CN113054185A - Positive and negative dual-purpose sodium ion battery material without phase change and preparation method and application thereof - Google Patents

Positive and negative dual-purpose sodium ion battery material without phase change and preparation method and application thereof Download PDF

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CN113054185A
CN113054185A CN202110281805.8A CN202110281805A CN113054185A CN 113054185 A CN113054185 A CN 113054185A CN 202110281805 A CN202110281805 A CN 202110281805A CN 113054185 A CN113054185 A CN 113054185A
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sodium
source compound
ion battery
nickel
iron
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章根强
彭波
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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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
    • H01M4/48—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
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 provides a positive and negative dual-purpose sodium ion battery material without phase change, and the chemical formula is Na0.7Ni0.25Fe0.2Ti0.55O2. The full battery assembled by the battery material with the dual purposes of the positive electrode and the negative electrode has the advantages of long cycle life, no phase change, high stability, good safety and low cost, and is an ideal electrode material of a sodium ion battery. In addition, the dual-purpose electrode material provided by the invention has the advantages of simple synthesis process, easiness in control, high yield, low price and easiness in mass production.

Description

Positive and negative dual-purpose sodium ion battery material without phase change and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a positive and negative dual-purpose sodium ion battery material without phase change and a preparation method and application thereof.
Background
In recent years, renewable clean energy has received much attention due to global warming and severe environmental pollution. However, these renewable energy sources, such as geothermal, wind and solar, suffer from inherent intermittent and regionally non-uniform disadvantages that make them inefficient for direct output as energy sources. It has therefore become important to develop suitable large-scale electrical energy storage system devices to balance peak and low peak usage.
Sodium ion batteries are considered to be one of the most promising candidates in large-scale energy storage devices due to their abundant sodium resources and high energy conversion efficiency. Nevertheless, full cell research for sodium ion batteries is still in the initial stage. The main bottleneck is to develop a suitable anode and cathode material. The anode material widely studied at present is a layered oxide, and the cathode material is mainly a carbon-based material. However, when these two materials are assembled into a full cell, since the sodium intercalation potential of the carbon material is relatively low, this may cause thermal runaway, thereby causing a safety problem of the cell. Such materials are therefore not suitable for large-scale energy storage facilities with extremely high requirements on long cycle and safety.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a phase-change-free dual-purpose positive and negative sodium ion battery material, and a preparation method and an application thereof.
In order to achieve the purpose, the invention provides a positive and negative dual-purpose sodium ion battery material without phase change, and the chemical formula is Na0.7Ni0.25Fe0.2Ti0.55O2。
The invention creatively develops a layered oxide which can be used as a positive electrode material and a negative electrode material, and the positive electrode material and the negative electrode material are both layered oxides, so that the overcharge of the battery can be supported, the volume expansion generated by the battery can be buffered (the volume expansion of the positive electrode and the negative electrode is just opposite in the charging and discharging process), the preparation cost of the materials is greatly reduced, the preparation process is simplified, and the actual application prospect of the sodium ion battery is greatly improved.
The invention provides a preparation method of the positive and negative dual-purpose sodium ion battery material without phase change, which comprises the following steps:
A) dissolving a sodium source compound, a nickel source compound, an iron source compound and a titanium source compound with a chelating agent in water according to a molar ratio, and heating to volatilize a solvent to obtain a gel precursor;
B) drying the gel precursor and then grinding to obtain precursor powder;
C) and sequentially carrying out primary calcination and secondary calcination on the precursor powder to obtain the positive and negative dual-purpose sodium ion battery material.
Preferably, the sodium source compound is selected from one or more of sodium acetate, sodium carbonate, sodium nitrate, sodium oxalate and sodium citrate;
the nickel source compound is selected from one or more of nickel acetate, nickel nitrate, nickel oxalate, nickel sulfate and nickel chloride;
the iron source compound is selected from one or more of iron acetate, iron nitrate, iron oxalate, iron sulfate and iron chloride;
the titanium source compound is selected from one or more of tetrabutyl titanate, titanium tetrachloride, tetraethyl titanate, titanium isooctanolate, isopropyl titanate and titanyl sulfate;
the chelating agent is one or more selected from citric acid, oxalic acid, tartaric acid and ethylenediamine tetraacetic acid.
Preferably, the heating rate of the first calcination is 2-10 ℃/min, the temperature is raised to 350-600 ℃, and the temperature is maintained until precursor powder is fully decomposed;
the temperature rise rate of the second calcination is 2-10 ℃/min, the temperature rises to 800-1000 ℃, and the temperature is kept for 10-24h until a P2 phase structure without impurity phase is formed;
the first calcination and the second calcination are carried out in an air atmosphere.
The invention also provides a preparation method of the positive and negative dual-purpose sodium ion battery material without phase change, which comprises the following steps:
A) carrying out solid phase grinding and mixing on a sodium source compound, a nickel source compound, an iron source compound and a titanium source compound according to a molar ratio to obtain precursor powder;
B) and calcining the precursor powder once or twice to obtain the positive and negative dual-purpose sodium ion battery material.
Preferably, the precursor powder is subjected to primary calcination;
the temperature rise rate of the primary calcination is 2-10 ℃/min, the temperature is raised to 800-1000 ℃, and the temperature is kept for 10-24h until a P2 phase structure without impurity phase is formed;
the sodium source compound is selected from one or more of sodium oxide and sodium carbonate;
the nickel source compound is selected from nickel oxide;
the iron source compound is selected from iron oxide;
the titanium source compound is selected from one or more of titanium dioxide, titanium oxide, sodium titanate and titanium monoxide.
Preferably, the precursor powder is subjected to two times of calcination;
the temperature rise rate of the first calcination is 2-10 ℃/min, the temperature is raised to 350-600 ℃, and the temperature is maintained until precursor powder is decomposed into oxides;
the temperature rise rate of the second calcination is 2-10 ℃/min, the temperature is raised to 800-1000 ℃, and the temperature is kept for 10-24h until a P2 phase structure without impurity phase is formed;
the sodium source compound is selected from one or more of sodium carbonate, sodium acetate, sodium nitrate, sodium oxalate and sodium citrate;
the nickel source compound is selected from one or more of nickel acetate, nickel nitrate, nickel oxalate and nickel sulfate;
the iron source compound is selected from one or more of iron acetate, iron nitrate, iron oxalate and iron sulfate;
the titanium source compound is selected from one or more of titanium oxides such as titanium dioxide, titanium sesquioxide, titanium monoxide, sodium titanate and the like.
The invention provides a positive electrode plate and a negative electrode plate of a sodium-ion battery, which are prepared from the positive-negative dual-purpose sodium-ion battery material or the positive-negative dual-purpose sodium-ion battery material prepared by the preparation method, a conductive additive, a binder and a solvent.
The invention provides a sodium ion battery, which consists of a positive electrode, a negative electrode, a diaphragm and organic electrolyte, wherein the positive electrode material and the negative electrode material are positive electrode plates and negative electrode plates of the sodium ion battery.
The invention provides application of the sodium ion battery in solar power generation, wind power generation, peak regulation of an intelligent power grid, and large-scale energy storage devices of a distributed power station or a communication base.
Compared with the prior art, the invention provides a positive and negative dual-purpose sodium ion battery material without phase change, and the chemical formula is Na0.7Ni0.25Fe0.2Ti0.55O2. The full battery assembled by the battery material with the dual purposes of the positive electrode and the negative electrode has the advantages of long cycle life, no phase change, high stability, good safety and low cost, and is an ideal electrode material of a sodium ion battery. In addition, the dual-purpose electrode material provided by the invention has the advantages of simple synthesis process, easiness in control, high yield, low price and easiness in mass production.
Drawings
FIG. 1 is the XRD spectrum of the target product obtained in example 1;
FIG. 2 is a SEM photograph of the target product obtained in example 1;
FIG. 3 shows the target product obtained in example 1 at 17mA g as a positive electrode-1A charge-discharge curve at current density;
FIG. 4 shows the target product obtained in example 1 as a negative electrode at 17mA g-1A charge-discharge curve at current density;
FIG. 5 shows the target product obtained in example 1 at 85mA g as a positive electrode-1Long cycle stability;
FIG. 6 shows that the target product obtained in example 1 is used as a negative electrode at 85mA g-1Long cycle stability;
FIG. 7 shows the target product obtained in example 1 at 17mA g as a positive electrode-1In-situ XRD data measured at current density;
FIG. 8 shows the target product obtained in example 1 as a negative electrode at 17mA g-1In-situ XRD data measured at current density;
FIG. 9 shows the target product obtained in example 1 as a sodium ion full cell assembled from dual-purpose positive and negative electrode materials at 17mA g-1A lower charge-discharge curve;
FIG. 10 shows the target product obtained in example 1, in 85mA g of a sodium ion full cell assembled by using the target product as a dual-purpose anode and cathode material-1Long cycle stability;
FIG. 11 is the XRD spectrum of the target product obtained in example 2;
FIG. 12 shows the target product obtained in example 2 at 17mA g as a positive electrode-1A charge-discharge curve at current density;
FIG. 13 shows that the target product obtained in example 2 was used as a negative electrode at 17mA g-1A charge-discharge curve at current density;
FIG. 14 is the XRD spectrum of the target product obtained in example 3;
FIG. 15 shows the target product obtained in example 3 at 17mA g as a positive electrode-1A charge-discharge curve at current density;
FIG. 16 shows that the target product obtained in example 3 was used as a negative electrode at 17mA g-1A charge-discharge curve at current density;
FIG. 17 is the XRD spectrum of the target product obtained in example 4;
FIG. 18 shows the target product obtained in example 4 at 17mA g as a positive electrode-1A charge-discharge curve at current density;
FIG. 19 shows that the target product obtained in example 4 was used as a negative electrode at 17mA g-1Charge and discharge curves at current density.
Detailed Description
The invention provides a positive and negative dual-purpose sodium ion battery material without phase change, and the chemical formula is Na0.7Ni0.25Fe0.2Ti0.55O2。
The positive and negative dual-purpose sodium ion battery material is a P2 phase layered oxide particle material, and the crystal space group is P63The particle diameter of the particles is 1-5 mu m.
In some embodiments of the present invention, the positive and negative dual-purpose sodium ion battery material is Na0.7Ni0.25Fe0.2Ti0.55O2. The lithium ion battery has long cycle life, high stability and good safety performance, and when the lithium ion battery is used as a positive electrode material, the lithium ion battery has a current of 85 milliamperes per gramAfter 500 cycles at density, the capacity retention was 71%. As an anode material, after cycling 200 cycles at a current density of 85 milliamps per gram, the capacity retention was 79.9%. Furthermore, the dual-purpose sodium ion battery material is respectively used as a positive electrode material and a negative electrode material to assemble a sodium ion full battery, and after the battery is cycled for 200 circles under the current density of 85 milliamperes per gram, the capacity retention rate is 91.7%. The anode and cathode dual-purpose material provided by the invention has huge application potential in future safe large-scale energy storage systems.
The invention provides a preparation method of the positive and negative dual-purpose sodium ion battery material without phase change, which adopts a sol-gel method and specifically comprises the following steps:
A) dissolving a sodium source compound, a nickel source compound, an iron source compound and a titanium source compound with a chelating agent in water according to a molar ratio, and heating to volatilize a solvent to obtain a gel precursor;
B) drying the gel precursor and then grinding to obtain precursor powder;
C) and sequentially carrying out primary calcination and secondary calcination on the precursor powder to obtain the positive and negative dual-purpose sodium ion battery material.
Preferably, the sodium source compound is selected from one or more of sodium acetate, sodium carbonate, sodium nitrate, sodium oxalate and sodium citrate.
Preferably, the nickel source compound is selected from one or more of nickel acetate, nickel nitrate, nickel oxalate, nickel sulfate and nickel chloride.
Preferably, the iron source compound is one or more selected from iron acetate, iron nitrate, iron oxalate, iron sulfate and iron chloride.
In a preferred embodiment of the present invention, the titanium source compound is selected from one or more of tetrabutyl titanate, titanium tetrachloride, tetraethyl titanate, titanium isooctanolate, isopropyl titanate, and titanyl sulfate.
In the invention, the molar ratio of the sodium source compound, the nickel source compound, the iron source compound and the titanium source compound is 0.7:0.25:0.2: 0.55.
Preferably, the chelating agent is one or more selected from citric acid, oxalic acid, tartaric acid and ethylenediamine tetraacetic acid.
Preferably, the molar ratio of the chelating agent to the total amount of the metal ions is 2: 1.
Preferably, the first calcination is carried out in an air atmosphere.
According to the invention, the heating rate of the first calcination is preferably 2-10 ℃/min.
The first calcination is preferably carried out at the temperature of 350-600 ℃, and the temperature is kept until precursor powder is fully decomposed.
Preferably, the second calcination is carried out in an air atmosphere.
According to the invention, the heating rate of the second calcination is preferably 2-10 ℃/min.
The second calcination is preferably carried out at the temperature of 800-1000 ℃, and the temperature is kept for 10-24 hours until a P2 phase structure without impurity phases is formed.
The invention also provides a preparation method of the positive and negative dual-purpose sodium ion battery material without phase change, which adopts a solid phase method and specifically comprises the following steps:
A) carrying out solid phase grinding and mixing on a sodium source compound, a nickel source compound, an iron source compound and a titanium source compound according to a molar ratio to obtain precursor powder;
B) and calcining the precursor powder once or twice to obtain the positive and negative dual-purpose sodium ion battery material.
In the invention, the molar ratio of the sodium source compound, the nickel source compound, the iron source compound and the titanium source compound is 0.7:0.25:0.2: 0.55.
Preferably, the above-mentioned one or two calcinations are carried out in an air atmosphere.
In the present invention, preferably, when the raw materials for preparing the precursor powder are all oxides, the precursor powder is subjected to one-time calcination.
According to the invention, the temperature rise rate of the primary calcination is preferably 2-10 ℃/min.
The invention preferably selects and concretes the method, the temperature of the primary calcination is raised to 800-1000 ℃, and the temperature is kept for 10-24h until a P2 phase structure without impurity phase is formed.
The sodium source compound is preferably one or more of sodium oxide and sodium carbonate.
The nickel source compound is preferably nickel oxide.
The iron source compound is preferably iron oxide.
The titanium source compound is preferably one or more of titanium dioxide, titanium sesquioxide, sodium titanate and titanium monoxide.
In the present invention, preferably, when the raw material for preparing the precursor powder is a salt, the precursor powder is subjected to two times of calcination.
According to the invention, the temperature rise rate of the first calcination is preferably 2-10 ℃/min.
Preferably, the first calcination is carried out at the temperature of 350-600 ℃, and the temperature is maintained until precursor powder is decomposed into oxides.
According to the invention, the temperature rise rate of the second calcination is preferably 2-10 ℃/min.
The invention preferably selects and concretely selects the second calcination, the temperature is raised to 800-1000 ℃, and the temperature is kept for 10-24h until a P2 phase structure without impurity phase is formed.
The sodium source compound is preferably one or more of sodium carbonate, sodium acetate, sodium nitrate, sodium oxalate and sodium citrate.
The nickel source compound is preferably one or more of nickel acetate, nickel nitrate, nickel oxalate and nickel sulfate.
The iron source compound is preferably one or more of iron acetate, iron nitrate, iron oxalate and iron sulfate.
The titanium source compound is preferably one or more of titanium dioxide, titanium sesquioxide, sodium titanate and titanium monoxide.
The invention also provides a positive electrode plate and a negative electrode plate of the sodium-ion battery, which are prepared from the positive-negative dual-purpose sodium-ion battery material or the positive-negative dual-purpose sodium-ion battery material prepared by the preparation method, a conductive additive, a binder and a solvent.
The positive and negative dual-purpose sodium ion battery materials are respectively used as a positive electrode material and a negative electrode material.
The conductive additive, binder and solvent are not particularly limited in the present invention, and may be any suitable conductive additive, binder and solvent known to those skilled in the art.
Preferably, the conductive additive is selected from one or more of Super-P, carbon black and Ketjen black.
Preferably, the binder is one or more selected from polyvinylidene fluoride or polyacrylic acid, sodium carboxymethylcellulose and sodium alginate.
In the preferred embodiment of the present invention, the solvent is selected from one of N-methyl pyrrolidone or deionized water.
The preparation method of the positive electrode and negative electrode plates of the sodium ion battery is not particularly limited, and can be a method known by those skilled in the art.
The invention is preferably prepared according to the following method:
the anode material and the cathode material are respectively mixed with a conductive additive, a binder and a solvent, and then smeared and dried to obtain the anode material.
The current collectors used are preferably all aluminum foils, which can reduce costs.
The present invention is not particularly limited to the specific methods for mixing, smearing and drying, and may be any methods known to those skilled in the art.
The invention also provides a sodium ion battery, which consists of a positive electrode, a negative electrode, a diaphragm and organic electrolyte, wherein the positive electrode material and the negative electrode material are the positive electrode plate and the negative electrode plate of the sodium ion battery.
The separator and the organic electrolyte solution are not particularly limited in the present invention, and may be any suitable materials known to those skilled in the art.
In the present invention, the solvent in the organic electrolytic solution is at least one selected from the group consisting of diethyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate and fluorinated ethylene carbonate, and more preferably a mixed solvent of propylene carbonate and fluorinated ethylene carbonate.
In the organic electrolytic solution of the present invention, the solute is preferably at least one selected from sodium hexafluorophosphate, sodium perchlorate and sodium bistrifluoromethylsulfonyl imide, and more preferably sodium perchlorate.
The separator is preferably glass fiber.
The invention provides application of the sodium ion battery in solar power generation, wind power generation, peak regulation of an intelligent power grid, and large-scale energy storage devices of a distributed power station or a communication base.
The invention has the following advantages and beneficial results:
(1) synthetic Na0.7Ni0.25Fe0.2Ti0.55O2The compound can be used as a positive electrode material and a negative electrode material of the sodium-ion battery, enriches the material system of the sodium-ion battery and simplifies the production process of the sodium-ion battery.
(2) Na provided by the invention0.7Ni0.25Fe0.2Ti0.55O2The positive and negative dual-purpose phase-change-free material has the advantages of long cycle life, high stability, good rate capability and low cost, and is an ideal electrode material of a sodium ion battery.
(3) The sodium ion battery provided by the invention has long cycle life, and after the full battery is assembled by using dual-purpose electrode materials and is cycled for 200 circles under the current density of 85 milliampere per gram, the capacity retention rate is 91.7%. Is suitable for large-scale energy storage equipment.
(4) The method can be synthesized by a simple sol-gel or solid phase method, has simple and easily controlled process, and is easy for mass production.
In order to further explain the present invention, the following describes in detail the positive and negative dual-purpose sodium ion battery material without phase change, and the preparation method and application thereof, provided by the present invention, with reference to the examples.
Example 1
Step 1, preparing P2 phase Na by sol-gel method0.7Ni0.25Fe0.2Ti0.55O2Positive and negative electrode material
Target productIs Na0.7Ni0.25Fe0.2Ti0.55O2The compound is prepared from sodium acetate, nickel acetate, ferric nitrate, tetrabutyl titanate, citric acid and water as solvent.
Dissolving raw materials of sodium acetate, nickel acetate, ferric nitrate, tetrabutyl titanate and citric acid (the molar ratio of the raw materials to the total of metal ions of nickel, iron, titanium and sodium is 2:1) in deionized water, and placing the deionized water in an oil bath kettle at 60 ℃ to be stirred and evaporated to dryness to form a gel precursor. And (3) drying the gel precursor in an oven at 150 ℃ for 8h, and grinding the gel precursor in a mortar to obtain precursor powder. And placing the precursor powder in a muffle furnace, heating at the rate of 2 ℃/min, and presintering at the temperature of 400 ℃ for 5h in the air atmosphere to obtain an intermediate product. Placing the intermediate product in a muffle furnace, calcining at 900 ℃ for 15h in the air atmosphere at the heating rate of 2 ℃/min to obtain the target product Na0.7Ni0.25Fe0.2Ti0.55O2。
Step 2, preparation of Na0.7Ni0.25Fe0.2Ti0.55O2Electrode plate made of anode and cathode materials
Mixing the prepared target product with Super P and a binding agent polyvinylidene fluoride according to the mass ratio of 8:1:1, adding a solvent N-methyl pyrrolidone, and performing pulping, smearing, drying and the like to obtain the positive and negative electrode material electrode slice containing the target product.
Step 3, assembling the target product Na0.7Ni0.25Fe0.2Ti0.55O2Is a sodium ion battery with dual-purpose positive and negative electrodes.
Respectively assembling the prepared target product positive electrode plate and the target product negative electrode plate with a metal sodium plate to form a sodium ion half-cell, wherein GF/F is a cell diaphragm, and the electrolyte is a carbonate electrolyte (1M NaClO)4The PC solution of (a) contains 5 vol% FEC).
Assembling the prepared target product positive electrode plate and negative electrode plate into a sodium ion full battery according to a certain mass ratio, wherein GF/F is a battery diaphragm, and the electrolyte is a carbonate electrolyte (1M NaClO)4The PC solution of (a) contains 5 vol% FEC).
Shown in FIG. 1As can be seen from the XRD pictures of the target product obtained in example 1, the synthesized material has better crystallinity, and the obtained target product belongs to the hexagonal crystal system P63And/mmc. Wherein, Ni ions, Fe ions and Ti ions respectively form an octahedral structure with six nearest neighbor oxygen atoms and are arranged in a common edge way to form transition metal layers, and Na ions are positioned between every two transition metal layers and form a triangular prism structure with the oxygen atoms.
FIG. 2 is a SEM photograph of the target product obtained in example 1, and it can be seen that the resulting particles have a particle size of 1 to 5 μm.
FIG. 3 shows the target product obtained in example 1 as a positive electrode at 17mA g-1The charging and discharging curve under the current density shows that the material has higher specific discharge capacity of 85mAh g when being applied to the sodium ion battery-1。
FIG. 4 shows the target product obtained in example 1 as a negative electrode at 17mA g-1The charging and discharging curve under the current density shows that the material has higher charging specific capacity of 124.3mAh g when being applied to the sodium ion battery-1。
FIG. 5 shows the target product obtained in example 1 at 85mA g as a positive electrode-1Long cycle stability at current density, as can be seen, the initial capacity is 80.3mAh g-1The capacity retention rate after 500 cycles was 71.1%, showing excellent cycle stability.
FIG. 6 shows that the target product obtained in example 1 was used as a negative electrode at 85mA g-1The cycle stability at current density, as can be seen, is 86.6mAh g as the initial capacity-1The capacity retention rate after 200 cycles was 79.9%, showing excellent cycle stability.
FIG. 7 shows the target product obtained in example 1 at 17mA g as a positive electrode-1In-situ XRD data obtained by testing under current density can be seen from the figure, the target product is used as an anode, no phase change occurs in the circulation process, and high structural stability is shown.
FIG. 8 shows that the target product obtained in example 1 was used as a negative electrode at 17mA g-1In-situ XRD data obtained by testing under current density can be seen from the figure, the target product is used as a cathode in circulationNo phase change occurs in the ring process, and high structural stability is shown.
FIG. 9 shows the total cell voltage of 17mA g assembled by the target products obtained in example 1 as positive and negative electrodes, respectively-1The charging and discharging curve under the current density is shown in the figure, and the full battery has higher specific discharging capacity of 112.7mAh g-1。
FIG. 10 shows the current of the full cell assembled by the target products obtained in example 1 as positive and negative electrodes at 85mA g-1The long cycle stability at current density, as can be seen, the initial capacity of the full cell is 75.2mAh g-1The capacity retention rate after 200 cycles was 91.7%, showing excellent cycle stability.
Example 2
Step 1, preparation of Na by solid phase method0.7Ni0.25Fe0.2Ti0.55O2Positive and negative electrode material
The target product is Na0.7Ni0.25Fe0.2Ti0.55O2The raw materials of the compound comprise sodium acetate, nickel acetate, ferric oxalate and titanium dioxide.
And (3) placing the raw materials in a mortar according to the stoichiometric ratio, fully grinding the raw materials and uniformly mixing the raw materials to obtain precursor powder. And then, placing the precursor powder in a muffle furnace, heating at the rate of 2 ℃/min, and presintering at 450 ℃ for 6h in the air atmosphere to obtain an intermediate product. Placing the intermediate product in a muffle furnace, calcining at 900 ℃ for 15h in the air atmosphere at the heating rate of 2 ℃/min to obtain the target product Na0.7Ni0.25Fe0.2Ti0.55O2。
Step 2, preparation of Na0.7Ni0.25Fe0.2Ti0.55O2The steps of the electrode plates made of the positive and negative electrode materials are the same as those in the embodiment 1.
Step 3, assembling the target product Na0.7Ni0.25Fe0.2Ti0.55O2Is a sodium ion battery with dual-purpose positive and negative electrodes.
Dividing the prepared target product positive electrode slice and the target product negative electrode slice intoThe sodium ion semi-cell is assembled with a metal sodium sheet, GF/F is a cell diaphragm, and the electrolyte is a carbonate electrolyte (1M NaClO)4The PC solution of (a) contains 5 vol% FEC).
FIG. 11 is an XRD picture of the target product obtained in example 2, which shows that the synthesized material has better crystallinity, and the obtained target product belongs to a hexagonal system P63/mmc。
FIG. 12 shows the target product obtained in example 2 at 17mA g as a positive electrode-1The charging and discharging curve under the current density shows that the material has higher specific discharging capacity of 79.1mAh g when being applied to the sodium ion battery-1。
FIG. 13 shows that the target product obtained in example 2 was used as a negative electrode at 17mA g-1The charging and discharging curve under the current density shows that the material has higher charging specific capacity of 91.1mAh g when being applied to the sodium ion battery-1。
Example 3
Step 1, preparation of Na by solid phase method0.7Ni0.25Fe0.2Ti0.55O2Positive and negative electrode dual-purpose material
The target product is Na0.7Ni0.25Fe0.2Ti0.55O2The raw materials of the compound comprise sodium carbonate, nickel oxide, iron oxide and titanium dioxide.
And (3) placing the raw materials in a mortar according to the stoichiometric ratio, fully grinding the raw materials, and uniformly mixing the raw materials to obtain precursor powder. Then, putting the precursor powder into a muffle furnace, calcining for 15h at 900 ℃ in the air atmosphere at the heating rate of 2 ℃/min to obtain the target product Na0.7Ni0.25Fe0.2Ti0.55O2。
FIG. 14 is an XRD picture of the target product obtained in example 3, which shows that the synthesized material has better crystallinity, and the obtained target product belongs to the hexagonal system P63/mmc。
FIG. 15 shows the target product obtained in example 3 at 17mA g as a positive electrode-1The charging and discharging curve under the current density is shown in the figure, and the material has higher performance when being applied to the sodium ion batterySpecific discharge capacity of 69.2mAh g-1。
FIG. 16 shows that the target product obtained in example 3 was used as a negative electrode at 17mA g-1The charging and discharging curve under the current density shows that the material has higher charging specific capacity of 87.5mAh g when being applied to the sodium ion battery-1。
Example 4
Step 1, preparation of Na by solid phase method0.7Ni0.25Fe0.2Ti0.55O2Positive and negative electrode dual-purpose material
The target product is Na0.7Ni0.25Fe0.2Ti0.55O2The raw materials of the compound comprise sodium carbonate, nickel oxide, ferric oxalate and titanium dioxide.
And (3) placing the raw materials in a mortar according to the stoichiometric ratio, fully grinding the raw materials, and uniformly mixing the raw materials to obtain precursor powder. And then, placing the precursor powder in a muffle furnace, heating at the rate of 2 ℃/min, and presintering at 450 ℃ for 6h in the air atmosphere to obtain an intermediate product. Placing the intermediate product in a muffle furnace, calcining at 900 ℃ for 15h in the air atmosphere at the heating rate of 2 ℃/min to obtain the target product Na0.7Ni0.25Fe0.2Ti0.55O2。
FIG. 17 is an XRD picture of the target product obtained in example 4, which shows that the synthesized material has better crystallinity, and the obtained target product belongs to the hexagonal system P63/mmc。
FIG. 18 shows the target product obtained in example 4 as a positive electrode at 17mA g-1The charging and discharging curve under the current density shows that the material has higher specific discharge capacity of 80.8mAh g when being applied to the sodium ion battery-1。
FIG. 19 shows that the target product obtained in example 4 was used as a negative electrode at 17mA g-1The charging and discharging curve under the current density shows that the material has higher specific charging capacity of 77.1mAh g when being applied to the sodium ion battery-1。
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (10)

1. A phase-change-free positive and negative dual-purpose sodium ion battery material is characterized in that the chemical formula is Na0.7Ni0.25Fe0.2Ti0.55O2。
2. The method for preparing the positive-negative dual-purpose sodium ion battery material without phase change of claim 1, comprising the following steps of:
A) dissolving a sodium source compound, a nickel source compound, an iron source compound and a titanium source compound with a chelating agent in water according to a molar ratio, and heating to volatilize a solvent to obtain a gel precursor;
B) drying the gel precursor and then grinding to obtain precursor powder;
C) and sequentially carrying out primary calcination and secondary calcination on the precursor powder to obtain the positive and negative dual-purpose sodium ion battery material.
3. The production method according to claim 2, wherein the sodium source compound is selected from one or more of sodium acetate, sodium carbonate, sodium nitrate, sodium oxalate, and sodium citrate;
the nickel source compound is selected from one or more of nickel acetate, nickel nitrate, nickel oxalate, nickel sulfate and nickel chloride;
the iron source compound is selected from one or more of iron acetate, iron nitrate, iron oxalate, iron sulfate and iron chloride;
the titanium source compound is selected from one or more of tetrabutyl titanate, titanium tetrachloride, tetraethyl titanate, titanium isooctanolate, isopropyl titanate and titanyl sulfate;
the chelating agent is one or more selected from citric acid, oxalic acid, tartaric acid and ethylenediamine tetraacetic acid.
4. The preparation method according to claim 2, wherein the temperature rise rate of the first calcination is 2-10 ℃/min, the temperature is raised to 350-600 ℃, and the temperature is maintained until the precursor powder is fully decomposed;
the temperature rise rate of the second calcination is 2-10 ℃/min, the temperature rises to 800-1000 ℃, and the temperature is kept for 10-24h until a P2 phase structure without impurity phase is formed;
the first calcination and the second calcination are carried out in an air atmosphere.
5. The method for preparing the positive-negative dual-purpose sodium ion battery material without phase change of claim 1, comprising the following steps of:
A) carrying out solid phase grinding and mixing on a sodium source compound, a nickel source compound, an iron source compound and a titanium source compound according to a molar ratio to obtain precursor powder;
B) and calcining the precursor powder once or twice to obtain the positive and negative dual-purpose sodium ion battery material.
6. The production method according to claim 5, wherein the precursor powder is subjected to primary calcination;
the temperature rise rate of the primary calcination is 2-10 ℃/min, the temperature is raised to 800-1000 ℃, and the temperature is kept for 10-24h until a P2 phase structure without impurity phase is formed;
the sodium source compound is selected from one or more of sodium oxide and sodium carbonate;
the nickel source compound is selected from nickel oxide;
the iron source compound is selected from iron oxide;
the titanium source compound is selected from one or more of titanium dioxide, titanium oxide, sodium titanate and titanium monoxide.
7. The production method according to claim 5, wherein the precursor powder is subjected to two times of calcination;
the temperature rise rate of the first calcination is 2-10 ℃/min, the temperature is raised to 350-600 ℃, and the temperature is maintained until precursor powder is decomposed into oxides;
the temperature rise rate of the second calcination is 2-10 ℃/min, the temperature is raised to 800-1000 ℃, and the temperature is kept for 10-24h until a P2 phase structure without impurity phase is formed;
the sodium source compound is selected from one or more of sodium carbonate, sodium acetate, sodium nitrate, sodium oxalate and sodium citrate;
the nickel source compound is selected from one or more of nickel acetate, nickel nitrate, nickel oxalate and nickel sulfate;
the iron source compound is selected from one or more of iron acetate, iron nitrate, iron oxalate and iron sulfate;
the titanium source compound is selected from one or more of titanium dioxide, titanium sesquioxide, titanium monoxide and sodium titanate.
8. A positive electrode plate and a negative electrode plate of a sodium-ion battery are characterized by being prepared from the positive-negative dual-purpose sodium-ion battery material of claim 1 or the positive-negative dual-purpose sodium-ion battery material prepared by the preparation method of any one of claims 2 to 7, a conductive additive, a binder and a solvent.
9. A sodium ion battery, which is characterized by comprising a positive electrode, a negative electrode, a diaphragm and an organic electrolyte, wherein the positive electrode material and the negative electrode material are the positive electrode plate and the negative electrode plate of the sodium ion battery according to claim 8.
10. Use of the sodium ion battery of claim 9 in solar power generation, wind power generation, smart grid peak shaving, distributed power plants or communication base large scale energy storage devices.
CN202110281805.8A 2021-03-16 2021-03-16 Positive and negative dual-purpose sodium ion battery material without phase change and preparation method and application thereof Pending CN113054185A (en)

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