous iron alkoxide precursor in a resistance furnace, and carrying out a heat treatment process to prepare the petal-shaped porous Fe2O3；
(3) Adding petal-shaped porous Fe into ethanol solvent2O3Adding ammonia water after ultrasonic dispersion is uniform, adjusting the pH value of the solution to 8-10, adding hexadecyl trimethyl ammonium bromide, dropwise adding an ethanol solution of ethyl orthosilicate, reacting for 18-36h at 0-5 ℃, centrifugally separating, washing a solid mixed product, and drying to prepare the ultrathin silicon precursor coated petal-shaped porous Fe2O3；
(4) Coating the ultrathin silicon precursor with petal-shaped porous Fe2O3Placing in a resistance furnace, and calcining to obtainPreparing to obtain ultrathin nano SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery.
2. The ultra-thin nano SiO of claim 12Coated with Fe2O3The sodium ion battery negative electrode material is characterized in that: the mass ratio of the sodium acetate to the polyethylene glycol to the ferric nitrate in the step (1) is 250-350:75-95: 100.
3. The ultra-thin nano SiO of claim 12Coated with Fe2O3The sodium ion battery negative electrode material is characterized in that: the magnetic stirring reaction device in the step (1) comprises a motor, the motor is movably connected with a rotating shaft, a large guide wheel rotating disc is fixedly connected above the rotating shaft, a large rotating magnet is fixedly connected with the large guide wheel rotating disc, a small gear disc is movably connected with the large guide wheel rotating disc, a small magnet is fixedly connected with the small gear disc, and a reaction bottle is arranged above the magnetic stirring reaction device.
4. The ultra-thin nano SiO of claim 12Coated with Fe2O3The sodium ion battery negative electrode material is characterized in that: the heating rate of the resistance furnace heat treatment process in the step (2) is 1-3 ℃/min, the heat treatment temperature is 480-520 ℃, and the heat treatment time is 45-90 min.
5. The ultra-thin nano SiO of claim 12Coated with Fe2O3The sodium ion battery negative electrode material is characterized in that: petal-shaped porous Fe in the step (3)2O3The mass ratio of the hexadecyl trimethyl ammonium bromide to the tetraethoxysilane is 100:14-20: 25-35.
6. The ultra-thin nano SiO of claim 12Coated with Fe2O3The sodium ion battery negative electrode material is characterized in that: the heating rate of the calcination process in the step (4) is 3-8 ℃/min, and the calcination temperature is 420-460 DEG CThe calcination time is 3-4 h.
CN202010887248.XA 2020-08-28 2020-08-28 Ultrathin nanometer SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery and the preparation method thereof Withdrawn CN111977699A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010887248.XA CN111977699A (en) 2020-08-28 2020-08-28 Ultrathin nanometer SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery and the preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010887248.XA CN111977699A (en) 2020-08-28 2020-08-28 Ultrathin nanometer SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery and the preparation method thereof

Publications (1)

Publication Number Publication Date
CN111977699A true CN111977699A (en) 2020-11-24

Family

ID=73440261

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010887248.XA Withdrawn CN111977699A (en) 2020-08-28 2020-08-28 Ultrathin nanometer SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery and the preparation method thereof

Country Status (1)

Country Link
CN (1) CN111977699A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113716624A (en) * 2021-08-31 2021-11-30 蜂巢能源科技有限公司 Composite material, preparation method thereof and lithium ion battery anode material
CN117117158A (en) * 2023-10-23 2023-11-24 浙江帕瓦新能源股份有限公司 Modified sodium ion battery positive electrode material, preparation method thereof and sodium ion battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113716624A (en) * 2021-08-31 2021-11-30 蜂巢能源科技有限公司 Composite material, preparation method thereof and lithium ion battery anode material
CN117117158A (en) * 2023-10-23 2023-11-24 浙江帕瓦新能源股份有限公司 Modified sodium ion battery positive electrode material, preparation method thereof and sodium ion battery
CN117117158B (en) * 2023-10-23 2024-01-23 浙江帕瓦新能源股份有限公司 Modified sodium ion battery positive electrode material, preparation method thereof and sodium ion battery

Similar Documents

Publication Publication Date Title
CN109216688B (en) Ternary lithium battery material, preparation method thereof and lithium ion battery
CN106997975B (en) method for recycling waste lithium iron phosphate battery and lithium manganate battery
JP7220360B2 (en) Method for recovering positive electrode material, obtained positive electrode material and use thereof
CN112194201B (en) Method for recycling valuable metals of waste lithium ion batteries and regenerating ternary positive electrode materials
CN105390693B (en) A kind of nanocrystalline positive electrode LiNi of high power capacity0.8Co0.1Mn0.1O2And its high pressure synthesis method
CN111081994B (en) Surface-modified lithium-rich layered transition metal oxide and preparation method and application thereof
CN104577067B (en) A kind of preparation method of the lithium cobaltate cathode material that perfluorocarbon black-envelope covers
CN111977699A (en) Ultrathin nanometer SiO2Coated with Fe2O3The negative electrode material of the sodium ion battery and the preparation method thereof
CN110904495A (en) Preparation method of monocrystal polyhedral lithium manganate positive electrode material
CN105070970A (en) Method for preparing lithium ion battery anode material by using mixed waste alkaline battery
CN114566727A (en) Modification method for direct pyrogenic repair and regeneration of lithium iron phosphate positive electrode material
CN112421009A (en) Positive electrode material, method for producing same, and secondary battery
CN106025182A (en) Titanium and chromium doped iron fluoride-carbon nanometer composite positive electrode material, and preparation method and application thereof
TWI550938B (en) Cathode material of lithium ion battery and method for making the same
CN116314622B (en) Single crystal cobalt-free aluminum doped lithium nickelate positive electrode material with self-precipitation coating layer, and preparation method and application thereof
CN110034293B (en) L iMn2O4Preparation method of ternary cathode material for coated lithium ion battery
CN115548334B (en) Positive electrode active material and lithium ion battery
CN111525097B (en) Negative electrode material, preparation method and application thereof
CN116443839A (en) Preparation method of lithium iron manganese phosphate
CN111029541A (en) Silicon-carbon composite electrode material for honeycomb-like lithium ion battery and preparation method thereof
CN113903896B (en) Secondary particle hard carbon composite material and preparation method and application thereof
CN113603156B (en) Washing sand grinding coating method for positive electrode material, preparation method, positive electrode material and battery
CN110767907B (en) Universal surface coating modification method for lithium ion battery anode material
CN110010855B (en) Electrode material processing method, processed electrode material and lithium ion battery
CN115959720B (en) High-nickel precursor material, high-nickel positive electrode material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20201124