[go: up one dir, main page]

WO2025078192A1 - Procédé de fabrication d'un précurseur pour un matériau actif de cathode - Google Patents

Procédé de fabrication d'un précurseur pour un matériau actif de cathode Download PDF

Info

Publication number
WO2025078192A1
WO2025078192A1 PCT/EP2024/077465 EP2024077465W WO2025078192A1 WO 2025078192 A1 WO2025078192 A1 WO 2025078192A1 EP 2024077465 W EP2024077465 W EP 2024077465W WO 2025078192 A1 WO2025078192 A1 WO 2025078192A1
Authority
WO
WIPO (PCT)
Prior art keywords
range
lithium
hydroxide
oxy
particulate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2024/077465
Other languages
English (en)
Inventor
Rafael Benjamin BERK
Joop Enno FRERICHS
Fabian Seeler
Maike WIRTZ
Thorsten BEIERLING
Kathrin Michel
Michael Krumm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2025078192A1 publication Critical patent/WO2025078192A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • aqueous solution (a) Providing an aqueous solution (a) containing water-soluble salts of Ni and lithium and of at least one transition metal selected from Co and Mn, and, optionally, at least one further metal selected from Ti, Zr, Mo, W, Al, Mg, Nb, and Ta, and an aqueous solution (P) containing sodium or potassium hydroxide and, optionally, an aqueous solution (y) containing ammonia, wherein the amount of lithium is in the range of from 0.01 to 2.5 mol-% with respect to TM,
  • Lithiated transition metal oxides are currently used as electrode active materials for lithium-ion batteries. Extensive research and developmental work have been performed in the past years to improve properties like charge density, specific energy, but also other properties like the reduced cycle life and capacity loss that may adversely affect the lifetime or applicability of a lithium-ion battery. Additional effort has been made to improve manufacturing methods.
  • properties of the precursor translate into properties of the respective cathode active material to a certain extent, such as particle size distribution, content of the respective transition metals, crystallographic defects and more. It is therefore possible to influence the properties of cathode active materials by steering the properties of the precursor.
  • Some traces of elements may have surprising influence on the manufacture or the performance of cathode active material.
  • lithium-nickel scrambling may negatively affect the mobility of the lithium ions during charging and discharge of an electrode, thus reducing the capacity and charging properties.
  • lithium-nickel scrambling nickel ions are located in lithium crystallographic sites and vice versa.
  • Lithium-nickel scrambling may also be termed lithium-nickel disorder or lithium-nickel displacements. Such displacements are believed to hamper the diffusion of lithium during charging and discharging.
  • the specific surface (BET) of the resultant precursor is in the range of from 1 to 70 m 2 /g, determined by nitrogen adsorption, for example in accordance with to DIN-ISO 9277:2003-05.
  • the outgassing temperature is 120°C.
  • the precursor is an (oxy)hydroxide of TM wherein TM comprises Ni and lithium and at least one metal selected from Co and Mn, and, optionally, at least one further element selected from Ti, Zr, Ca, Si, Mo, W, Al, Mg, Nb, and Ta, preferably a combination of Al, W, Mg and Nb or a combination of Ti, Zr, Al and Mg.
  • the amount of lithium is in the range of from 0.01 to 2.5 mol-% with respect to TM, preferably 0.05 to 1.5 mol-%.
  • TM is a combination of metals according to general formula (I)
  • Ni a CObMn c i.dMd (I) wherein a is in the range of from 0.6 to 0.95, preferably from 0.8 to 0.94, b is in the range of from 0.025 to 0.2, preferably from 0.025 to 0.15, c is in the range of from zero to 0.2, preferably from zero to 0.15, and d is in the range of from zero to 0.1 , preferably 0.02 to 0.05,
  • TM may contain traces of further metal ions other than the above, for example traces of ubiquitous metals such as sodium, calcium, iron, or zinc, as impurities but such traces will not be taken into account in the description of the present invention. Traces in this context will mean amounts of 0.05 mol-% or less, referring to the total metal content of TM.
  • Precursors as used herein are particulate materials. In one embodiment of the present invention, precursors have an average particle diameter D50 in the range of from 3 to 20 pm, preferably from 4 to 16 pm. The average particle diameter may be determined, e. g., by light scattering or LASER diffraction or electroacoustic spectroscopy. The particles are composed of primary particles, in particular they are agglomerates of primary particles, and the above particle diameter refers to the secondary particle diameter.
  • D50 is - strictly speaking - the median value rather than an average diameter both expressions are used interchangeably.
  • Said particles of precursors may have an irregular shape but in a preferred embodiment, said particulate material has a regular shape, for example spheroidal or even spherical.
  • the aspect ratio may be in the range of from 1 and 10, preferably from 1 to 3 and even more preferably from 1 to 1.5.
  • the aspect ratio is defined as the ratio of width to length or specifically the particle diameter in the longest dimension versus the particle diameter in the shortest dimension. Perfectly spherical particles have an aspect ratio of 1.
  • water-soluble salts of cobalt and nickel or manganese or lithium or of metals other than nickel and cobalt and manganese and lithium refers to salts that exhibit a solubility in distilled water at 25°C of 25 g/l or more, the amount of salt being determined under omission of crystal water and of water stemming from aquo complexes.
  • Water-soluble salts of nickel and cobalt and manganese may preferably be the respective water-soluble salts of Ni 2+ and Co 2+ and Mn 2+ .
  • Examples of water-soluble salts of nickel and cobalt and lithium are the sulfates, the nitrates, the acetates and the halides, especially chlorides.
  • nitrates and sulfates of which the sulfates of nickel and cobalt and nitrate and sulfate of lithium are more preferred. Even more preferred are the sulfates of nickel, cobalt and lithium.
  • lithium is added involuntarily as an impurity of nickel or cobalt obtained from work-up of spent lithium-ion batteries or off-spec batteries or off- spec battery materials.
  • water-soluble compounds of aluminum then refers to compounds like Al2(SO4)3, AI(NO 3 )3, KAI(SO4)2, NaAIC>2 and NaAI(OH)4.
  • the pH value of aqueous solution (a) may be in the range of from 1 to 3 or above 13.
  • MgSO4 MgSO4
  • Mg(NO 3 )2 magnesium acetate
  • MgCfe magnesium acetate
  • MgSC>4 being preferred.
  • Examples of suitable compounds of Ca are Ca(NO3)2, calcium acetate and CaCfe,
  • Suitable compounds of Si are sodium metasilicate, sodium orthosilicate, and silicic acid.
  • Zr zirconium acetate, Zr(SO4)2, ZrOSCk, ZrO(NO3)2, Zr(NO3)4, with Zr(SC>4)2 being preferred.
  • Suitable compounds of W are WO3, WO3 ⁇ H 2 O, Na 2 WO4, ammonium tungstate and tungstic acid.
  • Solution (a) may have a pH value in the range of from 2 to 6. In embodiments wherein higher pH values are desired, ammonia may be added to solution (a). However, it is preferred to not add ammonia to solution (a). In case it is intended to provide a solution containing NaAIO2 and NaAI(OH)4 it is preferred to provide at least two aqueous solutions, one containing nickel and at least one of cobalt and manganese and, optionally, at least one of Ti , Zr, Mo, W, Mg, Nb, and Ta, and another aqueous solution containing NaAICfe or NaAI(OH)4.
  • the concentration of nickel and other constituents of TM can be selected within wide ranges.
  • the respective total metal concentration is selected to be within a range of 1 to 1.8 mol of the metal/kg of solution, more preferably 1.3 to 1.7 mol of the metal/kg of solution.
  • the concentration of complexing agent(s) in solution (y) is in the range of froml to 30 % by weight.
  • the complexing agent is selected from ammonia its concentration is preferably in the range of from 10 to 30 % by weight.
  • the complexing agent(s) is or are selected from organic acids or their alkali or ammonium salts wherein said organic acid bears at least two functional groups per molecule and at least one of the functional groups is a carboxylate group
  • the concentration of said complexing agent in solution (y) may be in the range of from 0.2 to 10% by weight.
  • Step (b) may be carried out in one or more sub-steps.
  • Such sub-steps may be distinguished by at least one of pH value, temperature, composition of solution (a), stirring speed, residence time, or atmosphere.
  • step (b) solution (a) and solution (P) and - if applicable - solution (y) are combined, under precipitation of a hydroxide.
  • the percentage of mother liquor withdrawn in steps (b) and (c) may be in the range of from 200 to 1 ,200 g/l, preferably 800 to 1,200 g/l. However, despite the withdrawal of mother liquor, the slurry is still well stirrable.
  • Step (b) includes combining solution(s) (a) and solution (P) and, if applicable, solution (y), in a continuous reactor, thereby creating solid particles of a hydroxide of TM. Said solid particles are slurried.
  • step (b) the pH value of the liquid phase of the slurry is in the range of from 12.5 to 14.0.
  • the pH value is determined at 23°C in the liquid phase.
  • the average hydraulic residence time of the slurry in step (b) is in the range of from 30 minutes to 16 hours, preferably in the range from 1 to 12 hours, more preferred in the range of 2 to 8 hours.
  • step (b) is performed at a temperature in the range from 10 to 85°C, preferably at temperatures in the range from 20 to 70°C.
  • step (b) is performed at constant pressure, for example at ambient pressure. In other embodiments, step (b) is performed at elevated pressure, for example up to 50 bar.
  • mother liquor is removed from the continuous reactor during step (b).
  • the mother liquor contains water and sodium sulfate.
  • step (b) is performed in two sub-steps, (b1) and (b2).
  • Sub-step (b1) is performed at a pH value higher than (b2), for example 12.0 to 12.7 versus 10.0 to less than 12.0 but in any way distinguished by at least 0.5 units.
  • sub-step (b1) essentially particles of hydroxide are formed and in sub-step (b2), such particles of hydroxide are grown.
  • Filtration may be supported by suction or by pressure.
  • the solid-liquid separation step (c) may be performed at any temperature at which water is in the liquid state, for example 5 to 95°C, preferred is 20 to 60°C.
  • Step (c) includes drying the solid material.
  • Step (c) includes a thermal treatment of the solid, for example in a drying oven, in a rotary kiln or in a flash calciner.
  • the liquid phase obtained from step (c) may contain substances that should not be wasted or transferred to a sewage plant, e.g., lithium compounds.
  • liquid medium obtained from the solid-liquid separation step (c) is worked up in a separate step (d), for example by an electrolysis in order to crystallize lithium hydroxide, for example by precipitation.
  • a further aspect of the present invention refers to particulate (oxy)hydroxides or oxides of TM, hereinafter also referred to as inventive (oxy)hydroxides or inventive precursors.
  • inventive precursors are advantageously made according to the inventive process.
  • Inventive precursors are (oxy)hydroxides of or oxides TM wherein TM comprises nickel and 0.01 to 0.1 mol- %Li, referring to TM, and at least one transition metal selected from Co and Mn and at, optionally, at least one further element selected from Ti, Zr, Ca, Si, Mo, W, Al, Mg, Nb, and Ta.
  • TM is a combination according to formula (I), vide supra.
  • inventive precursors are selected from oxyhydroxides and oxides with an average oxidation state of TM in the range of from + 2.1 to + 2.6, determined by iodometric titration.
  • inventive precursors are comprised of secondary particles comprising asymmetric plate-like shaped primary particles that have a thickness of 20 to 200 nm and a length of 50 to 500 nm.
  • the primary particles are essentially radially aligned.
  • the portion of radially aligned primary particles may be determined, e.g., by SEM (Scanning Electron Microscopy) of a cross-section of at least arbitrarily selected 5 secondary particles.
  • Inventive precursors as oxides of TM have a moisture content in the range of from 100 to 10,000 ppm by weight, preferably 250 to 8,000 ppm and more preferably 300 to 5,000 ppm.
  • the moisture content may be determined by Karl-Fischer-titration.
  • TM of inventive (oxy)hydroxides corresponds to formula (I)
  • said calcination is preferably performed in an atmosphere of oxygen or oxygen-enriched air, for example with at least 60 vol-% of oxygen, preferably 80 vol-% of oxygen and more preferably at least 90 vol-% oxygen.
  • said calcination may be performed in air atmosphere.
  • Suitable set-ups for said calcination are rotary kilns, roller hearth kilns, and pusher kilns.
  • the mixture of precursor and source of lithium and compound of Al and, optionally, solvent(s), is heated to 700 to 1000 °C with a heating rate of 0.1 to 10 °C/min.
  • the inventive calcination is performed in an oxy- gen-containing atmosphere, for example in a nitrogen-air mixture, in a rare gas-oxygen mixture, in air, in oxygen or in oxygen-enriched air.
  • the atmosphere in in the inventive calcination is selected from air, oxygen and oxygen-enriched air.
  • Oxygen-enriched air may be, for example, a 50:50 by volume mix of air and oxygen.
  • Other options are 1 :2 by volume mixtures of air and oxygen, 1 :3 by volume mixtures of air and oxygen, 2:1 by volume mixtures of air and oxygen, and 3:1 by volume mixtures of air and oxygen.
  • the cathode active material so obtained is cooled down before further processing. Additional - optional - steps before further processing the resultant electrode active materials are sieving and de-agglomeration steps.
  • M is selected from Mg, Al, Ti, Zr, Mo, W, Al, Mg, Nb, and Ta, preferably selected from Al, Mg, Nb, W, Ti, and Zr, more preferably a combination of Mg and Al or a combination of Al, Mg, W and Nb or a combination of Mg and Al or a combination of Al, Mg, Ti and Zr.
  • a + b + c 1.
  • Another aspect of the present invention is a process for making a cathode active material comprising the steps of mixing an inventive precursor with a source of lithium, e.g., LIOH or LI2O2 or i2CO3, followed by a thermal treatment at a temperature in the range of from 675 to 1000°C.
  • a source of lithium e.g., LIOH or LI2O2 or i2CO3
  • inventive cathode active materials have a residual lithium carbonate content in the range of from 0.03 to 0.15% by weight, determined by titration, and a lattice parameter a in the range of from 2.8736 to 2.8743 as determined by X-Ray diffraction and Rietveld refinement.
  • the titration may be performed, for example, by for example by soaking inventive cathode active material with water, followed by titration with 0.1 M aqueous HCI.
  • One titration point corresponds to the sum of hydroxide and carbonate protonation, the second corresponds to the protonation of bicarbonate.
  • (C) 1 to 15 % by weight of binder material, percentages referring to the sum of (A), (B) and (C).
  • polypropylene is not only understood to mean homopolypropylene, but also copolymers of propylene which comprise at least 50 mol% of copolymerized propylene and up to 50 mol% of at least one further comonomer, for example ethylene and a- olefins such as butylene, 1 -hexene, 1 -octene, 1 -decene, 1 -dodecene and 1 -pentene.
  • Polypropylene is preferably isotactic or essentially isotactic polypropylene.
  • polystyrene is not only understood to mean homopolymers of styrene, but also copolymers with acrylonitrile, 1,3-butadiene, (meth)acrylic acid, Ci- Cio-alkyl esters of (meth)acrylic acid, divinyl benzene, especially 1,3-divinylbenzene, 1 ,2- diphenylethylene and a-methylstyrene.
  • Another preferred binder (C) is polybutadiene.
  • Binder (C) may be cross-linked or non-cross-linked (co)polymers.
  • binder (C) is selected from halogenated (co)polymers, especially from fluorinated (co)polymers.
  • Halogenated or fluorinated (co)polymers are understood to mean those (co)polymers which comprise at least one (co)polymerized (co)monomer which has at least one halogen atom or at least one fluorine atom per molecule, more preferably at least two halogen atoms or at least two fluorine atoms per molecule.
  • Examples are polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers and ethylene-chlorofluoroethylene copolymers.
  • Suitable binders (C) are especially polyvinyl alcohol and halogenated (co)polymers, for example polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene.
  • a further aspect of the present invention is a battery, containing at least one cathode comprising inventive cathode active material, carbon, and binder, at least one anode, and at least one electrolyte.
  • Said anode may contain at least one anode active material, such as carbon (graphite), TiCh, lithium titanium oxide, silicon or tin.
  • Said anode may additionally contain a current collector, for example a metal foil such as a copper foil.
  • Non-aqueous solvents for electrolytes can be liquid or solid at room temperature and is preferably selected from among polymers, cyclic or acyclic ethers, cyclic and acyclic acetals and cyclic or acyclic organic carbonates.
  • suitable polymers are, in particular, polyalkylene glycols, preferably poly-Ci-C4- alkylene glycols and in particular polyethylene glycols.
  • Polyethylene glycols can here comprise up to 20 mol% of one or more Ci-C4-alkylene glycols.
  • Polyalkylene glycols are preferably polyalkylene glycols having two methyl or ethyl end caps.
  • the molecular weight M w of suitable polyalkylene glycols and in particular suitable polyethylene glycols can be at least 400 g/mol.
  • the molecular weight M w of suitable polyalkylene glycols and in particular suitable polyethylene glycols can be up to 5 000 000 g/mol, preferably up to 2 000 000 g/mol.
  • Suitable acyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1 ,1 -dimethoxyethane and 1,1 -diethoxyethane.
  • Suitable cyclic acetals are 1,3-dioxane and in particular 1 ,3-dioxolane.
  • Suitable acyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
  • the solvent or solvents is/are preferably used in the water-free state, i.e. with a water content in the range from 1 ppm to 0.1% by weight, which can be determined, for example, by Karl-Fischer titration.
  • Preferred electrolyte salts are selected from among LiC(CF3SO2)3, LiN(CF3SO2)2, LiPFe, IJBF4, IJCIO4, with particular preference being given to LiPFe and LiN(CF3SO2)2.
  • Batteries according to the invention further comprise a housing which can have any shape, for example cuboidal or the shape of a cylindrical disk or a cylindrical can.
  • a metal foil configured as a pouch is used as housing.
  • Batteries according to the invention display a good discharge behavior, for example at low temperatures (zero °C or below, for example down to -10°C or even less), a very good discharge and cycling behavior.
  • the present invention further provides for the use of batteries according to the invention in appliances, in particular in mobile appliances.
  • mobile appliances are vehicles, for example automobiles, bicycles, aircraft or water vehicles such as boats or ships.
  • Other examples of mobile appliances are those which move manually, for example computers, especially laptops, telephones or electric hand tools, for example in the building sector, especially drills, battery-powered screwdrivers or battery-powered staplers.
  • LiOH and LI2CO3 were distinguished by the two distinct equivalent points in the titration curve.
  • the first equivalent point thereby corresponds to the protonation of the hydroxide and carbonate ions, whereas the second equivalent point equals the protonation of the hydrogen carbonate ions, thus making the differentiation of the two salt concentrations possible. Based on this the respective weight fractions of LiOH and LI2CO3 were calculated.
  • Nickel sulfate “NISO4 solution 1” was manufactured as follows:
  • Discharged end-of-life lithium-ion batteries were shredded, crushed, and milled until a black mass was obtained.
  • the current collectors were removed from the black mass by sieving, and metallic iron was separated off by using magnetic separation.
  • the resulting black mass was subjected to an acid leaching with concentrated sulfuric acid and SO2 at a pH value of below 2.0 until all metal oxides were dissolved.
  • the pH-value of the resulting solution was adjusted to 3
  • the remaining iron, aluminum and copper impurities were depleted by precipitation and subsequent filtration.
  • other metal impurities were separated by precipitation of the respective metal fraction by stepwise increasing the pH-value to 5.0.
  • Nickel sulfate/NISO4 solution 2 was manufactured as follows:
  • NISO4 solution 2 The valuable manganese and cobalt were recovered as aqueous sulfates by organic solvent extraction with kerosine as solvent and di-(2-ethylhexyl) phosphoric acid as extractant, while lithium remained in solution This resulted in 96 g/l Ni and 75 g/l IJ2SO4 in the NiSCk solution, which is referred as NISO4 solution 2.
  • the temperature Inside the vessel was set to 55 °C, the stirrer element was operated at 950 rpm and the aqueous solution (a.1), (0.1) and (y.1) were simultaneously introduced into the vessel through the corresponding tubes and the particles were grown until a particle diameter of
  • Step (c.2) The resulting slurry was filtered, washed with deionized water and an aqueous solution of sodium hydroxide (1kg of 25 wt% aqueous sodium hydroxide solution per kg of solid hydroxide and dried at 120 °C for 12 hours to obtain the inventive precursor P-CAM.2.
  • P-CAM.2 had an average particle diameter (D50) of 12.0 pm, a value of (D90-D10)/D50 of 0.33, a BET surface of 16.0 m 2 /g, and a lithium-content of 140 ppm.
  • D50 average particle diameter
  • step (b) aqueous solution (a.3) was used in step (b), hereinafter (b.3-1) and (b.3-2) .
  • Step (b.3) After 21 h of reaction time, the particle growth was ceased by stopping the feed dosing. The slurry obtained was collected and had an average particle diameter (D50) of 4.6 pm and (D90-D10)/D50 of 0.7. The remaining steps were as described as above.
  • a saggar was charged with the resultant mixture and transferred into a Linn oven. The temperature was raised at rate of 2 C/min to 765 °C under flowing oxygen and then held constant at 765 °C for 8 hours and subsequently allowed to naturally cool under flowing oxygen.
  • the resultant powder was then deagglomerated in a grinding mill and sieved. After de-agglomeration, the powder had an average particle diameter (D50) of 13.6 pm and a span of 0.37.
  • PVDF binder polyvinylidene difluoride, Solef® 5130
  • NMP Merck
  • binder solution 2.5 wt.%
  • carbon black Li 400, 2.5 wt.-%
  • inventive CAM.2 or C-CAM.1 95 wt.% was added and the suspension was stirred again to obtain a lump-free slurry.
  • the solids content of the slurry was adjusted to 65%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un (oxy)hydroxyde ou d'un oxyde particulaire de TM, TM comprenant du nickel et un métal de transition choisi parmi Co et Mn et, éventuellement, au moins un autre métal choisi parmi Ti, Zr, Mo, W, Al, Mg, Nb, et Ta, et ledit procédé comprenant les étapes consistant à : (a) fournir une solution aqueuse (a) contenant des sels hydrosolubles de Ni et de lithium et d'au moins un métal de transition choisi parmi Co et Mn, et éventuellement, au moins un autre métal choisi parmi Ti, Zr, Mo, W, Al, Mg, Nb, et Ta, et une solution aqueuse (P) contenant de l'hydroxyde de sodium ou de potassium et, éventuellement, une solution aqueuse (y) contenant de l'ammoniac, la quantité de lithium étant dans la plage de 0,01 à 2,5 % en moles par rapport à TM, (a) combiner une solution (a) et une solution (|3) et, le cas échéant, une solution (y) à une valeur de pH dans la plage de 10,0 à 12,7 en une ou plusieurs sous-étapes, créant ainsi des particules solides d'un hydroxyde contenant du nickel, lesdites particules solides étant mises en suspension, (b) retirer l'(oxy)hydroxyde particulaire de TM par un procédé de séparation solide/liquide, suivi d'un séchage.
PCT/EP2024/077465 2023-10-09 2024-09-30 Procédé de fabrication d'un précurseur pour un matériau actif de cathode Pending WO2025078192A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23202333.3 2023-10-09
EP23202333 2023-10-09

Publications (1)

Publication Number Publication Date
WO2025078192A1 true WO2025078192A1 (fr) 2025-04-17

Family

ID=88297138

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2024/077465 Pending WO2025078192A1 (fr) 2023-10-09 2024-09-30 Procédé de fabrication d'un précurseur pour un matériau actif de cathode

Country Status (1)

Country Link
WO (1) WO2025078192A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112607789A (zh) * 2020-12-15 2021-04-06 中南大学 废旧锂离子电池有价金属回收与正极材料再生的工艺
KR102272325B1 (ko) * 2020-11-19 2021-07-02 (주)로브 폐리튬이차전지를 재생한 용액을 이용한 니켈―코발트―망간 복합전구체의 제조 방법
WO2023101078A1 (fr) * 2021-11-30 2023-06-08 한국교통대학교산학협력단 Procédé de fabrication d'un matériau actif d'électrode, matériau actif d'électrode et batterie au lithium-ion le comprenant
US11757092B2 (en) * 2018-11-15 2023-09-12 Samsung Sdi Co., Ltd. Positive active material for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11757092B2 (en) * 2018-11-15 2023-09-12 Samsung Sdi Co., Ltd. Positive active material for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same
KR102272325B1 (ko) * 2020-11-19 2021-07-02 (주)로브 폐리튬이차전지를 재생한 용액을 이용한 니켈―코발트―망간 복합전구체의 제조 방법
CN112607789A (zh) * 2020-12-15 2021-04-06 中南大学 废旧锂离子电池有价金属回收与正极材料再生的工艺
WO2023101078A1 (fr) * 2021-11-30 2023-06-08 한국교통대학교산학협력단 Procédé de fabrication d'un matériau actif d'électrode, matériau actif d'électrode et batterie au lithium-ion le comprenant

Similar Documents

Publication Publication Date Title
JP7638966B2 (ja) 粒子状物質、その製造方法及び使用方法
EP4149889B1 (fr) Procédé de fabrication d'un (oxy)hydroxyde particulaire et matériau actif d'électrode fabriqué à partir de celui-ci
US12338133B2 (en) Process for making precursors for cathode active materials, precursors, and cathode active materials
WO2024033132A1 (fr) Procédé de fabrication d'un (oxy)hydroxyde et (oxy)hydroxydes
EP4100367A1 (fr) Matériau actif de cathode et procédé de fabrication d'un tel matériau actif de cathode
EP4263435B1 (fr) Procédé de fabrication d'un matériau actif d'électrode et matériau actif d'électrode
EP4222111B1 (fr) Procédé de fabrication d'un matériau actif de cathode dopée
EP4499575A1 (fr) Procédé de fabrication d'un matériau actif de cathode dopé
WO2025078192A1 (fr) Procédé de fabrication d'un précurseur pour un matériau actif de cathode
EP4095102A1 (fr) Procédé de fabrication d'un matériau actif d'électrode particulaire et matériau actif d'électrode
WO2025011920A1 (fr) Procédé de fabrication d'un matériau actif de cathode et de ses précurseurs
CN121443558A (zh) 用于制造阴极活性材料及其前体的方法
EP4494195A1 (fr) Procédé de fabrication de matériau actif d?électrode revêtue
WO2026008399A1 (fr) Procédé de fabrication d'un (oxy)hydroxyde ou d'un oxyde particulaire, (oxy)hydroxyde particulaire et utilisation associée
WO2024149636A1 (fr) Procédé de fabrication d'un (oxy)hydroxyde ou oxyde particulaire, (oxy)hydroxyde ou oxyde particulaire et utilisation
WO2026008425A1 (fr) Procédé de fabrication d'un (oxy)hydroxyde ou d'un oxyde particulaire, (oxy)hydroxyde ou oxyde particulaire et utilisation associée
WO2024208774A1 (fr) Matériaux actifs de cathode pour batteries lithium-ion et procédés de fabrication
WO2025061478A1 (fr) Procédé de fabrication de matériau actif de cathode, et matériau actif de cathode
EP4677657A1 (fr) Matériaux actifs de cathode ayant une structure noyau-enveloppe et leur fabrication

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24782299

Country of ref document: EP

Kind code of ref document: A1