CN108281636B - Preparation method and application of titanium dioxide coated iron sesquioxide composite material - Google Patents

Preparation method and application of titanium dioxide coated iron sesquioxide composite material Download PDF

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CN108281636B
CN108281636B CN201810080490.9A CN201810080490A CN108281636B CN 108281636 B CN108281636 B CN 108281636B CN 201810080490 A CN201810080490 A CN 201810080490A CN 108281636 B CN108281636 B CN 108281636B
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ferric oxide
titanium dioxide
dioxide coated
ethyl alcohol
absolute ethyl
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CN108281636A (en
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朱文均
胡跃辉
陈义川
张效华
胡克艳
帅伟强
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Jingdezhen Ceramic Institute
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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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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 and application of a titanium dioxide coated ferric oxide composite material. The titanium dioxide coated ferric oxide composite negative electrode material prepared by the method effectively combines the high specific capacity of ferric oxide and the excellent cycling stability of titanium dioxide, so that the material shows higher specific capacity and stable cycling performance, is an ideal lithium ion battery negative electrode material, and can be widely applied to lithium ion power batteries which need high energy density, long service life and high stability. Meanwhile, the method is simple, mild in condition, low in cost, easy in regulation and control of the material morphology and structure, easy in large-scale production and good in application prospect.

Description

Preparation method and application of titanium dioxide coated iron sesquioxide composite material
Technical Field
The invention belongs to the field of new energy materials of lithium ion batteries, and particularly relates to a preparation method and application of a titanium dioxide coated ferric oxide composite material.
Background
The lithium ion battery is widely applied to the fields of portable electronic equipment, electric automobiles, aerospace and the like as a novel, green and high-energy chemical power supply. With the development of society, people put higher demands on the performance of lithium ion batteries. The cathode material is used as an important component of the lithium ion battery,plays an important role in the overall performance of the battery. The specific capacity of the graphite-based negative electrode material adopted by the current commercial lithium ion battery is usually less than 350 mAh g-1This lower specific capacity is difficult to meet the actual development requirements. In addition, the graphite-based negative electrode material has low lithium intercalation potential which is similar to that of metallic lithium, and lithium dendrite is easy to generate in the continuous charging and discharging process, so that the battery is short-circuited, and the safety problem is caused. Therefore, research and development of new and efficient anode materials are urgently needed.
In recent years, transition metal oxides (e.g., Fe)2O3、Fe3O4、NiO、Co3O4Etc.) is considered to be a lithium ion battery cathode material with good application prospect due to the advantages of high specific capacity, wide sources and the like. Wherein Fe2O3The theoretical specific capacity of the nano-silver particles reaches 1008 mAh g-1And the specific capacity of the graphite-based negative electrode is equivalent to 3 times that of the traditional graphite-based negative electrode. Meanwhile, the iron source has the advantages of no toxicity, low price, easy obtainment and the like. Thus, a ferric oxide material is extensively studied as a high-efficiency negative electrode material. However, the electron transport of the ferric oxide material is relatively slow, resulting in poor rate performance. Meanwhile, the ferric oxide material can have large volume change in the charging and discharging process, so that the collapse of the material structure is caused, and the rapid attenuation of the capacity is caused.
The titanium dioxide material is used as the negative electrode material of the lithium ion battery, and the lithium desorption and insertion voltage platform of the titanium dioxide material is about 1.75V, so that the generation of lithium dendrites can be effectively avoided, and the use safety of the battery is improved. In addition, the titanium oxide forms an octahedral structure, the volume change is small in the charging and discharging process, and the structural integrity can be well maintained, so that the good cycle performance stability is obtained.
For this purpose, for Fe2O3The material can be fully combined with Fe by effectively coating titanium dioxide2O3The high specific capacity and the stable structure of the titanium dioxide effectively improve the defects of the ferric oxide material, thereby obtaining a composite material with higher specific capacity and excellent cycle performance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method and application of a titanium dioxide coated ferric oxide composite material with high specific capacity and stable cycle performance.
In order to solve the technical problems, the technical scheme of the invention is as follows: a preparation method of a titanium dioxide coated ferric oxide composite material is characterized by comprising the following steps:
the method comprises the following steps: weighing a certain amount of ferric nitrate nonahydrate, dissolving the ferric nitrate nonahydrate into a certain amount of mixed solution of glycerol and absolute ethyl alcohol, and stirring and dissolving to obtain an orange yellow solution;
step two: transferring the orange solution obtained in the step one into a 50ml hydrothermal kettle, reacting for 12-24 hours at 160-200 ℃, and then washing, centrifuging and drying at 60 ℃ to obtain a light red ferric oxide material;
step three: weighing 0.075g of the ferric oxide material obtained in the second step, dissolving the ferric oxide material in 100ml of absolute ethyl alcohol, then adding a proper amount of ammonia water solution with the concentration of 28%, carrying out ultrasonic treatment for 15 minutes, and then slowly dropwise adding a tetrabutyl titanate solution with a certain volume;
step four: reacting the mixed solution obtained in the third step in a water bath at 45 ℃ for 12-36 hours, and then washing, centrifugally separating and drying at 60 ℃ to obtain an amorphous titanium dioxide coated ferric oxide material;
step five: and (3) heating the ferric oxide material obtained in the step four to 400-800 ℃ in the air atmosphere, preserving the heat for 3-6 hours, and cooling to room temperature to obtain the final titanium dioxide coated ferric oxide composite negative electrode material.
In the first step, the concentration of iron ions is 0.02-0.10 mol/L.
In the first step, the volume ratio of the glycerol to the absolute ethyl alcohol is controlled to be 1:1 to 8.
In the third step, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 0.6-1.2: 100.
the volume ratio of the ammonia water solution to the absolute ethyl alcohol in the third step is 0.2-0.5: 100.
the application of the titanium dioxide coated ferric oxide composite material is characterized in that the prepared titanium dioxide coated ferric oxide composite material, acetylene black and PVDF are mixed according to the mass ratio of 8:1:1 to prepare slurry, the slurry is uniformly coated on a copper foil, and the copper foil is subjected to vacuum drying at 120 ℃ for 24 hours and then is punched to form a circular electrode pole piece.
According to the invention, a hydrothermal method is adopted to synthesize the ferric oxide microsphere with a porous structure, then a layer of amorphous titanium dioxide material is coated on the surface of the ferric oxide microsphere by a kinetic control water bath method, and then the titanium dioxide coated ferric oxide composite negative electrode material is obtained by heat treatment. The invention has the advantages of simple and mild preparation conditions, low equipment requirements, simple process route and convenience for large-scale production, and the obtained titanium dioxide coated ferric oxide composite negative electrode material has higher specific capacity and stable cycle performance, thereby having good application prospect.
Drawings
FIG. 1 is an XRD pattern of a titanium dioxide coated iron sesquioxide composite anode material prepared in example 1;
FIG. 2 is a scanning electron microscope picture of 50000 times of the titanium dioxide coated ferric oxide composite negative electrode material prepared in example 2;
FIG. 3 is a 10000 times scanning electron microscope picture of the titanium dioxide coated ferric oxide composite negative electrode material prepared in example 3;
FIG. 4 is a TEM image of the Titania-coated iron sesquioxide composite anode material prepared in example 4;
fig. 5 is a graph of the first three cyclic voltammetry curves of the titanium dioxide coated iron trioxide composite negative electrode material prepared in example 4.
Detailed Description
To further illustrate the technical means and effects of the present invention for achieving the predetermined objects, the following detailed description of the embodiments, methods, steps, features and effects of the method for preparing a titanium dioxide coated iron sesquioxide composite material and the application thereof according to the present invention with reference to the preferred embodiments is as follows:
example 1:
weighing 0.32g of ferric nitrate nonahydrate, dissolving in 5ml of glycerol and 35ml of absolute ethyl alcohol, and uniformly stirring to form an orange solution with the molar concentration of iron ions of 0.02 mol/orange; then transferring the mixed solution into a 50ml hydrothermal kettle, reacting for 24 hours at 170 ℃, then naturally cooling, washing, centrifuging and drying at 60 ℃ to obtain ferric oxide microspheres; weighing 0.075g of ferric oxide microspheres, dissolving in 100ml of absolute ethyl alcohol, adding an ammonia water solution with the concentration of 28%, wherein the ammonia water amount is 0.2% of the volume of the absolute ethyl alcohol, carrying out ultrasonic treatment for 15 minutes, slowly adding a tetrabutyl titanate (TBOT) solution under the stirring and stirring condition, wherein the TBOT amount is 0.6% of the absolute ethyl alcohol, completely dropwise adding within 5 minutes, transferring the mixed solution into a 45 ℃ water bath reaction device, and reacting for 24 hours under the stirring condition. Then carrying out centrifugation, washing, separation and drying at 60 ℃ to obtain the amorphous titanium dioxide coated iron sesquioxide composite material; and finally, preserving the heat for 4 hours at 400 ℃ in the air atmosphere, and cooling to room temperature to obtain the titanium dioxide coated ferric oxide composite negative electrode material powder.
Mixing the prepared titanium dioxide coated ferric oxide composite material, acetylene black and PVDF according to the mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil, carrying out vacuum drying at 120 ℃ for 24 hours, then stamping the slurry into a circular electrode plate, taking a metal lithium plate as a counter electrode and 1 mol/L LiPF6And the button cell is assembled by using DMC + EC (volume ratio of 1: 1) as electrolyte and Celgard 2300 as a diaphragm, and the electrochemical test is carried out, wherein the charge-discharge voltage range is 0.01-3.0V. At 100 mAg-1The reversible capacity of the material is still maintained to 942 mAh g after 50 times of circulation-1The first discharge capacity is 1315 mAh g-1The charging capacity is 863 mAh g-1。
Example 2:
weighing 0.32g of ferric nitrate nonahydrate, dissolving in 14ml of glycerol and 26ml of absolute ethyl alcohol, and uniformly stirring to form an orange solution with the molar concentration of iron ions of 0.02 mol/orange; then transferring the mixed solution into a 50ml hydrothermal kettle, reacting for 12 hours at 180 ℃, then naturally cooling, washing, centrifuging and drying at 60 ℃ to obtain ferric oxide microspheres; weighing 0.075g of ferric oxide microspheres, dissolving in 100ml of absolute ethyl alcohol, adding an ammonia water solution with the concentration of 28%, wherein the ammonia water amount is 0.4% of the volume of the absolute ethyl alcohol, carrying out ultrasonic treatment for 15 minutes, slowly adding a tetrabutyl titanate (TBOT) solution under the stirring and stirring condition, wherein the TBOT amount is 0.75% of the absolute ethyl alcohol, completely dropwise adding within 5 minutes, transferring the mixed solution into a 45 ℃ water bath reaction device, and reacting for 15 hours under the stirring condition. Then carrying out centrifugation, washing, separation and drying at 60 ℃ to obtain the amorphous titanium dioxide coated iron sesquioxide composite material; and finally, keeping the temperature at 500 ℃ for 5 hours in the air atmosphere, and cooling to room temperature to obtain the titanium dioxide coated ferric oxide composite negative electrode material powder.
Mixing the prepared titanium dioxide coated ferric oxide composite material, acetylene black and PVDF according to the mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil, carrying out vacuum drying at 120 ℃ for 24 hours, then stamping the slurry into a circular electrode plate, taking a metal lithium plate as a counter electrode and 1 mol/L LiPF6And the button cell is assembled by using DMC + EC (volume ratio of 1: 1) as electrolyte and Celgard 2300 as a diaphragm, and the electrochemical test is carried out, wherein the charge-discharge voltage range is 0.01-3.0V. At 100 mAg-1The reversible capacity of the material is still kept at 714 mAh g after 50 times of circulation-1Its first discharge capacity is 1025 mAh g-1The charge capacity is 812 mAh g-1。
Example 3:
weighing 0.64g of ferric nitrate nonahydrate, dissolving in 5ml of glycerol and 35ml of absolute ethyl alcohol, and uniformly stirring to form an orange solution with the molar concentration of iron ions of 0.04 mol/orange; then transferring the mixed solution into a 50ml hydrothermal kettle, reacting for 24 hours at 180 ℃, then naturally cooling, washing, centrifuging and drying at 60 ℃ to obtain ferric oxide microspheres; weighing 0.075g of ferric oxide microspheres, dissolving in 100ml of absolute ethyl alcohol, adding an ammonia water solution with the concentration of 28%, wherein the ammonia water amount is 0.5% of the volume of the absolute ethyl alcohol, carrying out ultrasonic treatment for 15 minutes, slowly adding a tetrabutyl titanate (TBOT) solution with the amount of 0.75% of the absolute ethyl alcohol under the condition of stirring and stirring, controlling the dropwise adding to be complete within 5 minutes, transferring the mixed solution into a 45 ℃ water bath reaction device, and carrying out reaction for 26 hours under the condition of stirring. Then carrying out centrifugation, washing, separation and drying at 60 ℃ to obtain the amorphous titanium dioxide coated iron sesquioxide composite material; and finally, preserving the heat for 6 hours at 600 ℃ in the air atmosphere, and cooling to room temperature to obtain the titanium dioxide coated ferric oxide composite negative electrode material powder.
Mixing the prepared titanium dioxide coated ferric oxide composite material, acetylene black and PVDF according to the mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil, carrying out vacuum drying at 120 ℃ for 24 hours, then stamping the slurry into a circular electrode plate, taking a metal lithium plate as a counter electrode and 1 mol/L LiPF6And the button cell is assembled by using DMC + EC (volume ratio of 1: 1) as electrolyte and Celgard 2300 as a diaphragm, and the electrochemical test is carried out, wherein the charge-discharge voltage range is 0.01-3.0V. At 100 mAg-1The reversible capacity of the material is still maintained at 738 mAh g after 50 times of circulation-1Its first discharge capacity is 1065 mAh g-1The charging capacity is 822 mAh g-1。
Example 4:
weighing 0.5g of ferric nitrate nonahydrate, dissolving in 8ml of glycerol and 32ml of absolute ethyl alcohol, and uniformly stirring to form an orange solution with the molar concentration of iron ions of 0.03 mol/orange; weighing 0.5g of ferric nitrate nonahydrate, dissolving in 5ml of glycerol and 35ml of absolute ethyl alcohol, and stirring to dissolve to obtain an orange yellow solution; then transferring the mixed solution into a 50ml hydrothermal kettle, reacting for 24 hours at 190 ℃, then naturally cooling, washing, centrifuging and drying at 60 ℃ to obtain ferric oxide microspheres; weighing 0.075g of ferric oxide microspheres, dissolving in 100ml of absolute ethyl alcohol, adding an ammonia water solution with the concentration of 28%, wherein the ammonia water amount is 0.3% of the volume of the absolute ethyl alcohol, carrying out ultrasonic treatment for 15 minutes, slowly adding a tetrabutyl titanate (TBOT) solution under the stirring and stirring condition, wherein the TBOT amount is 0.75% of the absolute ethyl alcohol, completely dropwise adding within 5 minutes, transferring the mixed solution into a 45 ℃ water bath reaction device, and reacting for 30 hours under the stirring condition. Then carrying out centrifugation, washing, separation and drying at 60 ℃ to obtain the amorphous titanium dioxide coated iron sesquioxide composite material; and finally, keeping the temperature of 700 ℃ for 4 hours in the air atmosphere, and cooling to room temperature to obtain the titanium dioxide coated ferric oxide composite negative electrode material powder.
Mixing the prepared titanium dioxide coated ferric oxide composite material, acetylene black and PVDF according to the mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil, carrying out vacuum drying at 120 ℃ for 24 hours, then stamping the slurry into a circular electrode plate, taking a metal lithium plate as a counter electrode and 1 mol/L LiPF6And the button cell is assembled by using DMC + EC (volume ratio of 1: 1) as electrolyte and Celgard 2300 as a diaphragm, and the electrochemical test is carried out, wherein the charge-discharge voltage range is 0.01-3.0V. At 100 mAg-1The reversible capacity of the material is still maintained at 752mAh g after 50 times of circulation-1The first discharge capacity is 1185 mAh g-1The charging capacity is 824 mAh g-1。
Example 5:
weighing 1.12g of ferric nitrate nonahydrate, dissolving in 5ml of glycerol and 35ml of absolute ethyl alcohol, and uniformly stirring to form an orange solution with the molar concentration of iron ions of 0.07 mol/orange; then transferring the mixed solution into a 50ml hydrothermal kettle, reacting for 24 hours at 180 ℃, then naturally cooling, washing, centrifuging and drying at 60 ℃ to obtain ferric oxide microspheres; weighing 0.075g of ferric oxide microspheres, dissolving in 100ml of absolute ethyl alcohol, adding an ammonia water solution with the concentration of 28%, wherein the ammonia water amount is 0.3% of the volume of the absolute ethyl alcohol, carrying out ultrasonic treatment for 15 minutes, slowly adding a tetrabutyl titanate (TBOT) solution under the stirring and stirring condition, wherein the TBOT amount is 0.75% of the absolute ethyl alcohol, completely dropwise adding within 5 minutes, transferring the mixed solution into a 45 ℃ water bath reaction device, and reacting for 35 hours under the stirring condition. Then carrying out centrifugation, washing, separation and drying at 60 ℃ to obtain the amorphous titanium dioxide coated iron sesquioxide composite material; and finally, preserving the heat for 4 hours at 800 ℃ in the air atmosphere, and cooling to room temperature to obtain the titanium dioxide coated ferric oxide composite negative electrode material powder.
Mixing the prepared titanium dioxide coated ferric oxide composite material, acetylene black and PVDF according to the mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil, carrying out vacuum drying at 120 ℃ for 24 hours, then stamping the slurry into a circular electrode plate, taking a metal lithium plate as a counter electrode and 1 mol/L LiPF6/ DMCAnd the button cell is assembled by using the electrolyte solution of which the volume ratio is 1:1 and the diaphragm of which is Celgard 2300, and the electrochemical test is carried out, wherein the charge-discharge voltage range is 0.01-3.0V. At 100 mAg-1The reversible capacity of the material is still kept at 920mAh g after 50 times of circulation-1The first discharge capacity is 1260 mAh g-1The charging capacity is 886 mAh g-1。
Example 6:
weighing 0.32g of ferric nitrate nonahydrate, dissolving in 5ml of glycerol and 35ml of absolute ethyl alcohol, and uniformly stirring to form an orange solution with the molar concentration of iron ions of 0.02 mol/orange; then transferring the mixed solution into a 50ml hydrothermal kettle, reacting for 15 hours at 180 ℃, then naturally cooling, washing, centrifuging and drying at 60 ℃ to obtain ferric oxide microspheres; weighing 0.075g of ferric oxide microspheres, dissolving in 100ml of absolute ethyl alcohol, adding an ammonia water solution with the concentration of 28%, wherein the ammonia water amount is 0.3% of the volume of the absolute ethyl alcohol, carrying out ultrasonic treatment for 15 minutes, slowly adding a tetrabutyl titanate (TBOT) solution under the stirring and stirring condition, wherein the TBOT amount is 0.9% of the absolute ethyl alcohol, completely dropwise adding within 5 minutes, transferring the mixed solution into a 45 ℃ water bath reaction device, and reacting for 12 hours under the stirring condition. Then carrying out centrifugation, washing, separation and drying at 60 ℃ to obtain the amorphous titanium dioxide coated iron sesquioxide composite material; and finally, preserving the heat for 6 hours at 800 ℃ in the air atmosphere, and cooling to room temperature to obtain the titanium dioxide coated ferric oxide composite negative electrode material powder.
Mixing the prepared titanium dioxide coated ferric oxide composite material, acetylene black and PVDF according to the mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil, carrying out vacuum drying at 120 ℃ for 24 hours, then stamping the slurry into a circular electrode plate, taking a metal lithium plate as a counter electrode and 1 mol/L LiPF6And the button cell is assembled by using DMC + EC (volume ratio of 1: 1) as electrolyte and Celgard 2300 as a diaphragm, and the electrochemical test is carried out, wherein the charge-discharge voltage range is 0.01-3.0V. At 100 mAg-1The reversible capacity of the material is still maintained at 762 mAh g after 50 times of circulation-1The first discharge capacity is 1056 mAh g-1The charge capacity is 812 mAh g-1。
Example 7:
weighing 0.32g of ferric nitrate nonahydrate, dissolving in 4.5ml of glycerol and 35.5ml of absolute ethyl alcohol, and uniformly stirring to form an orange solution with the molar concentration of iron ions of 0.02 mol/orange; then transferring the mixed solution into a 50ml hydrothermal kettle, reacting for 20 hours at 180 ℃, then naturally cooling, washing, centrifuging and drying at 60 ℃ to obtain ferric oxide microspheres; weighing 0.075g of ferric oxide microspheres, dissolving in 100ml of absolute ethyl alcohol, adding an ammonia water solution with the concentration of 28%, wherein the ammonia water amount is 0.3% of the volume of the absolute ethyl alcohol, carrying out ultrasonic treatment for 15 minutes, slowly adding a tetrabutyl titanate (TBOT) solution under the stirring and stirring condition, wherein the TBOT amount is 1.2% of the absolute ethyl alcohol, completely dropwise adding within 5 minutes, transferring the mixed solution into a 45 ℃ water bath reaction device, and reacting for 24 hours under the stirring condition. Then carrying out centrifugation, washing, separation and drying at 60 ℃ to obtain the amorphous titanium dioxide coated iron sesquioxide composite material; and finally, preserving the heat for 4 hours at the temperature of 600 ℃ in the air atmosphere, and cooling to room temperature to obtain the titanium dioxide coated ferric oxide composite negative electrode material powder.
Mixing the prepared titanium dioxide coated ferric oxide composite material, acetylene black and PVDF according to the mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil, carrying out vacuum drying at 120 ℃ for 24 hours, then stamping the slurry into a circular electrode plate, taking a metal lithium plate as a counter electrode and 1 mol/L LiPF6And the button cell is assembled by using DMC + EC (volume ratio of 1: 1) as electrolyte and Celgard 2300 as a diaphragm, and the electrochemical test is carried out, wherein the charge-discharge voltage range is 0.01-3.0V. At 100 mAg-1The reversible capacity of the material is still kept at 706mAh g after 50 times of circulation-1The first discharge capacity is 986 mAh g-1The charge capacity is 745 mAh g-1。
Example 8:
weighing 0.32g of ferric nitrate nonahydrate, dissolving in 20ml of glycerol and 20ml of absolute ethyl alcohol, and uniformly stirring to form an orange solution with the molar concentration of iron ions of 0.02 mol/orange; then transferring the mixed solution into a 50ml hydrothermal kettle, reacting for 24 hours at 180 ℃, then naturally cooling, washing, centrifuging and drying at 60 ℃ to obtain ferric oxide microspheres; weighing 0.075g of ferric oxide microspheres, dissolving in 100ml of absolute ethyl alcohol, adding an ammonia water solution with the concentration of 28%, wherein the ammonia water amount is 0.3% of the volume of the absolute ethyl alcohol, carrying out ultrasonic treatment for 15 minutes, slowly adding a tetrabutyl titanate (TBOT) solution under the stirring and stirring condition, wherein the TBOT amount is 0.75% of the absolute ethyl alcohol, completely dropwise adding within 5 minutes, transferring the mixed solution into a 45 ℃ water bath reaction device, and reacting for 24 hours under the stirring condition. Then carrying out centrifugation, washing, separation and drying at 60 ℃ to obtain the amorphous titanium dioxide coated iron sesquioxide composite material; and finally, preserving the heat for 4 hours at the temperature of 600 ℃ in the air atmosphere, and cooling to room temperature to obtain the titanium dioxide coated ferric oxide composite negative electrode material powder.
Mixing the prepared titanium dioxide coated ferric oxide composite material, acetylene black and PVDF according to the mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil, carrying out vacuum drying at 120 ℃ for 24 hours, then stamping the slurry into a circular electrode plate, taking a metal lithium plate as a counter electrode and 1 mol/L LiPF6And the button cell is assembled by using DMC + EC (volume ratio of 1: 1) as electrolyte and Celgard 2300 as a diaphragm, and the electrochemical test is carried out, wherein the charge-discharge voltage range is 0.01-3.0V. At 100 mAg-1The reversible capacity of the material is still maintained at 763mAh g after 50 times of circulation-1The first discharge capacity is 978 mAh g-1The charging capacity is 769 mAh g-1。
Example 9:
weighing 1.6g of ferric nitrate nonahydrate, dissolving in 5ml of glycerol and 35ml of absolute ethyl alcohol, and uniformly stirring to form an orange solution with the molar concentration of iron ions being 0.1 mol/orange; then transferring the mixed solution into a 50ml hydrothermal kettle, reacting for 24 hours at 180 ℃, then naturally cooling, washing, centrifuging and drying at 60 ℃ to obtain ferric oxide microspheres; weighing 0.075g of ferric oxide microspheres, dissolving in 100ml of absolute ethyl alcohol, adding an ammonia water solution with the concentration of 28%, wherein the ammonia water amount is 0.3% of the volume of the absolute ethyl alcohol, carrying out ultrasonic treatment for 15 minutes, slowly adding a tetrabutyl titanate (TBOT) solution under the stirring and stirring condition, wherein the TBOT amount is 0.75% of the absolute ethyl alcohol, completely dropwise adding within 5 minutes, transferring the mixed solution into a 45 ℃ water bath reaction device, and reacting for 24 hours under the stirring condition. Then carrying out centrifugation, washing, separation and drying at 60 ℃ to obtain the amorphous titanium dioxide coated iron sesquioxide composite material; and finally, preserving the heat for 4 hours at the temperature of 600 ℃ in the air atmosphere, and cooling to room temperature to obtain the titanium dioxide coated ferric oxide composite negative electrode material powder.
Mixing the prepared titanium dioxide coated ferric oxide composite material, acetylene black and PVDF according to the mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil, carrying out vacuum drying at 120 ℃ for 24 hours, then stamping the slurry into a circular electrode plate, taking a metal lithium plate as a counter electrode and 1 mol/L LiPF6And the button cell is assembled by using DMC + EC (volume ratio of 1: 1) as electrolyte and Celgard 2300 as a diaphragm, and the electrochemical test is carried out, wherein the charge-discharge voltage range is 0.01-3.0V. At 100 mAg-1The reversible capacity of the material is still maintained at 815mAh g after 50 times of circulation-1The first discharge capacity is 1002 mAh g-1The charging capacity is 849 mAh g-1。

Claims (4)

1. A preparation method of a titanium dioxide coated ferric oxide composite material is characterized by comprising the following steps:
the method comprises the following steps: weighing a certain amount of ferric nitrate nonahydrate, dissolving the ferric nitrate nonahydrate into a certain amount of mixed solution of glycerol and absolute ethyl alcohol, and stirring and dissolving to obtain an orange yellow solution;
step two: transferring the orange solution obtained in the step one into a 50ml hydrothermal kettle, carrying out solvothermal reaction for 12-24 hours at 160-200 ℃, and then washing, centrifuging and drying at 60 ℃ to obtain a light red porous ferric oxide material; the ferric oxide material is ferric oxide microspheres;
step three: weighing 0.075g of the ferric oxide material obtained in the second step, dissolving the ferric oxide material in 100ml of absolute ethyl alcohol, then adding a proper amount of ammonia water solution with the concentration of 28%, carrying out ultrasonic treatment for 15 minutes, and then slowly dropwise adding a tetrabutyl titanate solution with a certain volume;
step four: reacting the mixed solution obtained in the third step in a water bath at 45 ℃ for 12-36 hours, and then washing, centrifugally separating and drying at 60 ℃ to obtain an amorphous titanium dioxide coated ferric oxide material;
step five: heating the ferric oxide material obtained in the step four to 400-800 ℃ in air atmosphere, preserving heat for 3-6 hours, and cooling to room temperature to obtain a final titanium dioxide coated ferric oxide composite negative electrode material;
the volume ratio of the glycerol to the absolute ethyl alcohol in the first step is controlled to be 1: 1-8;
in the first step, the concentration of iron ions is 0.02-0.10 mol/L.
2. The method of claim 1, wherein: in the third step, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 0.6-1.2: 100.
3. the method of claim 1, wherein: the volume ratio of the ammonia water solution to the absolute ethyl alcohol in the third step is 0.2-0.5: 100.
4. the application of the titanium dioxide coated ferric oxide composite material prepared by the preparation method according to any one of claims 1-3 is characterized in that the prepared titanium dioxide coated ferric oxide composite material, acetylene black and PVDF are mixed according to the mass ratio of 8:1:1 to prepare slurry, the slurry is uniformly coated on a copper foil, and the copper foil is subjected to vacuum drying at 120 ℃ for 24 hours and then is punched into a circular electrode pole piece.
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