GB2621780A - Sodium-ion battery positive electrode material, and preparation method therefor and use thereof - Google Patents

Sodium-ion battery positive electrode material, and preparation method therefor and use thereof Download PDF

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GB2621780A
GB2621780A GB2318233.0A GB202318233A GB2621780A GB 2621780 A GB2621780 A GB 2621780A GB 202318233 A GB202318233 A GB 202318233A GB 2621780 A GB2621780 A GB 2621780A
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ion battery
preparation
filtrate
cathode material
sodium
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Yu Haijun
LU Zhixu
Li Aixia
Xie Yinghao
Zhang Xuemei
Li Changdong
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H—ELECTRICITY
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
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    • C01—INORGANIC CHEMISTRY
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    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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    • 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
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Abstract

The present invention belongs to the technical field of sodium-ion batteries. Disclosed are a sodium-ion battery positive electrode material, and a preparation method therefor and the use thereof. The chemical formula of the sodium-ion battery positive electrode material is Na0.67MnaZrbFcO2, wherein 0<a<1, 0<b<1, 0<c<1, and a+b+c＝1. Fluorine ions are doped in the sodium-ion battery positive electrode material prepared in the present invention. Fluorine ions can increase the distance between Na+ diffusion layers, so that the electronic conductivity of the positive electrode material is improved. Furthermore, Zr4+ is introduced to prevent crystal structure collapse caused by the dissolution of Mn3+ in the positive electrode material. In addition, Zr4+ replaces some of the manganese ions in the positive electrode material, so that the volume of the positive electrode material during a charging and discharging process is relatively small, the distortion of the material is reduced, and the cycle performance is improved.

Description

SODIUM-ION BATTERY POSITIVE ELECTRODE MATERIAL, AND PREPARATION METHOD THEREFOR AND USE THEREOF
TECHNICAL FIELD
The present invention belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery cathode material and a preparation method and application thereof
BACKGROUND
Lithium manganate (LiMn204), as a cathode material for lithium ion batteries, is famous for low price, high potential, environmental friendliness and high safety performance thereof At present, lithium manganate batteries are widely used in the field of new energy. According to statistics, the service life of lithium batteries is 3 years to 5 years, and the scrap of batteries reached the first peak in 2018, wherein the scrap of lithium manganate batteries exceeded 10,000 tons. The cathode materials of the lithium manganate batteries contain a lot of Li and Mn elements, which will cause serious pollution to the water environment if these elements are not treated safely and effectively.
Therefore, recycling of various battery materials can not only save the production costs of enterprises and promote the sustainable development of the new energy industry, but also reduce the environmental pollution caused by waste battery materials At present, many enterprises have the abilities for recycling batteries, but there are still many problems to be solved urgently. The lithium manganate batteries have poor specific capacity and rate performance, while the sodium ion batteries have the characteristics of high specific capacity and low cost. However, the cathode materials of the sodium ion batteries also have some shortcomings such as poor conductivity.
Therefore, it is urgent to provide a sodium ion battery cathode material and a preparation method, which can not only realize the recycling of lithium manganate batteries, but also improve the problem of insufficient performances of the sodium ion battery cathode material.
SUMMARY
The present invention aims at solving at least one of the above-mentioned technical problems in the existing technology. Therefore, the present invention provides a sodium ion battery cathode material and a preparation method and application thereof The sodium ion battery cathode material has high specific capacity and excellent cycle performance.
In order to achieve the above object, the present invention adopts the following technical solutions.
A sodium ion battery cathode material has a chemical formula of Nao67MnaZrbF,02, wherein 0<a<1, 0<b<1, 0<c<1, and a+b+c=1 A preparation method of the sodium ion battery cathode material includes the following steps of (1) subjecting a battery powder to acid leaching, adding a reducing agent for reaction, adding an alkali liquor to adjust a pH, subjecting the mixture to a precipitation reaction and then filtering to obtain a precipitate and a filtrate; (2) adding potassium permanganate into the filtrate, performing primary precipitation reaction and solid-liquid separation to obtain manganese dioxide and a filtrate, adjusting a pH of the filtrate and introducing carbon dioxide, performing secondary precipitation reaction and solid-liquid separation to obtain lithium carbonate and a fluorine-containing solution, (3) adding a sodium source, a zirconium salt and a complexing agent into the fluorine-containing solution for reacting and sintering to obtain a Na067ZraFh02 precursor; and (4) mixing the Nao 67ZraFb02 precursor with the manganese dioxide in step (2), and calcining to obtain the sodium ion battery cathode material Nao 67MnaZrbFc02.
Preferably, in step (1), the battery powder is obtained by discharging, crushing, calcining at high temperature and sieving waste lithium manganate Further preferably, the discharging refers to a discharge treatment performed in a saturated sodium chloride solution.
Further preferably, the calcining is performed at a temperature of 600°C to 900°C, and lasts for 2 hours to 6 hours.
Further preferably, a sieve mesh of the sieving ranges from 100 pm to 200 gm Preferably, in step (1), the acid used in the acid leaching process is at least one of malic acid or citric acid.
Preferably, in step (1), the acid leaching lasts for 4 hours to 12 hours.
Preferably, in step (1), the reducing agent is at least one of iron powder or aluminum powder.
Preferably, in step (1), the alkali liquor is sodium hydroxide.
Preferably, in step (1), the adjusting the pH refers to adjusting the pH of the solution to be 3 to Further preferably, in step (1), a concentration of the alkali liquor ranges from 0.5 mol/L to 3 mol/L.
Preferably, in step (2), a concentration ratio of manganese ions in the potassium permanganate to manganese ions in the solution is (2 to 3): 1 Preferably, in step (2), the pH of the filtrate is adjusted to be 9 to 10 Preferably, in step (2), the alkali liquor used for adjusting the pH of the filtrate is sodium hydroxide.
Preferably, in step (3), the sodium source is at least one of Na2CO3, NaNO3 or Na2SO4.
Preferably, in step (3), the zirconium salt is at least one of zirconium nitrate, zirconium acetate or zirconium citrate Preferably, in step (3), the complexing agent is at least one of glucose or sucrose.
Further, in the step (3), the sintering is performed at a temperature of 350°C to 450°C and lasts for 4 hours to 8 hours.
Preferably, in step (4), a molar ratio of the Na0.67.ZraFb02 precursor to the manganese dioxide is 1: (0.7 to 0.9).
Further, in the step (4), the calcining is performed at a temperature of 300°C to 400°C and lasts for 6 hours to 12 hours.
A battery includes the sodium ion battery cathode material Compared with the existing technology, the present invention has the following beneficial effects.
I. The sodium ion battery cathode material prepared by the present invention is doped with fluorine ions, which can increase a distance between Na diffusion layers, thereby improving an electronic conductivity of the cathode material; and then Zr' is introduced to prevent a crystal structure from collapsing caused by the dissolution of Mr0 in the cathode material, and Zr41 replaces part of manganese ions in the cathode material, so that a volume of the cathode material is small during the process of charging and discharging, which reduces distortion of the material and improves a cycle performance.
2. In the preparation method of the present invention, the waste lithium manganate is used as the raw material, and added into the acid solution for dissolving, and the final filtrate only contains fluorine ions through impurity removal, and the fluorine ions can be used for subsequent modification of the sodium ion battery cathode material. In the preparation method, the calcining is performed at the temperature of 300°C to 400°C. Under this condition, the crystal structure of the manganese dioxide is a-Mn02. The a-Mn02 has large specific surface area and good corrosion resistance, which is not only conducive to electron transmission, but also prevents active substances in the electrolyte and the cathode material from reacting with each other.
3. A part of the raw materials of the present invention are taken from the waste batteries, which not only solves the threat of the waste batteries to the environment, but also contributes to the sustainable development of the industry and accords with the concept of green development.
BRIEF DESCRIPTION OF DRAWINGS
FIG 1 is a flowchart of an embodiment of the present invention; FIG 2 is an SEM graph of Embodiment 1 of the present invention; and FIG. 3 is an SEM graph of Embodiment 2 of the present invention.
DETAILED DESCRIPTION
The concepts and the technical effects produced of the present invention will be clearly and completely described in conjunction with the embodiments so as to sufficiently understand the objects, the features and the effects of the present invention. Obviously, the described embodiments are merely some embodiments of the present invention, rather than all the embodiments. Other embodiments obtained by those skilled in the art without going through any creative effort shall all fall within the protection scope of the present invention Embodiment 1 A chemical formula of a sodium ion battery cathode material of this embodiment was Na0.67M110.87Zat10F0.0302.
A preparation method of the sodium ion battery cathode material of this embodiment included the following steps of: (1) discharging and crushing a waste lithium manganate battery material, and calcining at 900°C for 2 hours to obtain a battery powder; (2) adding 10 g of the battery powder above into 100 mL of manic acid solution with a concentration of 1 mol/L and reacting for 12 hours, adding 1 g of iron powder, then adding a NaOH solution with a concentration of 0.5 mol/L, adjusting a pH of the solution to 4, and filtering to obtain a filtrate; (3) adding 1 g of potassium permanganate into the filtrate above, performing primary precipitation reaction and solid-liquid separation to obtain manganese dioxide and a filtrate, adding a NaOH solution with a concentration of 1 mol/L into the filtrate to adjust a pH of the filtrate to be 10 and introducing carbon dioxide, performing secondary precipitation reaction for 3 hours and then performing solid-liquid separation to obtain a fluorine-containing solution and lithium carbonate; (4) mixing 0.5 mol of NaNO3, 0.1 mol of Zr(NO3)4-5H20 and 1 g of glucose, adding the mixture into the fluorine-containing solution in step (3), stirring and reacting in a water bath at 30°C for 24 hours, and then calcining at 300°C for 4 hours to obtain a Na0.67ZraFb02 material; and (5) feeding the Na0.67Zr3Fb02 material and the manganese dioxide in step (3) into a muffle furnace for calcining at 300°C for 12 hours, and finally generating a sodium ion battery cathode material (Na0.67Mnaii7Zro.NFo.0302) with an a-Mn02 crystal form.
Embodiment 2 A chemical formula of a sodium ion battery cathode material of this embodiment was Na0.67Mno.83Zro.10F0.0702.
A preparation method of the sodium ion battery cathode material of this embodiment included the following steps of: (1) discharging and crushing a waste lithium manganate battery material, and calcining at 900°C for 2 hours to obtain a battery powder; (2) adding 12 g of the battery powder above into 100 mL of malic acid solution with a concentration of 1.5 mol/L and reacting for 12 hours, adding 1.5 g of iron powder, then adding a NaOH solution with a concentration of 0.5 mol/L, adjusting a pH of the solution to 4, and filtering to obtain a filtrate; (3) adding 1.5 g of potassium permanganate into the filtrate above, performing primary precipitation reaction and solid-liquid separation to obtain manganese dioxide and a filtrate, adding a NaOH solution with a concentration of 1.5 mol/L into the filtrate to adjust a pH of the filtrate to be and introducing carbon dioxide, performing secondary precipitation reaction for 3 hours and then performing solid-liquid separation to obtain a fluorine-containing solution and lithium carbonate; (4) mixing 0.6 mol of Na2SO4, 0.1 mol of Zr(NO3)4-5H20 and 1.5 g of glucose, adding the mixture into the fluorine-containing solution in step (3), stirring and reacting in a water bath at 30°C for 24 hours, and then calcining at 300°C for 4 hours to obtain a Na0.67ZraFb02 material; and (5) feeding the Na0.67ZraFb02 material and the manganese dioxide in step (3) into a muffle furnace for calcining at 300°C for 12 hours, and finally generating a sodium ion battery cathode material (Nan.67Mn0.83Zro.10F0.0702) with an a-Mn02 crystal form. Embodiment 3 A chemical formula of a sodium ion battery cathode material of this embodiment was Na0.67Mno.8Zro.1F0.102.
A preparation method of the sodium ion battery cathode material of this embodiment included the following steps of: (1) discharging and crushing a waste lithium manganate battery material, and calcining at 900°C for 2 hours to obtain a battery powder; (2) adding 14 g of the battery powder above into 100 mL of malic acid solution with a concentration of 2 mol/L and reacting for 12 hours, adding 2 g of iron powder, then adding a NaOH solution with a concentration of 0.5 mol/L, adjusting a pH of the solution to 4, and filtering to obtain a filtrate; (3) adding 1.5 g of potassium permanganate into the filtrate above, performing primary precipitation reaction and solid-liquid separation to obtain manganese dioxide and a filtrate, adding a NaOH solution with a concentration of 2 mol/L into the filtrate to adjust a pH of the filtrate to be 10 and introducing carbon dioxide, performing secondary precipitation reaction for 3 hours and then performing solid-liquid separation to obtain a fluorine-containing solution and lithium carbonate; (4) mixing 0.6 mol of NaNO3, 0.1 mol of Zr(NO3)4.51-120 and 2.5 g of glucose, adding the mixture into the fluorine-containing solution in step (3), stirring and reacting in a water bath at 30°C for 24 hours, and then calcining at 300°C for 4 hours to obtain a Na0.67ZraF1,02 material; and (5) feeding the Na0.67ZraFb02 material and the manganese dioxide in step (3) into a muffle furnace for calcining at 300°C for 12 hours, and finally generating a sodium ion battery cathode material (Na0.67Mno. aro. 1E1).102) with an a-Mn02 crystal form.
Embodiment 4 A chemical formula of a sodium ion battery cathode material of this embodiment was Na0.67Mno.75Zro.iFo.15 A preparation method of the sodium ion battery cathode material of this embodiment included the following steps of: (1) discharging and crushing a waste lithium manganate battery material, and calcining at 900°C for 2 hours to obtain a battery powder; (2) adding 16 g of the battery powder above into 100 mL of malic acid solution with a concentration of 2.5 mot/ and reacting for 12 hours, adding 2 g of iron powder for stirring, then adding a NaOH solution with a concentration of 0.5 mol/L, adjusting a pH of the solution to 4, and filtering to remove iron and aluminum, and obtain a filtrate; (3) adding 2 g of potassium permanganate into the filtrate above, performing primary precipitation reaction and solid-liquid separation to obtain manganese dioxide and a filtrate, adding a NaOH solution with a concentration of 2 mol/L into the filtrate to adjust a pH of the filtrate to be 10 and introducing carbon dioxide, performing secondary precipitation reaction for 3 hours and then performing solid-liquid separation to obtain a fluorine-containing solution and lithium carbonate; (4) mixing 0.7 mol of NaNO3, 0.1 mol of Zr(NO3)4.5H20 and 2 g of glucose, adding the mixture into the fluorine-containing solution in step (3), stirring and reacting in a water bath at 30°C for 24 hours, and then calcining at 300°C for 4 hours to obtain a Na0.67ZraFb02 material; and (5) feeding the Na0.67ZraFb02 material and the manganese dioxide in step (3) into a muffle furnace for calcining at 300°C for 12 hours, and finally generating a sodium ion battery cathode material (Nan.67Mno.75Zro(F0.15) with ana-Mn02 crystal form.
Embodiment 5 A chemical formula of a sodium ion battery cathode material of this embodiment was Na0.67Mno.ilro.1F0.202.
A preparation method of the sodium ion battery cathode material of this embodiment included the following steps of: (1) discharging and crushing a waste lithium manganate battery material, and calcining at 800°C for 5 hours to obtain a battery powder and an electrode plate powder; (2) adding 18 g of the battery powder above into 100 mL of citric acid solution with a concentration of 2 mol/L and reacting for 10 hours, adding an iron powder, then adding a NaOH solution with a concentration of 2 mol/L, adjusting a pH of the solution to 4, and filtering to obtain a filtrate and a filter residue, (3) adding 3 g of potassium permanganate into the filtrate above, performing primary precipitation reaction and solid-liquid separation to obtain manganese dioxide and a filtrate, adding a NaOH solution with a concentration of 2 mol/L into the filtrate to adjust a pH of the filtrate to be 10 and introducing carbon dioxide, performing secondary precipitation reaction for 6 hours and then performing solid-liquid separation to obtain a fluorine-containing solution and lithium carbonate; (4) mixing 0.75 mol of Na2CO3, 0.1 mol of Zr(NO3)4.51120 and 3 g of glucose, adding the mixture into the fluorine-containing solution in step (3), stirring and reacting in a water bath at 55°C for 18 hours, and then calcining at 400°C for 8 hours to obtain a Na0.67ZraF(02 material; and (5) feeding the Na0.67Zr3Fb02 material and the manganese dioxide in step (3) into a muffle furnace for calcining at 400°C for 9 hours, and finally generating a sodium ion battery cathode material (Na0.671v1no.7ZraiLo.202) with ana-Mn02 crystal form.
Comparative Example 1 A chemical formula of a sodium ion battery cathode material of this comparative example was Na0.67Mn0.87F0.1302.
The preparation method of the sodium ion battery cathode material of this comparative example differed from Embodiment 1 in that: no Zr(NO3)4.51120 was added in step (4).
Comparative Example 2 A chemical formula of a sodium ion battery cathode material of comparative example was Na0.67Mno.s7Zro.1302.
The preparation method of the sodium ion battery cathode material of this comparative example differed from Embodiment 1 in that: in step (4), no fluorine-containing solution was added for reacting to obtain Nao 67Zr.02 Comparative Example 3 A chemical formula of a sodium ion battery cathode material of comparative example was Nao 67Mn02.
Analysis of Embodiments 1 to 4 and Comparative Examples 1 to 3: Table 1 Lattice parameters of cathode materials under different conditions Sample type/lattice constant a (A) b (A) c (A) Comparative Example 3 Nao67M1102 9.0621 26.312 2.794 Comparative Example 2 Na0.67Mn3Zrt02 9.0814 26.426 2.814 Comparative Example 1 Na367MnaEt02 9.0945 26.481 2.864 Embodiment 1 9.124 26.578 2.951 Embodiment 2 9.209 26.541 2.959 Embodiment 3 9.212 26.612 2.961 Embodiment 4 9.159 26.498 2.952 Embodiment 5 9.189 26.512 2.941 As shown in Table 1, when a raw material contains fluorine ions, the lattice constant of the raw material is larger than that of a raw material without fluorine ions, which proves that the fluorine ions increases the distance of Na-diffusion layers.
Table 2 Physical properties of cathode materials under different conditions Sample type Charge Specific Electronic Capacity Capacity transfer capacity conductivity after 100 retention impedance ((2) (m Ahg 0 (S/cm) cycles rate (%) Nalgri02 241 134 3.8*10-6 128.6 96.1 Na067Mno stZro I of, poM2 198 151 4 5*10-5 146.7 97.2 Nao oiMno s iZro 10F, ,0702 175 162 8.2*10-4 156.9 96.9 Nao 67Mno 8Zro IF° 102 152 172 9.1*104 167.8 97.6 Na067Mno tsZro 1 Fo 1502 164 162 7 6*10-4 157.4 97.2 Nao 67Mno 7Zro 1F0 202 180 158 6.9*10-4 153.4 97.1 It can be seen from the above table that Embodiments 1 to 5 of the present invention have high specific capacities, which may reach 172 mAhg I, and can still maintain high capacities after 100 cycles, and have good cycle performances and capacity retention rates.
FIG. 1 is a flowchart of an embodiment of the present invention. It can be seen from FIG. 1 that the battery powder is subjected to acid leaching to remove the black powder, and then added with the iron powder for reacting to remove copper, then added with the sodium carbonate to adjust the pH.
After removing iron and aluminum, the potassium permanganate is added for reacting to obtain the manganese dioxide and the filtrate, then the pH of the filtrate is adjusted, and carbon dioxide is introduced to precipitate lithium to obtain the lithium carbonate and the fluorine-containing solution. After that, the sodium salt, the zirconium salt and the complexing agent are added for reacting and sintering, and then mixed with manganese dioxide for calcining to obtain the sodium ion battery anode material, FIG. 2 is an SEM graph of Embodiment 1 of the present invention. It can be seen from FIG. 2 that the particles are uniform in size and smooth in surface.
FIG. 3 is an SEM graph of Embodiment 2 of the present invention. It can be seen from in FIG. 3 that the dosage change of the doped elements will not obviously affect the basic morphology of the material.
The embodiments of the present invention are described in detail with reference to the drawings above, but the present invention is not limited to the above embodiments, and various changes may also be made within the knowledge scope of those of ordinary skills in the art without departing from the purpose of the present invention. In addition, in case of no conflict, the embodiments in the present invention and the features in the embodiments may be combined with each other.

Claims (10)

  1. CLAIMSI. A sodium ion battery cathode material, wherein a chemical formula of the sodium ion battery cathode material is Na067MnalriTe02, and wherein 0<a<1, 0<b<1, 0<c<1, and a+b+c=1.
  2. 2. A preparation method of the sodium ion battery cathode material according to claim 1, s comprising the following steps of: (1) subjecting a battery powder to acid leaching, adding a reducing agent for reaction, adding an alkali liquor to adjust a p1-1, subjecting the mixture to a precipitation reaction and then filtering to obtain a precipitate and a filtrate; (2) adding potassium permanganate into the filtrate, performing primary precipitation reaction and solid-liquid separation to obtain manganese dioxide and a filtrate, adjusting a pH of the filtrate and introducing carbon dioxide, performing secondary precipitation reaction and solid-liquid separation to obtain lithium carbonate and a fluorine-containing solution; (3) adding a sodium source, a zirconium salt and a complexing agent into the fluorine-containing solution for reacting and sintering to obtain a Na0.67.ZraFb02 precursor; and (4) mixing the Na0.67ZraFb02 precursor with the manganese dioxide in step (2), and calcining to obtain the sodium ion battery cathode material Nao.67MnaZraFc02.
  3. 3. The preparation method according to claim 2, wherein in step (1), the acid used in the acid leaching process is at least one of malic acid or citric acid.
  4. 4. The preparation method according to claim 2, wherein in step (1), the reducing agent is at least one of iron powder or aluminum powder.
  5. 5. The preparation method according to claim 2, wherein in step (2), a concentration ratio of manganese ions in the potassium permanganate to manganese ions in the filtrate is (2 to 3): 1.
  6. 6. The preparation method according to claim 2, wherein in step (3), the zirconium salt is at least one of zirconium nitrate, zirconium acetate and zirconium citrate.
  7. 7. The preparation method according to claim 2, wherein in step (3), the sodium source is at least one of Na2CO3, NaNO3 and Na2SO4.
  8. 8. The preparation method according to claim 2, wherein in step (3), the complexing agent is at least one of glucose or sucrose.
  9. 9. The preparation method according to claim 2, wherein in step (4), the calcining is performed at a temperature of 300°C to 400°C, and lasts for 6 hours to 12 hours.
  10. 10. A battery, comprising the sodium ion battery cathode material according to claim I.
GB2318233.0A 2021-10-29 2022-08-12 Sodium-ion battery positive electrode material, and preparation method therefor and use thereof Pending GB2621780A (en)

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CN109860576A (en) * 2019-03-06 2019-06-07 四川大学 A kind of regulation method of stratiform-tunnel recombination material and its object Phase Proportion
CN113086996A (en) * 2021-03-25 2021-07-09 宁夏百川新材料有限公司 Recycling method of waste ternary fluorine-doped battery positive electrode material
CN114243013A (en) * 2021-10-29 2022-03-25 广东邦普循环科技有限公司 Sodium-ion battery positive electrode material and preparation method and application thereof

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CN109524649A (en) * 2018-11-12 2019-03-26 北京中科海钠科技有限责任公司 A kind of sodium-ion battery positive material of clad structure and its preparation method and application
CN109860576A (en) * 2019-03-06 2019-06-07 四川大学 A kind of regulation method of stratiform-tunnel recombination material and its object Phase Proportion
CN113086996A (en) * 2021-03-25 2021-07-09 宁夏百川新材料有限公司 Recycling method of waste ternary fluorine-doped battery positive electrode material
CN114243013A (en) * 2021-10-29 2022-03-25 广东邦普循环科技有限公司 Sodium-ion battery positive electrode material and preparation method and application thereof

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