CN110808365A - High-performance transition metal oxide negative electrode material and battery assembling method - Google Patents

High-performance transition metal oxide negative electrode material and battery assembling method Download PDF

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CN110808365A
CN110808365A CN201911123121.4A CN201911123121A CN110808365A CN 110808365 A CN110808365 A CN 110808365A CN 201911123121 A CN201911123121 A CN 201911123121A CN 110808365 A CN110808365 A CN 110808365A
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昝武
潘成伟
潘真如
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a high-performance transition metal oxide negative electrode material, which is prepared by the following steps of preparing a transition metal oxide, pretreating a carbon material, preparing a transition metal oxide/carbon material composite, and assembling a battery, wherein the battery assembling method comprises the following steps of preparing ① electrodes and assembling ② batteries.

Description

High-performance transition metal oxide negative electrode material and battery assembling method
Technical Field
The invention relates to the technical field of preparation of battery cathode materials, in particular to a high-performance transition metal oxide cathode material and a battery assembling method.
Background
With the development of society, energy and environmental problems become more severe and become important factors for restricting the economic development of a country. The use of traditional fossil fuels is easy to cause global environmental change and cause greenhouse effect. Various clean energy sources such as solar energy, wind energy, hydroelectric power generation and the like relieve the dependence of human society on fossil fuels to a certain extent. Therefore, the development of more efficient, green energy sources and new energy storage devices is also at an urgent need. Compared with the traditional secondary batteries such as lead-acid, nickel-chromium, nickel-hydrogen and the like, the lithium ion battery has the advantages of high energy density, long cycle life, environmental protection, no pollution, low self-discharge rate, no memory effect, and the like. With the increasing exhaustion of non-renewable resources such as petroleum and natural gas and the worsening of the environment, the implementation of new energy strategies has become a trend. The development of safe and high-performance lithium ion batteries has become one of the hot spots in the field of secondary energy research and development.
In recent years, lithium ion batteries have also begun to exhibit attractive potentials in the fields of pure electric vehicles, hybrid electric vehicles, and energy storage. Numerous manufacturers push out green energy vehicles based on the lithium ion battery technology, and obtain wide attention of society, and the rapid development of the lithium ion battery technology conforms to the requirements of modern science and technology on battery miniaturization and high energy, and also conforms to the requirements of times on green and environmental protection.
Lithium is the metal with the lowest atomic weight, the lowest density, the highest electrochemical lithium storage capacity and the most negative electrode potential. The earliest commercial lithium batteries had Li/SO2，Li/SOCl2，Li/SO2Cl2And Li/MnO2And various lithium primary battery systems using metallic lithium and alloys thereof as negative electrodes. Is applied to the fields of medical instrument power supplies, communication equipment, computers, liquid crystal displays and the like. The lithium secondary battery has not been successfully popularized due to poor safety, and research shows that: during the charging process, the potential distribution is not uniform due to the unevenness of the surface of the electrode material, so that the lithium metal is unevenly deposited on the surface of the electrode, and a large amount of lithium dendrites are formed. Part of the lithium dendrites are easily broken, so that the battery catches fire or even explodes.
The graphite has a good layered crystal structure, layers are combined through Van der Waals force, the de-intercalation reaction of lithium in the graphite is mainly flourishing between 0 and 0.25V, and Li enters the layers after lithium intercalationFormation of LiC in a layered structure6The change of interlayer spacing is about 9%, the charge-discharge voltage platform of graphite is lower, and the average output voltage of the battery formed by matching with the anode material is higher. When the potential of the alloy negative electrode material to lithium is between 0.1 and 1V, a plurality of metals can generate electrochemical reaction with Li to form a reversible alloy phase, and the silicon-based and tin-based negative electrode materials are pursued by people because the specific volume capacity and the mass ratio energy of the silicon-based and tin-based negative electrode materials are far higher than those of the graphite negative electrode materials. However, the biggest challenge to them is that the active material undergoes huge volume change and pulverization and shedding phenomena during charge and discharge, resulting in capacity degradation. Transition phosphide: the transition metal phosphide forms metallic lithium and phase Li by conversion reaction after intercalation of lithium3And P. The series of reactions are equivalent to oxidation-reduction reactions taking phosphorus molecules as centers, and the transition group phosphide is concerned because of high specific capacity and good electrochemical properties. The surface of the carbon cathode material of the existing lithium ion battery is easy to passivate in organic electrolyte to form a passivation layer, so that irreversible loss of initial capacity is caused; the potential of the carbon electrode is very close to that of the metal lithium, and when the battery is overcharged, the metal lithium is easily separated from the surface of the carbon electrode, so that short circuit can be caused; at high temperatures, the protective layer on the carbon negative electrode may decompose, causing the battery to ignite. Therefore, preparing a replaceable carbon negative electrode material with better performance is still an important topic for research on lithium ion batteries.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a high-performance transition metal oxide negative electrode material and a battery assembling method.
The technical scheme adopted by the invention for solving the technical problems is as follows: a high-performance transition metal oxide negative electrode material is prepared by the following steps:
step one, preparing a transition metal oxide:
① collecting 1-3 mmol of zinc nitrate (Zn (NO)3)2·6H2O) and 3-5 mmol of ferrous sulfate (FeSO)4·7H2O) in a beaker, then adding 50-70 mL of deionized water into the beaker, and carrying out magnetic field treatmentFully dissolving the mixture under the stirring of force to obtain a mixed solution I;
② adding 5-8 mmol of urea (CO (NH) into the mixed solution I obtained from ①2)2) And 3 to 5mmol of ammonium fluoride (NH)4F) Continuously stirring for 15-20 min at room temperature, and uniformly mixing to obtain a mixed solution II;
③ transferring the mixed solution II obtained in the step ② to a reaction kettle, then placing the reaction kettle in an oven at the temperature of 150-180 ℃, reacting for 10-14 h, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times respectively, placing the obtained precipitate in an oven at the temperature of 50-80 ℃, and performing vacuum drying for 48h to obtain a powdery solid;
④ placing the ③ obtained powdery solid into a quartz boat, placing the quartz boat into a tube furnace protected by argon for high-temperature calcination at 550-700 ℃ for 4h, and after the calcination is finished, naturally cooling the sample to room temperature along with the furnace to obtain a transition metal oxide ZnFe2O4；
Step two, pretreatment of the carbon material:
dissolving 1-1.5 g of carbon material in 30-50 mL of concentrated nitric acid, transferring the mixed solution to a 100mL reaction kettle, placing the reaction kettle in a drying oven at 150-180 ℃ for reaction for 12-20 h, finally washing the product obtained by the reaction with deionized water and absolute ethyl alcohol for three times respectively, placing the obtained precipitate in the drying oven at 50-70 ℃, and performing vacuum drying for 48 h;
step three, preparing the transition metal oxide/carbon material compound:
① dissolving 15-25 mg of polyvinylpyrrolidone in 30-50 mL of ethanol, performing ultrasonic treatment for 2-5 h to obtain a mixed solution III, and adding the transition metal oxide ZnFe obtained in the step one into the mixed solution III2O4Continuing performing ultrasonic treatment on the pretreated carbon material obtained in the step two for 1-1.5 hours to obtain a mixed solution IV;
② transferring the mixed solution IV into a 100mL reaction kettle, then placing the reaction kettle into an oven at 200-220 ℃, reacting for 12-36 h, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times respectively, placing the obtained precipitate into an oven at 50-80 ℃, and vacuum drying for 48h to obtain the transition metal oxide/carbon material composite.
In the high-performance transition metal oxide negative electrode material, the carbon material is carbon fiber or multi-wall carbon nano tube.
A method of assembling a battery comprising the steps of:
① the electrode is prepared by preparing binder I from sodium carboxymethylcellulose and deionized water, preparing binder II from polyvinylidene fluoride and polyvinylpyrrolidone, and preparing transition metal oxide ZnFe at a mass ratio of 7:2:12O4Conductive carbon black and a binder (binder I or binder II) for later use; transition metal oxide ZnFe2O4Grinding the conductive carbon black in an agate mortar, transferring the ground product into a binder, magnetically stirring for 5-8 h, dropwise adding a small amount of deionized water in the stirring process to adjust the viscosity, and uniformly mixing to form slurry with proper viscosity and uniform components; then, dipping the slurry by a glass rod, uniformly coating the slurry on a clean copper foil, and then putting the copper foil into a vacuum drying oven at 60 ℃ for drying for 12 hours; finally, taking out the dried electrode-copper foil, horizontally placing the electrode-copper foil on a roller press, compacting the electrode slice, cutting the electrode slice by using a button cell slicer to obtain an electrode slice, and storing the electrode slice in a vacuum drying oven for later use;
② assembling the battery in a glove box filled with argon, wherein the assembling sequence is that placing a positive electrode shell, gently placing an electrode plate in the center of the positive electrode shell by using tweezers, dropwise adding 1-2 drops of electrolyte above the positive electrode shell, dropwise adding 1-2 drops of electrolyte again after covering a diaphragm, then placing a metal lithium sheet, a steel sheet, a gasket and a negative electrode shell in sequence, and finally sealing the assembled battery by using a button cell sealing machine.
In the above method for assembling a battery, the separator is a polytetrafluoroethylene microporous separator.
In the above method for assembling a battery, the electrolyte is a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, in which 1mol/L lithium salt is dissolved, and the volume ratio of the ethylene carbonate to the dimethyl carbonate to the ethyl methyl carbonate is 1:1: 1.
Compared with the prior art, the invention has the following advantages and prominent effects:
the invention has the advantages that the preparation method of the transition metal oxide cathode material is simple and convenient to operate; the transition metal oxide/carbon material composite is used as a negative electrode material and assembled into a lithium ion battery, and the prepared lithium ion battery has excellent cycle performance and higher specific discharge capacity.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 shows that the transition metal oxide/carbon material composite of example 1 of the present invention is at 200mA g-1The charging and discharging curve diagrams of different testing turns under the current density;
FIG. 2 shows that the transition metal oxide/carbon material composite of example 1 of the present invention is at 200mA g-1Graph of cycling performance at current density.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
[ example 1 ]
A high-performance transition metal oxide negative electrode material is prepared by the following steps:
step one, preparing a transition metal oxide:
① Zinc nitrate (Zn (NO) 1.2mmol was taken3)2·6H2O) and 3.0mmol of ferrous sulfate (FeSO)4·7H2O) placing the mixture in a beaker, adding 50mL of deionized water into the beaker, and fully dissolving the mixture under magnetic stirring to obtain a mixed solution I;
② to the mixed solution I obtained in ①, 5mmol of urea (CO (NH) was added2)2) And 3mmol of ammonium fluoride (NH)4F) Continuously stirring for 15min at room temperature to uniformly mix to obtain a mixed solution II;
③ transferring the mixed solution II obtained from ② into a reaction kettle, then putting the reaction kettle into an oven at 170 ℃, reacting for 12 hours, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times respectively, putting the obtained precipitate into an oven at 60 ℃, and vacuum-drying for 48 hours to obtain powdery solid;
④ placing the ③ powder solid into a quartz boat, placing the quartz boat into a tube furnace protected by argon gas for high-temperature calcination at 600 deg.C for 4h, and naturally cooling the sample to room temperature to obtain transition metal oxide ZnFe2O4；
Step two, pretreatment of the carbon material:
dissolving 1.5g of carbon material in 30mL of concentrated nitric acid, transferring the mixed solution to a 100mL reaction kettle, putting the reaction kettle into an oven at 170 ℃ for reaction for 12 hours, finally washing the product obtained by the reaction with deionized water and absolute ethyl alcohol for three times respectively, putting the obtained precipitate into an oven at 55 ℃, and carrying out vacuum drying for 48 hours;
step three, preparing the transition metal oxide/carbon material compound:
① dissolving 15mg polyvinylpyrrolidone in 50mL ethanol, performing ultrasonic treatment for 5h to obtain a mixed solution III, and adding the transition metal oxide ZnFe obtained in the step one into the mixed solution III2O4Continuing to perform ultrasonic treatment on the pretreated carbon material obtained in the step two for 1h to obtain a mixed solution IV;
② transferring the mixed solution IV to a 100mL reaction kettle, then placing the reaction kettle in an oven at 200 ℃, reacting for 12h, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times respectively, placing the obtained precipitate in an oven at 55 ℃, and vacuum drying for 48h to obtain the transition metal oxide/carbon material composite.
Further, the carbon material is a multi-walled carbon nanotube.
A method of assembling a battery comprising the steps of:
① the electrode is prepared by preparing binder from sodium carboxymethylcellulose and deionized water at a mass ratio of 7:2:12O4Conductive carbon black,Binding agent for standby; transition metal oxide ZnFe2O4Grinding the conductive carbon black in an agate mortar, transferring the ground product into a binder, magnetically stirring for 5 hours, dropwise adding a small amount of deionized water in the stirring process to adjust the viscosity, and uniformly mixing to form slurry with proper viscosity and uniform components; then, dipping the slurry by a glass rod, uniformly coating the slurry on a clean copper foil, and then putting the copper foil into a vacuum drying oven at 60 ℃ for drying for 12 hours; finally, taking out the dried electrode-copper foil, horizontally placing the electrode-copper foil on a roller press, compacting the electrode slice, cutting the electrode slice by using a button cell slicer to obtain an electrode slice, and storing the electrode slice in a vacuum drying oven for later use;
② assembling the battery in a glove box filled with argon, wherein the assembling sequence is that placing a positive electrode shell, gently placing an electrode plate in the center of the positive electrode shell by using tweezers, dropwise adding 1-2 drops of electrolyte above the positive electrode shell, dropwise adding 1-2 drops of electrolyte again after covering a diaphragm, then placing a metal lithium sheet, a steel sheet, a gasket and a negative electrode shell in sequence, and finally sealing the assembled battery by using a button cell sealing machine.
Further, the diaphragm is a polytetrafluoroethylene microporous diaphragm.
Further, the electrolyte is a mixed solvent of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate with a volume ratio of 1:1:1 for dissolving 1mol/L lithium salt.
[ example 2 ]
A high-performance transition metal oxide negative electrode material is prepared by the following steps:
step one, preparing a transition metal oxide:
① mmol of zinc nitrate (Zn (NO) was taken3)2·6H2O) and 5mmol of ferrous sulfate (FeSO)4·7H2O) placing the mixture in a beaker, adding 50mL of deionized water into the beaker, and fully dissolving the mixture under magnetic stirring to obtain a mixed solution I;
② to the mixed solution I obtained in ①, 8mmol of urea (CO (NH) was added2)2) And 5mmol of ammonium fluoride (NH)4F) At room temperatureStirring for 20min to obtain a second mixed solution;
③ transferring the mixed solution II obtained from ② into a reaction kettle, then putting the reaction kettle into an oven at 180 ℃, reacting for 13 hours, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times respectively, putting the obtained precipitate into an oven at 80 ℃, and vacuum-drying for 48 hours to obtain powdery solid;
④ placing the ③ powder solid into a quartz boat, placing the quartz boat into a tube furnace protected by argon gas for high-temperature calcination at 700 deg.C for 4h, and naturally cooling the sample to room temperature to obtain transition metal oxide ZnFe2O4；
Step two, pretreatment of the carbon material:
dissolving 1g of carbon material in 45mL of concentrated nitric acid, transferring the mixed solution to a 100mL reaction kettle, putting the reaction kettle into an oven at 180 ℃ for reaction for 15h, washing the product obtained by the reaction with deionized water and absolute ethyl alcohol for three times respectively, putting the obtained precipitate into an oven at 60 ℃, and performing vacuum drying for 48 h;
step three, preparing the transition metal oxide/carbon material compound:
① dissolving 15mg polyvinylpyrrolidone in 50mL ethanol, performing ultrasonic treatment for 5h to obtain a mixed solution III, and adding the transition metal oxide ZnFe obtained in the step one into the mixed solution III2O4Continuing to perform ultrasonic treatment on the pretreated carbon material obtained in the step two for 1.5 hours to obtain a mixed solution IV;
② transferring the mixed solution IV to a 100mL reaction kettle, then placing the reaction kettle in an oven at 220 ℃, reacting for 20h, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times respectively, placing the obtained precipitate in an oven at 80 ℃, and vacuum drying for 48h to obtain the transition metal oxide/carbon material composite.
Further, the carbon material is carbon fiber.
A method of assembling a battery comprising the steps of:
① electrodeFirstly, preparing a binder by using polyvinylidene fluoride and polyvinylpyrrolidone; taking transition metal oxide ZnFe according to the mass ratio of 7:2:12O4Conductive carbon black and a binder for later use; transition metal oxide ZnFe2O4Grinding the conductive carbon black in an agate mortar, transferring the ground product into a binder, magnetically stirring for 8 hours, dropwise adding a small amount of deionized water in the stirring process to adjust the viscosity, and uniformly mixing to form slurry with proper viscosity and uniform components; then, dipping the slurry by a glass rod, uniformly coating the slurry on a clean copper foil, and then putting the copper foil into a vacuum drying oven at 60 ℃ for drying for 12 hours; finally, taking out the dried electrode-copper foil, horizontally placing the electrode-copper foil on a roller press, compacting the electrode slice, cutting the electrode slice by using a button cell slicer to obtain an electrode slice, and storing the electrode slice in a vacuum drying oven for later use;
② assembling the battery in a glove box filled with argon, wherein the assembling sequence is that placing a positive electrode shell, gently placing an electrode plate in the center of the positive electrode shell by using tweezers, dropwise adding 1-2 drops of electrolyte above the positive electrode shell, dropwise adding 1-2 drops of electrolyte again after covering a diaphragm, then placing a metal lithium sheet, a steel sheet, a gasket and a negative electrode shell in sequence, and finally sealing the assembled battery by using a button cell sealing machine.
Further, the diaphragm is a polytetrafluoroethylene microporous diaphragm.
Further, the electrolyte is a mixed solvent of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate with a volume ratio of 1:1:1 for dissolving 1mol/L lithium salt.
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should also be considered as falling within the scope of the present invention.

Claims (5)

1. The high-performance transition metal oxide negative electrode material is characterized in that the preparation method of the transition metal oxide negative electrode material is as follows:
step one, preparing a transition metal oxide:
① collecting 1-3 mmol of zinc nitrate (Zn (NO)3)2·6H2O) and 3-5 mmol of ferrous sulfate (FeSO)4·7H2O) placing the mixture in a beaker, adding 50-70 mL of deionized water into the beaker, and fully dissolving the mixture under magnetic stirring to obtain a mixed solution I;
② adding 5-8 mmol of urea (CO (NH) into the mixed solution I obtained from ①2)2) And 3 to 5mmol of ammonium fluoride (NH)4F) Continuously stirring for 15-20 min at room temperature, and uniformly mixing to obtain a mixed solution II;
③ transferring the mixed solution II obtained in the step ② to a reaction kettle, then placing the reaction kettle in an oven at the temperature of 150-180 ℃, reacting for 10-14 h, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times respectively, placing the obtained precipitate in an oven at the temperature of 50-80 ℃, and performing vacuum drying for 48h to obtain a powdery solid;
④ placing the ③ obtained powdery solid into a quartz boat, placing the quartz boat into a tube furnace protected by argon for high-temperature calcination at 550-700 ℃ for 4h, and after the calcination is finished, naturally cooling the sample to room temperature along with the furnace to obtain a transition metal oxide ZnFe2O4；
Step two, pretreatment of the carbon material:
dissolving 1-1.5 g of carbon material in 30-50 mL of concentrated nitric acid, transferring the mixed solution to a 100mL reaction kettle, placing the reaction kettle in a drying oven at 150-180 ℃ for reaction for 12-20 h, finally washing the product obtained by the reaction with deionized water and absolute ethyl alcohol for three times respectively, placing the obtained precipitate in the drying oven at 50-70 ℃, and performing vacuum drying for 48 h;
step three, preparing the transition metal oxide/carbon material compound:
① dissolving 15-25 mg of polyvinylpyrrolidone in 30-50 mL of ethanol, performing ultrasonic treatment for 2-5 h to obtain a mixed solution III, and adding the transition metal oxide ZnFe obtained in the step one into the mixed solution III2O4Continuing performing ultrasonic treatment on the pretreated carbon material obtained in the step two for 1-1.5 hours to obtain a mixed solution IV;
② transferring the mixed solution IV into a 100mL reaction kettle, then placing the reaction kettle into an oven at 200-220 ℃, reacting for 12-36 h, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times respectively, placing the obtained precipitate into an oven at 50-80 ℃, and vacuum drying for 48h to obtain the transition metal oxide/carbon material composite.
2. The high-performance transition metal oxide anode material as claimed in claim 1, wherein the carbon material is carbon fiber or multi-walled carbon nanotube.
3. A method of assembling a battery, comprising the steps of:
① the electrode is prepared by preparing binder I from sodium carboxymethylcellulose and deionized water, preparing binder II from polyvinylidene fluoride and polyvinylpyrrolidone, and preparing transition metal oxide ZnFe at a mass ratio of 7:2:12O4Conductive carbon black and a binder (binder I or binder II) for later use; transition metal oxide ZnFe2O4Grinding the conductive carbon black in an agate mortar, transferring the ground product into a binder, magnetically stirring for 5-8 h, dropwise adding a small amount of deionized water in the stirring process to adjust the viscosity, and uniformly mixing to form slurry with proper viscosity and uniform components; then, dipping the slurry by a glass rod, uniformly coating the slurry on a clean copper foil, and then putting the copper foil into a vacuum drying oven at 60 ℃ for drying for 12 hours; finally, taking out the dried electrode-copper foil, horizontally placing the electrode-copper foil on a roller press, compacting the electrode slice, cutting the electrode slice by using a button cell slicer to obtain an electrode slice, and storing the electrode slice in a vacuum drying oven for later use;
② assembling the battery in a glove box filled with argon, wherein the assembling sequence is that placing a positive electrode shell, gently placing an electrode plate in the center of the positive electrode shell by using tweezers, dropwise adding 1-2 drops of electrolyte above the positive electrode shell, dropwise adding 1-2 drops of electrolyte again after covering a diaphragm, then placing a metal lithium sheet, a steel sheet, a gasket and a negative electrode shell in sequence, and finally sealing the assembled battery by using a button cell sealing machine.
4. The method of claim 3, wherein the separator is a polytetrafluoroethylene microporous separator.
5. The method of claim 3, wherein the electrolyte is a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate in a volume ratio of 1:1:1 in which 1mol/L lithium salt is dissolved.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112382760A (en) * 2020-10-29 2021-02-19 厦门大学 Preparation method of aqueous conductive binder for positive electrode of lithium-sulfur battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112382760A (en) * 2020-10-29 2021-02-19 厦门大学 Preparation method of aqueous conductive binder for positive electrode of lithium-sulfur battery
CN112382760B (en) * 2020-10-29 2022-11-01 厦门大学 Preparation method of aqueous conductive binder for positive electrode of lithium-sulfur battery

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Application publication date: 20200218