CN116417590A - Positive electrode material of anion-cation co-doped coated sodium-ion battery and preparation method thereof - Google Patents

Positive electrode material of anion-cation co-doped coated sodium-ion battery and preparation method thereof Download PDF

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CN116417590A
CN116417590A CN202310144141.XA CN202310144141A CN116417590A CN 116417590 A CN116417590 A CN 116417590A CN 202310144141 A CN202310144141 A CN 202310144141A CN 116417590 A CN116417590 A CN 116417590A
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ion battery
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祁行涛
尤晓瑞
仰韻霖
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Guangdong Kaijin New 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
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    • H01M4/00—Electrodes
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    • 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
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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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Abstract

The invention discloses a positive electrode material of a sodium ion battery coated by co-doping anions and cations, which comprises an inner layer-shaped transition metal oxide and an outer layer-shaped transition metal oxide coating the inner layer-shaped transition metal oxide, wherein the chemical formula of the inner layer-shaped transition metal oxide is Na x Fe y Mn z M f O 2 Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.5, f is more than or equal to 0 and less than or equal to 0.3, the values of x, y, z and f meet the charge balance of chemical formulas, and M is at least one of Li, co, ni, mg, ca, sr, ba, al, be, B, ti, zr, cu, zn, ga, sn; the chemical formula of the outer layer transition metal oxide is Na j Ni a Fe b Mn c A d C e O 2‑e Wherein j is more than or equal to 1.0 and less than or equal to 1.08,0.3, a is more than or equal to 1 and less than or equal to 0.9,0.3 and less than or equal to 0.9, C is more than or equal to 0 and less than or equal to 0.3, d is more than or equal to 0.001 and less than or equal to 0.01, e is more than or equal to 0.001 and less than or equal to 0.7, the values of j and a, b, C, d, e meet the charge balance of chemical formulas, A is a cation, and C is an anion. The sodium ion battery anode material has the advantages of wide voltage window, high capacity, high first efficiency, high rate performance, cyclic stability and the like.

Description

Positive electrode material of anion-cation co-doped coated sodium-ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of sodium ion battery anode materials, in particular to an anion-cation co-doped coated sodium ion battery anode material and a preparation method thereof.
Background
Based on the increasing consumption of fossil energy, the rapid development of various new energy sources (wind energy, tidal energy, solar energy and the like) is accelerated, but the rapid development is limited by the fact that the energy sources cannot be applied in a large scale due to factors such as geography, weather and the like. Electrochemical energy is represented by lithium ion batteries, and the lithium ion batteries occupy a large share in the market by virtue of the advantages of high voltage, no memory effect, high capacity and the like, and particularly, the lithium ion batteries rapidly develop in the fields of electric automobiles and large-scale energy storage. However, the limited storage and uneven distribution of lithium resources indirectly lead to the rise of water and ship costs. Scientific researchers find that sodium has a similar working principle to a lithium ion battery due to the advantages of abundant reserves and low price, so that the sodium ion battery is gradually studied.
Wherein, the layered metal oxide type sodium ion battery positive electrode material (Na x TMO 2 Tm=transition metals such as Co, fe, mn, ni, etc., 0<x<1) Because of its low cost, low toxicity and high theoretical specific capacity, it is one of the potential candidates for positive electrodes of sodium ion batteries, and has attracted great interest to researchers. However, at the end of the discharge process, mn appears in this material 3+ The ginger taylor effect and phase change of the battery lead to capacity fading in the charge and discharge processes of the battery. Secondly, the layered metal oxide has poor air stability, is easy to react with water and carbon dioxide in the air, promotes the formation of alkaline substances, and also aggravates the performance attenuation of the battery cell. In order to improve the performance and improve the defects, the coating, doping and other methods are generally used for carrying out modification treatment.
As for the coating method, the conventional improvement method is to coat a single oxide (Al 2 O 3 、TiO 2 LLZO) is used as a physical protective layer to slow down the corrosion of electrolyte, and the improvement effect is not obvious and can be reducedEnergy density. There are also the disadvantages of coating a layer of conductive polymer such as polythiophene, polyaniline, etc., that the compatibility with electrolyte is too poor, and the dissolution is easy, which affects the battery performance.
Meanwhile, the current doping modification method has limited improvement degree on performance, and is far lower than the requirement of the current practical application of the battery cell on the performance. As in the literature (ACS appl. Mater. Interfaces 2019,11,24122-24131, chem. Mater.2022,34, 4153-4165) cationic doping, although suppressing lattice distortion of the crystal structure during charge and discharge, only limited improvements in energy density and stability of the material are noted, the literature (ACS Materials Lett.2019,1,89-95) also indicates anionic doping by substituting for O 2- Doping suppresses the structural damage of the crystal caused by the precipitation of irreversible oxygen, but the capacity improvement is limited.
Disclosure of Invention
In view of the above problems, the invention aims to provide an anion-cation co-doped coated sodium ion battery anode material and a preparation method thereof, wherein the sodium ion battery anode material has the advantages of wide voltage window, high capacity, high first efficiency, high rate performance, cyclic stability and the like.
In order to achieve the aim, the invention provides an anode material of an anion-cation co-doped coated sodium ion battery, which comprises an inner layered transition metal oxide and an outer layered transition metal oxide coating the inner layered transition metal oxide,
the chemical formula of the inner layer-shaped transition metal oxide is Na x Fe y Mn z M f O 2 Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.5, f is more than or equal to 0 and less than or equal to 0.3, the values of x, y, z and f meet the charge balance of chemical formulas, and M is at least one of Li, co, ni, mg, ca, sr, ba, al, be, B, ti, zr, cu, zn, ga, sn;
the chemical formula of the outer layer transition metal oxide is Na j Ni a Fe b Mn c A d C e O 2-e Wherein j is more than or equal to 1.0 and less than or equal to 1.08,0.3, a is more than or equal to 1.0 and less than or equal to 0.9,0.3 and less than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.3, d is more than or equal to 0.001 and less than or equal to 0.01, e is more than or equal to 0.001 and less than 0.7, j and a, b, c, d, e are taken outThe value satisfies the charge balance of the chemical formula, A is a cation, and C is an anion.
In some embodiments, a is at least one of Li, K, cu, nb, mg, al, ti, zn, zr, sr, W, mo, V, ca, B.
In some embodiments, C is at least one of F, N, P.
In some embodiments, the outer layer transition metal oxide is 0.5% -10% of the inner layer transition metal oxide by mass.
Correspondingly, the invention also provides a preparation method of the positive electrode material of the anion-cation co-doped coated sodium-ion battery, which comprises the following steps:
(1) Sodium salt, nickel salt, ferric salt and manganese salt. Premixing the cationic salt and the anionic salt according to a certain proportion to obtain a solid mixture;
(2) Mixing the solid mixture with a solvent to obtain a slurry;
(3) Mixing the slurry with an inner layer transition metal oxide, and performing spray drying treatment to obtain a mixed material;
(4) And calcining the mixed material, cooling, crushing, and sieving to obtain the sodium ion battery anode material.
In some embodiments, the sodium salt is selected from at least one of sodium nitrate, sodium hydroxide, sodium fluoride, sodium iodide, sodium peroxide, sodium carbonate, sodium acetate.
In some embodiments, the manganese salt is selected from at least one of manganese nitrate, manganese sulfate, manganese chloride, manganese oxide.
In some embodiments, the nickel salt is selected from at least one of nickel nitrate, nickel sulfate, nickel chloride, nickel hydroxide.
In some embodiments, the iron salt is selected from at least one of ferric nitrate, ferric sulfate, ferric chloride, ferric hydroxide.
In some embodiments, the cationic salt is at least one of a Li salt, a K salt, an Al salt, a Cu salt, a Nb salt, a Mg salt, a Ti salt, a Zn salt, a Zr salt, a Sr salt, a W salt, a Mo salt, a V salt, a Ca salt, a B salt.
In some embodiments, the anionic salt is at least one of F, N, P salts.
In some embodiments, the solvent is at least one of deionized water, ethanol, butanediol, isopropanol, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone.
In some embodiments, the calcination temperature is 800 to 1000 ℃.
In some embodiments, the spray drying process is at a temperature of 180 to 220 ℃.
The beneficial effects of the invention are as follows:
the cathode material is a ternary material formed by coating an inner layer transition metal oxide with an outer layer transition metal oxide formed by co-doping anions and cations, and the surface of the cathode material is provided with a compact multi-material protection layer with an anion-cation co-doping structure, so that the air stability is improved, the contact area between the inner layer transition metal oxide and electrolyte is reduced, the occurrence of interface side reaction is slowed down, and the material circulation stability is improved; and cations of the outer layer transition metal oxide enter Transition Metal (TM) sites, doping cations helps to reduce the effective coordination of O atoms, and enhances the TM-O bond strength number to make TMO 2 The layer is narrowed, and meanwhile, anions and oxygen form a covalent bond, so that the anion-anion synergic modification regulates and controls the crystal structure mechanism of the material, the sodium interlayer spacing can be enlarged, sodium ion transmission is facilitated, the loss of lattice oxygen is reduced, the structural stability can be improved, the voltage window can be enlarged, and the specific capacity, high first efficiency and cycle stability can be improved. Therefore, the positive electrode material of the sodium ion battery has the advantages of wide voltage window, high capacity, high first efficiency, high rate performance, cyclic stability and the like.
Drawings
Fig. 1 is an SEM image of a positive electrode material of a sodium ion battery prepared in example 1 of the present invention.
Fig. 2 is a graph showing XRD test results of the positive electrode material for sodium ion battery prepared in example 1 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
The invention provides a positive electrode material of a sodium ion battery coated by co-doping anions and cations, which comprises an inner layered transition metal oxide and an outer layered transition metal oxide coating the inner layered transition metal oxide, wherein the chemical formula of the inner layered transition metal oxide is Na x Fe y Mn z M f O 2 Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.5, f is more than or equal to 0 and less than or equal to 0.3, the values of x, y, z and f meet the charge balance of chemical formulas, and M is at least one of Li, co, ni, mg, ca, sr, ba, al, be, B, ti, zr, cu, zn, ga, sn. Further, x is more than or equal to 0.9 and less than or equal to 1, y is more than or equal to 0.3 and less than or equal to 0.4,0.2, z is more than or equal to 0.3,0.2 and f is more than or equal to 0.3.
Wherein, the preparation steps of the inner layer transition metal oxide are as follows:
(1) Weighing M salt, manganese salt, ferric salt and sodium salt, and premixing according to a certain proportion to obtain a solid mixture;
(2) Calcining the solid mixture under the condition of introducing gas, cooling, crushing and sieving to obtain the inner layer transition metal oxide.
In some embodiments, the M salt is at least one of a Li salt, a Co salt, a Ni salt, a Mg salt, a Ca salt, a Sr salt, a Ba salt, an Al salt, a Be salt, a B salt, a Ti salt, a Zr salt, a Cu salt, a Zn salt, a Ga salt, and a Sn salt.
In some embodiments, the manganese salt is selected from at least one of manganese nitrate, manganese sulfate, manganese chloride, and manganese oxide.
In some embodiments, the iron salt is selected from at least one of ferric nitrate, ferric sulfate, ferric chloride, and ferric hydroxide;
in some embodiments, the sodium salt is at least one of sodium nitrate, sodium hydroxide, sodium fluoride, sodium iodide, sodium peroxide, sodium carbonate, and sodium acetate.
In some embodiments, the gas is at least one of air, oxygen, nitrogen, argon, hydrogen argon, and preferably air.
In some embodiments, the calcination temperature is 800 to 1000 ℃, preferably 950 ℃; the calcination time is 10-25 h, preferably 12h, and the cooling mode is natural cooling.
In some embodiments, the internal layer transition metal oxide has a Dv50 of 4 to 8 μm, preferably 5 to 7 μm.
Wherein the outer layer transition metal oxide is a layered transition metal oxide material co-doped with anions and cations, and the chemical formula is Na j Ni a Fe b Mn c A d C e O 2-e Wherein j is more than or equal to 1.0 and less than or equal to 1.08,0.3, a is more than or equal to 0.9,0.3 and less than or equal to 0.9, C is more than or equal to 0 and less than or equal to 0.3, d is more than or equal to 0.001 and less than or equal to 0.01, e is more than or equal to 0.001 and less than or equal to 0.7, the values of a, b, C, d and e satisfy the charge balance of chemical formulas, A is a cation, and C is an anion.
The invention also provides a preparation method of the positive electrode material of the anion-cation co-doped coated sodium-ion battery, which comprises the following steps:
(1) Premixing sodium salt, nickel salt, ferric salt and manganese salt with cation salt and anion salt according to a certain proportion to obtain a solid mixture;
(2) Mixing the solid mixture with a solvent to obtain a slurry;
(3) Mixing the slurry with an inner layer transition metal oxide, and performing spray drying treatment to obtain a mixed material;
(4) Calcining the mixed material, cooling, crushing and sieving to obtain the sodium ion battery anode material.
In some embodiments, the sodium salt is at least one of sodium nitrate, sodium hydroxide, sodium fluoride, sodium iodide, sodium peroxide, sodium carbonate, and sodium acetate.
In some embodiments, the manganese salt is selected from at least one of manganese nitrate, manganese sulfate, manganese chloride, and manganese oxide.
In some embodiments, the nickel salt is selected from at least one of nickel nitrate, nickel sulfate, nickel chloride, nickel hydroxide;
in some embodiments, the iron salt is selected from at least one of ferric nitrate, ferric sulfate, ferric chloride, and ferric hydroxide.
In some embodiments, the cationic salt is at least one of a Li salt, a K salt, a Cu salt, a Nb salt, an Al salt, a Mg salt, a Ti salt, a Zn salt, a Zr salt, a Sr salt, a W salt, a Mo salt, a V salt, a Ca salt, and a B salt. Illustratively, the cationic salt is a Li salt, ti salt, B salt, or the like, specifically, the Li salt may be at least one of, but not limited to, lithium hydroxide, lithium fluoride, lithium carbonate, lithium nitrate; the Ti salt may be, but is not limited to, at least one of titanium oxide, titanium chloride; the B salt may be at least one of, but not limited to, diboron trioxide, sodium borohydride.
In some embodiments, the anionic salt is at least one of F, N, P. Illustratively, the anionic salt is a F salt, specifically, at least one of lithium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, fluorosilicate.
In some embodiments, the solvent is at least one of deionized water, ethanol, butanediol, isopropanol, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone. Further, the solid content of the slurry is 5% to 40%, preferably 10% to 20%.
In some embodiments, the slurry is sanded to obtain a suitable metal particle size to facilitate subsequent uniform mixing. Illustratively, the metal particle size of the control slurry is in the range of 0.2 to 1 μm, preferably 0.3 to 0.5 μm. In particular embodiments, the slurry may be treated with, but is not limited to, a sand mill.
In some embodiments, the mass ratio of the slurry to the inner layer transition metal oxide is from 0.1 to 1:1, preferably from 0.2 to 0.5:1.
in some embodiments, the spray drying process is carried out at a temperature of 180 to 220 ℃, preferably 190 to 210 ℃.
In some embodiments, the calcination is performed in a gaseous atmosphere, the gas being at least one of air, oxygen, nitrogen, argon, hydrogen argon, and preferably air.
In some embodiments, the calcination temperature is 800 to 1000 ℃, preferably 900 ℃; the calcination time is 10-25 h, preferably 15h, and the cooling mode is natural cooling.
In some embodiments, the Dv50 of the positive electrode material of the sodium ion battery is 10 to 15 μm, preferably 10 to 12 μm.
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Example 1
The preparation method of the positive electrode material of the anion-cation co-doped coated sodium-ion battery comprises the following steps:
(1) Premixing 85g of sodium carbonate, 37.7g of nickel oxide, 40.5g of ferric oxide, 32g of manganese oxide, 8g of lithium hydroxide and 6.5g of sodium fluoride to obtain a solid mixture;
(2) Dissolving the solid mixture in 200mL of pure water to obtain brown liquid, and obtaining a mixed solution with the solid content of 30%;
(3) Treating the mixed solution with a sand mill at 2000r/min for 2h to obtain slurry with particle diameter of 0.42 μm, taking out 200mL of the liquid slurry, and adding 10g of layered transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Stirring, and performing spray drying treatment at 200 ℃ to obtain black powder;
(4) Calcining black powder in air atmosphere at 900 deg.C for 15 hr, cooling, crushing, and sieving to obtain NaLi 1/9 Ni 1/3 Fe 1/3 Mn 2/9 F 0.1 O 1.9 Coating NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Is used as the positive electrode material of the sodium ion battery,
wherein, the layered transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Is prepared as follows:
(1) 55.64g of nickel oxide, 24.9g of ferric oxide and 26.61g of manganese oxide are poured into a stirrer to be mixed;
(2) Will beThe above-mentioned mixed material and Na 2 CO 3 Mixing according to a molar ratio of 1:1.05, gradually heating to 950 ℃ at a speed of 4 ℃/min, sintering in an air atmosphere for 12 hours, cooling, crushing and sieving to obtain the inner layer transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 。
Example 2
The preparation method of the positive electrode material of the anion-cation co-doped coated sodium-ion battery comprises the following steps:
(1) Premixing 85g of sodium carbonate, 37.7g of nickel oxide, 40.5g of ferric oxide, 32g of manganese oxide, 8.5g of aluminum oxide and 6.5g of sodium fluoride to obtain a solid mixture;
(2) Dissolving the solid mixture in 200mL of pure water to obtain brown liquid, and obtaining a mixed solution with the solid content of 30%;
(3) Treating the mixed solution with a sand mill at 2000r/min for 2h to obtain slurry with particle diameter of 0.42 μm, taking out 200mL of the liquid slurry, and adding 10g of layered transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Stirring, and performing spray drying treatment at 200 ℃ to obtain black powder;
(4) Calcining black powder in air atmosphere at 900 deg.C for 15 hr, cooling, crushing, and sieving to obtain NaNi 1/3 Fe 1/3 Mn 2/9 Al 1/9 F 0.1 O 1.9 Coating NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Is used as the positive electrode material of the sodium ion battery,
wherein, the layered transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Reference example 1.
Example 3
The preparation method of the positive electrode material of the anion-cation co-doped coated sodium-ion battery comprises the following steps:
(1) Premixing 85g of sodium carbonate, 37.7g of nickel oxide, 40.5g of ferric oxide, 32g of manganese oxide, 13.3g of copper oxide and 6.5g of sodium fluoride to obtain a solid mixture;
(2) Dissolving the solid mixture in 200mL of pure water to obtain brown liquid, and obtaining a mixed solution with the solid content of 30%;
(3) Treating the mixed solution with a sand mill at 2000r/min for 2h to obtain slurry with particle diameter of 0.42 μm, taking out 200mL of the liquid slurry, and adding 10g of layered transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Stirring, and performing spray drying treatment at 200 ℃ to obtain black powder;
(4) Calcining black powder in air atmosphere at 900 deg.C for 15 hr, cooling, crushing, and sieving to obtain NaNi 1/3 Fe 1/3 Mn 2/9 Cu 1/9 F 0.05 O 1.95 Coating NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Is used as the positive electrode material of the sodium ion battery,
wherein, the layered transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Reference example 1.
Comparative example 1
The preparation method of the positive electrode material of the sodium ion battery of the comparative example comprises the following steps:
(1) Premixing 85g of sodium carbonate, 37.7g of nickel oxide, 40.5g of ferric oxide, 32g of manganese oxide and 8g of lithium hydroxide to obtain a solid mixture;
(2) Dissolving the solid mixture in 200mL of pure water to obtain brown liquid, and obtaining a mixed solution;
(3) Treating the mixed solution with a sand mill at 2000r/min for 2h to obtain slurry with particle diameter of 0.42 μm, taking out 200mL of the liquid slurry, and adding 10g of layered transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Stirring, and performing spray drying treatment at 200 ℃ to obtain black powder;
(4) Calcining black powder in air at 900 deg.C for 15 hr, cooling, crushing, and sievingObtaining NaLi 1/9 Ni 1/3 Fe 1/3 Mn 2/9 O 2 Coating NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Is used as the positive electrode material of the sodium ion battery,
wherein, the layered transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Reference example 1.
Comparative example 2
The preparation method of the positive electrode material of the sodium ion battery of the comparative example comprises the following steps:
(1) Premixing 85g of sodium carbonate, 37.7g of nickel oxide, 40g of ferric oxide, 43.5g of manganese oxide and 6.5g of sodium fluoride to obtain a solid mixture;
(2) Dissolving the solid mixture in 200mL of pure water to obtain brown liquid, and obtaining a mixed solution;
(3) Treating the mixed solution with a sand mill at 2000r/min for 2h to obtain slurry with particle diameter of 0.42 μm, taking out 200mL of the liquid slurry, and adding 10g of layered transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Stirring, and performing spray drying treatment at 200 ℃ to obtain black powder;
(4) Calcining black powder in air atmosphere at 900 deg.C for 15 hr, cooling, crushing, and sieving to obtain NaNi 1/3 Fe 1/3 Mn 1/3 F 0.1 O 1.9 Coating NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Sodium ion battery positive electrode material of (2).
Wherein, the layered transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Reference example 1.
Comparative example 3
The preparation method of the positive electrode material of the sodium ion battery of the comparative example comprises the following steps:
(1) Premixing 85g of sodium carbonate, 37.7g of nickel oxide, 40.5g of ferric oxide, 16g of manganese oxide, 22.3g of niobium oxide and 5.8g of boron oxide to obtain a solid mixture;
(2) Dissolving the solid mixture in 200mL of pure water to obtain brown liquid, and obtaining a mixed solution;
(3) Treating the mixed solution with a sand mill at 2000r/min for 2h to obtain slurry with particle diameter of 0.42 μm, taking out 200mL of the liquid slurry, and adding 10g of layered transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Stirring, and performing spray drying treatment at 200 ℃ to obtain black powder;
(4) Calcining black powder in air atmosphere at 900 deg.C for 15 hr, cooling, crushing, and sieving to obtain NaNi 1/3 Fe 1/3 Mn 1/9 Nb 1/9 B 1/9 O 2 Coating NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Sodium ion battery positive electrode material of (2).
Wherein, the layered transition metal oxide NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Reference example 1.
Fig. 1 shows an SEM image of the positive electrode material of the sodium ion battery prepared in example 1. As can be seen from FIG. 1, the shape of the positive electrode material of the sodium-ion battery coated by the co-doping of the anions and the cations is elliptical, and meanwhile, the single crystal material obtained by the coating is more beneficial to keeping the structural integrity of the material in the cell cycle process and prolonging the cycle life.
Fig. 2 shows the XRD pattern of the positive electrode material of the sodium ion battery prepared in example 1. As can be seen from fig. 2, the XRD pattern shows that the positive electrode material of the sodium ion battery is O3 phase and has good crystallization.
The positive electrode materials for sodium ion batteries of examples 1 to 3 and comparative examples 1 to 3 were subjected to electrochemical performance tests, and the results thereof are shown in table 1.
Electrochemical performance test: the positive electrode material of the sodium ion battery is used as an active substance, a metal sodium sheet is used as a negative electrode sheet, a diaphragm is Celgard2400, and an electrolyte is NaClO with the concentration of 1M 4 The solution (the solvent is the mixed solution of ethylene carbonate and propylene carbonate with the volume ratio of 1:1) is added with 5 percent of fluoroethylene carbonate to assemble the CR2430 button cell. Positive electrodeThe preparation process of the pole piece comprises the following steps: the positive electrode active material, the conductive agent acetylene black and the binder PVDF are mixed according to the mass percentage of 90:6:4, mixing N-methyl pyrrolidone serving as a solvent to prepare slurry, coating the slurry on an aluminum foil, vacuum drying, and compacting by a pair of rollers to prepare a positive electrode plate; and (3) performing charge and discharge test under a voltage window of 2.0V-4.2V at 0.1C/0.1C on a LAND battery test system of the Wuhan blue electric and electronic company, so as to obtain the first discharge specific capacity.
Table 1 test results
Figure BDA0004088514100000121
As can be seen from the results in table 1, the cathode materials of the sodium ion batteries of examples 1 to 3, which are co-doped with anions and cations, have better specific capacity and initial charge-discharge efficiency than those of comparative examples 1 to 3. The surface of the positive electrode material is provided with a compact multi-element material protection layer with an anion-cation co-doping structure, so that the air stability is improved, the contact area between the internal layered transition metal oxide and electrolyte is reduced, the occurrence of interface side reaction is slowed down, and the material circulation stability is improved; and cations of the outer layer transition metal oxide enter Transition Metal (TM) sites, doping cations helps to reduce the effective coordination of O atoms, and enhances the TM-O bond strength number to make TMO 2 The layer is narrowed, and meanwhile, anions and oxygen form a covalent bond, so that the anion-anion synergic modification regulates and controls the crystal structure mechanism of the material, the sodium interlayer spacing can be enlarged, sodium ion transmission is facilitated, the loss of lattice oxygen is reduced, the structural stability can be improved, the voltage window can be enlarged, and the specific capacity, high first efficiency and cycle stability can be improved.
Comparative example 1 NaLi 1/9 Ni 1/3 Fe 1/3 Mn 2/9 O 2 Coating NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The coating layer only contains cation dopingCompared with example 1, the lithium ion battery has poorer initial discharge specific capacity and initial charge-discharge efficiency.
Comparative example 2 NaNi 1/3 Fe 1/3 Mn 1/3 F 0.1 O 1.9 Coating NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The positive electrode material of sodium ion battery of (2) has a coating layer containing only anion doping and no cation doping, and has poorer initial discharge specific capacity and initial charge-discharge efficiency than that of example 1.
Comparative example 3 NaNi was obtained 1/3 Fe 1/3 Mn 1/9 Nb 1/9 B 1/9 O 2 Coating NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The positive electrode material of sodium ion battery of (2) has a coating layer containing a plurality of cation doping but no anion doping, and has poorer initial discharge specific capacity and initial charge-discharge efficiency than that of example 1.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

1. The positive electrode material of the sodium ion battery coated by the co-doping of anions and cations is characterized by comprising an inner layered transition metal oxide and an outer layered transition metal oxide coating the inner layered transition metal oxide,
the chemical formula of the inner layer-shaped transition metal oxide is Na x Fe y Mn z M f O 2 Wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.5, f is more than or equal to 0 and less than or equal to 0.3, the values of x, y, z and f meet the charge balance of chemical formulas, and M is at least one of Li, co, ni, mg, ca, sr, ba, al, be, B, ti, zr, cu, zn, ga, sn;
chemistry of the outer layer-like transition metal oxideNa is Na j Ni a Fe b Mn c A d C e O 2-e Wherein j is more than or equal to 1.0 and less than or equal to 1.08,0.3, a is more than or equal to 1 and less than or equal to 0.9,0.3 and less than or equal to 0.9, C is more than or equal to 0 and less than or equal to 0.3, d is more than or equal to 0.001 and less than or equal to 0.01, e is more than or equal to 0.001 and less than or equal to 0.7, the values of j and a, b, C, d, e meet the charge balance of chemical formulas, A is a cation, and C is an anion.
2. The positive electrode material of an ion-cation co-doped coated sodium ion battery of claim 1, wherein a is at least one of Li, K, cu, nb, al, mg, ti, zn, zr, sr, W, mo, V, ca, B.
3. The positive electrode material of an ion-cation co-doped coated sodium ion battery of claim 1, wherein C is at least one of F, N, P.
4. The positive electrode material of the anion-cation co-doped and coated sodium ion battery according to claim 1, wherein the outer layer transition metal oxide is 0.5% -10% of the inner layer transition metal oxide according to mass ratio.
5. The method for preparing the positive electrode material of the anion-cation co-doped and coated sodium-ion battery according to any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) Premixing sodium salt, nickel salt, ferric salt, manganese salt, cationic salt and anionic salt according to a certain proportion to obtain a solid mixture;
(2) Mixing the solid mixture with a solvent to obtain a slurry;
(3) Mixing the slurry with an inner layer transition metal oxide, and performing spray drying treatment to obtain a mixed material;
(4) And calcining the mixed material, cooling, crushing, and sieving to obtain the sodium ion battery anode material.
6. The method for preparing an anode material of an anion-cation co-doped coated sodium ion battery according to claim 5, wherein the sodium salt is at least one selected from sodium nitrate, sodium hydroxide, sodium fluoride, sodium iodide, sodium peroxide, sodium carbonate and sodium acetate;
the manganese salt is selected from at least one of manganese nitrate, manganese sulfate, manganese chloride and manganese oxide;
the nickel salt is at least one selected from nickel nitrate, nickel sulfate, nickel chloride and nickel hydroxide;
the ferric salt is at least one selected from ferric nitrate, ferric sulfate, ferric chloride and ferric hydroxide.
7. The method for preparing the positive electrode material of the anion-cation co-doped coated sodium ion battery according to claim 5, wherein the cation salt is at least one of Li salt, K salt, cu salt, al salt, nb salt, mg salt, ti salt, zn salt, zr salt, sr salt, W salt, mo salt, V salt, ca salt and B salt;
the anion salt is at least one of F salt, N salt and P salt.
8. The method for preparing an anode material of an anion-cation co-doped coated sodium ion battery according to claim 5, wherein the solvent is at least one of deionized water, ethanol, butanediol, isopropanol, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
9. The method for preparing an anode material of an anion-cation co-doped and coated sodium-ion battery according to claim 5, wherein the calcination temperature is 800-1000 ℃.
10. The method for preparing an anode material of an anion-cation co-doped coated sodium ion battery according to claim 5, wherein the spray drying treatment temperature is 180-220 ℃.
CN202310144141.XA 2023-02-21 2023-02-21 Positive electrode material of anion-cation co-doped coated sodium-ion battery and preparation method thereof Pending CN116417590A (en)

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