CN115312698A - Sodium ion battery layered oxide positive electrode material, preparation method and application - Google Patents

Sodium ion battery layered oxide positive electrode material, preparation method and application Download PDF

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CN115312698A
CN115312698A CN202211139801.7A CN202211139801A CN115312698A CN 115312698 A CN115312698 A CN 115312698A CN 202211139801 A CN202211139801 A CN 202211139801A CN 115312698 A CN115312698 A CN 115312698A
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sodium
ion battery
positive electrode
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yarn
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张国安
冒泽阳
黄志锋
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Suzhou Dega Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
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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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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

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Abstract

The invention discloses a layered oxide positive electrode material of a sodium ion battery, which has a general formula of Na x Li a Ni b Al c M d O 2‑y F y (ii) a Wherein: m is one or more of variable valence metals Mn, fe, cu, co, V, cr, zr and Zn; x, a, b, c, d and y are respectively the mol percentage of the corresponding elements, and each component in the general formula satisfies the conservation of charge and stoichiometry and is 0.67<x<2，0<y<0.5; the relationship of a, b, c, d satisfies a + b + c + d =1, where 0<a<1.0；0<b<1.0；0<c<1.0；0≤d<1.0. The invention improves the high-pressure performance of the layered oxide material by doping anions and cations simultaneously, promotes the reversible redox reaction of the anion oxygen, and improves the integral capacity of the battery. Ni 2+ Inherently has a higher redox potential. Introduction of Li into metal layer of layered oxide + And Al 3+ Li-O and Al-O bonds can effectively excite oxygen element to generate reversible redox reaction under high voltage, and F is introduced into oxygen layer ﹣ The electronegativity of the material is enhanced, and the reversibility of valence-variable oxygen is improved.

Description

Sodium ion battery layered oxide positive electrode material, preparation method and application
Technical Field
The invention relates to the technical field of sodium ion battery materials, in particular to a sodium ion battery layered oxide positive electrode material, a preparation method and application.
Background
With the successful commercialization of lithium ion batteries by sony corporation in 1991, lithium ion batteries have become an essential part in our production and life, and are widely applied to the fields of portable electronic equipment, electric automobiles, energy storage power stations and the like. But the lithium resources in the crust are very limited and the distribution is extremely uneven. The rapid development of the lithium ion battery is bound to be accompanied with the rapid consumption of lithium resources and the improvement of production cost, so that China is limited in the field of energy storage. Therefore, research into alternatives to, or supplements to, lithium ion batteries is becoming increasingly important.
In recent years, sodium-ion batteries have been considered by many as a promising alternative to lithium-ion batteries because sodium is abundant in nature, widely distributed, in the same main group as lithium, has similar physicochemical properties, and has a similar energy storage mechanism as lithium-ion batteries. The positive electrode materials of the current sodium-ion battery mainly comprise: layered oxides, prussian blue compounds, polyanionic compounds and organic compounds. Among them, the layered oxide has received a wide attention because of its high energy density, simple structure and easy synthesis. However, the layered oxide positive electrode material also has many problems, such as unstable structure, easy phase change, poor stability of the material, poor cycle performance, etc. For the energy density of the material, although the cut-off voltage in the charging process is improved, the energy density of the sodium ion battery can be effectively improved. However, as the cut-off voltage increases, the material itself may face a series of problems, such as irreversible phase transition, collapse of the material structure, and the like, so that the cycling stability of the sodium ion battery is worried. Because the improvement of the working voltage and the cycle stability of the layered oxide material is an urgent problem to be solved.
Disclosure of Invention
The invention aims to provide a layered oxide positive electrode material of a sodium ion battery, a preparation method and application thereof, which are used for improving the charge cut-off voltage and discharge capacity of the sodium ion battery, improving the cycling stability of the battery by a carbon coating method, prolonging the cycle life and having high practical value.
In order to solve the technical problems, the invention adopts the following technical scheme: a layered oxide positive electrode material for sodium ion battery with general formula of Na x Li a Ni b Al c M d O 2-y F y (ii) a Wherein: m is one or more of variable valence metals Mn, fe, cu, co, V, cr, zr and Zn; x, a, b, c, d and y are respectively the mole percentage of the corresponding elements, each component in the general formula satisfies the conservation of charge and stoichiometry and is 0.67<x<2，0<y<0.5; the relationship of a, b, c, d satisfies a + b + c + d =1, where 0<a<1.0；0<b<1.0；0<c<1.0；0≤d<1.0。
Further, in the above-mentioned case, the above-mentioned 0.7-yarn-woven x-yarn-woven fabric is 1.8, 0.05-yarn-woven fabric is 0.4.
Further, upper 0.05 yarn-woven (a) yarn-woven (0.2) and 0.2 yarn-woven (b) yarn-woven (0.8) and 0.05 yarn-woven (c) yarn-woven (0.2) and 0.2 yarn-woven (d) yarn-woven (0.8) are provided.
The invention provides a preparation method of a layered oxide positive electrode material of a sodium ion battery, which comprises the following steps:
mixing a sodium source, a lithium source, a nickel source, an aluminum source and a variable valence metal M source according to a stoichiometric ratio;
step two, uniformly mixing the mixed powder by adopting a ball milling mode to obtain mixture powder, wherein the ball milling time is 3-20 h, and the rotating speed of a ball mill is 200-1000 rpm;
calcining the obtained mixture powder in air and cooling to room temperature to obtain a precursor of the anode material, wherein the calcining temperature is 500-1500 ℃, the heat preservation time is 5-12h, the heating rate is 1-10 ℃/min, and the cooling rate is 1-10 ℃/min;
uniformly dispersing the precursor of the anode material in a polyvinylidene fluoride (PVDF) solution, and putting the solution into an oven to dry the solvent, wherein the temperature of the oven is 50-200 ℃, and the heat preservation time is 10-20h;
and step five, grinding the solid dried in the step four into powder, calcining in the air again, and cooling to room temperature to obtain the shell-core structured positive electrode material.
Further, the sodium source is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium oxide or sodium nitrate;
the lithium source is one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium oxide or lithium peroxide;
the nickel source is one or more of nickel carbonate, nickel hydroxide, nickel oxide or nickel nitrate;
the aluminum source is one or more of aluminum oxide or aluminum hydroxide;
the M source is an oxide of the M source, a hydroxide of the M source or a carbonate of the M source; the valence-variable metal M specifically comprises one or more of Mn, fe, cu, co, V, cr, zr and Zn.
The invention provides a positive pole piece of a sodium ion battery, which comprises: the current collector, the binder coated on the current collector, the conductive additive and the layered oxide cathode material, wherein the ratio of the binder to the conductive additive to the layered oxide cathode material is 1.
Further, the current collector is an aluminum foil.
Further, the binder is one or more of polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), styrene Butadiene Rubber (SBR) or sodium alginate.
Further, the conductive additive is one or more of conductive carbon black, acetylene black, graphene, chopped carbon fibers or carbon nanotubes.
The invention also provides a sodium ion battery comprising the positive pole piece.
Has the advantages that: compared with the prior art, the invention dopes anions and cations simultaneouslyThe high-pressure performance of the layered oxide material is improved, the reversible redox reaction of anionic oxygen is promoted, and the integral capacity of the battery is improved. Ni 2+ Inherently has a higher redox potential. Introducing Li into the metal layer of a layered oxide + And Al 3+ Li-O and Al-O bonds can effectively excite oxygen element to generate reversible redox reaction under high voltage, and F is introduced into oxygen layer ﹣ The electronegativity of the material is enhanced, and the reversibility of valence-variable oxygen is improved. F is achieved in one step by calcining the precursor together with PVDF ﹣ Doping and carbon cladding. Through carbon coating, the ion and electron transmission dynamics are effectively improved, the structural stability of the material is enhanced, the cycle stability of the high-voltage layered oxide is effectively improved, and the cycle life is prolonged.
Drawings
Fig. 1 is a charge-discharge curve of a sodium ion battery provided in embodiment 1 of the present invention at 1.5-4.6V;
FIG. 2 is a charge-discharge curve of a sodium ion battery of comparative example 1 of the present invention at 2-4.3V;
FIG. 3 is a charge-discharge curve of 2-4.0V for a sodium-ion battery according to comparative example 2 of the present invention;
fig. 4 is a charge-discharge curve of the sodium ion battery provided in embodiment 2 of the present invention at 1.5-4.5V.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully hereinafter with reference to the accompanying drawings. The invention may be embodied in different forms and is not limited to the embodiments described herein. Rather, the embodiments are provided so that this disclosure will be thorough and complete.
Example 1
This example provides a high voltage, high capacity sodium ion battery layered oxide positive electrode material Na 0.9 Li 0.1 Ni 0. 3 Al 0.1 Mn 0.5 O 1.9 F 0.1 Preparation and use of (a).
(1) Preparing materials:
weighing sodium carbonate, lithium carbonate, nickel oxide, aluminum oxide and manganese dioxide according to the required stoichiometric ratio, fully mixing and then placing in a ball milling tank, wherein the ball material ratio is 30;
placing the fully mixed material in a tubular furnace, calcining in the air atmosphere, heating to 900 ℃ at the heating rate of 10 ℃/min, preserving heat for 10h, and cooling to room temperature;
grinding the calcined material into powder, dispersing the powder into a PVDF NMP solution, putting the powder into an oven for 12 hours, and drying the solvent, wherein the temperature of the oven is 120 ℃;
grinding the dried solid into powder, calcining in a tube furnace again at a heating rate of 10 ℃/min to 500 ℃, keeping the temperature for 7h, cooling to a heating temperature, grinding into powder, and bottling for later use.
(2) Assembling a sodium ion battery:
the prepared Na 0.9 Li 0.1 Ni 0.3 Al 0.1 Mn 0.5 O 1.9 F 0.1 The powder, with conductive additive conductive carbon black and binder PVD according to 8.
The whole process of the cell assembly is carried out in a glove box filled with argon, a metal sodium sheet is used as a counter electrode, and 1mol/L of NaClO 4 The solution dissolved in the PC solvent is electrolyte, and the glass fiber is a diaphragm, so that the CR2032 button cell is assembled.
(3) And (3) electrochemical performance testing:
the assembled battery is subjected to constant-current charge and discharge test on a blue-ray test system, the current density is 50mA/g, the charge and discharge voltage window is 1.5-4.6V, the first-circle discharge specific capacity of the battery is 210mAh/g, and the capacity retention rate is 93.7% after 100 circles.
Comparative example 1
The comparative example provides a layered oxide cathode material NaLi for a sodium-ion battery 0.1 Ni 0.3 Al 0.1 Mn 0.5 O 2 Preparation and use of (a).
(1) Preparing materials:
weighing sodium carbonate, lithium carbonate, nickel oxide, aluminum oxide and manganese dioxide according to the required stoichiometric ratio, fully mixing and then placing in a ball milling tank, wherein the ball material ratio is 30;
placing the fully mixed material in a tubular furnace, calcining in the air atmosphere, heating to 900 ℃ at the heating speed of 10 ℃/min, preserving heat for 10h, cooling to room temperature, grinding the calcined material into powder, and bottling for later use;
(2) Assembling a sodium ion battery:
pole pieces and assembled cells were prepared according to the protocol in example 1.
(3) Electrochemical performance test
The assembled battery is subjected to constant-current charge and discharge test on a blue-ray test system, the current density is 50mA/g, the charge and discharge voltage window is 2-4.3V, the discharge specific capacity of the first circle of the battery is 145mAh/g, and the capacity retention rate is 42.5% after 100 circles.
Comparative example 2
The comparative example provides a layered oxide cathode material Na for a sodium-ion battery 0.9 Ni 0.4 Al 0.1 Mn 0.5 O 2 Preparation and use of (a).
(1) Preparing materials:
the positive electrode material was prepared according to the scheme of comparative example 1 but the stoichiometry of the precursors of sodium carbonate, nickel oxide, aluminum oxide, manganese dioxide used was different from that of comparative example 1.
(2) Assembling a sodium ion battery:
pole pieces and assembled cells were prepared according to the protocol in example 1.
(3) And (3) electrochemical performance testing:
the assembled battery is subjected to constant-current charge and discharge test on a blue-ray test system, the current density is 50mA/g, the charge and discharge voltage window is 1.5-4.0V, the discharge specific capacity of the first circle of the battery is 160mAh/g, and the capacity retention rate is 36.3% after 100 circles.
Example 2
The present embodiment provides a high voltage, high capacity sodium ion batteryCell layered oxide positive electrode material Na 0.75 Li 0.15 Ni 0.1 Al 0.15 Fe 0.1 Mn 0.5 O 1.85 F 0.15 Preparation and use of (2).
(1) Preparing materials:
weighing sodium carbonate, lithium carbonate, nickel oxide, aluminum oxide, ferric oxide and manganese dioxide according to the required stoichiometric ratio, fully mixing and placing in a ball milling tank, wherein the ball-material ratio is 40;
placing the fully mixed material in a tubular furnace, calcining in the air atmosphere, heating to 900 ℃ at the heating speed of 10 ℃/min, keeping the temperature for 12h, and cooling to room temperature;
grinding the calcined material into powder, dispersing the powder into a PVDF NMP solution, putting the powder into an oven for 12 hours, and drying the solvent, wherein the temperature of the oven is 120 ℃;
grinding the dried solid into powder, placing the powder into a tubular furnace again for calcination, heating to 500 ℃ at the heating speed of 10 ℃/min, keeping the temperature for 7h, cooling to the heating temperature, grinding into powder, and bottling for later use.
(2) Assembling a sodium ion battery:
the prepared Na 0.75 Li 0.15 Ni 0.1 Al 0.15 Fe 0.1 Mn 0.5 O 1.85 F 0.15 The powder, with conductive additive conductive carbon black and binder PVD according to 8.
The whole process of the cell assembly is carried out in a glove box filled with argon, a metal sodium sheet is used as a counter electrode, and 1mol/L of NaClO 4 The solution dissolved in the PC solvent is electrolyte, and the glass fiber is a diaphragm, so that the CR2032 button cell is assembled.
(3) And (3) electrochemical performance testing:
the assembled battery is subjected to constant-current charge and discharge test on a blue-ray test system, the current density is 50mA/g, the charge and discharge voltage window is 1.5-4.5V, the first-circle discharge specific capacity of the battery is 204mAh/g, and the capacity retention rate is 90.3% after 100 circles.
Example 3
This example provides a high voltage sodium, high capacity layered oxide positive electrode material Na for ion batteries 1.59 Li 0.22 Ni 0.25 Al 0.15 Cu 0.2 Fe 0.18 O 1.7 F 0.3 Preparation and use of (a).
(1) Preparing materials:
weighing sodium carbonate, lithium carbonate, nickel oxide, aluminum oxide, copper oxide and iron oxide according to the required stoichiometric ratio, fully mixing and then placing the mixture into a ball milling tank, wherein the ball material ratio is 40;
placing the fully mixed material in a tubular furnace, calcining in the air atmosphere, heating to 500 ℃ at the heating speed of 10 ℃/min, preserving heat for 7h, and cooling to room temperature;
grinding the calcined material into powder, dispersing the powder into a PVDF NMP solution, putting the solution into an oven for 12 hours, and drying the solvent, wherein the temperature of the oven is 120 ℃;
grinding the dried solid into powder, calcining in a tube furnace again at a heating rate of 10 ℃/min to 500 ℃, keeping the temperature for 7h, cooling to a heating temperature, grinding into powder, and bottling for later use.
(2) Assembling a sodium ion battery:
pole pieces and assembled cells were prepared according to the protocol in example 1.
(3) And (3) electrochemical performance testing:
the assembled battery is subjected to constant-current charge and discharge test on a blue-ray test system, the current density is 50mA/g, the charge and discharge voltage window is 1.5-4.5V, the discharge specific capacity of the first circle of the battery is 195mAh/g, and the capacity retention rate is 87.1% after 100 circles.
Example 4
This example provides a high voltage, high capacity sodium ion battery layered oxide positive electrode material Na 0.9 Li 0.05 Ni 0.33 Al 0.05 Co 0.07 Mn 0.5 O 1.9 F 0.1 Preparation and use of (a).
(1) Preparing materials:
weighing sodium carbonate, lithium carbonate, nickel oxide, aluminum oxide, cobalt oxide and manganese dioxide according to the required stoichiometric ratio, fully mixing and placing in a ball milling tank, wherein the ball-material ratio is 40;
placing the fully mixed material in a tubular furnace, calcining in the air atmosphere, heating to 900 ℃ at the heating rate of 10 ℃/min, preserving heat for 10h, and cooling to room temperature;
grinding the calcined material into powder, dispersing the powder into a PVDF NMP solution, putting the powder into an oven for 12 hours, and drying the solvent, wherein the temperature of the oven is 120 ℃;
grinding the dried solid into powder, placing the powder into a tubular furnace again for calcination, heating to 500 ℃ at the heating speed of 10 ℃/min, keeping the temperature for 7h, cooling to the heating temperature, grinding into powder, and bottling for later use.
(2) Assembling a sodium ion battery:
pole pieces and assembled cells were prepared according to the protocol in example 1.
(3) And (3) electrochemical performance testing:
the assembled battery is subjected to constant-current charge and discharge test on a blue-ray test system, the current density is 50mA/g, the charge and discharge voltage window is 1.5-4.5V, the discharge specific capacity of the first circle of the battery is 180mAh/g, and the capacity retention rate is 72.5% after 100 circles.
Example 5
This example provides a high voltage, high capacity sodium ion battery layered oxide positive electrode material Na 0.97 Li 0.15 Ni 0.25 Al 0.15 Mn 0.45 O 1.87 F 0.13 Preparation and use of (a).
(1) Preparing materials:
a cathode material was prepared according to the protocol of example 1 but the stoichiometry of the precursors sodium carbonate, lithium carbonate, nickel oxide, aluminum oxide, manganese dioxide used was different from that of example 1.
(2) Assembling a sodium ion battery:
pole pieces and assembled cells were prepared according to the protocol in example 1.
(3) And (3) electrochemical performance testing:
the assembled battery is subjected to constant-current charge and discharge test on a blue-ray test system, the current density is 50mA/g, the charge and discharge voltage window is 1.5-4.5V, the discharge specific capacity of the first circle of the battery is 201mAh/g, and the capacity retention rate is 91.2% after 100 circles.
Example 6
This example provides a high voltage, high capacity sodium ion battery layered oxide positive electrode material Na 0.53 Li 0.2 Ni 0.21 Al 0.15 Mn 0.44 O 1.8 F 0.2 Preparation and use of (a).
(1) Preparing materials:
a cathode material was prepared according to the protocol of example 1 but the stoichiometry of the precursors sodium carbonate, lithium carbonate, nickel oxide, aluminum oxide, manganese dioxide used was different from that of example 1.
(2) Assembling a sodium ion battery:
pole pieces and assembled cells were prepared according to the protocol in example 1.
(3) And (3) electrochemical performance testing:
the assembled battery is subjected to constant-current charge and discharge test on a blue-ray test system, the current density is 50mA/g, the charge and discharge voltage window is 1.5-4.3V, the first-circle discharge specific capacity of the battery is 189mAh/g, and the capacity retention rate is 88.9% after 100 circles.
Example 7
This example provides a high voltage, high capacity sodium ion battery layered oxide positive electrode material Na 1.1 Li 0.3 Ni 0.1 Al 0.2 Mn 0.4 O 1.8 F 0.2 Preparation and use of (a).
(1) Preparing materials:
a cathode material was prepared according to the protocol of example 1 but the stoichiometry of the precursors sodium carbonate, lithium carbonate, nickel oxide, aluminum oxide, manganese dioxide used was different from that of example 1.
(2) Assembling the sodium-ion battery:
pole pieces and assembled cells were prepared according to the protocol in example 1.
(3) And (3) electrochemical performance testing:
the assembled battery is subjected to constant-current charge and discharge test on a blue-ray test system, the current density is 50mA/g, the charge and discharge voltage window is 1.5-4.3V, the discharge specific capacity of the first circle of the battery is 164mAh/g, and the capacity retention rate is 83.3% after 100 circles.
TABLE 1 comparison of electrochemical performances of examples 1 to 7 and comparative examples 1 to 2
Figure BDA0003853093170000121
As shown in Table 1, it can be seen that by comparing example 1 with comparative examples 1 and 2, al is introduced into the layered oxide material 3+ ，Li + The oxygen element can be effectively excited to generate reversible oxidation-reduction reaction under high voltage, and the reversible capacity of the anode material is increased. While achieving F by a simple one-step process ﹣ Doping and carbon coating effectively improve the overall ion and electron transmission dynamics of the material, enhance the structural stability of the material, improve the cycle stability of the high-voltage and high-capacity layered oxide and prolong the cycle life.
It can be seen from comparative example 1 and examples 5 to 7 that although Al is contained in 3+ ，Li + Doping of metal layers of layered oxides with Al 3+ ，Li + Reversible redox of oxygen ions can be excited, but Al 3+ ，Li + During the operation of the sodium ion battery, the sodium ion battery belongs to invariable valence ions, and the addition of excessive invariable valence ions can reduce the proportion of active sites in the material, thereby reducing the specific capacity of the material. While excessive Al 3+ ，Li + But also reduces the stability of the crystal structure of the material and the cycle stability of the material.
Comparative examples 1 to 3 it was found that the rotational speed of the ball mill and the mixing time during the preparation of the material during mixing affect the consistency of the initial precursor powder. When the calcination is performed, the calcination temperature is too low, and the holding time is too short, which results in poor stability and uniformity of the phase structure of the layered oxide. Therefore, the reasonable control of the parameters in the mixing and calcining processes has great significance for improving the electrochemical performance of the material.
In the above embodiments, all functions may be implemented, or a part of the functions may be implemented as necessary.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

Claims (10)

1. A layered oxide positive electrode material for sodium ion battery with general formula of Na x Li a Ni b Al c M d O 2-y F y (ii) a Wherein: m is one or more of variable valence metals Mn, fe, cu, co, V, cr, zr and Zn; x, a, b, c, d and y are respectively the mole percentage of the corresponding elements, each component in the general formula satisfies the conservation of charge and stoichiometry and is 0.67<x<2，0<y<0.5; the relationship of a, b, c, d satisfies a + b + c + d =1, where 0<a<1.0；0<b<1.0；0<c<1.0；0≤d<1.0。
2. The layered oxide positive electrode material of the sodium-ion battery as claimed in claim 1, wherein: 0.7 yarn-woven x yarn-woven 1.8,0.05 yarn-woven y yarn-woven 0.4.
3. The layered oxide positive electrode material of the sodium-ion battery as claimed in claim 1, wherein: 0.05 yarn-a-yarn-woven 0.2,0.2 yarn-b-yarn 0.8,0.05 yarn-c-yarn-woven 0.2,0.2 yarn-woven 0.8.
4. A preparation method of a layered oxide positive electrode material of a sodium ion battery is characterized by comprising the following steps:
mixing a sodium source, a lithium source, a nickel source, an aluminum source and a variable valence metal M source according to a stoichiometric ratio;
step two, uniformly mixing the mixed powder by adopting a ball milling mode to obtain mixture powder, wherein the ball milling time is 3-20 h, and the rotating speed of a ball mill is 200-1000 rpm;
calcining the obtained mixture powder in air and cooling to room temperature to obtain a precursor of the anode material, wherein the calcining temperature is 500-1500 ℃, the heat preservation time is 5-12h, the heating rate is 1-10 ℃/min, and the cooling rate is 1-10 ℃/min;
uniformly dispersing the precursor of the anode material in a polyvinylidene fluoride (PVDF) solution, and putting the solution into an oven to dry the solvent, wherein the temperature of the oven is 50-200 ℃, and the heat preservation time is 10-20h;
and step five, grinding the dried solid in the step four into powder, calcining in air again, and cooling to room temperature to obtain the shell-core structured positive electrode material.
5. The layered oxide positive electrode material of the sodium-ion battery as claimed in claim 4, wherein:
the sodium source is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium oxide or sodium nitrate;
the lithium source is one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium oxide or lithium peroxide;
the nickel source is one or more of nickel carbonate, nickel hydroxide, nickel oxide or nickel nitrate;
the aluminum source is one or more of aluminum oxide or aluminum hydroxide;
the M source is one or more of an oxide of an M source, a hydroxide of the M source or a carbonate of the M source, and the valence-variable metal M specifically comprises one or more of Mn, fe, cu, co, V, cr, zr and Zn.
6. The utility model provides a positive pole piece of sodium ion battery which characterized in that: the layered oxide cathode material comprises a current collector, a binder coated on the current collector, a conductive additive and the layered oxide cathode material in a ratio of 1.
7. The positive electrode plate of the sodium-ion battery as claimed in claim 6, wherein: the current collector is an aluminum foil.
8. The positive electrode plate of the sodium-ion battery as recited in claim 6, wherein: the binder is one or more of polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), styrene Butadiene Rubber (SBR) or sodium alginate.
9. The positive electrode plate of the sodium-ion battery as claimed in claim 6, wherein: the conductive additive is one or more of conductive carbon black, acetylene black, graphene, chopped carbon fibers or carbon nanotubes.
10. A sodium ion battery, characterized in that: a sodium ion battery comprising the positive electrode sheet of any one of claims 6 to 9.
CN202211139801.7A 2022-09-19 2022-09-19 Sodium ion battery layered oxide positive electrode material, preparation method and application Pending CN115312698A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116525814A (en) * 2023-06-29 2023-08-01 宁波容百新能源科技股份有限公司 Positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery
CN117199379A (en) * 2023-11-06 2023-12-08 山东海化集团有限公司 Oxygen-valence-variable sodium ion battery layered oxide positive electrode material and preparation method thereof
CN117383627A (en) * 2023-12-13 2024-01-12 泾河新城陕煤技术研究院新能源材料有限公司 Preparation method of sodium-electricity layered anode material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116525814A (en) * 2023-06-29 2023-08-01 宁波容百新能源科技股份有限公司 Positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery
CN116525814B (en) * 2023-06-29 2023-11-28 宁波容百新能源科技股份有限公司 Positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery
CN117199379A (en) * 2023-11-06 2023-12-08 山东海化集团有限公司 Oxygen-valence-variable sodium ion battery layered oxide positive electrode material and preparation method thereof
CN117199379B (en) * 2023-11-06 2024-06-07 山东海化集团有限公司 Oxygen-valence-variable sodium ion battery layered oxide positive electrode material and preparation method thereof
CN117383627A (en) * 2023-12-13 2024-01-12 泾河新城陕煤技术研究院新能源材料有限公司 Preparation method of sodium-electricity layered anode material
CN117383627B (en) * 2023-12-13 2024-03-12 泾河新城陕煤技术研究院新能源材料有限公司 Preparation method of sodium-electricity layered anode material

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