WO2023066740A1 - Procédé de fabrication d'un matériau actif d'electrode revêtue, et matériau actif d'électrode revêtue - Google Patents

Procédé de fabrication d'un matériau actif d'electrode revêtue, et matériau actif d'électrode revêtue Download PDF

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WO2023066740A1
WO2023066740A1 PCT/EP2022/078324 EP2022078324W WO2023066740A1 WO 2023066740 A1 WO2023066740 A1 WO 2023066740A1 EP 2022078324 W EP2022078324 W EP 2022078324W WO 2023066740 A1 WO2023066740 A1 WO 2023066740A1
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range
active material
zero
electrode active
metals
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PCT/EP2022/078324
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Aleksandr KONDRAKOV
Xiaohan WU
Leonhard KARGER
Torsten Brezesinski
Sandipan MAITI
Hadar SCLAR
Doron Aurbach
Rajashree KONAR
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Basf Se
Karlsruher Institut für Technologie
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Publication of WO2023066740A1 publication Critical patent/WO2023066740A1/fr

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, 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
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • 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
    • C01P2006/80—Compositional purity
    • 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

  • the present invention is directed towards a process for the manufacture of a coated cathode active material comprising the steps of
  • step (d) treating the residue obtained from step (c) thermally.
  • 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.
  • NCM materials lithiated nickel-cobalt-man- ganese oxide
  • NCA materials lithiated nickel-cobalt-aluminum oxide
  • a so-called precursor is being formed by co-precipitating the transition metals as carbonates, oxides or preferably as (oxy)hydroxides.
  • the precursor is then mixed with a lithium compound such as, but not limited to LiOH, U2O or U2CO3 and calcined (fired) at high temperatures.
  • Lithium compound(s) can be employed as hydrate(s) or in dehydrated form.
  • the calcination - or firing - generally also referred to as thermal treatment or heat treatment of the precursor - is usually carried out at temperatures in the range of from 600 to 1 ,000 °C.
  • hydroxides or carbonates are used as precursors a removal of water or carbon dioxide occurs first and is followed by the lithi- ation reaction.
  • the thermal treatment is performed in the heating zone of an oven or kiln.
  • cathode active materials such as energy density, charge-discharge performance such as capacity fading, and the like.
  • energy density energy density
  • charge-discharge performance such as capacity fading
  • cathode active materials suffer from limited cycle life and voltage fade. This applies particularly to many Mn-rich cathode active materials.
  • inventive proves The inventive process comprises the following steps, hereinafter also referred to as step (a), step (b), step (c) and step (d) or more briefly as (a), (b), (c) and (d):
  • step (d) treating the residue obtained from step (c) thermally.
  • Steps (a) to (d) are performed subsequently or may have an overlap. Steps (a) to (d) will be described in more detail below.
  • step (a) a particulate electrode active material based on a lithiated oxide of TM wherein TM includes one or more metals and TM contains at least one of Ni and Mn, preferably both Mn and Ni.
  • TM consists of exactly one of Ni and Mn
  • TM contains more nickel than manganese.
  • TM then corresponds to general formula (I a)
  • electrode active materials provided in step (a) contain more manganese than nickel.
  • cathode active materials include spinel LiMn2O4, high-voltage spinels of an idealized formula LiNio.5Mn1.5O4, doped high-voltage spinels, for example doped with at least one of Na + , Mg 2+ , Al 3+ , Ti 4+ , Cr 34 , Fe 3+ , Zn 2+ , or Co 3+ , and in particular so-called lithium rich materials with a layered structure, general formula Lin.fTM1.fO2 wherein f is in the range of from 0.1 to 0.35 and TM includes two or more transition metals, and 50 to 85 mol-%of TM is Mn, preferably 60 to 70 mol-%. Even more preferably, TM in Lii+fTMi.fO2 is free from cobalt.
  • electrode active material provided in step (a) has the composition Lii +x TMi- x O2 wherein x is in the range of from 0.05 to 0.2, preferably 0.12 to 0.2, and TM is a combination of elements of the general formula (I b)
  • said electrode active material provided in step (a) has the composition Lii +g TM*2- g -hO4-h wherein g is in the range of from -0.1 to +0.3, h is in the range of from zero to 0.2, and TM* corresponds to formula (I b)
  • M 3 being one or more of Ni, Co, Al, Ti, Zr, W, Mo, Mg, and t being in the range of from to 0.3 to 1.
  • Some metals are ubiquitous such as sodium, calcium or zinc and traces of them virtually present everywhere, 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 TM. Analogously, traces of sulfate or carbonate that may stem from the precursor manufacture are neglected as well.
  • M 1 - or M 2 if applicable - may be dispersed homogeneously or unevenly in particles of inventive cathode active material.
  • M 1 - or M 2 if applicable - is distributed unevenly in particles of electrode active material provided in step (a), even more preferably as a gradient, with the concentration of M 1 - or M 2 , if applicable - in the outer shell being higher than in the center of the particles.
  • electrode active material provided in step (a) is comprised of spherical particles, that are particles have a spherical shape.
  • Spherical particles shall include not just those which are exactly spherical but also those particles in which the maximum and minimum diameter of at least 90% (number average) of a representative sample differ by not more than 10%.
  • electrode active material provided in step (a) is comprised of secondary particles that are agglomerates of primary particles.
  • electrode active material provided in step (a) is comprised of spherical secondary particles that are agglomerates of primary particles.
  • electrode active material provided in step (a) is comprised of spherical secondary particles that are agglomerates of platelet primary particles.
  • said primary particles of electrode active material provided in step (a) have an average diameter in the range from 1 to 2000 nm, preferably from 10 to 1000 nm, particularly preferably from 50 to 500 nm.
  • the average primary particle diameter can, for example, be determined by SEM or TEM. SEM is an abbreviation of scanning electron microscopy, TEM is an abbreviation of transmission electron microscopy.
  • electrode active material provided in step (a) has a monomodal particle diameter distribution.
  • such material has a bi- modal particle diameter distribution, for example with a maximum in the range of from 3 to 6 pm and another maximum in the range of from 9 to 30 pm, preferably 9 to 12 pm.
  • the pressed density of electrode active material provided in step (a) is in the range of from 2.75 to 3.6 g/cm 3 , determined at a pressure of 250 MPa, preferred are 2.85 to 3.50 g/cm 3 .
  • Step (b) includes treating said particulate electrode active material with a slurry of WS2 or WSe2, or a combination of WS2 or WSe2 wherein said slurry contains WS2 or WSe2 dispersed in the form of nanosheets.
  • Said slurry may also be referred to as dispersion.
  • at least 50 mol-% WS2 or WSe2 contained in the slurry used in step (b) is dispersed in the form of nanosheets. More preferably, all WS2 or WSe2 contained in the slurry used in step (b) is dispersed in the form of nanosheets.
  • dispersions in the context are slurries, suspensions, and colloids, sometimes also referred to as colloidal suspensions.
  • the weight ratio of electrode active material provided in step (a) to WS2 or WSe2, respectively is in the range of from 1 : 10' 5 to 1 : 10' 2 .
  • a minor fraction of WS2 or WSe2, respectively, may be in the form of a powder. It is preferred, though, to apply WS2 or WSe2, respectively, in the form of nanosheets.
  • Nanosheets in this context refers to sheets of 10 to 200 nm lateral size, having a thickness of from 1 to 20 atomic layers, preferably 1 to 3 atomic layers.
  • An atomic layer refers to one layer of tungsten but includes the required S or Se in accordance with the WS2 or WSe2 stoichiometry.
  • Nano-sheets of WS2 or WSe2, respectively, may be manufactured by converting W foil with S or Se gas, followed by exfoliation in a suitable organic solvent or water or mixture of suitable water-miscible organic solvent and water. Said exfoliation may be supported by ultrasound I ultra- sonification or mechanical forces, e.g., shear forces.
  • WS2 nanosheets may be manufactured by liquid phase exfoliation.
  • WS2 powder is mixed with an aqueous solution of sodium cholate (e.g., 2 g/L) and exfoliated by ultrasound or ultra- sonification.
  • the unexfoliated material is removed by sedimentation in a centrifuge.
  • the continuous phase (dispersant) may be exchanged by high-speed centrifugation and replacement of the dispersant.
  • WS2 nanosheets may be manufactured by liquid phase exfoliation with a surfactant other than sodium cholate, for example sodium lauryl sulfate.
  • WS2 nanosheets may be manufactured by exfoliating with a mixture of an organic solvent instead of an aqueous solution of a surfactant.
  • Such dispersion may have a solids content in the range of from 1 : 10' 5 to 1 : 10' 2 g/L
  • Such dispersion has a continuous phase, hereinafter also referred to as dispersant.
  • Said dispersant may be water or one or more organic solvent(s) or a mixture of water and water-miscible organic solvent.
  • water-miscible organic solvents are N-methyl pyrrolidone (NMP), N,N-dimethyl formamide (DMF), cyclohexanone, acetone, tert.-butanol, N,N-dimethylethanola- mine, N-methyldiethanolamine, diethylenetriamine, and Ci-Cs-alkanols, especially methanol, ethanol, and isopropanol.
  • NMP N-methyl pyrrolidone
  • DMF N,N-dimethyl formamide
  • Ci-Cs-alkanols especially methanol, ethanol, and isopropanol.
  • tert.-butanol is solid, and it is therefore not preferred for many temperatures. More preferred are ethanol and
  • the weight ratio of dispersion of WS2 or WSe2, respectively, to electrode active material provided in step (a) may be in the range of from 10 : 1 to 1 : 2, preferably 10 : 1 to 5 : 3. In embodiments where lower amounts of dispersion are applied, too significant amounts of electrode active material may remain untreated. In embodiments where higher amounts of dispersion are applied, too much of dispersant needs to be removed in the course of step (c).
  • step (b) is performed under mixing operations.
  • Mixing may be supported by ball-milling, stirring, for example with a high-speed stirrer, or - on laboratory scale - by simple shaking or with a roller-mixer.
  • step (b) is performed at a temperature in the range of from zero to 50°C, preferably 20 to 30°C. Usually, in step (b) the boiling point of the dispersant is not exceeded.
  • step (b) is performed at normal pressure (“ambient pressure”), for example 1013 mbar (abs).
  • ambient pressure for example 1013 mbar (abs).
  • step (b) has a duration in the range of from 15 minutes to 6 hours, preferably 30 minutes to 3 hours.
  • step (c) the continuous phase - thus, the dispersant - is removed, step (c).
  • solid-liquid separation methods are feasible, for example filtration or separation by a centrifuge, it is preferred to remove the dispersant by evaporation.
  • Removed shall not only refer to a complete removal of the dispersant but also include a partial removal so that the residue is a moist-containing powder, preferably a free-flowing powder, for example with a residual moisture content in the range of from 0.1 to 5% by weight, determined, e.g., by measuring the loss on ignition (“LOI”).
  • LOI loss on ignition
  • step (c) is performed at a temperature in the range of from 50 to 120°C, preferably 90 to 100°C. Usually, in step (c) the boiling point of the dispersant is exceeded. Preferably, as well, step (c) is performed at a temperature higher than step (b) but lower than step (d).
  • step (c) is performed at reduced pressure, compared to normal pressure, for example 1 to 500 mbar (abs).
  • step (c) has a duration in the range of from 15 minutes to 15 hours, preferably 6 to 10 hours.
  • Step (d) includes treating the residue obtained from step (c) thermally.
  • the temperature of step (d) is in the range of from 100 to 400°C, preferably from 300 to 400°C but in any way higher than in the respective step (c).
  • step (d) is performed under an oxidizing atmosphere, for example air, oxygen-enriched air or oxygen.
  • step (d) is performed under a non-oxidizing atmosphere, for example nitrogen or a noble gas such as argon.
  • Step (d) may be performed in the same vessel as step (b) or in a different one, for example in a rotary kiln.
  • the duration of step (d) is in the range of from 30 minutes to 10 hours, preferably 45 minutes to 5 hours.
  • step (d) dispersant from step (b) is removed.
  • dispersant from step (b) is removed.
  • coated electrode active materials are obtained.
  • coated shall include not only fully but also partially coated electrode active materials.
  • a further aspect of the present invention is directed to coated electrode active materials, hereinafter also referred to as inventive cathode active materials.
  • inventive cathode active materials have a core based on a lithiated oxide of TM wherein TM includes one or more metals and contains at least one of Ni and Mn, and wherein said particulate material contains an at least partial coating based on a compound of tungsten or at least two compounds of tungsten wherein the compound or at least one of the compounds of tungsten is selected from WS2 or WSe2.
  • TM consists of exactly one of Ni and Mn are LiNiC>2, LiMnCh and LiMn2C>4.
  • TM contains more nickel than manganese.
  • TM then corresponds to general formula (I a) (Ni a CObMric)i-dM 1 d (I a) with a being in the range of from 0.6 to 0.99, preferably from 0.6 to 0.95, more preferably from 0.8 to 0.93, b being zero or in the range of from 0.01 to 0.2, preferably from 0.05 to 0.1 , c being in the range of from zero to 0.2, preferably from 0.03 to 0.15, and d being in the range of from zero to 0.1 , preferably from 0.01 to 0.05,
  • the core of inventive cathode active materials contains more manganese than nickel.
  • examples include spinel LiMn2O4, high-voltage spinels of an idealized formula LiNio.5Mn1.5O4, doped high-voltage spinels, for example doped with at least one of Na + , Mg 2+ , Al 3+ , Ti 4+ , Cr 34 , Fe 3+ , Zn 2+ , or Co 3+ , and in particular so-called lithium rich materials with a layered structure, general formula Lii +x TMi- x O2 wherein x is in the range of from 0.05 to 0.20 and TM includes two or more transition metals, and 50 to 85 mol-%of TM is Mn, preferably 60 to 70 mol- %. Even more preferably, TM in Lii +x TMi. x O2 is free from cobalt.
  • TM in cores of inventive cathode active materials is a combination of elements of the general formula (I b)
  • cores of inventive cathode active materials have the composition Lii +g TM*2- g -hO4-h wherein g is in the range of from -0.1 to +0.3, h is in the range of from zero to 0.2, and TM* corresponds to formula (I b)
  • M 3 being one or more of Ni, Co, Al, Ti, Zr, W, Mo, Mg, and t being in the range of from to 0.3 to 1.
  • M 1 - or M 2 if applicable - may be dispersed homogeneously or unevenly in the core of inventive cathode active material.
  • M 1 - or M 2 if applicable - is distributed unevenly in the core of inventive cathode active materials, even more preferably as a gradient, with the concentration of M 1 - or M 2 , if applicable - in the outer shell being higher than in the center of the particles.
  • inventive cathode active materials is comprised of spherical particles, that are particles have a spherical shape.
  • Spherical particles shall include not just those which are exactly spherical but also those particles in which the maximum and minimum diameter of at least 90% (number average) of a representative sample differ by not more than 10%.
  • inventive cathode active materials is comprised of secondary particles that are agglomerates of primary particles.
  • electrode active material provided in step (a) is comprised of spherical secondary particles that are agglomerates of primary particles.
  • electrode active material provided in step (a) is comprised of spherical secondary particles that are agglomerates of platelet primary particles.
  • said primary particles of inventive cathode active materials have an average diameter in the range from 1 to 2000 nm, preferably from 10 to 1000 nm, particularly preferably from 50 to 500 nm.
  • the average primary particle diameter can, for example, be determined by SEM or TEM. SEM is an abbreviation of scanning electron microscopy, TEM is an abbreviation of transmission electron microscopy.
  • inventive cathode active materials have a mono- modal particle diameter distribution.
  • such material has a bimodal particle diameter distribution, for example with a maximum in the range of from 3 to 6 pm and another maximum in the range of from 9 to 30 pm, preferably 9 to 12 pm.
  • the pressed density of inventive cathode active materials is in the range of from 2.75 to 3.6 g/cm 3 , determined at a pressure of 250 MPa, preferred are 2.85 to 3.50 g/cm 3 .
  • Said core is at least partially covered with a coating that is based on a compound of tungsten or on at least two compounds of tungsten wherein the compound or at least one of the compounds of tungsten is selected from WS2 or WSe2.
  • a coating that is based on a compound of tungsten or on at least two compounds of tungsten wherein the compound or at least one of the compounds of tungsten is selected from WS2 or WSe2.
  • Further compounds of tungsten may be WO3, U2WO4, U2WS4.
  • Further compounds that may be found in the coating are WO2 and sulfates, especially U2SO4.
  • Said at least partial coating is in the form of nanosheets.
  • said coating covers from 20 to 95% of the outer surface of the particles of said cathode active material.
  • Inventive cathode active materials may be obtained by the inventive process. Without wishing to be bound by any theory, it is assumed that a high entropy oxide of M 2 is formed that is enriched at the surface of the primary particles of the compound of general formula Lii +x TMi- x O2.
  • Inventive cathode active materials display excellent properties especially with respect to cycling stability and low capacity fade.
  • a further aspect of the present invention refers to electrodes comprising at least one electrode active material according to the present invention. They are particularly useful for lithium ion batteries, with a liquid non-aqueous electrolyte or with a solid electrolyte. Lithium ion batteries comprising at least one electrode according to the present invention exhibit a good discharge behavior. Electrodes comprising at least one electrode active material according to the present invention are hereinafter also referred to as inventive cathodes or cathodes according to the present invention.
  • inventive cathodes contain
  • binder also referred to as binders or binders (C)
  • binders also referred to as binders or binders (C)
  • inventive cathodes contain
  • (C) 1 to 15 % by weight of binder, percentages referring to the sum of (A), (B) and (C).
  • Cathodes according to the present invention can comprise further components. They can comprise a current collector, such as, but not limited to, an aluminum foil. They can further comprise conductive carbon and a binder.
  • Cathodes according to the present invention contain carbon in electrically conductive modification, in brief also referred to as carbon (B).
  • Carbon (B) can be selected from soot, active carbon, carbon nanotubes, graphene, and graphite, and from combinations of at least two of the foregoing.
  • Suitable binders (C) are preferably selected from organic (co)polymers.
  • Suitable (co)polymers i.e. , homopolymers or copolymers, can be selected, for example, from (co)polymers obtainable by anionic, catalytic or free-radical (co)polymerization, especially from polyethylene, polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers selected from ethylene, propylene, styrene, (meth)acrylonitrile and 1 ,3-butadiene.
  • Polypropylene is also suitable.
  • Polyisoprene and polyacrylates are additionally suitable. Particular preference is given to polyacrylonitrile.
  • polyacrylonitrile is understood to mean not only polyacrylonitrile homopolymers but also copolymers of acrylonitrile with 1 ,3-butadiene or styrene. Preference is given to polyacrylonitrile homopolymers.
  • polyethylene is not only understood to mean homopolyethylene, but also copolymers of ethylene which comprise at least 50 mol-% of copolymerized ethylene and up to 50 mol-% of at least one further comonomer, for example a-olefins such as propylene, butylene (1 -butene), 1 -hexene, 1 -octene, 1 -decene, 1 -dodecene, 1 -pentene, and also isobutene, vinylaromatics, for example styrene, and also (meth)acrylic acid, vinyl acetate, vinyl propionate, Ci-C -alkyl esters of (meth)acrylic acid, especially methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-but
  • polypropylene is not only understood to mean homo-pol- ypropylene, 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- Cw-alkyl esters of (meth)acrylic acid, divinylbenzene, especially 1 ,3-divinylbenzene, 1 ,2-diphe- nylethylene and a-methylstyrene.
  • Another preferred binder (C) is polybutadiene.
  • Suitable binders (C) are selected from polyethylene oxide (PEO), cellulose, carboxymethylcellulose, polyimides and polyvinyl alcohol.
  • binder (C) is selected from those (co)polymers which have an average molecular weight M w in the range from 50,000 to 1 ,000,000 g/mol, preferably to 500,000 g/mol.
  • Binder (C) may be selected from 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)pol- ymerized (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 fluoridehexafluoropropylene 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.
  • inventive cathodes may comprise 1 to 15% by weight of binder(s), referring to electrode active material. In other embodiments, inventive cathodes may comprise 0.1 up to less than 1% by weight of binder(s).
  • Inventive cathodes used in lithium ion batteries with liquid electrolytes usually contain a binder.
  • Inventive cathodes used in so-called all-solid-state lithium ion batteries - or “solid-state batteries” - usually contain some solid electrolyte and, optionally, a binder.
  • inventive cathodes comprise a solid-state electrolyte.
  • Such solid-state is solid at ambient temperature.
  • such solid electrolyte has a lithium-ion conductivity at 25 °C of > 0.1 mS/cm, preferably in the range of from 0.1 to 30 mS/cm, measurable by, e.g., impedance spectroscopy.
  • such solid electrolyte comprises U3PS4, yet more preferably orthorhombic P-U3PS4.
  • solid electrolyte is selected from the group consisting of U2S-P2S5, Li2S-P2Ss-Li I , Li2S-P2Ss-Li2O, U2S-P2S5-L i2O-l_il , Li2S-SiS2-P2Ss-Lil, U2S-P2S5- Z m Sn wherein m and n are positive numbers and Z is a member selected from the group consisting of germanium, gallium and zinc, Li2S-SiS2-Li3PC>4, Li2S-SiS2-Li y PO z , wherein y and z are positive numbers, IJ7P3S11, U3PS4, U11S2PS12, Li?P2S8l, and Li7-r-2sPS6- r -sX r wherein X is chlorine, bromine or iodine, and the variables are defined as follows: 0.8 ⁇ r
  • inventive cathodes for solid-state batteries contain in the range of from 5 to 30% by weight and in the ranger of from 0.5 to 3% by weight of carbon (B).
  • a further aspect of the present invention is a battery, containing at least one cathode comprising inventive electrode 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), TiC>2, lithium titanium oxide, metallic lithium, silicon or tin.
  • Said anode may additionally contain a current collector, for example a metal foil such as a copper foil.
  • Said electrolyte may comprise at least one non-aqueous solvent, at least one electrolyte salt and, optionally, additives.
  • 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.
  • polyalkylene glycols examples include poly-Ci-C4-al- kylene 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 ethers are, for example, diisopropyl ether, di-n-butyl ether, 1 ,2-di- methoxyethane, 1 ,2-diethoxyethane, with preference being given to 1 ,2-dimethoxyethane.
  • Suitable cyclic ethers are tetrahydrofuran and 1 ,4-dioxane.
  • 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.
  • Suitable cyclic organic carbonates are compounds according to the general formulae (II) and (III)
  • R 1 , R 2 and R 3 can be identical or different and are selected from among hydrogen and Ci-C4-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tertbutyl, with R 2 and R 3 preferably not both being tert-butyl.
  • R 1 is methyl and R 2 and R 3 are each hydrogen, or R 1 , R 2 and R 3 are each hydrogen. In another embodiment, R 1 is fluorine and R 2 and R 3 are each hydrogen.
  • Another preferred cyclic organic carbonate is vinylene carbonate, formula (IV).
  • 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.
  • Electrolyte further comprises at least one electrolyte salt.
  • Suitable electrolyte salts are, in particular, lithium salts.
  • Preferred electrolyte salts are selected from among LiC(CF3SO2)3, LiN(CF3SC>2)2, LiPFe, UBF4, LiCICL, with particular preference being given to LiPFe and LiN(CF3SC>2)2.
  • batteries according to the invention comprise one or more separators by means of which the electrodes are mechanically separated.
  • Suitable separators are polymer films, in particular porous polymer films, which are unreactive toward metallic lithium.
  • Particularly suitable materials for separators are polyolefins, in particular film-forming porous polyethylene and film-forming porous polypropylene.
  • Separators composed of polyolefin, in particular polyethylene or polypropylene, can have a porosity in the range from 35 to 45%. Suitable pore diameters are, for example, in the range from 30 to 500 nm.
  • separators can be selected from among PET nonwovens filled with inorganic particles.
  • Such separators can have porosities in the range from 40 to 55%. Suitable pore diameters are, for example, in the range from 80 to 750 nm.
  • solid electrolyte may serve as separator.
  • 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.
  • Batteries according to the invention can comprise two or more electrochemical cells that combined with one another, for example can be connected in series or connected in parallel. Connection in series is preferred.
  • at least one of the electrochemical cells contains at least one cathode according to the invention.
  • the majority of the electrochemical cells contains a cathode according to the present invention.
  • all the electrochemical cells contain cathodes according to the present invention.
  • 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, aircrafts 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.
  • D50 Average particle diameters (D50) were determined by dynamic light scattering (“DLS”). Percentages are % by weight unless specifically noted otherwise.
  • LiOH H 2 O was purchased from Rockwood Lithium.
  • base electrode active materials were manufactured in a box furnace, type: VMK-80-S, Linn High Term.
  • Isopropanol and toluene were pre-dried according to standard laboratory methods.
  • the precipitation reaction was performed at 55°C under a nitrogen atmosphere using a continuous stirred tank reactor with a volume of 2.3 I.
  • the continuous stirred tank reactor was charged with 1.5 I of the above aqueous solution of (NH ⁇ SC).
  • the pH value of the solution was adjusted to 11.5 using a 25% by weight aqueous solution of sodium hydroxide.
  • An aqueous metal solution containing NiSCU, CoSO4 and MnSC>4 (molar ratio 85:10:5, total metal concentration: 1.65 mol/kg), aqueous sodium hydroxide (25wt% NaOH) and aqueous ammonia solution (25wt% ammonia) were simultaneously introduced into the vessel.
  • the molar ratio between ammonia and metal was adjusted to 0.265.
  • the sum of volume flows was set to adjust the mean residence time to 5 hours.
  • the flow rate of the NaOH was adjusted by a pH regulation circuit to keep the pH value in the vessel at a constant value of 11.58.
  • the apparatus was operated continuously keeping the liquid level in the vessel constant.
  • a mixed hydroxide of Ni, Co and Mn was collected via free overflow from the vessel.
  • the resulting product dispersion contained about 120g/l mixed hydroxide of Ni, Co and Mn with an average particle size (D50) of 10.5 pm, P-CAM.1.
  • Step (a.1) Subsequently, P-CAM.1 was mixed with LiOH H 2 O at a molar ratio of Li : TM of 1 .02:1 and calcined at 780 °C with a dwell time of 10 hours in a flow of pure oxygen. The heating rate was 3 °C/min. Particulate B-CAM.1 was obtained and sieved using a mash size of 32 pm. Karl-Fischer titration showed the moisture content to be below detection level, 50 ppm.
  • the precipitation reaction was performed at 50°C under a nitrogen atmosphere using a continuous stirred tank reactor with a volume of 50 I.
  • An aqueous metal solution containing NiSCL and MnSCL (molar ratio 25:75), aqueous sodium hydroxide (25wt% NaOH) and aqueous ammonia solution (25wt% ammonia) were simultaneously introduced into the stirred tank reactor.
  • the sum of volume flows was set to adjust the mean residence time to 11.1 hours.
  • the flow rate of the NaOH was adjusted by a pH regulation circuit to keep the pH value in the stirred tank reactor at a constant value of 11.4.
  • the resulting product dispersion contained about 120 g/l mixed hydroxide of Ni and Mn with an average particle size (D50) of 14 pm, P-CAM.2.
  • P-CAM.2 was mixed with LiOH H 2 O at a molar ratio of Li : TM of 1 :2 and calcined at 650 and 820 °C with a dwell time of 6 hours in a flow of pure oxygen.
  • Particulate B- CAM.2 was obtained and sieved using a mash size of 32 pm.
  • the average particle size (D50) of B-CAM.2 was 14 pm.
  • Solvent transfer is conducted by redispersion of the sediment in isopropanol, sedimentation at 3000 g and redispersion in dry isopropanol twice.
  • concentration of the thus obtained dispersion is measured by filtering 200 pL of dispersion through a PTFE syringe filter >200 nm pore size and careful gravimetric analysis.
  • Step (a.1) 9.9 g of B-CAM.1 were provided.
  • Step (b.1) A plastic bottle container was charged with 100 mg WSe2 nanosheets dispersed in 10 ml of isopropanol. Further dispersion was effected under ultrasound for 30 minutes. 9.9 g of B-CAM.1 were added and a slurry was obtained. Cylindrical zirconia balls (1 :8 by weight: B- CAM.1 : zirconia ball) were added and the plastic bottle with the slurry and the zirconia balls was put on a roller mixer for 2 hours at 500 rpm at ambient temperature.
  • Step (c.1) In an air oven at 80°C and under air, the isopropanol was then evaporated to dryness and the dried powder material was further mixes in the same roller mixer for another 15 min at 500 rpm at ambient temperature. A residue was obtained.
  • Step (d.1) the residue from step (c.2) was heated at 150 °C for 2 hours under N2 flow in a rotary evaporator equipped with a thermocouple and a heater at 150 °C. CAM.1 was obtained.
  • Step (b.2) A plastic bottle container was charged with 100 mg WSe2 nanosheets dispersed in 10 ml of isopropanol. Further dispersion was effected under ultrasound for 30 minutes. 9.9 g of B-CAM.2 were added and a slurry was obtained. Cylindrical zirconia balls (1 :8 by weight: B- CAM.2: zirconia ball) were added and the plastic bottle with the slurry and the zirconia balls was put on a roller mixer for 2 hours at 500 rpm at ambient temperature.
  • Step (c.2) In an air oven at 80°C and under air, the isopropanol was then evaporated to dryness and the dried powder material was further mixes in the same roller mixer for another 15 min at 500 rpm at ambient temperature. A residue was obtained.
  • Step (d.2) the residue from step (c.1) was heated at 150 °C for 2 hours under N2 flow in a rotary evaporator equipped with a thermocouple and a heater at 150 °C. CAM.2 was obtained.
  • Step (b.3) A flask equipped with a PTFE coated magnetic stir bar was charged with 1 g of B- CAM.1 and 3 mL dry isopropanol. Under stirring, an amount of 10 g of a 10 g/l WS2 dispersion in isopropanol was added dropwise. After the addition is completed, the mixture was stirred for another 10 min. Then the mixture was left to separate.
  • Step (c.3) The liquid phase was discarded after centrifuge separation and the sediment was washed twice with 3 mL dry isopropanol. The solid so obtained was dried for 5 hours in vacuo at 100°C.
  • Step (d.3) The residue from step (c.3) was transferred to an alumina crucible and calcined for 1 hour at 400°C under 2 atm/h in oxygen atmosphere. The temperature ramp speed was with 3K/min. Then, CAM.3 so obtained was allowed to cool to ambient temperature.
  • the cathode slurries necessary for cathode preparation were prepared by first mixing a 7.5 wt% binder solution of polyvinylidene difluoride (PVDF, Solef 5130, Solvay) in /V-methyl-2-pyrroli- done (NMP, > 99.5%, Merck KGaA) with conductive carbon black (Super C65, TIMCAL Ltd.) and NMP in a planetary centrifugal mixer (ARE-250, Thinky) for 3 min at 2000 rpm followed by 3 min at 400 rpm After the first mixing, the either B-CAM.1 , CAM.1 or CAM:2 was added to the slurry in an open mixing cup was used.
  • PVDF polyvinylidene difluoride
  • NMP > 99.5%, Merck KGaA
  • conductive carbon black Super C65, TIMCAL Ltd.
  • ARE-250 planetary centrifugal mixer
  • Solid-state battery manufacture (“SSB cells”), general protocol, including battery manufacture
  • CAM.3, 10 mg of amorphous carbon (C65) and 300 mg of - LiePSsCI and 10 zirconia balls 10mm diameter were mixed at 140 rpm for 30 min to yield a cathode composite.
  • the electrochemical cells used for electrochemical testing use an anode composite containing Li4Ti50i2, conductive carbon (C65) and LiePSsCI (30 : 10 : 60 wt.-%), separator and the cathode as described above.
  • a custom setup was used for testing of the SSB cells (0 10 mm).
  • LiePSsCI 100 mg was compressed at 62 MPa to yield a solid electrolyte pellet.
  • the anode composite (65 mg, ⁇ 4.0 mA h cm -2 ) was pressed to the solid electrolyte pellet , and finally the cathode composite (10 to 12 mg, 1.7 to 2.0 mA h cm -2 ) was pressed onto the other side of the solid electrolyte pellet at 437 MPa.
  • a pressure of 81 MPa was maintained.
  • CR2032 lithium ion battery cells (“LIB”) were assembled in an argon-filled glovebox (H2O ⁇ 0.5 ppm and O2 ⁇ 0.5 ppm) and comprised a cathode (13 mm diameter) according to 111.1 , a GF/D glass microfiber or Celgard 2500 separator (17 mm diameter; GE Healthcare Life Science, Whatman), a lithium metal anode (15 mm diameter), and 100 pl of electrolyte, consisting of 1.0 M LiPFe in 3:7 EC:EMC (ethyl methyl ketone) by weight.
  • LIB lithium ion battery cells
  • the first cycle involved galvanostatic cycling at 0.2C in a voltage window between 2.8-4.3 V, followed by a long-term cycling at 1C in the same voltage range.
  • Table 1 Electrochemistry: C-Rate results for lithium ion batteries with a liquid electrolyte

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Abstract

L'invention concerne un procédé de fabrication d'un matériau actif de cathode revêtue comprenant les étapes consistant à (a) fournir un matériau actif d'électrode particulaire à base d'un oxyde lithié de TM, TM contenant au moins un élément parmi Ni et Mn, (b) traiter ledit matériau actif d'électrode particulaire avec une suspension de WS2 ou de WSe2, ladite suspension contenant WS2 ou WSe2 sous la forme de nanofeuilles, (c) éliminer la phase continue de la suspension, (d) traiter thermiquement le résidu obtenu à l'étape (c).
PCT/EP2022/078324 2021-10-19 2022-10-12 Procédé de fabrication d'un matériau actif d'electrode revêtue, et matériau actif d'électrode revêtue WO2023066740A1 (fr)

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WO2019039893A1 (fr) * 2017-08-24 2019-02-28 한양대학교 산학협력단 Matériau actif positif, son procédé de préparation, et batterie rechargeable au lithium le comprenant

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Publication number Priority date Publication date Assignee Title
WO2019039893A1 (fr) * 2017-08-24 2019-02-28 한양대학교 산학협력단 Matériau actif positif, son procédé de préparation, et batterie rechargeable au lithium le comprenant

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A. MOUMEN ET AL., ACS APPL. MATER. INTERFACES, vol. 13, 2021, pages 4316
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GRIGORIEV S N ET AL: "Formation of thin catalytic WSexlayer on graphite electrodes for activation of hydrogen evolution reaction in aqueous acid", INORGANIC MATERIALS: APPLIED RESEARCH, PLEIADES PUBLISHING, MOSCOW, vol. 7, no. 2, 12 May 2016 (2016-05-12), pages 285 - 291, XP035682047, ISSN: 2075-1133, [retrieved on 20160512], DOI: 10.1134/S2075113316020118 *
QIU XIAOMING ET AL: "Immobilization of tungsten disulfide nanosheets on active carbon fibers as electrode materials for high performance quasi-solid-state asymmetric supercapacitors", JOURNAL OF MATERIALS CHEMISTRY A, vol. 6, no. 17, 1 January 2018 (2018-01-01), GB, pages 7835 - 7841, XP093018799, ISSN: 2050-7488, DOI: 10.1039/C8TA01047A *

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