CN114551832A - Preparation method of nano composite material and lithium ion electrode negative electrode material thereof - Google Patents

Preparation method of nano composite material and lithium ion electrode negative electrode material thereof Download PDF

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CN114551832A
CN114551832A CN202210165549.0A CN202210165549A CN114551832A CN 114551832 A CN114551832 A CN 114551832A CN 202210165549 A CN202210165549 A CN 202210165549A CN 114551832 A CN114551832 A CN 114551832A
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shell
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composite material
mose
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李娟�
徐蓉
杨丽楠
杨慧贞
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Yangzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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 a preparation method of a nano composite material and a lithium ion electrode cathode material thereof, and aims to provide a preparation method of a nano composite materialα‑Fe2O3The cube is used as a template, phenolic resin is coated on the surface of the cube in situ, the carbon-coated ferroferric oxide cube is formed by annealing treatment, and then the carbon-coated ferroferric oxide cube is partially etched by hydrochloric acid to form a carbon box (Fe) taking ferroferric oxide as a core and a shell (Fe)3O4@ C); then, molybdenum selenide is coated in situ on the carbon shell through hydrothermal reaction, and the flaky molybdenum selenide coated nano composite material Fe taking ferroferric oxide as the core and carbon box as the shell is prepared after annealing3O4@C/MoSe2. The nano composite material of the invention prepares Fe by a step-by-step growth strategy3O4@C/MoSe2The nano composite material has the advantages of uniform dispersion, large inner cavity volume, good electrochemical performance, good cycle stability and rate capability when being used as a lithium ion electrode cathode material, and the like.

Description

Preparation method of nano composite material and lithium ion electrode negative electrode material thereof
Technical Field
The invention relates to the technical field of lithium ion electrode materials, in particular to a nano composite material for a lithium ion battery cathode.
Background
In order to meet the increasing energy demand of human beings, it is important to develop new generation Lithium Ion Batteries (LIBs) having excellent performance. The cathode material is used as an important component of the lithium ion battery, and influences the electrochemical performance of the whole battery. The conventional LIBs prepared by using graphite materials for preparing negative electrodes have low specific capacity (372 mA h g)-1) It is difficult to meet the increasingly high application requirements of human beings on LIBs in the application fields of portable electronic devices, electric vehicles, large-scale energy storage and the like. Therefore, finding a negative electrode material with low price, high energy density and good cycle performance has become a hot spot in the research field of lithium ion batteries.
Ferroferric oxide is recognized as one of the most promising negative electrode materials of high-performance Lithium Ion Batteries (LIBs) due to the characteristics of abundant reserves, low cost, environmental friendliness, easy synthesis, high theoretical capacity and the like. However, the inherent defects of low conductivity, large volume expansion effect, low initial coulombic efficiency and the like of the ferroferric oxide seriously hinder the large-scale application of the ferroferric oxide as an LIBs cathode material. In order to overcome the defects, researchers have made a lot of researches on the modification of ferroferric oxide. For example, by controlling the size of the composite material at a nanometer level, structural pulverization and agglomeration during charging and discharging are reduced; the core-shell nano structure is constructed, the internal space of the core-shell nano structure ensures enough electrode-electrolyte contact area and a large number of electrochemical active sites, the diffusion distance of lithium ions and electrons can be greatly reduced, and the volume change of an electrode material in the charge and discharge process is relieved; the carbon material is used as a functional additive to improve the conductivity of the electrode material.
Disclosure of Invention
Aiming at the problem of poor electrochemical performance of ferroferric oxide as the cathode material of the lithium ion battery, the invention provides Fe with uniform dispersion, large inner cavity volume and good electrochemical performance3O4@C/MoSe2Composite materialSo as to improve the cycling stability and rate capability of ferroferric oxide as the lithium ion electrode material.
The object of the invention is achieved by a nanocomposite for the negative electrode of a lithium ion battery, characterized in thatα-Fe2O3The cube is used as a template, phenolic resin is coated on the surface of the cube in situ, the carbon-coated ferroferric oxide cube is formed by annealing treatment, and then the carbon-coated ferroferric oxide cube is partially etched by hydrochloric acid to form a carbon box (Fe) taking ferroferric oxide as a core and a shell (Fe)3O4@ C); then, molybdenum selenide is coated in situ on the carbon shell through hydrothermal reaction, and the flaky molybdenum selenide coated nano composite material Fe taking ferroferric oxide as the core and carbon box as the shell is prepared after annealing3O4@C/MoSe2
The nano-blue composite material in the invention prepares Fe by a step-by-step growth strategy3O4@C/MoSe2The nano composite material as the negative electrode material of the lithium ion battery has the following advantages: firstly, the unique structure taking ferroferric oxide as a core and a carbon box as a shell not only relieves the volume effect of the electrode material in the charging and discharging process, but also shortens the transmission path of electrons and ions, greatly accelerates the migration rate of lithium ions, and enhances the electrode reaction kinetics process. Second, the carbon box not only enhances overall conductivity, but also serves as a structural binder to aid structural integrity during charging and discharging. And finally, coating the molybdenum selenide nanosheets on the outer part of the carbon box in a high-surface-area manner to provide more active sites for electrochemical reaction. Therefore, the unique components and the synergistic effect and structural characteristics of the layer-by-layer coating enable Fe3O4@C/MoSe2The nano composite material as the negative electrode of the lithium ion battery shows excellent cycling stability and rate capability.
Further, step 1, preparing Fe with core-shell structure3O4@ C: to be provided withα-Fe2O3The cube is used as a templateα-Fe2O3Dispersing nanocubes in a dispersion medium with a volume ratio of (2-2.5): 1: (20-25) in a mixed solution of water, ammonia water and absolute ethyl alcohol, whereinα-Fe2O3Dispersion in mixed liquorThe concentration is 50 mg/100mL, the dispersion liquid is mechanically stirred at the water bath temperature of 25-35 ℃ and uniformly dispersed, then the mixed solution of resorcinol and formaldehyde is added, the constant-temperature stirring is continued for 20-30 hours, after the reaction is finished, the precipitated solid phase is centrifugally collected, the solid phase is subjected to vacuum drying, annealing treatment is carried out under the protection of argon, the annealed solid phase is etched for 25-35 minutes by hydrochloric acid, then the etched solid phase is centrifugally separated, washed by deionized water for 2 or 3 times, and then subjected to vacuum drying, so that the carbon box taking ferroferric oxide as the core (Fe) shell (the core is obtained3O4@ C).
Step 2, preparing flaky MoSe2Coated core-shell Fe3O4@ C: mixing selenium powder and hydrazine hydrate, stirring for 3-5 h at room temperature to obtain solution A, and adding Na2MoO4∙2H2Mixing O and deionized water to prepare a solution B, mixing the solution A into the solution B under the stirring condition, stirring for 0.5-1 h, adding ethylenediamine into the solution, continuously stirring for 0.5-1 h, and adding the core-shell Fe prepared in the step 13O4The method comprises the following steps of (@) ultrasonically vibrating a @ C nano material for 0.5-1 h, finally transferring the solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction, centrifugally collecting precipitates after the reaction is cooled to room temperature, placing the precipitates into a vacuum drying oven for drying treatment, and calcining the precipitates in a tubular furnace under the protection of argon to obtain Fe3O4@C/MoSe2。
Further, in the step 1,α-Fe2O3the feeding proportion of the resorcinol and the formaldehyde is 70-200: 95: 1.
further, the concentration of hydrochloric acid for etching was 4 mol/L.
Further, in the step 1, the annealing temperature is 700-750 ℃, the annealing time is 3-5 hours, the vacuum drying temperature is 60 ℃, and the vacuum drying time is 12 hours.
Furthermore, in the second step, the feeding ratio of the selenium powder to the hydrazine hydrate is 1.6-8.0 g/100mL, and Na is added2MoO4∙2H2The feeding proportion of O and deionized water is as follows: 0.32 g to 2.4g/100 mL; mixing solution A and solution B, adding selenium powder and Na2MoO4∙2H2The molar ratio of O is 2:1, the feeding ratio of the selenium powder to the ethylenediamine is 3.2-24 g/100 mL; the selenium powder and the core-shell Fe3O4The mass ratio of @ C is 6-2: 1.
And furthermore, in the second step, the hydrothermal temperature is 220-240 ℃, the hydrothermal reaction time is 22-24 hours, the vacuum drying temperature is 60 ℃, and the vacuum drying time is 12 hours. The annealing temperature is 700-750 ℃, and the annealing time is 2-3 h.
Another object of the present invention is to provide a Fe alloy containing the above-mentioned Fe3O4@C/MoSe2The nano composite material is used for preparing the lithium ion electrode negative material, and specifically comprises Fe with the mass ratio of 7:2:13O4@C/MoSe2Acetylene black conductive agent and PVDF binder.
Fe of the present invention3O4@C/MoSe2Compared with the prior art, the composite material used as the lithium ion battery cathode material has the following advantages:
(1) selection of Fe3O4The negative pole is due to Fe3O4Has 924 mAh g-1High theoretical capacity of (a), low cost, low toxicity and natural abundance of iron;
(2) using unique Fe3O4The @ C core-shell structure not only relieves the volume expansion, but also shortens the transmission path of electrons and ions, greatly accelerates the migration rate of lithium ions, enhances the dynamic process of electrode reaction, and thus greatly enhances the rate capability of the lithium ion battery; in addition not only enhances the overall conductivity of the material but also contributes to structural integrity as a structural binder during charging and discharging.
(3) Fe3O4@C/MoSe2The composite material is externally coated by the high-surface-area molybdenum selenide nanosheets, so that Fe is effectively reduced3O4@ C aggregates and provides more active sites for electrochemical reactions.
Drawings
FIG. 1 is a graph prepared in example 1α-Fe2O3Nanocubes (FIG. 1 a), Fe3O4@ C (FIG. 1b) and Fe3O4@ C/MoSe2Scanning electron micrograph of the composite (fig. 1 c).
FIG. 2 is prepared as in example 1α-Fe2O3Nanocubes (FIG. 2 a), Fe3O4@ C (FIG. 2b) and Fe3O4@C/MoSe2Transmission electron micrograph of the composite (fig. 2 c).
FIG. 3 is Fe prepared in example 13O4@C/MoSe2And Fe3O4@C、C/MoSe2XRD spectrum of the composite material.
FIG. 4 shows Fe prepared in example 1 and comparative example 13O4@C/MoSe2And Fe3O4@C、C/MoSe2The composite material is used as a battery cathode at 100 mA g-1Comparative graph of cycling performance for 70 cycles at current density.
FIG. 5 shows Fe prepared in example 1 and comparative example 13O4@C/MoSe2And Fe3O4@C、C/MoSe2The composite material is used as a comparison graph of the rate performance of a battery cathode at different current densities.
Detailed Description
Example 1
First, core-shell Fe is prepared3O4@ C: 80mg prepared in laboratoryα-Fe2O3The nano-cube, water and ammonia water are uniformly dispersed in ethanol under ultrasonic, wherein the volume ratio of water to ammonia water to absolute ethyl alcohol is 2.5: 1: 20,α-Fe2O3the dispersion concentration of (2) is 50 mg/100mL, the mixed solution is placed in a 250 mL three-neck flask, mechanical stirring is carried out under the condition that the water bath temperature is 30 ℃, then 30mg of resorcinol and 64 mu L of formaldehyde solution are added, stirring is carried out for 24 hours, after the reaction is finished, precipitates are collected centrifugally, and the precipitates are placed in a vacuum drying oven to be dried for 12 hours at 60 ℃. Then annealing at 700 ℃ for 3h under the protection of argon in a tube furnace, etching the annealed sample for 30min by using 40 mL hydrochloric acid (4 mol/L), then washing, centrifugally separating out an etched solid phase, and finally transferring to a vacuum drying oven for drying at 60 ℃ for 12h to obtain the carbon box with ferroferric oxide as a core and a shell (Fe)3O4@ C).
(2) Preparation of flaky MoSe2Clad core shellFe3O4@ C: adding 0.16g of selenium powder into 10mL of hydrazine hydrate, stirring for 5h at room temperature to obtain solution A, and taking 0.24g of Na2MoO4∙2H2Adding O into 50mL of deionized water to prepare a solution B, adding the solution A into the solution B under the stirring condition, stirring for 0.5h, adding 5mL of ethylenediamine into the solution, continuously stirring for 0.5h, adding 30mg of core-shell Fe3O4@ C ultrasonic 1 h. Finally transferring the solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours under the hydrothermal condition at 240 ℃, centrifugally collecting precipitates after the reaction is cooled to room temperature, then washing the precipitates for a plurality of times by deionized water and ethanol, finally drying the precipitates in a vacuum drying oven at 60 ℃ for later use, and calcining the precipitates for 2 hours at 700 ℃ in a tubular furnace under the protection of argon to obtain the flaky molybdenum selenide coated Fe nano composite material with ferroferric oxide as a core carbon box as a shell3O4@C/MoSe2。
Example 2
(1) Preparation of core-Shell Fe3O4@ C: preparation of core-Shell Fe3O4@ C: 80mg prepared in laboratoryα-Fe2O3The nano-cubic, water and ammonia water are uniformly dispersed in ethanol under ultrasonic, wherein the volume ratio of water to ammonia water to absolute ethyl alcohol is 2: 1: 25,α-Fe2O3the dispersion concentration of the resorcinol is 50 mg/100mL, the mixed solution is poured into a 250 mL three-neck flask, mechanical stirring is carried out at the water bath temperature of 25 ℃, 25mg of resorcinol and 54 mu L of formaldehyde solution are added, stirring is carried out for 30h, after the reaction is finished, the precipitate is centrifugally collected, and the precipitate is placed in a vacuum drying oven to be dried for 12h at the temperature of 60 ℃; then annealing at 750 ℃ for 5h under the protection of argon in a tube furnace, etching the annealed sample with 40 mL hydrochloric acid (4 mol/L) for 30min, washing with deionized water for 2 times, and finally transferring to a vacuum drying oven for drying at 60 ℃ for 12h to obtain the carbon box taking ferroferric oxide as the core (Fe) for the practical application3O4@ C).
(2) Preparation of flaky MoSe2Coated core-shell Fe3O4@ C: adding 0.80g selenium powder into 10mL hydrazine hydrate, stirring at room temperature for 5h to obtain solution A, and collecting 1.20 g selenium powderNa2MoO4∙2H2Adding O into 50mL of deionized water to prepare a solution B, adding the solution A into the solution B under the stirring condition, stirring for 0.5h, adding 5mL of ethylenediamine into the solution, continuously stirring for 0.5h, and adding 150mg of core-shell Fe3O4@ C ultrasonic 1 h. And finally transferring the solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 22h at 220 ℃, after the reaction is cooled to room temperature, centrifugally collecting the precipitate, washing for 3 times by using deionized water and ethanol, and finally drying in a vacuum drying oven at 60 ℃ for later use. Then calcining the mixture for 3 hours at 750 ℃ in a tubular furnace under the protection of argon to obtain the flaky molybdenum selenide coated nano composite material Fe taking ferroferric oxide as a core carbon box as a shell3O4@C/MoSe2。
Example 3
(1) Preparation of core-Shell Fe3O4@ C: 80mg prepared in laboratoryα-Fe2O3The nano-cubic, water and ammonia water are uniformly dispersed in ethanol under ultrasonic, wherein the volume ratio of water to ammonia water to absolute ethyl alcohol is 2: 1: 23,α-Fe2O3the dispersion concentration of (2) is 50 mg/100mL, the mixed solution is poured into a 250 mL three-neck flask, mechanical stirring is carried out at the water bath temperature of 35 ℃, 75mg of resorcinol and 160 mu L of formaldehyde solution are added, stirring is carried out for 24 hours, after the reaction is finished, water precipitate is centrifugally collected, and the mixture is placed in a vacuum drying oven to be dried for 12 hours at the temperature of 60 ℃. Then annealing at 720 ℃ for 4h under the protection of argon in a tube furnace, etching the annealed sample with 40 mL hydrochloric acid (4 mol/L) for 30min, washing with deionized water for 3 times, and finally transferring to a vacuum drying oven for drying at 60 ℃ for 12h to obtain the carbon box taking ferroferric oxide as the core (Fe) for the practical application3O4@ C).
(2) Preparation of flaky MoSe2Coated core-shell Fe3O4@ C: adding 0.10g of selenium powder into 10mL of hydrazine hydrate, stirring for 5h at room temperature to obtain solution A, and taking 0.16g of Na2MoO4∙2H2Adding O into 50mL of deionized water to obtain a solution B, adding the solution A into the solution B under the condition of stirring, stirring for 0.5h, and adding the solution A into the solution BAdding 5mL of ethylenediamine into the solution, continuing stirring for 0.5h, and adding 60mg of core-shell Fe3O4@ C ultrasonic 1 h. And finally transferring the solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 230 ℃, after the reaction is cooled to room temperature, centrifugally collecting the precipitate, washing for 3 times by using deionized water and ethanol, and finally drying in a vacuum drying oven at 60 ℃ for later use. Then calcining the mixture for 3 hours at 750 ℃ in a tubular furnace under the protection of argon to obtain the flaky molybdenum selenide coated nano composite material Fe taking ferroferric oxide as a core carbon box as a shell3O4@C/MoSe2。
Comparative example 1:
based on example 1, the step 2) is omitted, and the core-shell Fe is directly prepared3O4@ C nanomaterial.
Comparative example 2:
based on example 1, the core-shell Fe in step 1)3O4Etching all of @ C to form a hollow C box, and core-shell Fe in step 2)3O4Changing @ into hollow C box to prepare C/MoSe2And (3) nano materials.
Secondly, preparing a battery:
in this example, the composite material obtained in example 1 and comparative examples 1 and 2 was used as a negative electrode of a lithium ion battery to assemble the lithium ion battery.
NMP (N-methyl pyrrolidone) is used as a solvent, and the prepared Fe3O4@C/MoSe2The composite material is used as an active substance, acetylene black is used as a conductive agent, PVDF (polyvinylidene fluoride) is used as a binder, the mass ratio of the three substances is 7:2:1, slurry is prepared by magnetic stirring for 8 hours, then the slurry is uniformly coated on the surface of copper foil, the copper foil is dried for 12 hours at 120 ℃ in a vacuum drying oven, and the copper foil is taken out and cut into a circular electrode slice with a certain size by a cutting machine. The circular electrode sheet was weighed with an analytical balance, the amount of active material was calculated, and then it was placed in a glove box together with a battery case and the like, and the battery was assembled under argon.
At the same time, in the same way, respectively with Fe3O4@C、C/MoSe2Assembling the battery for the negative electrode material, and the likeAnd (5) testing the cycle performance and the rate performance under the test condition.
Third, product characteristic analysis
FIG. 1 shows a film prepared in example 1α-Fe2O3 nanocubes, core-shells Fe3O4@ C and Fe3O4@C/MoSe2Scanning electron micrographs of the composite. As clearly shown in FIG. 1(a)α-Fe2O3Is a cubic structure with a diameter of about 400 nm. FIG. 1(b) shows Fe3O4The SEM image of the @ C composite material shows that the core-shell structure (Fe) with ferroferric oxide as the core and the carbon box as the shell3O4@ C). FIG. 1(c) shows that molybdenum selenide is coated outside the core-shell structure in the form of nanosheet and Fe is calcined at high temperature3O4@C/MoSe2The composite material still inherits the core-shell structure of the precursor, but because the molybdenum selenide nanosheets are coated on Fe3O4The @ C surface covers the core-shell structure, so Fe3O4@C/MoSe2An irregular structure is present.
FIG. 2 is a photograph of a film prepared in example 1α-Fe2O3Nanocubes, core-shells Fe3O4@ C and Fe3O4@C /MoSe2Transmission electron microscope image of the composite material. The preparation is clearly evident from FIG. 2(a)α-Fe2O3Is of a solid cubic structure. FIG. 2(b) shows Fe3O4The TEM image of the @ C composite material can obviously show the core-shell structure taking ferroferric oxide as the core and the carbon box as the shell. From FIG. 2(c), it can be clearly seen that the molybdenum selenide nanosheets are uniformly coated on Fe3O4@ C surface.
FIG. 3 shows Fe prepared in example 1 and comparative examples 1 and 23O4@C/MoSe2 、Fe3O4@ C and C/MoSe2XRD spectrum of the composite material. In Fe3O4@C/MoSe2In (1), we did not observe Fe3O4Is due to Fe3O4Is wrapped innermost. And Fe3O4@C/MoSe2In the composite material, 2 θ was 31.0 eachThere were 3 distinct characteristic diffraction peaks at 7 °, 37.78 ° and 55.43 °, corresponding to MoSe, respectively2Crystal planes of (100), (103) and (110), and MoSe2Is a perfect match with the standard PDF card (JCPDS card No. 29-0914).
FIG. 4 shows Fe prepared in example 1 and comparative examples 1 and 23O4@C/MoSe2 、Fe3O4@ C and C/MoSe2The composite material is used as the cathode of the lithium ion battery at 100 mA g-1The current density of the current is respectively circulated for 70 circles, and the voltage interval is a cyclic performance test chart of 0.01-3V. As is evident from FIG. 5, the Fe3O4@ C/MoSe2 composite material has higher specific capacity than the Fe3O4@ C, C/MoSe2, the capacity is still kept to 878 mAhg < -1 > after 70 cycles, and the capacity of the Fe3O4@ C, C/MoSe2 electrode is only 559mAhg < -1 > and 606mAhg < -1 >. Therefore, the Fe3O4@ C/MoSe2 composite material has good cycle stability.
FIG. 5 shows Fe prepared in example 1 and comparative examples 1 and 23O4@C/MoSe2 、Fe3O4@ C and C/MoSe2The composite material is used as a multiplying power performance test chart of the lithium ion battery cathode under different current densities, and the voltage interval is 0.01-3.0V. When charging and discharging, the current density is 100 mA g-1、200 mA g-1、500 mA g-1、1000 mA g-1、2000 mA g-1、5000 mA g-1When compared with the comparative material, the discharge capacity of the material is respectively and basically and smoothly maintained at 1006 mAh g-1、886 mAh g-1、796 mAh g-1、716 mAh g-1、665 mAh g-1、553 mAh g-1. When the current density returns to 100 mA g-1When the discharge capacity of the lithium ion battery is increased, the discharge capacity of the lithium ion battery can be smoothly returned to 944 mAh g-1Description of Fe prepared by the method of the present invention3O4@C/MoSe2The composite material has excellent rate performance and good reversibility.

Claims (8)

1. A method for preparing a nanocomposite material, characterized in thatα-Fe2O3The cube is used as a template, the surface of the cube is coated with phenolic resin in situ, and carbon is formed by annealing treatmentCoating ferroferric oxide cube, and partially etching with hydrochloric acid to form carbon box (Fe) with ferroferric oxide as core3O4@ C); then, molybdenum selenide is coated in situ on the carbon shell through hydrothermal reaction, and the flaky molybdenum selenide coated nano composite material Fe taking ferroferric oxide as the core and carbon box as the shell is prepared after annealing3O4@C/MoSe2。
2. The method of claim 1, wherein the method comprises the steps of:
step 1, preparing Fe with a core-shell structure3O4@ C: to be provided withα-Fe2O3The cube is used as a templateα-Fe2O3Dispersing nanocubes in a solvent with the volume ratio of (2-2.5): 1: (20-25) in a mixed solution of water, ammonia water and absolute ethyl alcohol, whereinα-Fe2O3The dispersion concentration of the dispersion in the mixed solution is 50 mg/100mL, the dispersion is mechanically stirred at the water bath temperature of 25-35 ℃ and uniformly dispersed, then the mixed solution of resorcinol and formaldehyde is added, the constant-temperature stirring is continued for 20-30 hours, after the reaction is finished, a precipitated solid phase is centrifugally collected, the solid phase is subjected to vacuum drying, annealing treatment is carried out under the protection of argon, the annealed solid phase is etched for 25-35 min by hydrochloric acid, then the etched solid phase is centrifugally separated, washed for 2 or 3 times by deionized water and then subjected to vacuum drying, and the carbon box taking ferroferric oxide as a core carbon box shell (Fe) is obtained (the concentration is Fe is 50 mg/100 mL)3O4@ C);
step 2, preparing flaky MoSe2Coated core-shell Fe3O4@ C: mixing selenium powder and hydrazine hydrate, stirring for 3-5 h at room temperature to obtain solution A, and adding Na2MoO4∙2H2Mixing O and deionized water to prepare a solution B, mixing the solution A into the solution B under the stirring condition, stirring for 0.5-1 h, adding ethylenediamine into the solution, continuously stirring for 0.5-1 h, adding the core-shell Fe3O4@ C nano material prepared in the step 1, ultrasonically vibrating for 0.5-1 h, finally transferring the solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction, and cooling to room temperature after the reactionThen, centrifugally collecting precipitates, washing the precipitates by deionized water and ethanol in sequence, placing the precipitates in a vacuum drying oven for drying treatment, and calcining the precipitates in a tubular furnace under the protection of argon to obtain Fe3O4@C/MoSe2。
3. The method for preparing a nanocomposite as claimed in claim 2, wherein, in the step 1,α-Fe2O3the feeding proportion of the resorcinol and the formaldehyde is as follows according to the mass: 70-200: 95: 1.
4. The nanocomposite as claimed in claim 2, wherein the concentration of the hydrochloric acid for etching in the step 1 is 4 mol/L.
5. The preparation method of the nanocomposite material according to claim 2, wherein in the step 1, the annealing temperature is 700 to 750 ℃, the annealing time is 3 to 5 hours, the vacuum drying temperature is 60 ℃, and the vacuum drying time is 12 hours.
6. The method for preparing the nano composite material as claimed in claim 1, wherein in the step 2, the feeding ratio of the selenium powder to the hydrazine hydrate is 1.6-8.0 g/100mL, and Na is added2MoO4∙2H2The feeding proportion of O and deionized water is as follows: 0.32 g to 2.4g/100 mL; mixing solution A and solution B, adding selenium powder and Na2MoO4∙2H2The molar ratio of O is 2:1, the feeding ratio of the selenium powder to the ethylenediamine is 3.2-24 g/100 mL; the selenium powder and the core-shell Fe3O4The mass ratio of @ C is 6-2: 1.
7. The method for preparing the nanocomposite material according to claim 1, wherein in the step 2, the hydrothermal temperature is 220 to 240 ℃, the hydrothermal reaction time is 22 to 24 hours, the vacuum drying temperature is 60 ℃, the vacuum drying time is 12 hours, the annealing temperature is 700 to 750 ℃, and the annealing time is 2 to 3 hours.
8. Use of a kit according to any of claims 1 to 7The lithium ion electrode negative electrode material prepared from the nano composite material is characterized by comprising Fe with the mass ratio of 7:2:13O4@C/MoSe2Acetylene black conductive agent and PVDF binder.
CN202210165549.0A 2022-02-23 2022-02-23 Preparation method of nano composite material and lithium ion electrode negative electrode material thereof Pending CN114551832A (en)

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