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KR-20260063335-A - A METHOD OF PRODUCING LITHIUM COMPOUNDS FROM LITHIUM-ION BATTERY WASTE

KR20260063335AKR 20260063335 AKR20260063335 AKR 20260063335AKR-20260063335-A

Abstract

The present invention relates to a method for producing lithium compounds from lithium-ion battery waste, wherein black mass is separated and products such as anhydrous LiOH, hydrated LiOH, or Li₂CO₃ are obtained through alkaline washing, heat treatment, acid leaching, and conversion. The method reduces water usage and increases the yield of the products by increasing the efficiency of heat treatment and acid leaching, thereby providing an environmentally friendly lithium-ion battery recycling method.

Inventors

  • 정욱진
  • 그레이스 니솔라
  • 존 에드워드 시오
  • 시박 마크
  • 게브레메덴 게브레미카엘

Assignees

  • 에스이엠 주식회사

Dates

Publication Date
20260507
Application Date
20241030

Claims (11)

  1. Separating black mass from lithium-ion battery waste; Alkaline washing of the above black mass; Heat-treating the above alkali-washed black mass together with a reducing agent; Acid leaching of the above heat-treated black mass; and A method for producing a lithium compound from lithium-ion battery waste, comprising converting an acid leaching product into a lithium compound.
  2. In paragraph 1, A method for producing a lithium compound from lithium-ion battery waste, wherein the black mass comprises Li a Me b O c (wherein Me is one or more selected from the group consisting of Ni, Co, Mn, Al, Cu, Fe, Mg, B, Ga, Zn, Ta, and V, and a, b, and c are each independently real numbers of 0.01 or greater); and impurities that do not contain lithium.
  3. In paragraph 1, A method for producing a lithium compound from lithium-ion battery waste, wherein the black mass comprises particles with a particle size of 100 μm or less.
  4. In paragraph 1, A method for producing a lithium compound from lithium-ion battery waste, wherein the above alkaline washing is performed using a 1 to 5 M NaOH or KOH solution at a solid-liquid ratio of 250 to 1000 g/L.
  5. In paragraph 1, The above reducing agent is, One or more solid reducing agents selected from the group consisting of carbamide, ammonium carbonate, ammonium formate, ammonium oxalate, and ammonium carbamate; One or more gaseous reducing agents selected from the group consisting of ammonia, hydrogen, and carbon monoxide; or A method for manufacturing a lithium compound from lithium-ion battery waste, which is a combination of these.
  6. In paragraph 5, The above heat treatment is, A method for producing a lithium compound from lithium-ion battery waste, wherein the above alkali-washed black mass and the above solid reducing agent are mixed in a mass ratio of 1:0.1 to 1:2 and heat-treated.
  7. In paragraph 1, The above heat treatment is, A method for producing a lithium compound from lithium-ion battery waste, wherein the method involves heating to 400 to 650°C under an inert gas.
  8. In paragraph 1, The above acid leaching is, A method for producing a lithium compound from lithium-ion battery waste, wherein an acid is added to the heat-treated black mass at a solid-liquid ratio of 40 to 80 g/L to maintain the pH at 1 to 4.
  9. In paragraph 1, Converting to the above lithium compound is, A method for producing a lithium compound from lithium-ion battery waste, wherein NaOH is added to the above acid leaching product to obtain LiOH or a hydrate thereof.
  10. In paragraph 1, Converting to the above lithium compound is, A method for producing a lithium compound from lithium-ion battery waste, wherein Na₂CO₃ is added to the above acid leaching product to obtain Li₂CO₃ .
  11. In Paragraph 10, Converting to the above lithium compound is, A method for producing a lithium compound from lithium-ion battery waste, further comprising adding Ca(OH )2 to the above Li2CO3 to produce LiOH or a hydrate thereof.

Description

A method of producing lithium compounds from lithium-ion battery waste The present invention relates to a method for producing a lithium compound from lithium-ion battery waste. Due to their high energy density, stability, and excellent charge/discharge performance, lithium-ion batteries (LIBs) are widely used in a wide range of applications, from small devices such as mobile phones, computers, and power tools to electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs) powered by electric motors; electric two-wheeled vehicles (E-bikes) and electric scooters; electric golf carts; and medium-to-large devices such as power storage systems, and demand is steadily increasing. With the increasing demand for lithium-ion batteries, the demand for various lithium precursor compounds, such as LiOH (lithium anhydride), LiOH· H₂O (lithium hydroxide monohydrate), and Li₂CO₃ (lithium carbonate) , is also rising. Conventionally, these lithium precursor compounds were generally obtained from non-renewable resources such as salt lakes or spodumene; however, these methods commonly involved environmental pollution issues, such as the destruction of surrounding ecosystems, water waste, and soil contamination. Meanwhile, as the use of lithium-ion batteries increases, environmentally friendly disposal methods are being researched, and recently, more sustainable options utilizing lithium-ion battery waste are gaining attention. Manufacturing lithium compounds from lithium-ion battery waste preserves the environment and prevents resource depletion, while also promoting the global distribution of resources by reducing dependence on non-renewable resources for countries that are not lithium-producing nations. Black mass (BM) is a material derived from the recycling process of lithium-ion battery waste and contains not only lithium but also other rare metals such as nickel and cobalt. Black mass can be obtained by separating positive and negative active materials from other components of lithium-ion batteries, such as separators, binders, and electrolytes, through the discharge, mechanical disassembly, and crushing of lithium-ion batteries. The positive and negative active materials may still contain binders, and black mass can be obtained by removing the binders through thermal or chemical treatment. However, such obtaining processes are incomplete, and the black mass may still contain organic materials, graphite, aluminum, copper, iron, and fluorine derived from binders, electrode plates, or electrolytes as impurities, which remains a challenge for the manufacture of lithium compounds through black mass recycling. FIG. 1 is a conceptual diagram showing the steps of a method for manufacturing a lithium compound according to one embodiment of the present invention. Figure 2(a) is a TGA/DTG curve obtained by thermogravimetric analysis of black mass obtained in one embodiment of the present invention, and (b) is a graph confirming the particle size distribution of black mass measured according to ASTM E11. Figures 3(a) to 3(d) are SEM images of a black mass obtained in one embodiment of the present invention. Figure 4(a) shows a graphite region in an SEM image of a black mass obtained in one embodiment of the present invention, and (b) is an image of the region mapped by element (O, F, P, S, C, Na, Al, Ni) by EDS analysis. Figure 5(a) shows the NCM region (active material) in an SEM image of a black mass obtained in one embodiment of the present invention, and (b) is an image of the region mapped by element (O, Mn, Co, C, Ni, Na, Al, Cu) by EDS analysis. Figures 6 (a) to (c) are XRD spectra of components contained in black mass obtained in one embodiment of the present invention. FIG. 7 is a conceptual diagram showing the steps of a method for manufacturing a lithium compound according to one embodiment of the present invention. FIG. 8 is a conceptual diagram showing the steps of a method for manufacturing a lithium compound according to one embodiment of the present invention. Figure 9 shows the results of XPS analysis of black mass before and after alkaline washing and after heat treatment according to one embodiment of the present invention. Figure 10 (a) is an XRD spectrum before and after alkaline washing according to one embodiment of the present invention, (b) is an XRD spectrum of BM-3 heat-treated after alkaline washing between 2θ = 18 and 25°, (c) is an XRD spectrum of BM-3 heat-treated after alkaline washing between 2θ = 30 and 80°, and (d) is an XRD spectrum before and after leaching according to one embodiment of the present invention. Figures 11 (a) to (d) are images showing the change when a magnet is brought near a black mass obtained during the process of manufacturing a lithium compound according to one embodiment of the present invention. Figures 12 (a) to (d) are SEM images of a black mass obtained during the process of manufacturing a lithium compound according to one e