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KR-20260062776-A - Up-cycling technology for cathode materials from waste lithium-ion secondary batteries using deep eutectic solvents

KR20260062776AKR 20260062776 AKR20260062776 AKR 20260062776AKR-20260062776-A

Abstract

The present invention provides a method for manufacturing a cathode material using waste batteries, comprising the steps of: S1) mixing black powder derived from waste batteries with a deep eutectic solution (DES) to leach out metal contained in the black powder to produce a leachate; S2) supplementing the leachate with a cathode material raw material to produce a cathode material mixture; S3) drying and calcining the cathode material mixture to remove organic matter; and S4) crushing the cathode material mixture from which organic matter has been removed and then calcining it to produce a cathode material, thereby providing a method for recycling waste lithium-ion batteries that is simple and economical.

Inventors

  • 이기태
  • 박윤태
  • 장호걸

Assignees

  • 전북대학교산학협력단

Dates

Publication Date
20260507
Application Date
20250110
Priority Date
20241029

Claims (17)

  1. S1) A step of preparing a leaching solution by mixing black powder derived from waste batteries with a deep eutectic solution (DES) to leach out metal contained in the black powder; S2) A step of preparing an anode material mixture by supplementing the above leaching solution with an anode material raw material; S3) A step of drying and calcining the above anode material mixture to remove organic matter; and S4) A step of manufacturing a cathode material by crushing the cathode material mixture from which the organic matter has been removed and then calcining it; comprising a method for manufacturing a cathode material using waste batteries.
  2. In paragraph 1, A method for manufacturing a cathode material using waste batteries, wherein the deep eutectic solvent comprises hydrogen bond acceptors (HBA) and hydrogen bond donors (HBD).
  3. In paragraph 2, The above hydrogen bond acceptors are choline chloride, choline bromide, 2-(chlorocarbonyl oxy)-N,N,N-trimethylethenaminium chloride, benzyltriphenylphosphonium chloride, N-benzyl-2-hydroxy-N,N-dimethylethanaminium, tetra-n-butylammonium bromide, N,N-diethylethanolammonium chloride, methyltriphenylphosphonium bromide, lidocaine, and tetra-n-ethylammonium A method for manufacturing a cathode material using a waste battery, comprising one or more selected from the group consisting of tetra-n-ethylammonium chloride, tetramethylammonium chloride, alanine, glycine, proline, histidine, nicotinic acid, choline fluoride, betaine, imidazole, and tetra-n-butyl ammonium bromide.
  4. In paragraph 2, The above hydrogen-bonded urea, glycerol, adipic acid, acetamide, phenol, benzamide, benzoic acid, ethylene glycol, malic acid, thiourea, succinic acid, 1,2-dimethyl urea (1,3-Dimethyl Urea), oxalic acid, lactic acid, citric acid, 1-methyl urea, glucose, 1,1-dimethyl urea, 1,4-butanediol, decanoic acid, fructose, triethylene glycol A method for manufacturing a cathode material using a waste battery, comprising one or more selected from the group consisting of Glycol, Dodecanoic Acid, Menthol, Thymol, 1-Naphthol, Imidazole, Zinc Chloride (ZnCl2), 2,2,2-Trifluoroacetamid, phenyllactic acid, phenylpropionic acid (tricarballylic acid), levulinic acid, and p-Toluenesulfonic acid.
  5. In paragraph 2, A method for manufacturing a cathode material using waste batteries, wherein the deep eutectic solvent comprises citric acid and ethylene glycol as a hydrogen bond acceptor and a hydrogen bond donor in a molar ratio of 1:5.
  6. In paragraph 2, A method for manufacturing a cathode material using waste batteries, wherein the deep eutectic solvent comprises Choline Chloride and Citric Acid as a hydrogen bond acceptor and a hydrogen bond donor in a molar ratio of 1:1 to 3:1.
  7. In paragraph 2, A method for manufacturing a cathode material using waste batteries, wherein the deep eutectic solvent comprises Choline Chloride, Citric Acid, and Ethylene Glycol in a molar ratio of 1:1:5 as a hydrogen bond acceptor and a hydrogen bond donor.
  8. In paragraph 2, A method for manufacturing a cathode material using spent batteries, wherein the deep eutectic solvent comprises Choline Chloride, p-Toluene sulfonic acid, and Ethylene Glycol in a molar ratio of 1:1:5 as a hydrogen bond acceptor and a hydrogen bond donor.
  9. In paragraph 2, A method for manufacturing a cathode material using waste batteries, wherein the deep eutectic solvent comprises Choline bromide and Citric Acid in a 1:1 molar ratio as a hydrogen bond acceptor and a hydrogen bond donor.
  10. In paragraph 2, A method for manufacturing a cathode material using waste batteries, wherein the deep eutectic solvent comprises Choline bromide, p-Toluene sulfonic acid, and Ethylene glycol as a hydrogen bond acceptor and a hydrogen bond donor in a molar ratio of 1:1:5.
  11. In paragraph 2, A method for manufacturing a cathode material using spent batteries, wherein the deep eutectic solvent comprises Tetra-n-butylammonium bromide, p-Toluene sulfonic acid, and Ethylene glycol in a molar ratio of 1:1:5 as a hydrogen bond acceptor and a hydrogen bond donor.
  12. In paragraph 1, A method for manufacturing a cathode material using waste batteries, wherein the above metal comprises one or more selected from the group consisting of Li, Co, Mn and Ni.
  13. In paragraph 1, A method for manufacturing a cathode material using waste batteries, wherein the above-mentioned cathode material raw material comprises Li salt, Co salt, Al salt, Ni salt, Mn salt, or a combination thereof.
  14. In paragraph 1, The above step S3) is a method for manufacturing a cathode material using waste batteries, wherein the amount of the cathode material input is determined through an inductively coupled plasma spectroscopy analyzer (ICP-OES).
  15. In paragraph 1, A method for manufacturing a cathode material using waste batteries, wherein in step S4) above, drying is performed at 80 to 200 ℃ for 5 to 30 hours.
  16. In paragraph 1, A method for manufacturing a cathode material using waste batteries, wherein the above calcination is performed at 500 to 1000℃ for 10 to 30 hours.
  17. A method for manufacturing a cathode material using waste batteries, wherein the cathode material comprises LCO, NCA, NCM111, and NCM811.

Description

Upcycling technology for cathode materials from waste lithium-ion secondary batteries using deep eutectic solvents The present invention relates to a method for manufacturing a new positive electrode active material by recycling metal obtained from waste batteries. In general, lithium-ion secondary batteries not only possess high operating voltage and high energy density but also allow for lightweight construction, making them the power source for most small portable devices. Currently, lithium-ion secondary batteries are widely used in communication and information devices such as mobile phones, laptops, digital devices, cameras, and camcorders, and demand is increasing significantly. These lithium-ion secondary batteries consist of a positive electrode, a negative electrode, an organic electrolyte, and an organic separator, and lithium cobalt oxide (LiCoO2) is commercially available as the positive electrode active material due to its excellent reversibility, low self-discharge rate, high capacity, high energy density, and ease of synthesis. Although lithium-ion secondary batteries with such a composition have excellent charge-discharge cycles and a relatively long lifespan, they are consumables with a lifespan of approximately 500 charge-discharge cycles, so the amount of waste increases along with the increase in usage. However, since these spent lithium-ion batteries are classified as designated waste under the Enforcement Rules of the Waste Management Act, a rapid increase in the amount of waste leads to a worsening shortage of landfill sites and causes environmental damage. To address these environmental issues, various measures have been discussed to recycle and reuse spent lithium-ion batteries. Conventionally, methods such as pyrolysis, wet smelting, regeneration, etching, or Echeron battery recycling have been used to recycle spent lithium-ion secondary batteries. However, pyrolysis is a simple process but requires a large amount of energy, resulting in high costs; wet smelting allows for the recovery of cathode materials with high purity but is a very complex process; regeneration is simple but does not yield high purity; and Echeron battery recycling is limited to use only for LFP (Li-FePO4). Furthermore, the aforementioned methods generate large amounts of wastewater and toxic gases due to strong acids or alkaline leaching agents, leading to environmental pollution problems. Furthermore, even if metals, metal salts, or precursors were recovered from the cathode material using the aforementioned method, additional processes were required to separate and synthesize them. Consequently, the process was somewhat complex, and there were issues such as environmental pollution caused by new waste generated from the novel synthesis process and increased costs for the recycling process. Accordingly, there is a need for a recycling method for waste lithium-ion batteries that does not cause environmental pollution compared to conventional technology, is economical, and can produce cathode materials without additional manufacturing processes. Figure 1 shows a flowchart of an embodiment of the present invention. FIG. 2 shows an XRD graph and an SEM photograph according to one embodiment of the present invention. Figure 3 compares the XRD graph and SEM image of an embodiment of the present invention and a used NCM. Figure 4 is a graph showing the rate capability characteristics of the electrode used in the present invention. The present invention is capable of various modifications and may have various embodiments; specific embodiments are illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and it should be understood that it includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the present invention. In describing the present invention, detailed descriptions of related prior art are omitted if it is determined that such detailed descriptions may obscure the essence of the present invention. Terms such as "first," "second," etc., may be used to describe various components, but said components should not be limited by said terms. These terms are used solely for the purpose of distinguishing one component from another. The terms used in this application are used merely to describe specific embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, terms such as "comprising" or "having" are intended to specify the presence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof. The present invention provides