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CN-121974409-A - Preparation method for preparing ternary material by utilizing nickel-iron alloy and ternary material

CN121974409ACN 121974409 ACN121974409 ACN 121974409ACN-121974409-A

Abstract

The invention discloses a preparation method for preparing ternary materials by utilizing ferronickel and the ternary materials, and belongs to the technical field of ternary material preparation, comprising the following steps of S1, carrying out crushing and roasting pretreatment on ferronickel, then carrying out acid leaching in sulfuric acid solution, and filtering and collecting mixed solution; S2, sequentially adding a sodium sulfide solution and a sodium fluoride solution into the mixed solution, filtering, collecting a refined solution, S3, supplementing a cobalt source and a manganese source into the refined solution, adjusting the molar ratio of Ni 2+ 、Co 2+ 、Mn 2+ in the solution to be x:1-x-y, wherein x=0.6-0.8 and y=0.1-0.2, adjusting the pH of the refined solution to 10.5-11.5, filtering, collecting a precipitate, and obtaining a ternary precursor, S4, uniformly mixing the ternary precursor, the lithium source and the doping agent to obtain a mixture, wherein the doping agent is yttrium salt and zirconium salt, and sintering the mixture to obtain the ternary material.

Inventors

  • HOU JUNKE
  • WANG LONG
  • LI QIFENG
  • CHEN ZHIXIN
  • LONG BIAO
  • CHEN LIPENG

Assignees

  • 福安国隆纳米材料有限公司

Dates

Publication Date
20260505
Application Date
20260202

Claims (10)

  1. 1. A method for preparing ternary material by utilizing nickel-iron alloy, which is characterized by comprising the following steps: s1, crushing and roasting nickel-iron alloy, then leaching in sulfuric acid solution, and filtering and collecting mixed solution; s2, sequentially adding a sodium sulfide solution and a sodium fluoride solution into the mixed solution, filtering, and collecting a refined solution; S3, adding a cobalt source and a manganese source into the refined solution, adjusting the molar ratio of Ni 2+ 、Co 2+ 、Mn 2+ in the solution to be x, wherein x is 1-x-y, x=0.6-0.8 and y=0.1-0.2; s4, uniformly mixing the ternary precursor, the lithium source and the doping agent to obtain a mixture, wherein the doping agent is yttrium salt and zirconium salt, and sintering the mixture to obtain the ternary material.
  2. 2. The method for preparing ternary materials by utilizing nickel-iron alloy according to claim 1, wherein the nickel-iron alloy comprises the chemical elements of 15-40% of Ni, 0.30-0.5% of Co, 0.030-0.02% of Mn, 0.030-0.050% of Cu, 0.004-0.009% of Ca, 0.001-0.007% of Mg and Fe.
  3. 3. The method for preparing ternary materials by utilizing ferronickel alloy according to claim 1, wherein in S1, the roasting is performed in a mixed atmosphere of air and nitrogen, and the volume ratio of air to nitrogen in the mixed atmosphere is 1:3-5; And/or in S1, roasting at 600-900 ℃ for 2-6 hours, and finally cooling along with the furnace; and/or S1, performing crushing and ball milling treatment to obtain the material, wherein the ball milling rotating speed is 300-450 r/min, the ball milling time is 2-4 h, and then sieving the material with a 100-150 mesh sieve.
  4. 4. The method for preparing ternary material by utilizing nickel-iron alloy according to claim 1, wherein in S1, the pH of the mixed solution is 3.0-4.5; And/or in S1, the concentration of the sulfuric acid solution is 1.0-2.0 mol/L; and/or in S1, the liquid-solid ratio of the nickel-iron alloy to the sulfuric acid solution is 5-8 mL/g; And/or, in S1, adding hydrogen peroxide with the mass of 10-30% of that of the sulfuric acid solution in the acid leaching process.
  5. 5. The method for preparing ternary materials by utilizing ferronickel alloy according to claim 1, wherein in S2, the concentration of the sodium sulfide solution is 0.04-0.07 mol/L, and the addition amount of the sodium sulfide solution is 2-5% of the volume of the mixed solution; and/or in S2, the concentration of the sodium fluoride solution is 0.05-0.08 mol/L, and the addition amount of the sodium fluoride solution is 2-5% of the volume of the mixed solution, preferably 2-3%; and/or in S2, adding the sodium fluoride solution, wherein the dropping speed is 6-7 mL/min, stirring for 20-50 min after the completion of the dropping, and standing for more than or equal to 3h at the temperature of less than or equal to 5 ℃.
  6. 6. The method for preparing ternary material by utilizing nickel-iron alloy according to claim 1, wherein in S3, the cobalt source is at least one of cobalt sulfate, cobalt nitrate or cobalt chloride; and/or in S3, the manganese source is at least one of manganese sulfate, manganese nitrate or manganese chloride; And/or in S3, the pH is adjusted by adopting sodium hydroxide solution and ammonia water; And/or in S3, the active component of the ternary precursor is Ni x Co y Mn 1-x-y (OH) 2 , x=0.6-0.8, and y=0.1-0.2.
  7. 7. The method for preparing ternary materials by utilizing ferronickel according to claim 1, wherein in S4, yttrium source is yttrium nitrate, zirconium source is zirconyl nitrate, and the molar ratio of Y/Zr in the yttrium source and the zirconium source is 1/2-3; And/or, in S4, the lithium source is lithium hydroxide or lithium carbonate; and/or in S4, the adding amount of the doping agent is 0.3-0.8% of the mass of the ternary precursor; And/or in S4, the mole number of Li in the lithium source/the total mole number of Ni+Co+Mn in the ternary precursor is 1.05-1.15/1; and/or in S4, sintering at 1000-1200 ℃ for 6-10 hours in an oxygen atmosphere.
  8. 8. A ternary material characterized by being obtained by the preparation method of any one of claims 1 to 7.
  9. 9. The ternary material of claim 8, wherein the ternary material has an active ingredient having a chemical formula LiNi x Co y Mn 1-x-y O 2 , wherein x is 0.6 to 0.8 and y is 0.1 to 0.2.
  10. 10. The ternary material of claim 9, wherein the ternary material has a tap density of 2.0-2.5 g/cm 3 ; And/or the specific surface area of the ternary material is 10-20m 2 /g.

Description

Preparation method for preparing ternary material by utilizing nickel-iron alloy and ternary material Technical Field The invention belongs to the technical field of ternary material preparation, and particularly relates to a preparation method for preparing a ternary material by utilizing nickel-iron alloy and the ternary material. Background The nickel-iron alloy is mainly applied to the fields of stainless steel and high-nickel high-cobalt alloy steel, has rich nickel content and low cost, and part of alloy steel scraps also have recycling values. With the rapid development of new energy automobiles and energy storage battery industries, the demand of the ternary positive electrode material for nickel resources is continuously increased, the nickel-iron alloy is gradually changed from the traditional metallurgical field to the battery-grade nickel sulfate preparation raw material by virtue of the self resource advantage, and the nickel sulfate solution obtained after acid leaching can be further used for the production of the ternary positive electrode material, so that the ternary positive electrode material has great industrial value. The traditional sulfuric acid leaching process has low leaching efficiency and excessive residual acid content, the pH value of the mixed solution after leaching is less than 3, and additional neutralization treatment is needed subsequently, so that the production cost and the process complexity are increased. Patent document 202110152830.6 discloses a method for leaching nickel-containing iron powder by sulfuric acid-phosphoric acid mixed acid, which realizes nickel-iron separation and synchronously prepares nickel sulfate and ferric phosphate by proportioning regulation, and has simple process and lower energy consumption. However, the process has the disadvantages of large phosphoric acid consumption, high cost and great subsequent phosphorus removal difficulty, and if the ternary material is prepared, phosphorus impurities in the nickel sulfate solution are easy to remain, so that the electrochemical performance of the ternary material is influenced. The patent document with the application number 202310987675.9 is subjected to electrolytic corrosion to dissolve the nickel-containing iron alloy, the ferric phosphate dihydrate and the nickel ammonia solution are separated by utilizing the complexation characteristic of ammonium, and then the impurity is removed to prepare a nickel sulfate product, so that the overflow of hydrogen sulfide is avoided. However, the process needs to be provided with a special titanium-coated lead dioxide basket anode and an electrolysis device, the inter-electrode voltage control is complex, the power consumption is high, the industrial application cost is high, the process comprises a plurality of complex steps of ammonia distillation, acidolysis and the like, the process is complex, and the equipment investment is high. The patent document with the application number 202510872127.0 adopts two displacement reactions to dissolve the ferronickel alloy, so that the problem of acid dissolution and gas production is avoided, and the quality of the ferronickel solution is improved. However, the process depends on the recycling of copper sulfate, has extremely high requirement on the precision of copper ion concentration control, needs to treat copper-containing slag independently, has long flow, is influenced by the granularity difference of raw materials, has high difficulty in regulating and controlling the rate of displacement reaction, does not relate to the preparation of subsequent ternary materials, and has incomplete technical chain. Disclosure of Invention The invention aims to overcome the technical problems, and therefore provides a preparation method for preparing a ternary material by utilizing nickel-iron alloy and the ternary material. According to the invention, the ferronickel waste is recycled, the ferronickel is pretreated by roasting to improve the acid dissolution efficiency, then the precursor purity is improved by directional distribution and impurity removal, and finally the high-quality ternary material is obtained by a low-cost preparation method. The invention solves the technical problems through the following technical proposal. The invention discloses a method for preparing ternary materials by utilizing nickel-iron alloy, which comprises the following steps: s1, crushing and roasting nickel-iron alloy, then leaching in sulfuric acid solution, and filtering and collecting mixed solution; s2, sequentially adding a sodium sulfide solution and a sodium fluoride solution into the mixed solution, filtering, and collecting a refined solution; S3, adding a cobalt source and a manganese source into the refined solution, adjusting the molar ratio of Ni 2+、Co2+、Mn2+ in the solution to be x, wherein x is 1-x-y, x=0.6-0.8 and y=0.1-0.2; s4, uniformly mixing the ternary precursor, the lithium source and the doping agent to obta