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WO2025045774A1 - Procédé de fabrication de précurseurs de matériaux actifs de cathode pour batteries aux ions de lithium - Google Patents

Procédé de fabrication de précurseurs de matériaux actifs de cathode pour batteries aux ions de lithium Download PDF

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Publication number
WO2025045774A1
WO2025045774A1 PCT/EP2024/073715 EP2024073715W WO2025045774A1 WO 2025045774 A1 WO2025045774 A1 WO 2025045774A1 EP 2024073715 W EP2024073715 W EP 2024073715W WO 2025045774 A1 WO2025045774 A1 WO 2025045774A1
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Prior art keywords
range
hydroxide
oxy
nickel
process according
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English (en)
Inventor
Arnd Garsuch
Thomas Michael RYLL
Lukas Karl METZGER
Thorsten BEIERLING
Rafael Benjamin BERK
Dirk Klingler
Sigmar Braeuninger
Felix Eberle
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BASF SE
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BASF SE
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/422—Electrodialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B01D61/462—Apparatus therefor comprising the membrane sequence AA, where A is an anion exchange membrane
    • 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
    • C01G53/80—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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/22—Inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/083—Separating products
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water

Definitions

  • the present invention is directed towards a process for making an (oxy)hydroxide of TM wherein TM is nickel or a combination of metals that comprises at least 60 mol-% nickel, referring to TM, and, optionally, at least one of cobalt and manganese, wherein said process comprises the steps of:
  • step (b) providing an electrochemical cell comprising at least three compartments separated from each other by anion- exchange membranes, said compartments comprising anode and anolyte in an anode compartment, aqueous solution provided in step (a) in a middle compartment, and cathode and catholyte in a cathode compartment, respectively,
  • Lithium-ion secondary batteries are modern devices for storing energy. Many application fields have been and are contemplated, from small devices such as mobile phones and laptop computers through car batteries and other batteries for e-mobility. Various components of the batteries have a decisive role with respect to the performance of the battery such as the electrolyte, the electrode materials, and the separator. Particular attention has been paid to the cathode materials. Several materials have been suggested, such as lithium iron phosphates, lithium cobalt oxides, and lithium nickel cobalt manganese oxides.
  • the cathode material is of crucial importance for the properties of a lithium-ion battery.
  • Lithium-containing mixed transition metal oxides have gained particular significance, for example spinels and mixed oxides of layered structure, especially lithium-containing mixed oxides of nickel, manganese and cobalt; see, for example, EP 1 189 296.
  • Such lithium-containing mixed oxides of nickel, manganese and cobalt are generally prepared in a two-stage process. In a first stage, a sparingly soluble salt of the transition metal(s) is prepared by precipitating it from a solution, for example a carbonate or a hydroxide. This sparingly soluble compound is in many cases also referred to as a precursor. In a second stage, the precursor is mixed with a lithium compound, for example U2CO3, LIOH or U2O, and calcined at high temperatures, for example at 600 to 1100°C.
  • a lithium compound for example U2CO3, LIOH or U2O
  • the sulfates of transition metals such as nickel, cobalt and manganese are used as starting materials.
  • the stoichiometric amounts of sulfate are undesired by-products that need to be disposed of.
  • cathode active materials are made from precursors that are made by oxidation of metals and simultaneous precipitation.
  • the process leads to disadvantages when manganese is present because under the prevailing alkaline conditions, manganese may be precipitated as MnC>2 that is not incorporated well into the precursor.
  • the magnetic separation as suggested for the removal of unreacted metals does not work for many materials such as, but not limited to aluminum and manganese.
  • inventive process was found, hereinafter also referred to as inventive process or process according to the (present) invention.
  • inventive process may be carried out as a batch process or as a continuous or semi-batch process.
  • the inventive process comprises steps (a) to (f), hereinafter also referred to as (a), (b), (c), (d), (e) and (f), respectively. Steps (a) to (f) shall be described in more detail below.
  • the inventive process is suitable for making particulate (oxy)hydroxides and oxides of TM wherein TM represents metals, and wherein TM comprises nickel and at least one metal selected from cobalt and aluminum and manganese.
  • TM comprises at least 60 mol-% nickel. More preferably, TM comprises at least 60 mol-% nickel and at least one of manganese and aluminum.
  • particulate (oxy)hydroxide and oxides of TM are selected from hydroxides and oxyhydroxides and oxides of TM wherein TM is nickel or a combination of metals according to general formula (I)
  • Said particulate (oxy)hydroxide or oxide of TM may contain traces of further metal ions, 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.
  • TM is nickel
  • Particulate (oxy)hydroxide or oxide of TM is in particulate form.
  • the mean particle diameter (D50) of particulate (oxy)hydroxide or oxide of TM is in the range of from 1 to 50 m, preferably 2 to 20 pm, more preferably 2.5 to 7 pm.
  • the mean particle diameter (D50) in the context of the present invention refers to the median of the volume-based particle diameter, as can be determined, for example, by light scattering.
  • the particulate (oxy)hydroxides and oxides of TM have a monomodal particle diameter distribution.
  • the particle distribution of the particulate (oxy)hydroxides and oxides of TM may be bimodal, for example with one maximum in the range of from 1 to 5 pm and a further maximum in the range of from 7 to 16 pm. Monomodal is preferred.
  • the mean particle diameter (D50) of particulate (oxy)hydroxide or oxide of TM is in the range of from 1 to 7 pm, preferably 2 to 6 pm, more preferably 3 to 5 pm.
  • the particle shape of the secondary particles of said particulate (oxy)hydroxides and oxides of TM is preferably spheroidal, that are particles that have a spherical shape.
  • Spheroidal shall include not just those which are exactly spherical but also those particles with a form factor in the range of from 0.7 to 1 and an axis ratio of the bounding box in the range of from 1 .00 to 1 .25.
  • Form factor (4rr area)/ (perimeter) 2 . While a perfect sphere would possess a form factor of 1 .0, any deviation from perfect sphericity leads to form factors below 1 .0.
  • said particulate (oxy)hydroxides and oxides of TM are comprised of secondary particles that are composed of primary particles.
  • said precursor is comprised of spherical secondary particles that are agglomerates of primary particles.
  • said precursor is comprised of spherical secondary particles that are agglomerates of plate-shaped, rod-shaped or needle-shaped primary particles or platelets.
  • said particulate (oxy)hydroxides and oxides of TM may have a particle diameter distribution span in the range of from 0.9 to 2.0, the span being defined as [(D90) - (D10)] divided by (D50), all being determined by LASER analysis.
  • said precursor may have a particle diameter distribution span in the range of from 1 to 4.
  • the specific surface (BET) of said precursor is in the range of from 2 to 15 m 2 /g or even 15 to 100 m 2 /g, determined by nitrogen adsorption, for example in accordance with to DIN-ISO 9277:2003-05.
  • an aqueous solution that contains water-soluble salt(s) of metals that constitute TM.
  • water-soluble salt(s) of metals that constitute TM For example, in embodiments where an (oxy)hydroxide of nickel and cobalt in a molar ratio in the range of from 3:1 to 10:1 is desired, an aqueous solution of water-soluble salts of nickel and cobalt in the respective molar ratio in the range of from 3:1 to 10:1 is provided.
  • TM is nickel
  • a solution of a water-soluble nickel salt is provided.
  • Aqueous solution provided in step (a) may have a TM concentration in the range of from 0.1 to 2.0 mol/l, preferred from 0.15 to 1 mol/l, more preferred in the range from 0.2 to 0.75 mol/l.
  • aqueous solution provided in step (a) may have a concentration of TM in the range of from 0.02 up to 0.1 mol/l, for example 0.099 mol/l as upper limit.
  • manganese it may be advantageous to provide a diluted solution in step (a).
  • Aqueous solution provided in step (a) further contains an alkali metal salt, preferably with the same counteranion as water-soluble salt(s) of metals that constitute TM.
  • alkali metal salts are the sodium salts.
  • Particularly preferred salt is sodium sulfate.
  • the concentration of alkali metal salt in aqueous solution as provided in step (a) is in the range of from 0.1 to 2.0 mol/l, preferred 0.15 to 1 mol/l, more preferred in the range from 0.2 to 0.75 mol/l. In another embodiment of the present invention, the concentration of alkali metal salt in aqueous solution as provided in step (a) is in the range of from 0.02 up to 0.1 mol/l, for example 0.099 mol/l as upper limit.
  • Aqueous solution provided in step (a) may have a pH value in the range of from 4 to 8, preferably 4 to 7.
  • aqueous solution provided in step (a) may contain one or more additives, for example a complexing agent such as, but not limited to ammonia.
  • aqueous solution provided in step (a) does not contain any additive.
  • Step (b) includes providing an electrochemical cell comprising at least three compartments separated from each other by anion-exchange membranes, said compartments comprising anode and anolyte, aqueous solution provided in step (a), and cathode and catholyte, respectively.
  • the compartments may have the same size or different sizes.
  • anion-exchange membranes are polymer membranes formed by an organic polymer backbone with covalently attached cationic groups.
  • Cationic groups are alkylated quaternary ammonium groups linked to polymer backbones of polystyrene, polysulfone, poly(ethersulfone), or poly(phenylene oxide) through benzylic methylene groups.
  • Preferred cationic groups are trimethylammonium groups.
  • DSA-electrodes examples include DSA-electrodes, DSA-electrodes with a iridium- or iridium oxide-coating, iridium-oxide-coating being preferred.
  • DSA electrodes are so-called dimensionally stable anodes. They are based on titanium coated with iridium or iridium oxide. Ruthenium/ruthenium oxide can also be part of the coating.
  • iridium-containing DSA-electrodes can be replaced by a nickel anodes.
  • the occurring oxidation reaction on the anode side will be the oxidative dissolution of nickel.
  • Nickel salt, preferably nickel sulfate will be formed as reaction product.
  • Suitable materials for the cathode are steel and stainless steel, for example SS36, with stainless steel being preferred.
  • the compartment that contains aqueous solution provided in step (a) is located between the compartment that contains anode and anolyte on one side ("anode compartment”) and cathode and catholyte on the other side ("cathode compartment”), and it is separated from the anode compartment and from the cathode compartment with anion exchange membranes.
  • the compartment that contains aqueous solution provided in step (a) is designed to allow a constant flow of solution provided into and through the electrochemical cell.
  • the compartment that contains aqueous solution provided in step (a) is also referred to as "middle compartment”. The dimensions of the compartments may be selected in a wide range.
  • the volume of the cathode compartment is in the range of from one to twenty liters, preferably from two to ten liters. In one embodiment of the present invention, the volume of the anode compartment is in the range of from one to twenty liters, preferably from two to ten liters. In one embodiment of the present invention, the volume of the compartment that contains aqueous solution provided in step (a) is in the range of from one to 40 liters, preferably two to twenty liters.
  • the volume of the cathode compartment may be in the range of from 40 to 50 ml. In such embodiments, the volume of the anode compartment is in the range of from 40 to 50 ml. In such embodiments, the volume of the compartment that contains aqueous solution provided in step (a) is in the range of from 70 to 120 ml.
  • the electrochemical cell as provided in step (b) has an active cell area in the range of from 50 cm 2 to 3 m 2 .
  • the active cell area is defined as area of two electrodes - anode and cathode - facing each other.
  • each compartment is shaped in a way that respective aqueous medium can pass it, for example in an intermittent or continuous flow.
  • continuous or intermittent flow neither allows short-cuts nor dead space, or at least as little dead space as possible, for example 1 vol-% of the compartment volume or less.
  • anolytes are aqueous solutions of alkali metal sulfate, for example Na2SO4 in embodiments with DSA anodes.
  • concentration may be in the range of from 0.1 to 2 molar with respect to sulfate, 0.5 to 1 .5 molar being preferred. Due to the electrochemical reaction, the pH value of the anolyte drops to 0.5 to 3.
  • anolytes are aqueous solutions of sulfuric acid when nickel electrodes are employed.
  • concentration may be in the range of from 0.1 to 1 molar with respect to sulfate, with 0.05 to 0.35 molar being preferred. Due to the electrochemical reaction, the pH value of the anolyte drops to 0.2 to 1.
  • catholytes are aqueous solutions of alkali metal hydroxide, for example NaOH.
  • concentration may be in the range of from 0.05 to 1 molar, preferred are 0.1 to 0.5 molar.
  • the pH value of the catholyte is preferably higher than 9, for example 10 to 14.
  • Step (c) of the inventive process includes passing solution as provided in step (a) through the middle compartment. Said passing may be performed continuously, intermittently or by simply replacing aqueous medium from the middle compartment through discharging and re-charging. Although it is possible to run the inventive process batch-wise, a continuous mode of operation is preferred. While a batch-wise operation is possible for laboratory-scale experiments, for example with one liter of solution to be provided in step (a), a continuous or intermittent operation of step (c) is preferred. In step (c), a passing rate from 10 to 400 liters per hour, preferred from 60 to 90 liters per hour may be achieved. A lower passing rate may result in a strong depletion of metals that constitute TM. It may further result in a deposition of residues of (oxy)hydroxide of TM in the electrochemical cell.
  • Too high a passing rate may result in turbulences that are disadvantageous in the particle growth in the subsequently described steps. Too high a passing rate may further limit the particle growth.
  • Step (d) includes applying an electrical current with a current density of from 10 to 500 cm 2 , preferably from 50 to 500 mA/cm 2 , more preferably 50 to 200 mA/cm 2 .
  • a current density of from 10 to 500 cm 2 , preferably from 50 to 500 mA/cm 2 , more preferably 50 to 200 mA/cm 2 .
  • such current density may result in a voltage in the range of from 2 to 20 V, preferably from 2 to 10 V and more preferably from 3 to 7 V.
  • such current density may result in a voltage in the range of from 20 to 30 V.
  • step (d) a current density of 50 mA/cm2 is applied.
  • Such current density results in cell voltages ranging from 5 to 7.5 V Said voltage may be constant or vary in a range of from 6.0 ⁇ 0.5 V in a steady state-operation.
  • Oxygen is formed at the anode, and the pH value may drop to 2.5 or lower, for example to 1 .5.
  • a diluted sulfuric acid is formed that may be used for other steps in battery material manufacture, for example in dissolution of nickel-containing ores, nickel metal, or in the leaching of spent batteries.
  • nickel cations are formed at the anode.
  • the pH value is then preferably below 1, for example to 0.6.
  • An acidic nickel sulfate solution is formed that may be used in subsequent steps in the middle compartment.
  • a hydrogen oxidation reaction is performed at the anode.
  • hydrogen gas is introduced at the anode and oxidized to H + .
  • the pH value adopts values as from 11 to 14, preferably from 12 to 13.
  • step (d) While performing step (d), hydroxide ions migrate from the catholyte through the anion exchange membrane into the middle compartment. As a consequence, a hydroxide of TM precipitates. Without wishing to be bound by any theory, we assume that hydroxide ions are immediately consumed by TM and removed by precipitation. A significant increase in pH value is hard to detect. In order to secure electroneutrality, counteranion of TM, preferably sulfate, migrates through the anion exchange membrane into the anolyte. Upon complete consumption of TM the pH value raises considerably. In one embodiment of the present invention, the electric conductivity of the anolyte is in the range of from 30 to 150 mS/cm during step (d).
  • the electric conductivity of the catholyte is in the range of from 30 to 150 mS/cm during step (d).
  • the temperature of anolyte, catholyte and solution provided in step (a) is in the range of from ambient temperature to 70°C.
  • the temperature refers to the performance of step (d). It is preferred that the difference in temperature in the three compartments is less than 5°C at a given time.
  • Ambient temperature is in the range of from 15 to 25°C and preferably from 20 to 25°C.
  • a steady state in step (d) may be achieved by circulating each of filtrate, anolyte and catholyte at least in part, and adding fresh alkali metal salt such as Na2SO4 to anolyte and sulfate of TM to the solution to be fed.
  • fresh alkali metal salt such as Na2SO4
  • TM in step (a) and TM in (f) may have the same composition or be different.
  • the manganese content of TM in step (f) is higher than in steps (a) to (e), for example at the expense of nickel. More preferably, no manganese is present in steps (a) to (e) and any manganese to be introduced into a precursor is introduced in the course of step (f).
  • (Oxy)hydroxide of TM is then collected by a solid-liquid separation method such as a filtration or centrifugation.
  • the liquid phase - e.g., the filtrate or centrifugate - contains alkali metal salt, preferably alkali metal sulfate and particularly preferably sodium sulfate, and may be recycled for the manufacture of electrolyte for the middle compartment in steps (b) and (c).
  • Precursor as generated by the inventive process is an aspect of the present invention as well.
  • Anode Ir-containing DSA
  • cathode stainless steel SS316 mesh 1 mm
  • the cell temperature was set to 40°C.
  • Step (c.1) Solution (a.1) was passed through the middle compartment with a flow rate of 80 l/h
  • Step (e.1) The resultant slurry of the green solid was removed from the cell. The solid was recovered by filtration and washing with distilled water, followed by drying in a desiccator at ambient temperature under air. The analysis of the solid showed it was Ni (OH)2. Particles with a diameter of from 1 to 50 pm can be detected. An SEM image is displayed in Figure 1.
  • Step (a.2) The following solution was provided:
  • Step (b.2) The above cell was provided.
  • Anode nickel mesh 1 mm
  • cathode stainless steel SS316 mesh 1 mm
  • the cell temperature was set to 40°C.
  • Step (c.2) Solution (a.1) was passed through the middle compartment with a flow rate of 80 l/h
  • Step (d.2) an electric current with a current density of 50 mA/cm 2 was applied. The immediate precipitation of a green solid was observed.
  • Step (e.2) The resultant slurry of the green solid was removed from the cell. The solid was recovered by filtration and washing with distilled water, followed by drying in a desiccator at ambient temperature under air. The analysis of the solid showed it was Ni(OH)2.
  • Example 3 Synthesis of high-Ni NCM precursor (Ni-Co-Mn: 91 - 4.5 - 4.5)
  • Step (a.3) The following solutions were provided:
  • Step (b.3) The above cell was provided.
  • Anode Ir-containing DSA
  • cathode stainless steel SS316 mesh 1 mm
  • the cell temperature was set to 40°C.
  • Step (c.3) Solution (a.3) was passed through the middle compartment with a flow rate of 80 l/h
  • Step (d.3) an electric current with a current density of 150 mA/cm 2 was applied and ammonia (25%) was added dropwise. The immediate precipitation of a green-brown solid was observed.
  • Step (e.3) The resultant slurry of the green-brown solid was removed from the cell.
  • the solid was recovered by filtration and washing with distilled water, followed by drying in a desiccator at ambient temperature under air.
  • the analysis of the solid showed it was Ni-Co-Mn(OH)2, molar ratio of nickel : cobalt : manganese of 91 . 4.5 : 4.5. Particles with a diameter of from 1 to 50 pm could be detected.

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Abstract

L'invention concerne un procédé de fabrication d'un (oxy)hydroxyde de TM, TM étant du nickel ou une combinaison de métaux qui comprend au moins 60 % en moles de nickel, par rapport à TM, et, éventuellement, du cobalt et/ou du manganèse, ledit procédé comprenant les étapes consistant à : (a) fournir une solution aqueuse contenant un sel soluble dans l'eau de métaux qui constituent TM, (b) fournir une cellule électrochimique comprenant au moins trois compartiments séparés les uns des autres par des membranes échangeuses d'anions, lesdits compartiments comprenant respectivement une anode et un anolyte, une solution aqueuse fournie à l'étape (a), et une cathode et un catholyte, (c) faire passer ladite solution de métaux constituant TM à travers le compartiment intermédiaire et (d) appliquer un courant électrochimique ayant une densité de courant dans la plage de 50 à 500 mA/cm2, (e) éliminer l'(oxy)hydroxyde de TM de la cellule électrochimique.
PCT/EP2024/073715 2023-08-31 2024-08-23 Procédé de fabrication de précurseurs de matériaux actifs de cathode pour batteries aux ions de lithium Pending WO2025045774A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP23194586 2023-08-31
EP23194586.6 2023-08-31
EP24152894 2024-01-19
EP24152894.2 2024-01-19
EP24171968.1 2024-04-25
EP24171968 2024-04-25

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Citations (6)

* Cited by examiner, † Cited by third party
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JPH1197076A (ja) * 1997-09-18 1999-04-09 Toshiba Corp 電池の処理方法
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EP1189296A2 (fr) 2000-09-14 2002-03-20 Ilion Technology Corporation Matériau à base d'oxide lithié et sa méthode de fabrication
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