WO2023046689A1 - Oxyde composite nickel lithium et procédé de préparation - Google Patents

Oxyde composite nickel lithium et procédé de préparation Download PDF

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Publication number
WO2023046689A1
WO2023046689A1 PCT/EP2022/076111 EP2022076111W WO2023046689A1 WO 2023046689 A1 WO2023046689 A1 WO 2023046689A1 EP 2022076111 W EP2022076111 W EP 2022076111W WO 2023046689 A1 WO2023046689 A1 WO 2023046689A1
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composite oxide
nickel composite
lithium nickel
oxide material
lithium
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PCT/EP2022/076111
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English (en)
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Fiona Claire COOMER
James Alexander CORBIN
Cameron Jon WALLAR
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Ev Metals Uk Limited
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    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 relates to improved particulate lithium nickel composite oxide materials which are useful as cathode materials in lithium secondary batteries.
  • the present invention also provides processes for preparing such lithium nickel composite oxide materials, and electrodes and electrochemical cells comprising the materials.
  • Lithium nickel composite oxide materials find utility as cathode materials in lithium-ion batteries. With demand increasing for lithium-ion batteries in high-end applications such as electric vehicles (EVs), it is imperative to use cathode materials which provide not only acceptable discharge capacity but also excellent retention of that capacity over a large number of charging cycles, so that the range of the vehicle after each charge over its lifetime is as consistent as possible.
  • EVs electric vehicles
  • lithium nickel composite oxide materials can lead to increases in surface impurities levels which can affect battery cell performance, and a reduction in certain aspects of electrochemical performance of battery cells incorporating such materials, such as internal resistance. There therefore remains a need for improved lithium transition metal oxide materials and processes for their manufacture.
  • the present inventors have found that by controlling methods of production, advantageous lithium nickel composite oxide materials with a CeC>2 crystalline phase may be produced with a particularly excellent balance of electrochemical properties, such as capacity retention, and levels of lithium surface impurities, in particular lithium hydroxide.
  • a particulate lithium nickel composite oxide material satisfying the following requirements: (i) the particulate lithium nickel composite oxide material comprises a CeC>2 crystalline phase; and
  • the particulate lithium nickel composite oxide material comprises less than 0.015 wt% of lithium in the form of surface lithium hydroxide.
  • a particulate lithium nickel composite oxide material with a surface layer enriched with cobalt and I or aluminium and wherein the particulate lithium nickel composite oxide material comprises a CeC>2 crystalline phase.
  • the materials of the third aspect comprise a CeC>2 crystalline phase.
  • a fourth aspect of the invention provides a process for preparing a particulate lithium nickel composite oxide material according to the first, second or third aspects, the process comprising the steps of:
  • a fifth aspect of the invention provides a particulate lithium nickel composite oxide obtained or obtainable by a process described herein.
  • a sixth aspect of the invention provides a cathode comprising the particulate lithium nickel composite oxide material according to the first, second or third aspects.
  • a seventh aspect of the invention provides a lithium secondary cell or battery (e.g. a secondary lithium ion battery) comprising the cathode according to the sixth aspect.
  • the battery typically further comprises an anode and an electrolyte.
  • An eight aspect of the invention provides the use of the particulate lithium nickel composite oxide according to the first, second or third aspects for the preparation of a cathode of a secondary lithium battery (e.g. a secondary lithium ion battery).
  • a secondary lithium battery e.g. a secondary lithium ion battery
  • Figure 1 shows x-ray diffraction (XRD) analysis of (i) a base material and (ii) a lithium nickel composite oxide material formed in Example 4.
  • Figure 2 shows scanning electron microscope (SEM) images of secondary particles of lithium nickel composite oxide material with a 2 at% cerium surface modification.
  • Figure 3 shows an energy dispersive X-ray spectroscopy (EDS) analysis of secondary particles of lithium nickel composite oxide material with a 2 at% cerium surface modification.
  • EDS energy dispersive X-ray spectroscopy
  • the present invention relates to particulate lithium nickel composite oxide materials.
  • lithium nickel composite oxide as used herein means a mixed metal oxide comprising lithium and nickel.
  • the lithium nickel composite oxide comprises nickel in combination with cobalt and I or manganese.
  • lithium nickel composite oxides have layered structure (such as an a-NaFeCh-type structure).
  • the particulate lithium nickel composite oxide materials as described herein comprise a CeC>2 crystalline phase. This phase may be identified by powder x-ray diffraction (XRD) analysis.
  • the particulate lithium nickel composite oxide materials as described herein have a surface which comprises cerium-containing particles.
  • the presence of particles on the surface of the lithium nickel composite oxide material may be readily determined by the skilled person, for example using microscopy, such as scanning electron microscopy (SEM).
  • SEM scanning electron microscopy
  • the presence of cerium in the surface particles may be determined by energy dispersive X- ray spectroscopy (EDS).
  • the particulate lithium nickel composite oxide material may have a composition according to Formula I:
  • M is Mn and I or Co
  • X is selected from Al, V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Sr, Ca, S, La, Mo, Nb,
  • the particulate lithium nickel composite oxide material has a composition according to Formula 2.
  • compositions recited herein may be determined by Inductively Coupled Plasma (ICP) analysis as described in the Examples section below. It may be preferred that the compositions recited herein are ICP compositions. As used herein, the at% (atom %) content of the metals is given with respect to the total metal content (excluding lithium) of the lithium nickel composite oxide material.
  • ICP Inductively Coupled Plasma
  • 0.8 ⁇ a ⁇ 1.2 In some embodiments a is greater than or equal to 0.9, 0.95, 0.99 or 1.0. In some embodiments, a is less than or equal to 1.1 , or less than or equal to 1.05. In some embodiments, 0.90 ⁇ a ⁇ 1.10, for example 0.95 ⁇ a ⁇ 1.05. In some embodiments, 0.99 ⁇ a ⁇ 1.05 or 1 .0 ⁇ a ⁇ 1.05. It may be particularly preferred that 0.95 ⁇ a ⁇ 1.05.
  • x is less than or equal to 0.99, 0.98, 0.97, 0.96, 0.95, 0.94, 0.93, or 0.92. In some embodiments, x is greater than or equal to 0.85, 0.87, 0.88 or 0.89.
  • 0.8 ⁇ x ⁇ 0.99 for example 0.85 ⁇ x ⁇ 0.98, 0.85 ⁇ x ⁇ 0.97, 0.85 ⁇ x ⁇ 0.96 or 0.87 ⁇ x ⁇ 0.93. It may be particularly preferred that 0.85 ⁇ x ⁇ 0.98.
  • M is one or more of Co and Mn.
  • the general formula may alternatively be written as LiaNixCoyaMnybMg z CepXqO2+b, wherein ya+yb satisfies 0 ⁇ ya+yb ⁇ 0.5, wherein either ya or yb may be 0. It may be preferred that M is Co alone, i.e. the lithium nickel composite oxide contains no Mn.
  • z is greater than 0, for example in Formula 2, 0 ⁇ z ⁇ 0.05. In some embodiments z is greater than or equal to 0.001 , 0.003, 0.006 or 0.007. In some embodiments, z is less than or equal to 0.040 0.035, 0.030, 0.025, 0.020, 0.015, 0.012 or 0.010.
  • 0.001 ⁇ p ⁇ 0.05 In some embodiments, p is less than or equal to 0.045, 0.040, 0.035, 0.030, 0.025, or 0.020. In some embodiments p is greater than or equal to 0.002, 0.003, 0.004 or 0.005. It may be preferred that 0.003 ⁇ p ⁇ 0.05, 0.004 ⁇ p ⁇ 0.05, 0.005 ⁇ p ⁇ 0.05, 0.005 ⁇ p ⁇ 0.04, 0.005 ⁇ p ⁇ 0.03, 0.005 ⁇ p ⁇ 0.025, or 0.015 ⁇ p ⁇ 0.025.
  • b is greater than or equal to -0.1. In some embodiments b is less than or equal to 0.1. In some embodiments, - 0.1 ⁇ b ⁇ 0.1. In some embodiments, b is 0 or about 0. In some embodiments, b is 0.
  • X is one or more selected from Al, V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Sr, Ca, S, La, Mo, Nb, P, Sb, and W. It may be preferred that X is one or more selected from Al, Ti, B, and Zr. It may be further preferred that X is Al.
  • the particulate lithium nickel composite oxide material is a polycrystalline material, meaning that each particle of lithium nickel composite oxide material is made up of multiple crystal grains (also known as primary particles) which are agglomerated together. The crystal grains are typically separated by grain boundaries. Where the particulate lithium nickel composite oxide is polycrystalline, it will be understood that the particles of lithium nickel composite oxide comprising multiple crystal grains are secondary particles.
  • the particulate lithium nickel composite oxide material has a surface layer enriched with cobalt and I or aluminium, i.e. comprises a core material which has been surface modified (subjected to a surface modification process) to form an enriched surface layer. It has been found that the combination of cerium and cobalt enrichment at the surface, or cerium and aluminium enrichment at the surface, provides an excellent balance between discharge capacity retention, surface lithium impurities and internal resistance.
  • the surface modification results from contacting the core material with a cobalt-containing and I or an aluminium-containing compound, and then optionally carrying out heat treatment of the material.
  • the compounds may be in solution, and in such context herein the term “compound” refers to the corresponding dissolved species.
  • the discussions of the composition according to Formula I and Formula 2 herein when in the context of particles with an enriched surface layer relate to the overall particle, i.e. the particle including the enriched surface layer.
  • enriched surface and “enriched surface layer” refer to a particulate material which comprises a core material which has undergone a surface modification or surface enrichment process to increase the concentration of one or more elements at or near to the surface of the particles.
  • enriched surface layer therefore typically refers to a layer of material at or near to the surface of the particles which contains a greater concentration of an element, such as cobalt and I or aluminium, than the remaining material of the particle, i.e. the core of the particle.
  • elements may migrate between the core and the surface layer during preparation, storage or use of the material.
  • an element is stated to be present in (or absent from, or present in certain quantities in) the core, this is to be understood to refer to that element being intentionally added to, (or excluded from, or added in a particular quantity to) the core, and is not intended to exclude from the scope of protection materials where the distribution of elements is altered by migration during preparation, storage or use.
  • an element is stated to be present in (or absent from, or present in certain quantities in) the surface enriched layer, this is to be understood to refer to that element being intentionally added to, (or excluded from, or added in a particular quantity to) the surface enriched layer, and is not intended to exclude from the scope of protection materials where the distribution of elements is altered by migration during preparation, storage or use.
  • the surface enriched layer includes 1 at% cobalt, this means that 1 at% of the cobalt is added in the surface enrichment step, but does not preclude materials where some of the cobalt added in the surface enrichment step has migrated into the core.
  • the enriched surface layer comprises cobalt in an amount of 0.1 to 5 at % cobalt based on total metal content (excluding lithium).
  • the surface enriched layer may include at least 0.2, 0.3, or 0.5 at% cobalt.
  • the surface enriched layer may include less than or equal to 4, 3, 2.5, 2, or 1.5 at% cobalt.
  • the surface enriched layer may include 0.5 to 3, 0.7 to 3, 0.5 to 1.5 or 0.7 to 1.5 at% cobalt.
  • the enriched surface layer comprises aluminium in an amount of 0.1 to 5 at % aluminium based on total metal content (excluding lithium).
  • the surface enriched layer may include at least 0.2, 0.3, or 0.5 at% aluminium.
  • the surface enriched layer may include less than or equal to 4, 3, 2.5, 2, or 1.5 at% aluminium.
  • the surface enriched layer may include 0.5 to 3, 0.7 to 3, 0.5 to 1.5 or 0.7 to 1.5 at% aluminium.
  • lithium nickel composite oxide material comprises less than 0.015 wt% of lithium in the form of surface lithium hydroxide, for example less than 0.014, 0.013, 0.012, 0.011, 0.010, 0.009, 0.008, 0.007 or 0.005 wt% of lithium in the form of surface lithium hydroxide. It may have 0 wt% of lithium in the form of surface lithium hydroxide, but in some embodiments, there may be at least 0.001 wt% of lithium in the form of surface lithium hydroxide, for example between 0.001 and 0.015 wt %, or preferably between 0.001 and 0.010 wt%.
  • LiOH readily reacts with atmospheric carbon dioxide to form U2CO3, which is known to cause problems with cell gassing and the presence of high levels of surface LiOH has a negative effect on processability during electrode formation and can lead to gelling.
  • the amount of lithium in the form of surface lithium hydroxide may be determined by titration with HOI using a phenolphthalein indicator.
  • the titration protocol may include the following steps:
  • the particulate lithium nickel composite oxide material comprises less than 0.1 wt% of surface lithium carbonate. It may comprise less than 0.08 wt% of surface lithium carbonate, e.g. less than 0.07 wt%, less than 0.06 wt%, or less than 0.5 wt%. It may have 0 wt% surface lithium carbonate, but in some embodiments there may be at least 0.01 wt% or 0.02 wt% of surface lithium carbonate. It is preferred to minimise lithium carbonate impurities since their presence leads to lower active mass, and a reduction in the amount of lithium available for charge and discharge capacity. Additionally, surface lithium carbonate is known to cause problems with cell gassing.
  • the amount of surface lithium carbonate may be determined by titration with HCI using bromophenol blue indicator.
  • a first titration step with HCI and phenolphthalein indicator is carried out before titration with bromophenol blue indicator to remove any lithium hydroxide.
  • the titration protocol may include the following steps:
  • Extract surface lithium carbonate from sample of particulate lithium nickel composite oxide material by agitating in deionised water for 5 minutes to provide an extractate solution, and separate extractate solution from residual solid;
  • the particulate lithium nickel composite oxide material typically has a D50 particle size of at least 1 pm, e.g. at least 2 pm, at least 3 pm, at least 4 pm, at least 5 pm, at least 5.5 pm, at least 6.0 pm or at least 6.5 pm.
  • the particles of lithium nickel composite oxide typically have a D50 particle size of 20 pm or less, e.g. 15 pm or less or 12 pm or less. In some embodiments, the D50 particle size is from about 1 pm to about 20 pm, for example about 3 pm to about 20 pm.
  • the term D50 as used herein refers to the median particle diameter of the volume-weighted distribution.
  • the D50 may be determined by using a laser diffraction method. For example, the D50 may be determined by suspending the particles in water and analysing using a Malvern Mastersizer 3000.
  • the tapped density of the particulate lithium nickel composite oxide is from about 1.9 g/cm 3 to about 2.8 g/cm 3 , e.g. about 1.9 g/cm 3 to about 2.5 g/cm 3 .
  • the tapped density of the material can suitably be measured by loading a graduated cylinder with 25 mL of powder. The mass of the powder is recorded. The loaded cylinder is transferred to a Copley Tapped Density Tester JV Series. The material is tapped 2000 times and the volume re-measured. The re-measured volume divided by the mass of material is the recorded tap density.
  • the particulate lithium nickel composite oxide of the invention is characterised by an improved capacity retention for cells which incorporate the material as a cathode, in particular a high retention of capacity after 50 cycles.
  • an improved capacity retention for cells which incorporate the material as a cathode in particular a high retention of capacity after 50 cycles.
  • materials according to the invention may provide a capacity retention of greater than 95% after 50 cycles, and in some cases as high as around 96%.
  • the % capacity retention after 50 cycles is defined as the capacity of the cell after the 50 th cycle as a percentage of the initial capacity of the cell after its first charge. For clarity, one cycle includes a complete charge and discharge of the cell.
  • 90% capacity retention means that after the 50 th cycle the capacity of the cell is 90% of the initial capacity.
  • the process for preparing the particulate lithium nickel composite oxide typically comprises the steps of: (i) contacting a precursor of the lithium nickel composite oxide material with a cerium- containing compound, and optionally a cobalt-containing compound and I or an aluminium compound, to form a mixture;
  • the precursor of the lithium nickel composite oxide material is a mixed metal oxide or hydroxide, such as a lithium transition metal oxide. It may be preferred that the precursor of the lithium nickel composite oxide material is a core material having Formula 3:
  • M is Mn and I or Co
  • X’ is selected from Al, V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Sr, Ca, S, La, Mo, Nb, P, Sb, and W and combinations thereof.
  • step (i) the precursor of the lithium nickel composite oxide material is contacted with a cerium-containing compound.
  • step (i) the precursor of the lithium nickel composite oxide material is contacted with a cerium-containing compound and a cobalt-containing compound and I or an aluminium-containing compound.
  • step (i) comprises contacting the precursor material with an additional metal selected from one or more of X, and I or lithium .
  • additional metal selected from one or more of X, and I or lithium .
  • the inclusion of a lithium-containing compound in the treatment step (i) is proposed to be beneficial in order to avoid voids or defects in the structure of the particulate lithium nickel composite oxide material which may lead to a reduced lifetime.
  • the cerium-containing compound, and optional cobalt-, aluminium-, lithium- and/or X- containing compounds are typically provided in solution, such as an aqueous solution. It has been found by the present inventors that additives are not required in the solution of cerium in order to form the desired materials, which provides benefits associated with reduced complexity of the process at industrial scale. It may therefore be preferred that the precursor of the lithium nickel composite oxide material is contacted with an aqueous solution consisting essentially of the cerium-containing compound, and optional cobalt-, aluminium-, lithium- and/or X- containing compounds.
  • the precursor of the lithium nickel composite oxide material is contacted with the cerium- containing compound, and optional cobalt-, aluminium-, lithium- and/or X- containing compounds, in the absence of any polymeric material, such as polyvinyl alcohol.
  • the cerium-containing compound, and optional cobalt-, aluminium-, lithium- and/or X- containing compounds are typically salts, such as inorganic salts. It may be preferred that the compounds are independently selected from nitrates, sulfates or acetates. Nitrates may be particularly preferred.
  • the cerium-containing compound may suitably be cerium (III) nitrate, or a hydrate thereof. Other suitable cerium-containing compounds include cerium (III) salts including cerium acetate, cerium citrate and cerium oxalate.
  • the cobalt-containing compound may suitably be cobalt nitrate. Other suitable compounds include cobalt acetate, cobalt chloride and cobalt sulfate.
  • the aluminium-containing compound may suitably be aluminium nitrate.
  • the step (i) comprises contacting the precursor material with the cerium-containing compound, and any additional metal-containing compounds, in an aqueous solution.
  • the precursor material may be added to the aqueous solution to form a slurry or suspension.
  • the slurry is agitated or stirred.
  • the weight ratio of core material to water in the slurry after addition of the core material to the aqueous solution is from about 1.5:1 to about 1:1.5, for example from about 1.4:1 to about 1 :1.4, about 1.3:1 to about 1 :1.3, about 1.2:1 to about 1 :1.2 or about 1.1:1 to about 1:1.1.
  • the weight ratio may be about 1:1.
  • the precursor material may be contacted with the cerium-containing compound at a temperature in the range from 10 to 80 °C, for example at a temperature of at least 10, 15 or 20°C, 30 °C, or 40 °C, for example at a temperature of less than or equal to 80, 75, 70°C.
  • a temperature range of 40 to 70 °C may be particularly preferred, and it can lead to reduced surface lithium impurities.
  • the mixture is spray dried to form a spray-dried intermediate. It may be preferred that the outlet temperature of the spray-dryer is set at a temperature greater than 100 °C, such as in the range of including 110 to 140°C.
  • step (iii) of the process the spray-dried intermediate is heated to form the lithium nickel composite oxide material.
  • the heat treatment step may be carried out at a temperature of at least 500 °C, at least 600 °C or at least 650 °C.
  • the heat treatment step may be carried out at a temperature of 1000 °C or less, 900 °C or less, 800 °C or less or 750 °C or less. It may be particularly preferred that the heat treatment is carried out at temperature in the range of and including 650 to 800 °C.
  • the material to be heat treated may be at a temperature of at least 500 °C, at least 600 °C or at least 650 °C for a period of at least 30 minutes, at least 1 hour or at least 2 hours. The period may be less than 8 hours.
  • the heat treatment step may be carried out under a CCh-free atmosphere.
  • CC>2-free air may be flowed over the materials to be calcined during heat treatment and optionally during cooling.
  • the CCh-free air may, for example, be a mix of oxygen and nitrogen.
  • the CCh-free atmosphere may be oxygen (e.g. pure oxygen).
  • the atmosphere is an oxidising atmosphere.
  • CCh-free is intended to include atmospheres including less than 100 ppm CO2, e.g. less than 50 ppm CO2, less than 20 ppm CO2 or less than 10 ppm CO2. These CO2 levels may be achieved by using a CO2 scrubber to remove CO2.
  • the CCh-free atmosphere comprises a mixture of O2 and N2. In some embodiments, the mixture comprises a greater amount of N2 than O2. In some embodiments, the mixture comprises N2 and O2 in a ratio of from 50:50 to 90:10, for example from 60:40 to 90:10, for example about 80:20.
  • the process may include one or more milling steps, which may be carried out after the heat treatment steps.
  • the nature of the milling equipment is not particularly limited. For example, it may be a ball mill, a planetary ball mill or a rolling bed mill.
  • the materials may be manually ground, e.g. using a pestle and mortar.
  • the milling may be carried out until the particles (e.g. secondary particles) reach the desired size.
  • the particles of lithium nickel composite oxide (e.g. secondary particles) are typically milled until they have a D50 particle size of 20 pm or less, e.g. 15 pm or less or 13 pm or less, for example a D50 particle size in the range of 2 to 20 pm, or of 5 to 15 pm.
  • the process of the present invention may further comprise the step of forming an electrode (typically a cathode) comprising the lithium nickel composite oxide material.
  • an electrode typically a cathode
  • this is carried out by forming a slurry of the particulate lithium nickel composite oxide, applying the slurry to the surface of a current collector (e.g. an aluminium current collector), and optionally processing (e.g. calendaring) to increase the density of the electrode.
  • the slurry may comprise one or more of a solvent, a binder, carbon material and further additives.
  • the electrode of the present invention will have an electrode density of at least
  • the electrode density is the electrode density (mass/volume) of the electrode, not including the current collector the electrode is formed on. It therefore includes contributions from the active material, any additives, any additional carbon material, and any remaining binder.
  • the process of the present invention may further comprise constructing a battery or electrochemical cell including the electrode comprising the lithium nickel composite oxide.
  • the battery or cell typically further comprises an anode and an electrolyte.
  • the battery or cell may typically be a secondary (rechargeable) lithium (e.g. lithium ion) battery.
  • Example 1 Preparation of a lithium nickel composite oxide material with a 0.5 at% cerium coating
  • the material was immediately collected and loaded into an alumina saggar and the material calcined in a furnace with the following parameters: atmosphere - 1 L/min of artificial (CO2/H2O free) air, calcination profile - room temperature to 450°C at a heating rate of 5°C/min, 1 hr hold at 450°C, 450 to 700°C at a heating rate of 2°C/min, 2hr hold at 700°C, furnace cool to ⁇ 200 °C. After cooling to ⁇ 200 °C the material as removed from the furnace and immediately transferred to a nitrogen filled glovebox.
  • atmosphere - 1 L/min of artificial (CO2/H2O free) air atmosphere - 1 L/min of artificial (CO2/H2O free) air
  • calcination profile - room temperature to 450°C at a heating rate of 5°C/min, 1 hr hold at 450°C, 450 to 700°C at a heating rate of 2°C/min, 2hr hold at 700
  • composition of the sample of Example 1 was determined by ICP analysis to be Lil.018Ni0.902CO0.079Mg0.008Ce0.005O2.
  • Example 1 Further examples were produced using the method of Example 1 with the following changes: (i) the amount of cerium and other elements used for the coating composition were varied as set out in Table 1 and (ii) the base material slurry was held at 65 °C prior to the addition of cerium nitrate (except for Example 3 which was held at ambient temperature). In Examples 7 and 8, cobalt and aluminium were added to the cerium nitrate aqueous solution as cobalt nitrate and aluminium nitrate respectively. The formed products were analysed by ICP to determine their chemical composition.
  • the lithium nickel composite oxide materials were tested to determine their surface LiOH impurity levels and their surface U2CO3 impurity levels.
  • Surface LiOH content was determined by titration.
  • surface lithium hydroxide was extracted from a sample of each material by ultrasonication in methanol for 10 minutes, and separation of the methanol solution to provide an extractate solution. Phenolphthalein indicator was added to the extractate solution, and the extracted solution was titrated using HCI solution until the extractate solution became colourless. The amount of lithium hydroxide in the extractate solution was calculated from this titration, and the wt% of surface LiOH was calculated assuming 100% extraction of surface lithium hydroxide into the extractate solution.
  • ICP Inductively Coupled Plasma
  • the elemental composition of the compounds was measured by ICP-OES. For that, 0.1 g of material are digested with 10% aqua regia (3:1 ratio of hydrochloric acid and nitric acid) and 1 % H2SO4 using a Milestone Ultrawave microwave system and made up to 100 mL.
  • the ICP-OES analysis was carried out on an Agilent 5800 using matrix matched calibration standards and yttrium as an internal standard. The lines and calibration standards used were instrument-recommended.
  • Electrodes were made in a 94:3:3 active:carbon:binder formulation with an ink at 64 % solids. 0.30 g of SuperC65 carbon was mixed with 2.88 g of N-methyl pyrrolidone (NMP) on a Thinky® mixer. 9.40 g of active material was added and further mixed using the Thinky® mixer. Finally, 3.00 g of Solef® 5130 binder solution (10 wt% in NMP) was added and mixed in the Thinky mixer. The resulting ink was cast onto aluminium foils using a 150 pm fixed blade coater and dried at 120 °C for 60 minutes. Once dry, the electrode sheet was calendared in an MTI calendar to achieve a density of 3 g/cm 3 . Individual electrodes were cut and dried under vacuum overnight before transferring to an argon filled glovebox.
  • NMP N-methyl pyrrolidone
  • Coin cells were built using a lithium anode and 1M LiPFe in 1 :1 :1 EC (ethylene carbonate) : EMC (ethyl methyl carbonate) : DMC (dimethyl carbonate) + 1 wt% VC (vinylene carbonate) electrolyte. Electrodes selected had a loading of 9.0 mg/cm 2 and a density of 3 g/cm 3 . Electrochemical measurements were taken from averages of three cells measured at 23 °C, and a voltage window of 3.0-4.3V.
  • Electrochemical characteristics evaluated include 1.0 C specific capacity at cycle 1 and cycle 50, capacity retention, first cycle efficiency (FCE) and DCIR growth using a 10s pulse and a 1s pulse. Capacity retention and DCIR growth were determined based on performance after 50 cycles at 1C. The results are given in Table 3. Table 3 - The results of electrochemical testing of the base material and Examples 1 to 8.
  • the discharge capacity retention may be further enhanced by the addition of cerium in combination with surface enrichment with cobalt or aluminium.
  • a combination of the addition of cerium and surface enrichment with cobalt and aluminium also provides an improvement in internal resistance values.

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Abstract

L'invention concerne un matériau d'oxyde composite de lithium-nickel particulaire satisfaisant aux exigences suivantes : le matériau d'oxyde composite de lithium-nickel particulaire comprend une phase cristalline de CeO2; et le matériau d'oxyde composite de lithium-nickel particulaire comprend moins de 0,015 % en poids de lithium sous la forme d'hydroxyde de lithium de surface. L'invention concerne également des procédés de fabrication de tels matériaux. Les matériaux trouvent une utilisation dans la fabrication de cathodes pour batteries secondaires au lithium.
PCT/EP2022/076111 2021-09-22 2022-09-20 Oxyde composite nickel lithium et procédé de préparation WO2023046689A1 (fr)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
EP3442056A1 (fr) * 2016-03-25 2019-02-13 Ecopro Bm Co., Ltd. Procédé de fabrication de matériau actif d'électrode positive d'accumulateur au lithium, et matériau actif d'électrode positive d'accumulateur au lithium ainsi fabriqué
US20200112024A1 (en) * 2018-10-04 2020-04-09 Samsung Electronics Co., Ltd. Composite cathode active material, cathode and lithium battery each containing composite cathode active material, and method of preparing composite cathode active material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3442056A1 (fr) * 2016-03-25 2019-02-13 Ecopro Bm Co., Ltd. Procédé de fabrication de matériau actif d'électrode positive d'accumulateur au lithium, et matériau actif d'électrode positive d'accumulateur au lithium ainsi fabriqué
US20200112024A1 (en) * 2018-10-04 2020-04-09 Samsung Electronics Co., Ltd. Composite cathode active material, cathode and lithium battery each containing composite cathode active material, and method of preparing composite cathode active material

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Title
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YUAN W ET AL: "Surface modification of Li(Li0.17Ni0.2Co0.05Mn0.58)O2with CeO2as cathode material for Li-ion batteries", ELECTROCHIMICA ACTA, ELSEVIER, AMSTERDAM, NL, vol. 135, 9 May 2014 (2014-05-09), pages 199 - 207, XP028860033, ISSN: 0013-4686, DOI: 10.1016/J.ELECTACTA.2014.04.181 *

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