WO2022119262A1 - 폐 리튬이차전지 양극재로부터 리튬전구체의 회수방법 - Google Patents
폐 리튬이차전지 양극재로부터 리튬전구체의 회수방법 Download PDFInfo
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- WO2022119262A1 WO2022119262A1 PCT/KR2021/017806 KR2021017806W WO2022119262A1 WO 2022119262 A1 WO2022119262 A1 WO 2022119262A1 KR 2021017806 W KR2021017806 W KR 2021017806W WO 2022119262 A1 WO2022119262 A1 WO 2022119262A1
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- Prior art keywords
- lithium
- recovering
- secondary battery
- mixture
- precursor
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002699 waste material Substances 0.000 title claims abstract description 34
- 239000002243 precursor Substances 0.000 title claims abstract description 29
- 239000007774 positive electrode material Substances 0.000 title abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 131
- 239000000203 mixture Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000010406 cathode material Substances 0.000 claims description 38
- 238000011084 recovery Methods 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 238000010304 firing Methods 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052723 transition metal Inorganic materials 0.000 description 12
- 150000003624 transition metals Chemical class 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000006182 cathode active material Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910003548 Li(Ni,Co,Mn)O2 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- RLJDSHNOFWICBY-UHFFFAOYSA-N [P]=O.[Fe].[Li] Chemical compound [P]=O.[Fe].[Li] RLJDSHNOFWICBY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- -1 transition metal salt Chemical class 0.000 description 1
Images
Classifications
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/28—Purification; Separation
- C01D1/30—Purification; Separation by crystallisation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
- C22B47/00—Obtaining manganese
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- 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
- H01M10/052—Li-accumulators
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- 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
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- 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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Definitions
- the present invention relates to a method for recovering a lithium precursor from a cathode material of a waste lithium secondary battery.
- the lithium secondary battery market is expanding into various fields such as information technology (IT) device batteries, electric vehicles, and energy storage devices (ESS), and the demand is increasing day by day. As demand increases, the amount of waste lithium secondary batteries is also increasing day by day.
- IT information technology
- ESS energy storage devices
- the cathode material accounts for more than 60% of the cost of lithium secondary batteries, and lithium cobalt oxide (LiCoO 2 ), which has excellent reversibility, low self-discharge rate, high capacity, and high energy density, and is easy to synthesize, is used. .
- the waste cathode material is extracted with strong acids such as hydrochloric acid, sulfuric acid and nitric acid, and then neutralized with an alkali to precipitate cobalt, nickel, etc. as hydroxide and recover it
- strong acids such as hydrochloric acid, sulfuric acid and nitric acid
- an alkali to precipitate cobalt, nickel, etc. as hydroxide and recover it
- a process of dissolving a cathode material with sulfuric acid or nitric acid in the presence of hydrogen peroxide and hydrogen peroxide and then separating and recovering the metal by a neutralization precipitation method has been generally used.
- a strong acid in the extraction process serious environmental pollution due to evaporation into the atmosphere and, in particular, problems such as corrosion of equipment by acid are very serious.
- An object of the present invention is to provide a method for recovering lithium hydroxide in high yield at a low temperature from a waste lithium secondary battery cathode material.
- the present invention is a first invention.
- c) provides a method for recovering a lithium precursor comprising the step of separating the lithium precursor by washing the second mixture with water.
- the firing temperature may be 450 °C to 600 °C.
- step b) may be performed in an inert gas atmosphere.
- the water washing may be performed at 20 °C to 90 °C.
- an aqueous solution of lithium hydroxide may be generated through the water washing treatment.
- step c) may further include crystallizing lithium hydroxide.
- 5 to 50 parts by weight of the urea may be mixed with respect to 100 parts by weight of the cathode material.
- the cathode material may be represented by the following formula (1).
- M is selected from the group consisting of Mn, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, and B; , 0 ⁇ x ⁇ 1.1, 2 ⁇ y ⁇ 2.02, 0.5 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5).
- the recovery rate of lithium hydroxide from the cathode material of the waste lithium secondary battery may be 50% or more.
- the lithium precursor recovery method from the cathode material of a waste lithium secondary battery according to the present invention has an advantage in that lithium hydroxide can be recovered in high yield even at a low temperature of 600° C. or less by using urea as a reducing agent.
- lithium hydroxide can be efficiently recovered without using a strong acid such as sulfuric acid.
- FIG. 1 is a flowchart illustrating a method for recovering a lithium precursor according to an embodiment of the present invention.
- the term “precursor” is used to comprehensively refer to a compound including a specific metal to provide a specific metal included in the electrode active material.
- nickel which can increase the capacity of a lithium secondary battery
- lithium hydroxide which can be easily synthesized
- lithium hydroxide which has a lower melting point than lithium carbonate, is synthesized with nickel to increase the nickel content, it is easy to synthesize a “high nickel” cathode material, so lithium hydroxide is a major raw material for high-capacity lithium secondary batteries.
- the present invention provides a method of recovering a lithium precursor including lithium hydroxide from a waste lithium secondary battery cathode material in line with the trend of the high-capacity lithium secondary battery market.
- the recovery method comprises the steps of: a) mixing a waste lithium secondary battery cathode material with urea to prepare a first mixture; b) calcining the first mixture to prepare a second mixture containing lithium hydroxide; and c) separating the lithium precursor by washing the second mixture with water;
- Step a) is a step of mixing a waste lithium secondary battery cathode material and a solid reducing agent urea, and may further include obtaining a cathode material from a waste lithium secondary battery before step a).
- the waste lithium secondary battery may include a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, and the positive and negative electrodes may include a positive electrode or negative electrode active material layer coated on a positive electrode or negative electrode current collector, respectively.
- the waste lithium secondary battery is a lithium secondary battery that cannot be reused (charged/discharged), for example, a lithium secondary battery whose charge/discharge performance has significantly decreased due to long-term use or a lithium secondary battery destroyed by physical shock or chemical reaction.
- the waste cathode may include a cathode current collector and a cathode active material layer, and the cathode active material layer may include a cathode active material, a conductive material, and a binder.
- the conductive material may include a carbon-based material such as graphite, carbon black, graphene, carbon nanotubes, and the like
- the binder is a vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), It may include polyvinylidenefluoride (PVDF), polyacrylonitrile, and polymethylmethacrylate.
- the recovered waste anode may be subjected to heat treatment in an oxidizing atmosphere of 100 to 500 °C, preferably 350 to 450 °C. Accordingly, substantially all of the conductive material and the binder included in the positive electrode active material layer may be removed, and 95 wt% or more may be removed without limitation.
- the waste positive electrode that has been subjected to the heat treatment may be manufactured in a powder form by desorbing the positive electrode current collector through a pulverization treatment. Specifically, after pulverizing the waste cathode, a cathode material can be obtained by using 5 to 100 ⁇ m mesh screening. In this case, the grinding may be performed using a ball mill, but is not limited thereto.
- a positive electrode current collector component is substantially removed, and a positive electrode material in which 90 wt% or more of carbon-based components derived from the conductive material and the binder are removed may be obtained.
- the cathode material may be exemplarily represented by the following formula (1).
- M is selected from the group consisting of Mn, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, and B; , 0 ⁇ x ⁇ 1.1, 2 ⁇ y ⁇ 2.02, 0.5 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5).
- the first mixture may be prepared by mixing 5 to 50 parts by weight, preferably 7 to 30 parts by weight, and more preferably 10 to 25 parts by weight of the urea with respect to 100 parts by weight of the cathode material.
- the mixing may be dry mixing rather than mixing according to the addition of a liquid material such as a solvent, and may be performed in a fluidized bed reactor. Specifically, the mixing process may be performed at 15 to 90 °C, preferably at 25 to 50 °C for 1 to 3 hours.
- the cathode material is sufficiently reduced to increase the conversion rate to lithium hydroxide, and lithium hydroxide can be recovered in a high yield after step c).
- Step b) is a step of preparing a second mixture by calcining the first mixture prepared in step a), 450 to 600 °C, preferably 470 to 600 °C, more preferably 500 to 550 °C 1 to It can be carried out for 4 hours, preferably 2 to 3 hours.
- the sintering process may be performed in an inert gas atmosphere, and as a non-limiting example, the inert gas may include argon or nitrogen.
- the inert gas atmosphere may be replaced by a method of purging the above-described inert gas inside the reactor.
- the recovery refers to the recovery rate of lithium hydroxide from the cathode material of the spent lithium secondary battery, and specifically, the total content of lithium in the cathode material before recovery is analyzed as a standard of 100%, and the lithium content in the recovered lithium hydroxide is analyzed and hydroxide
- the lithium recovery rate may be a calculated value.
- the second mixture prepared in step b) may include a mixture containing lithium hydroxide (LiOH) and a transition metal.
- the transition metal-containing mixture may include a transition metal and a transition metal-containing oxide, and the transition metal may include nickel, cobalt, manganese, and the like.
- the transition metal of the transition metal-containing mixture may be formed by separating the transition metal component in the process in which the lithium composite oxide, which is the cathode material, is converted into lithium hydroxide through the sintering process of step b).
- Step c) is a step of water washing the second mixture prepared in step b), and may be performed at 20 to 90°C, preferably 20 to 60°C. Specifically, it may be carried out using distilled water, pure water, or soft water as the washing liquid for the water washing treatment.
- the second mixture and the washing solution may be mixed at a solid-liquid ratio of 10 g/L to 500 g/L.
- the water washing process may be repeated 1 to 3 times, and the process time for one washing process may be 30 minutes to 2 hours.
- an aqueous solution containing lithium hydroxide may be separated from the second mixture.
- the transition metal-containing mixture among the second mixture may be precipitated in the aqueous solution, and a lithium precursor including high-purity lithium hydroxide may be obtained through filtration.
- the precipitation-separated transition metal-containing mixture may be treated with an acid solution to form a precursor in the form of each transition metal salt.
- an acid solution for example, by using sulfuric acid as the acid solution, NiSO 4 , MnSO 4 and CoSO 4 which are transition metal precursors may be recovered, respectively.
- Step c) may further include crystallizing lithium hydroxide in the separated aqueous solution.
- crystalline lithium hydroxide can be obtained through the process of concentrating the aqueous solution.
- the concentration method can be selected without limitation as long as it can be used as a concentration method for obtaining a crystalline form in an aqueous solution, such as reduced pressure concentration, freeze concentration, evaporation concentration, heating concentration, precipitation concentration, reverse osmosis concentration, etc.
- FIG. 1 is a view showing a flow chart for recovering a lithium precursor from a waste lithium secondary battery according to an embodiment of the present invention.
- Step 1 Preparation of a cathode material for a waste lithium secondary battery
- the positive electrode includes a positive electrode active material layer including LiNi 0.8 Co 0.1 Mn 0.1 O 2 positive electrode active material, a Denka black conductive material, and a PVDF binder in a weight ratio of 92:5:3.
- Step 2 Recovering a lithium precursor from a waste lithium secondary battery cathode material
- step 2 of Example 1 the calcination temperature was performed at the temperature shown in Table 1 below instead of 450°C.
- step 2 of Example 1 solid carbon (carbon black, Denka) was used instead of urea, and the same procedure was performed except that the calcination temperature was performed at the temperature shown in Table 1 below.
- Example 1 Element 450 51 0 10.5 0 51
- Example 2 Element 480 75 0 15.7 0 75
- Example 3 Element 500 83 0 19.8 0 83
- Example 4 Element 530 89 0 22.3 0 89
- Example 5 Element 550 91 0 23.6 0 91
- Example 6 Element 600 92 1.0 24.2 0 88
- Example 7 Element 400 10 0 0 0 0 0 0 Comparative Example 1 solid carbon 450 6 0 0 0 0 0 Comparative Example 2 solid carbon 840 54 1.1 0 10.2 49
- the lithium conversion rate means the ratio of the lithium content in the aqueous solution obtained in the washing process to the total content of lithium in the positive electrode material before the reaction, and the content (wt%) of lithium carbonate, lithium hydroxide and lithium oxide is, in step 2 It is the content based on the total weight of the obtained preliminary precursor mixture, and the recovery rate of lithium hydroxide means the lithium content in the recovered lithium hydroxide compared to the total amount of lithium in the positive electrode material before recovery.
- Examples 1 to 6 using the reducing agent showed a higher recovery rate of lithium hydroxide than Comparative Examples 1 to 2 using the solid carbon reducing agent.
- the content of lithium hydroxide showed a tendency to increase as the calcination temperature increased.
- the calcination temperature is less than 450°C (Example 7)
- the content of lithium hydroxide is decreased, so it can be seen that the preferred calcination temperature is 450 to 600°C.
- Comparative Example 1 using solid carbon as a reducing agent the calcination process was performed under the same conditions as in Example 1, but the contents of lithium hydroxide and lithium carbonate in the recovered product were 0. That is, when solid carbon is used as a reducing agent, it can be seen that at a temperature of 450° C., lithium hydroxide is not produced at all, and the lithium conversion rate is also very low at 6%.
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Abstract
Description
환원제 | 소성온도 (℃) |
리튬 전환율 (%) |
탄산리튬 (중량%) |
수산화리튬 (중량%) |
산화리튬 (중량%) |
수산화리튬 회수율(%) |
|
실시예 1 | 요소 | 450 | 51 | 0 | 10.5 | 0 | 51 |
실시예 2 | 요소 | 480 | 75 | 0 | 15.7 | 0 | 75 |
실시예 3 | 요소 | 500 | 83 | 0 | 19.8 | 0 | 83 |
실시예 4 | 요소 | 530 | 89 | 0 | 22.3 | 0 | 89 |
실시예 5 | 요소 | 550 | 91 | 0 | 23.6 | 0 | 91 |
실시예 6 | 요소 | 600 | 92 | 1.0 | 24.2 | 0 | 88 |
실시예 7 | 요소 | 400 | 10 | 0 | 0 | 0 | 0 |
비교예 1 | 고체탄소 | 450 | 6 | 0 | 0 | 0 | 0 |
비교예 2 | 고체탄소 | 840 | 54 | 1.1 | 0 | 10.2 | 49 |
Claims (9)
- a) 폐 리튬이차전지 양극재를 요소 (Urea)와 혼합하여 제1혼합물을 제조하는 단계;b) 상기 제1혼합물을 소성하여 수산화리튬을 포함하는 제2혼합물을 제조하는 단계; 및c) 상기 제2혼합물을 수세처리하여 리튬전구체를 분리하는 단계;를 포함하는 리튬전구체의 회수방법.
- 제1항에 있어서,상기 소성온도는 450℃ 내지 600℃인 리튬전구체의 회수방법.
- 제1항에 있어서,상기 b) 단계는 불활성 기체 분위기에서 수행되는 리튬전구체의 회수방법.
- 제1항에 있어서,상기 수세 처리는 20℃내지 90℃에서 수행되는 리튬전구체의 회수방법.
- 제1항에 있어서,상기 수세 처리를 통해 수산화리튬 수용액이 생성되는 리튬전구체의 회수방법.
- 제1항에 있어서,상기 c) 단계는 수산화리튬을 결정화하는 단계를 더 포함하는 리튬전구체의 회수방법.
- 제1항에 있어서,상기 양극재 100 중량부에 대하여, 상기 요소 5 내지 50 중량부를 혼합하는 리튬전구체의 회수방법.
- 제1항에 있어서,상기 양극재는 하기 화학식 1로 표시되는 리튬전구체의 회수방법:[화학식 1]LixNiaCobM(1-a-b)Oy(화학식 1중, M은 Mn, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga 및 B로 이루어진 군에서 선택되고, 0<x≤1.1, 2≤y≤2.02, 0.5≤a≤1, 0≤b≤0.5임).
- 제1항에 있어서,상기 폐 리튬이차전지 양극재로부터의 수산화리튬 회수율은 50% 이상인 리튬전구체의 회수방법.
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EP21900950.3A EP4254601A4 (en) | 2020-12-02 | 2021-11-30 | METHOD FOR RECOVERING A LITHIUM PRECURSOR FROM Spent LITHIUM SECONDARY BATTERY POSITIVE ELECTRODE MATERIAL |
US18/255,807 US20230416103A1 (en) | 2020-12-02 | 2021-11-30 | Method for recovering lithium precursor from waste lithium secondary battery positive electrode material |
JP2023533893A JP2023551615A (ja) | 2020-12-02 | 2021-11-30 | 廃リチウム二次電池正極材からリチウム前駆体の回収方法 |
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