CN110061229B - High-power-density long-cycle-life sodium ion battery positive electrode material and preparation method and application thereof - Google Patents

High-power-density long-cycle-life sodium ion battery positive electrode material and preparation method and application thereof Download PDF

Info

Publication number
CN110061229B
CN110061229B CN201910379118.2A CN201910379118A CN110061229B CN 110061229 B CN110061229 B CN 110061229B CN 201910379118 A CN201910379118 A CN 201910379118A CN 110061229 B CN110061229 B CN 110061229B
Authority
CN
China
Prior art keywords
sodium
ion battery
acetate
target product
positive electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910379118.2A
Other languages
Chinese (zh)
Other versions
CN110061229A (en
Inventor
章根强
彭波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CN201910379118.2A priority Critical patent/CN110061229B/en
Publication of CN110061229A publication Critical patent/CN110061229A/en
Application granted granted Critical
Publication of CN110061229B publication Critical patent/CN110061229B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive 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

Abstract

The invention provides a sodium ion battery anode material with high power density and long cycle life, and the chemical formula is Na0.67Ni0.33‑x‑ yCuxZnyMn0.67O2(0<x<0.33,0<y<0.33,0 < x + y < 0.33). The anode material provided by the invention has the advantages of long cycle life, high stability, good rate capability, high output voltage and low cost, and is an ideal anode material for a sodium-ion battery. In addition, the synthesis process of the cathode material provided by the invention is simple and easy to control, and is easy for mass production.

Description

High-power-density long-cycle-life sodium ion battery positive electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a sodium ion battery anode material with high power density and long cycle life, and a preparation method and application thereof.
Background
With the development of clean energy and the further popularization of smart grids, energy storage systems become an important part of the integration of renewable energy infrastructures. In recent years, researchers have been working on rechargeable secondary batteries as energy storage devices. Compared with lithium ion batteries, sodium ion batteries have the characteristics of abundant reserves and similarity to lithium ion batteries, and are more suitable for energy storage systems. The positive electrode material is an important ring in the development of sodium ion batteries because it determines the energy density and output voltage of the battery. Recently, transition metal layered oxides have received much attention because of their ease of synthesis and high specific capacity. However, their low cycle life and low power density limit their practical applications. Therefore, it is important to improve the long cycle stability of the oxide positive electrode material and to achieve high power density.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a sodium ion battery cathode material with high power density and long cycle life, and a preparation method and an application thereof.
The invention provides a sodium ion battery anode material with high power density and long cycle life, and the chemical formula is Na0.67Ni0.33-x-yCuxZnyMn0.67O2Wherein 0 is<x<0.33,0<y<0.33,0＜x+y＜0.33。
The invention also provides a sol-gel preparation method of the sodium ion battery anode material, which comprises the following steps:
A) dissolving a chelating agent and a sodium source compound, a nickel source compound, a copper source compound, a zinc source compound and a manganese source compound in water according to a molar ratio, and heating to volatilize the solvent to obtain a gel precursor;
B) drying the gel precursor and then grinding to obtain precursor powder;
C) and calcining the precursor powder for two times in sequence to obtain the sodium-ion battery anode material.
Preferably, the sodium source compound is selected from one or more of 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, nickel sulfate and nickel chloride;
the copper source compound is selected from one or more of copper acetate, copper nitrate, copper oxalate, copper sulfate and copper chloride;
the zinc source compound is selected from one or more of zinc acetate, zinc nitrate, zinc oxalate, zinc sulfate and zinc chloride;
the manganese source compound is selected from one or more of manganese acetate, manganese nitrate, manganese oxalate, manganese sulfate and manganese chloride;
the chelating agent is selected from citric acid, oxalic acid, tartaric acid or ethylenediamine tetraacetic acid.
Preferably, the two times of calcination are carried out in an air atmosphere and are divided into a first time of calcination and a second time of calcination, the temperature rise rate of the first time of calcination is 2-10 ℃/min, the temperature is raised to 350-600 ℃, and the temperature is maintained until the organic matter is fully decomposed; and 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 invention also provides a solid-phase preparation method of the sodium-ion battery positive electrode material, which comprises the following steps:
A) carrying out solid phase ball milling and mixing on a sodium source compound, a nickel source compound, a copper source compound, a zinc source compound and a manganese source compound according to a molar ratio to obtain precursor powder;
B) and calcining the precursor powder once or twice to obtain the sodium-ion battery anode material.
Preferably, the sodium source compound is selected from one or more of sodium oxide, sodium carbonate, sodium acetate, sodium nitrate, sodium oxalate and sodium citrate;
the nickel source compound is selected from one or more of nickel oxide, nickel acetate, nickel nitrate, nickel oxalate and nickel sulfate;
the copper source compound is selected from one or more of copper oxide, copper acetate, copper nitrate, copper oxalate and copper sulfate;
the zinc source compound is selected from one or more of zinc oxide, zinc acetate, zinc nitrate, zinc oxalate and zinc sulfate;
the manganese source compound is selected from one or more of manganese oxide, manganese acetate, manganese nitrate, manganese oxalate and manganese sulfate.
Preferably, when the preparation raw materials of the precursor powder are all oxides, the calcination is carried out for one time, the temperature rise rate of the one-time 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;
when the preparation raw materials of the precursor powder are all salts, the calcination is divided into a first calcination and a second calcination through 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 preserved until the salts are decomposed into oxides; and 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 invention also provides a positive plate of the sodium-ion battery, which is prepared from the positive material, a conductive additive, a binder and a solvent, wherein the positive material is selected from the positive materials.
The invention also provides a sodium ion battery, which consists of a positive electrode, a diaphragm, organic electrolyte and negative metal sodium, wherein the positive electrode is the positive plate of the sodium ion battery.
The invention also provides application of the sodium ion battery in solar power generation, wind power generation, intelligent power grid peak regulation, distributed power stations or communication base large-scale energy storage devices.
Compared with the prior art, the invention provides the positive electrode material of the sodium-ion battery with high power density and long cycle life, and the chemical formula is Na0.67Ni0.33-x-yCuxZnyMn0.67O2(0<x<0.33,0<y<0.33,0 < x + y < 0.33). The anode material provided by the invention has the advantages of long cycle life, high stability, good rate capability, high output voltage and low cost, and is an ideal anode material for a sodium-ion battery. In addition, the synthesis process of the cathode material provided by the invention is simple and easy to control, and is easy for 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-1A charge-discharge curve at current density;
FIG. 4 shows the target product obtained in example 1 at 0.1mV s-1CV curve at sweep rate;
FIG. 5 shows that the target product obtained in example 1 is 1700mA g-1Long cycle stability;
FIG. 6 shows that the target product obtained in example 1 is 1700mA g-1Cyclic stability of energy density;
FIG. 7 is the XRD spectrum of the target product obtained in example 2;
FIG. 8 shows the target product obtained in example 2 at 17mA g-1Charge and discharge curve at current density；
FIG. 9 is the XRD spectrum of the target product obtained in example 3;
FIG. 10 shows the target product obtained in example 3 at 17mA g-1A charge-discharge curve at current density;
FIG. 11 is the XRD spectrum of the target product obtained in example 4;
FIG. 12 shows the target product obtained in example 4 at 17mA g-1A charge-discharge curve at current density;
FIG. 13 is the XRD spectrum of the target product obtained in example 5;
FIG. 14 shows the target product obtained in example 5 at 17mA g-1A charge-discharge curve at current density;
FIG. 15 is the XRD spectrum of the target product obtained in example 6;
FIG. 16 shows the target product obtained in example 6 at 17mA g-1A charge-discharge curve at current density;
FIG. 17 is the XRD spectrum of the target product obtained in example 7;
FIG. 18 shows the target product obtained in example 7 at 17mA g-1A charge-discharge curve at current density;
FIG. 19 is the XRD spectrum of the target product obtained in example 8;
FIG. 20 shows the target product obtained in example 8 at 17mA g-1A charge-discharge curve at current density;
FIG. 21 is the XRD spectrum of the target product obtained in example 9;
FIG. 22 shows the target product obtained in example 9 at 17mA g-1A charge-discharge curve at current density;
FIG. 23 is the XRD spectrum of the target product obtained in example 10;
FIG. 24 shows the target product obtained in example 10 at 17mA g-1A charge-discharge curve at current density;
FIG. 25 is the XRD spectrum of the target product obtained in example 11;
FIG. 26 shows the target product obtained in example 11 at 17mA g-1Charge and discharge curves at current density.
Detailed Description
The invention provides a sodium ion battery anode material with high power density and long cycle life, and the chemical formula is Na0.67Ni0.33-x-yCuxZnyMn0.67O2Wherein 0 is<x<0.33, preferably 0<x<0.2，0<y<0.33, preferably 0<y<0.33, more preferably 0<y<0.1，0＜x+y<0.33. The positive electrode material is a layered oxide particle material, and the particle size of the particles is 1-5 mu m.
In some embodiments of the invention, the positive electrode material of the sodium-ion battery is Na0.67Ni0.18Cu0.1Zn0.05Mn0.67O2. The power density is high, and the power density is 5542W kg-1Still, 197Wh kg can be achieved-1The energy density of (1) is maintained at 154Wh kg after 2000 weeks of circulation-1And is suitable for high-power equipment.
The invention also provides a preparation method of the sodium ion battery anode material with high power density and long cycle life, which is a sol-gel method and comprises the following steps:
A) dissolving a chelating agent and a sodium source compound, a nickel source compound, a copper source compound, a zinc source compound and a manganese source compound in water according to a molar ratio, and heating to volatilize the solvent to obtain a gel precursor;
B) drying the gel precursor and then grinding to obtain precursor powder;
C) and calcining the precursor powder for two times in sequence to obtain the sodium-ion battery anode material.
The invention adopts a sol-gel method to synthesize the sodium ion battery anode material, and firstly prepares a gel precursor. Specifically, a sodium source compound, a nickel source compound, a copper source compound, a zinc source compound and a manganese source compound are dissolved in water together with a chelating agent according to a required stoichiometric ratio to obtain a mixed solution.
The sodium source compound is a water-soluble sodium source compound, is selected from one or more of sodium acetate, sodium nitrate, sodium oxalate and sodium citrate, and is preferably sodium acetate;
the nickel source compound is a water-soluble nickel source compound, is selected from one or more of nickel acetate, nickel nitrate, nickel oxalate, nickel sulfate and nickel chloride, and is preferably nickel acetate;
the copper source compound is a water-soluble copper source compound, is selected from one or more of copper acetate, copper nitrate, copper oxalate, copper sulfate and copper chloride, and is preferably copper acetate;
the zinc source compound is a water-soluble zinc source compound, is selected from one or more of zinc acetate, zinc nitrate, zinc oxalate, zinc sulfate and zinc chloride, and is preferably zinc acetate;
the manganese source compound is a water-soluble manganese source compound, is selected from one or more of manganese acetate, manganese nitrate, manganese oxalate, manganese sulfate and manganese chloride, and is preferably manganese acetate.
The chelating agent is selected from citric acid, oxalic acid, tartaric acid or ethylenediamine tetraacetic acid.
Wherein the ratio of the total molar amount of metal ions in the sodium source compound, the nickel source compound, the copper source compound, the zinc source compound and the manganese source compound to the molar amount of the chelating agent is 1 (1-3).
And heating to volatilize the solvent after obtaining the mixed solution, thereby obtaining the gel precursor. Wherein the heating mode is stirring in an oil bath.
And after obtaining a gel precursor, drying the gel precursor and then grinding to obtain precursor powder. The drying temperature and time are such that the precursor gel has a moisture content of less than 1%.
And then, calcining the precursor powder twice in sequence to obtain the positive electrode material of the sodium-ion battery.
The two times of calcination are carried out in an air atmosphere and are divided into a first time of calcination and a second time of calcination, the temperature rise rate of the first time of calcination is 2-10 ℃/min, preferably 4-8 ℃/min, the temperature is raised to 350-600 ℃, preferably 400-550 ℃, and the temperature is kept until organic matters are fully decomposed; the temperature rise rate of the second calcination is 2-10 ℃/min, preferably 4-8 ℃/min, the temperature rises to 800-1000 ℃, preferably 850-950 ℃, and the temperature is kept for 10-24 hours.
The invention also provides a preparation method of the sodium ion battery anode material with high power density and long cycle life, which is a solid phase method and comprises the following steps:
A) carrying out solid phase ball milling and mixing on a sodium source compound, a nickel source compound, a copper source compound, a zinc source compound and a manganese source compound according to a required molar ratio to obtain precursor powder;
B) and calcining the precursor powder once or twice to obtain the sodium-ion battery anode material.
Wherein the sodium source compound is selected from one or more of sodium oxide, sodium carbonate, sodium acetate, sodium nitrate, sodium oxalate and sodium citrate, preferably sodium oxide or sodium acetate;
the nickel source compound is selected from one or more of nickel oxide, nickel acetate, nickel nitrate, nickel oxalate and nickel sulfate, and is preferably nickel oxide or nickel acetate;
the copper source compound is selected from one or more of copper oxide, copper acetate, copper nitrate, copper oxalate and copper sulfate, and is preferably copper oxide or copper acetate;
the zinc source compound is selected from one or more of zinc oxide, zinc acetate, zinc nitrate, zinc oxalate and zinc sulfate, and is preferably zinc oxide or zinc acetate;
the manganese source compound is selected from one or more of manganese oxide, manganese acetate, manganese nitrate, manganese oxalate and manganese sulfate, and is preferably manganese oxide or manganese acetate.
And carrying out ball milling to obtain uniform precursor powder, and then sequentially calcining the precursor powder once or twice to obtain the sodium-ion battery anode material.
When the preparation raw materials of the precursor powder are all oxides, the calcination is carried out for one time, the temperature rise rate of the one-time calcination is 2-10 ℃/min, preferably 4-8 ℃/min, the temperature is raised to 800-1000 ℃, preferably 850-950 ℃, and the temperature is kept for 10-24h until a P2 phase structure without impurity phases is formed;
when the preparation raw materials of the precursor powder are all salts, the calcination is carried out twice, and the calcination is divided into a first calcination and a second calcination, wherein the temperature rise rate of the first calcination is 2-10 ℃/min, preferably 4-8 ℃/min, the temperature is raised to 350-600 ℃, preferably 400-550 ℃, and the temperature is kept until the salts are decomposed into oxides; the temperature rise rate of the second calcination is 2-10 ℃/min, preferably 4-8 ℃/min, the temperature is raised to 800-1000 ℃, preferably 850-950 ℃, and the temperature is kept for 10-24h until a P2 phase structure without impurity phase is formed.
The invention also provides a positive plate of the sodium ion battery, which is prepared from the positive material, a conductive additive, a binder and a solvent, wherein the positive material is selected from the positive material of the sodium ion battery.
Wherein the conductive additive is selected from one or more of Super-P, carbon black and Ketjen black; the binder is selected from one or more of polyvinylidene fluoride or polyacrylic acid, sodium carboxymethylcellulose and sodium alginate; the solvent is selected from one of N-methyl pyrrolidone or deionized water.
The invention also provides a preparation method of the sodium ion battery positive plate, which is prepared by mixing the positive material, the conductive additive, the binder and the solvent, smearing and drying.
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 diaphragm, organic electrolyte and negative metal sodium, wherein the positive electrode is the positive plate of the sodium ion battery. The organic electrolyte is a carbonate electrolyte, and the concentration of the carbonate electrolyte is 0.1-2M, preferably 1M;
in the organic electrolyte, a solvent is selected from at least one of diethyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate and fluorinated ethylene carbonate, and is preferably a mixed solvent of propylene carbonate and fluorinated ethylene carbonate;
the solute is at least one selected from sodium hexafluorophosphate, sodium perchlorate and sodium bistrifluoromethylsulfonyl imide, and is preferably sodium perchlorate.
The separator is preferably glass fiber.
The invention also provides application of the sodium ion battery in large-scale energy storage devices such as solar power generation, wind power generation, smart grid peak shaving, distributed power stations or communication bases.
The invention has the following advantages and beneficial results:
(1) na synthesized by sol-gel method0.67Ni0.33-x-yCuxZnyMn0.67O2(0<x<0.33,0<x<0.33,0.33≥x+y>0) The compound can be used as a positive electrode material of a sodium ion battery, and enriches the material system of the sodium ion battery.
(2) Invention Na0.67Ni0.33-x-yCuxZnyMn0.67O2(0<x<0.33,0<x<0.33,0.33≥x+y>0) The anode material has the advantages of long cycle life, high stability, good rate performance, high output voltage and low cost, and is an ideal anode of the sodium-ion battery.
(3) Preferred Na of the invention0.67Ni0.18Cu0.1Zn0.05Mn0.67O2The power density of the anode material is high, and is 5542W kg-1Still, 197Wh kg can be achieved-1The energy density of (1) is maintained at 154Wh kg after 2000 weeks of circulation-1And is suitable for high-power 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.
For further understanding of the present invention, the high power density and long cycle life sodium ion battery positive electrode material provided by the present invention and the preparation method and application thereof are described below with reference to the following examples, and the protection scope of the present invention is not limited by the following examples.
Example 1
Step 1, preparing Na by a sol-gel method0.67Ni0.18Cu0.1Zn0.05Mn0.67O2Positive electrode material
The target product is Na0.67Ni0.18Cu0.1Zn0.05Mn0.67O2The compound is prepared from sodium acetate, nickel acetate, copper acetate, zinc acetate, manganese acetate and citric acid, and deionized water as solvent.
Dissolving raw material metal ions and citric acid in deionized water according to a certain molar ratio of 1:2, placing the deionized water in a 60 ℃ oil bath kettle, stirring and evaporating to dryness to form gel. And (3) drying the gel in an oven at 150 ℃ for 8h, and grinding the gel 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 Na0.67Ni0.18Cu0.1Zn0.05Mn0.67O2。
Step 2, preparation of Na0.67Ni0.18Cu0.1Zn0.05Mn0.67O2Positive electrode material electrode plate
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 target product oxide-containing positive electrode material electrode plate.
Step 3, assembling the target product Na0.67Ni0.18Cu0.1Zn0.05Mn0.67O2A sodium ion battery which is a positive electrode.
Assembling the prepared target product anode electrode plate and a metal sodium cathode into a sodium ion battery, 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).
Fig. 1 shows an XRD picture of the target product obtained in example 1, which shows that the synthesized material has better crystallinity, and the obtained target product belongs to the hexagonal system P63/mmc.
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 117mA g-1The charging and discharging curve under the current density shows that the material has higher specific discharge capacity of 106.4mAh g when being applied to the sodium ion battery-1And has a high output voltage of 3.62V.
FIG. 4 shows the cyclic voltammogram of the target product obtained in example 1 at a sweep rate of 0.1mV/s, and it can be seen that the cyclic voltammogram corresponds to the charge-discharge curve.
FIG. 5 shows that the target product obtained in example 1 is 1700mA g-1Long cycle stability at current density, as can be seen, the initial capacity is 60.4mAh g-1The capacity retention rate after 2000 weeks of cycling was 80.5%, showing excellent cycling stability.
FIG. 6 shows that the target product obtained in example 1 is 1700mA g-1The energy density at current density is stable in circulation, and the initial energy density is 197.1Wh kg-1The energy density retention after 2000 cycles was 78.2%, showing excellent energy density retention.
Example 2
The preparation method was the same as in example 1 except that the temperature rise rate in both the pre-firing and calcining processes was changed to 5 deg.C/min.
Fig. 7 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 the hexagonal system P63/mmc.
FIG. 8 shows the target product obtained in example 2 at 17mA g-1The charge-discharge curve under the current density shows that the material has higher specific discharge capacity of 109.4mAh g when being applied to the sodium-ion battery-1。
Example 3
The preparation method was the same as in example 1 except that the temperature rise rate in both the pre-firing and calcining processes was changed to 8 deg.C/min.
Fig. 9 shows 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. 10 shows the target product obtained in example 3 at 17mA g-1The charging and discharging curve under the current density shows that the material has higher specific discharge capacity of 107.2mAh g when being applied to the sodium ion battery-1。
Example 4
The preparation method was the same as in example 1 except that the temperature rise rate in both the pre-firing and calcining processes was changed to 10 deg.C/min.
Fig. 11 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. 12 shows the target product obtained in example 4 at 17mA g-1The charging and discharging curve under the current density shows that the material has higher specific discharge capacity of 106.2mAh g when being applied to the sodium ion battery-1。
Example 5
The preparation method was the same as in example 1 except that the pre-firing temperature was changed to 350 ℃.
Fig. 13 is an XRD picture of the target product obtained in example 5, which shows that the synthesized material has better crystallinity, and the obtained target product belongs to the hexagonal system P63/mmc.
FIG. 14 shows the target product obtained in example 5 at 17mA g-1The charging and discharging curve under the current density shows that the material has higher specific discharge capacity of 105.3mAh g when being applied to the sodium ion battery-1。
Example 6
The preparation method was the same as in example 1 except that the pre-firing temperature was changed to 550 ℃.
Fig. 15 is an XRD picture of the target product obtained in example 6, which shows that the synthesized material has better crystallinity, and the obtained target product belongs to the hexagonal system P63/mmc.
FIG. 16 shows the target product obtained in example 6 at 17mA g-1The charging and discharging curve under the current density shows that the material has higher specific discharging capacity of 112.7mAh g when being applied to the sodium ion battery-1。
Example 7
Preparation method and phase of example 1Meanwhile, the raw materials are only proportioned according to Na0.67Ni0.13Cu0.1Zn0.1Mn0.67O2Is added in a stoichiometric ratio.
Fig. 17 is an XRD picture of the target product obtained in example 7, 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 7 at 17mA g-1The charge-discharge curve under the current density shows that the material has higher specific discharge capacity of 87.2mAh g when being applied to the sodium-ion battery-1。
Example 8
The preparation method is the same as example 1, except that the raw material ratio is Na0.67Ni0.2075Cu0.1Zn0.025Mn0.67O2Is added in a stoichiometric ratio.
Fig. 19 is an XRD picture of the target product obtained in example 6, which shows that the synthesized material has better crystallinity, and the obtained target product belongs to the hexagonal system P63/mmc.
FIG. 20 shows the target product obtained in example 6 at 17mA g-1The charging and discharging curve under the current density shows that the material has higher specific discharge capacity of 111mAh g when being applied to the sodium ion battery-1。
Example 9
The preparation method is the same as example 1, except that the raw material ratio is Na0.67Ni0.18Cu0.125Zn0.025Mn0.67O2Is added in a stoichiometric ratio.
Fig. 21 is an XRD picture of the target product obtained in example 6, which shows that the synthesized material has better crystallinity, and the obtained target product belongs to the hexagonal system P63/mmc.
FIG. 22 shows the target product obtained in example 6 at 17mA g-1The charging and discharging curve under the current density shows that the material has higher specific discharge capacity of 110mAh g when being applied to the sodium ion battery-1。
Example 10
Step 1, preparation of Na by solid phase method0.67Ni0.18Cu0.1Zn0.05Mn0.67O2Positive electrode material
The target product is Na0.67Ni0.18Cu0.1Zn0.05Mn0.67O2The compound is prepared from sodium acetate, nickel acetate, copper acetate, zinc acetate and manganese acetate.
And (3) placing the raw material metal acetate in a mortar according to the stoichiometric ratio, and fully grinding to uniformly mix the raw material metal acetate and the mortar to obtain precursor powder. And then, 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 Na0.67Ni0.18Cu0.1Zn0.05Mn0.67O2。
Step 2, preparation of Na0.67Ni0.18Cu0.1Zn0.05Mn0.67O2The procedure for the positive electrode material electrode sheet was the same as in example 1.
Fig. 23 is an XRD picture of the target product obtained in example 6, which shows that the synthesized material has better crystallinity, and the obtained target product belongs to the hexagonal system P63/mmc.
FIG. 24 shows the target product obtained in example 6 at 17mA g-1The charging and discharging curve under the current density shows that the material has higher specific discharge capacity of 110.4mAh g when being applied to the sodium ion battery-1。
Example 11
Step 1, preparation of Na by solid phase method0.67Ni0.18Cu0.1Zn0.05Mn0.67O2Positive electrode material
The target product is Na0.67Ni0.18Cu0.1Zn0.05Mn0.67O2The raw materials of the compound comprise sodium carbonate, nickel oxide, copper oxide, zinc oxide and manganese oxide.
Mixing the above raw materialsAnd (3) fully grinding the metal oxide in a mortar according to the stoichiometric ratio to uniformly mix the metal oxide and the mortar 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 Na0.67Ni0.18Cu0.1Zn0.05Mn0.67O2。
Fig. 25 is an XRD picture of the target product obtained in example 6, which shows that the synthesized material has better crystallinity, and the obtained target product belongs to the hexagonal system P63/mmc.
FIG. 26 shows the target product obtained in example 6 at 17mA g-1The charging and discharging curve under the current density shows that the material has higher specific discharge capacity of 100.6mAh g when being applied to the sodium ion battery-1。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. The positive electrode material of the sodium ion battery with high power density and long cycle life is characterized in that the chemical formula is Na0.67Ni0.18Cu0.1Zn0.05Mn0.67O2；
The preparation method of the positive electrode material of the sodium-ion battery comprises the following steps:
A) carrying out solid phase ball milling and mixing on sodium acetate, nickel acetate, copper acetate, zinc acetate and manganese acetate according to a molar ratio to obtain precursor powder;
B) and calcining the precursor powder twice to obtain the sodium-ion battery anode material.
2. The solid-phase preparation method of the positive electrode material of the sodium-ion battery according to claim 1, which is characterized by comprising the following steps:
A) carrying out solid phase ball milling and mixing on sodium acetate, nickel acetate, copper acetate, zinc acetate and manganese acetate according to a molar ratio to obtain precursor powder;
B) and calcining the precursor powder twice to obtain the sodium-ion battery anode material.
3. The preparation method according to claim 2, wherein the two times of calcination are divided into a first calcination and a second 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 salts are decomposed into oxides; and 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.
4. The positive plate of the sodium-ion battery is characterized by being prepared from a positive material, a conductive additive, a binder and a solvent, wherein the positive material is selected from the positive material in claim 1.
5. A sodium ion battery, which is characterized by comprising a positive electrode, a diaphragm, an organic electrolyte and metal sodium of a negative electrode, wherein the positive electrode is the positive plate of the sodium ion battery according to claim 4.
6. Use of the sodium ion battery of claim 5 in solar power generation, wind power generation, smart grid peak shaving, distributed power plants or communication base large scale energy storage devices.
CN201910379118.2A 2019-05-08 2019-05-08 High-power-density long-cycle-life sodium ion battery positive electrode material and preparation method and application thereof Active CN110061229B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910379118.2A CN110061229B (en) 2019-05-08 2019-05-08 High-power-density long-cycle-life sodium ion battery positive electrode material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910379118.2A CN110061229B (en) 2019-05-08 2019-05-08 High-power-density long-cycle-life sodium ion battery positive electrode material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110061229A CN110061229A (en) 2019-07-26
CN110061229B true CN110061229B (en) 2021-04-23

Family

ID=67322540

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910379118.2A Active CN110061229B (en) 2019-05-08 2019-05-08 High-power-density long-cycle-life sodium ion battery positive electrode material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110061229B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114447314A (en) * 2020-11-05 2022-05-06 南开大学 Sodium-ion battery positive active material with stable air and long cycle life, and preparation method and application thereof
CN114447300B (en) * 2022-01-18 2023-03-10 中国科学技术大学 Preparation method of sodium ion battery positive electrode material with tunnel phase and lamellar phase composite structure, prepared material and application thereof
CN114613981A (en) * 2022-01-25 2022-06-10 南方锰业集团有限责任公司 Zinc-doped and zinc-oxide-combined manganese-based layered oxide material, and preparation method and application thereof
CN114715953A (en) * 2022-03-14 2022-07-08 中国科学技术大学 Method for preparing Cu and Zn doped layered oxide sodium ion battery anode material with assistance of precursor and application of method
CN114520323A (en) * 2022-03-23 2022-05-20 中国科学技术大学 Double-strategy modified layered oxide sodium ion battery positive electrode material and preparation method and application thereof
CN114956203B (en) * 2022-04-29 2023-11-28 贵州振华新材料有限公司 Zinc-containing positive electrode material for sodium ion battery and preparation method and application thereof
CN114927663A (en) * 2022-05-26 2022-08-19 中国科学技术大学 Five-membered layered oxide sodium ion battery positive electrode material and preparation method and application thereof
CN115057485A (en) * 2022-06-17 2022-09-16 中国科学技术大学 Non-metal boron-doped layered oxide sodium ion battery positive electrode material and preparation method and application thereof
CN115224254B (en) * 2022-07-07 2024-04-23 中国科学技术大学 Cu, zn and Mg co-doped layered oxide sodium ion battery positive electrode material, and preparation method and application thereof
CN115394988A (en) * 2022-09-07 2022-11-25 天津理工大学 P2-type layered metal oxide sodium ion battery positive electrode material and preparation method thereof
CN116143192A (en) * 2023-02-21 2023-05-23 深圳华钠新材有限责任公司 Sodium-inlaid layered transition metal oxide material, preparation method and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015176678A (en) * 2014-03-13 2015-10-05 日産自動車株式会社 Positive electrode active material for sodium ion battery and sodium ion battery using the same
CN104795551B (en) * 2014-07-17 2017-07-14 中国科学院物理研究所 A kind of layered copper oxide material and its production and use
CN108987711B (en) * 2018-07-19 2021-05-11 中南大学 Spherical quaternary material for positive electrode of sodium-ion battery and preparation method thereof

Also Published As

Publication number Publication date
CN110061229A (en) 2019-07-26

Similar Documents

Publication Publication Date Title
CN110061229B (en) High-power-density long-cycle-life sodium ion battery positive electrode material and preparation method and application thereof
CN102738458B (en) Surface modification method of lithium-rich cathode material
CN111082058B (en) Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material and preparation method thereof
CN101752562B (en) Compound doped modified lithium ion battery anode material and preparation method thereof
CN115224254B (en) Cu, zn and Mg co-doped layered oxide sodium ion battery positive electrode material, and preparation method and application thereof
CN108598394B (en) Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof
CN106784726B (en) Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof
CN114715953A (en) Method for preparing Cu and Zn doped layered oxide sodium ion battery anode material with assistance of precursor and application of method
CN107093739B (en) Potassium manganese oxide for potassium ion battery anode material and preparation method thereof
CN113104824B (en) Se doped Fe 2 Preparation method of P self-supporting sodium ion battery cathode material
CN114927663A (en) Five-membered layered oxide sodium ion battery positive electrode material and preparation method and application thereof
CN114937774B (en) P2 and P3 mixed phase layered oxide sodium ion battery positive electrode material, and preparation method and application thereof
CN113078299A (en) Sodium-lithium-iron-manganese-based layered oxide material, preparation method and application
CN109560258A (en) A kind of anion appraises at the current rate layered oxide material, preparation method and purposes
CN114520323A (en) Double-strategy modified layered oxide sodium ion battery positive electrode material and preparation method and application thereof
CN112701282B (en) Large-radius ion-doped modified sodium vanadium fluorophosphate cathode material and preparation method thereof
CN109286002B (en) Multi-bark biomass carbon-loaded red phosphorus sodium ion battery negative electrode material and preparation method thereof
CN107946564B (en) Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof
CN115057485A (en) Non-metal boron-doped layered oxide sodium ion battery positive electrode material and preparation method and application thereof
CN113479860A (en) SbPO4Preparation method of/nitrogen-doped carbon composite material
CN110790248B (en) Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof
CN110504443B (en) Sodium-magnesium-manganese-based layered oxide material with anion valence change, preparation method and application
CN113054185A (en) Positive and negative dual-purpose sodium ion battery material without phase change and preparation method and application thereof
CN111525120A (en) Oxide material containing Mg, Cu and Mn as well as preparation method and application thereof
CN116805684A (en) Al, zn, ti and Fe co-doped biphase layered oxide sodium ion battery high-entropy positive electrode material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant