WO2021191617A1 - Matériau de cathode et procédé - Google Patents

Matériau de cathode et procédé Download PDF

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Publication number
WO2021191617A1
WO2021191617A1 PCT/GB2021/050730 GB2021050730W WO2021191617A1 WO 2021191617 A1 WO2021191617 A1 WO 2021191617A1 GB 2021050730 W GB2021050730 W GB 2021050730W WO 2021191617 A1 WO2021191617 A1 WO 2021191617A1
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Prior art keywords
nickel oxide
lithium nickel
oxide material
material according
particulate lithium
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PCT/GB2021/050730
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English (en)
Inventor
Joanna Helen CLARK
Andrew Diamond
Eva-Maria Hammer
Anna PALACIOS PADROS
Olivia Rose WALE
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Johnson Matthey Public Limited Company
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Publication of WO2021191617A1 publication Critical patent/WO2021191617A1/fr

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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—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
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 oxide materials which are useful as cathode materials in lithium secondary batteries.
  • the present invention also provides processes for preparing such lithium nickel oxide materials, and electrodes and cells comprising the materials.
  • Lithium transition metal oxide materials having the formula LiMO 2 , where M typically includes one or more transition metals find utility as cathode materials in lithium ion batteries. Examples include LiNiO 2 and LiCoO 2 .
  • US 6921609 B2 describes a composition suitable for use as a cathode material of a lithium battery which includes a core composition having an empirical formula Li x M' z Ni 1 - y M” y O 2 and a coating on the core which has a greater ratio of Co to Ni than the core.
  • WO 2013/025328 A1 describes a particle including a plurality of crystallites including a first composition having a layered ⁇ -NaFeO 2 -type structure.
  • the particles include a grain boundary between adjacent crystallites, and the concentration of cobalt in the grain boundaries is greater than the concentration of cobalt in the crystallites.
  • Cobalt enrichment is achieved by treatment of the particles with a solution of LiNO 3 and Co(NO 3 ) 2 , followed by spray drying and calcining.
  • cathode materials which provide not only acceptable specific 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. Capacity retention is also commonly referred to simply as the “cyclability” of the battery.
  • the present invention provides a particulate lithium nickel oxide material comprising particles having Formula I
  • the present inventors have found that materials according to the present invention provide an excellent balance of capacity and capacity retention.
  • the present inventors have also found that materials according to the present invention perform particularly well when subjected to electrochemical testing across a wide voltage window. Good capacity retention across a wider voltage window is typically challenging to achieve.
  • the present invention also provides a cathode material for a lithium secondary battery comprising the particulate lithium nickel oxide material according to the first aspect, and a cathode comprising the particulate lithium nickel oxide material according to the first aspect.
  • the present invention also provides a lithium secondary cell or battery (e.g. a secondary lithium ion battery) comprising the cathode.
  • the battery typically further comprises an anode and an electrolyte.
  • the particulate lithium nickel oxide material has a composition according to Formula I defined above.
  • the compositions recited herein may be determined by Inductively Coupled Plasma (ICP) analysis as described in the Examples section below.
  • compositions recited herein are ICP compositions.
  • wt% content of elements in the particulate lithium nickel oxide materials may be determined using ICP analysis.
  • the wt% values recited herein are determined by ICP and are with respect to the total weight of the particle analysed (except wt% lithium carbonate which is defined separately below).
  • 0.88 ⁇ x ⁇ 0.92 It may be particularly preferred that 0.88 ⁇ x ⁇ 0.91.
  • -0.1 ⁇ b ⁇ 0.1 It may be preferred that -0.05 ⁇ b ⁇ 0.05. In some embodiments, b is 0 or about 0. In some embodiments, b is 0.
  • the particulate lithium nickel oxide material is a crystalline (or substantially crystalline) material. It may have the ⁇ -NaFeO 2 -type structure. It may be a polycrystalline material, meaning that each particle of lithium nickel oxide material is made up of multiple crystallites (also known as crystal grains or primary particles) which are agglomerated together. The crystal grains are typically separated by grain boundaries. Where the particulate lithium nickel oxide is polycrystalline, it will be understood that the particles of lithium nickel oxide comprising multiple crystals are secondary particles.
  • the particulate lithium nickel oxide material of Formula I comprises an enriched surface, i.e. comprises a core material which has been surface modified (subjected to a surface modification process) to form an enriched surface layer. In some embodiments the surface modification results from contacting the core material with one or more further metal-containing compounds, and then optionally carrying out calcination 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 herein when in the context of surface-modified particles relate to the overall particle, i.e. the particle including the enriched surface layer.
  • the terms “surface modified”, “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 metals, e.g. aluminium and/or cobalt at or near to the surface of the particles.
  • the term “enriched surface layer” therefore refers to a layer of material at or near to the surface of the particles which contains a greater concentration of one or more metals, e.g. aluminium and/or cobalt, than the remaining material of the particle, i.e. the core of the particle.
  • the particle comprises a greater concentration of Al in the enriched surface layer than in the core. In some embodiments, all or substantially all of the Al in the particle is in the enriched surface layer. In some embodiments, the core does not contain Al or contains substantially no Al, for example less than 0.01 wt% Al based on the total particle weight.
  • the particle comprises a greater concentration of Co in the enriched surface layer than in the core.
  • the enriched surface layer includes 1wt% or more Co, for example 1.5, 2.0 or 2.3 wt% Co or more.
  • the enriched surface layer includes 3.5 wt% or less, e.g. 3.0 or 2.7 wt% or less cobalt.
  • the enriched surface layer may include 2.0 to 3.0 wt%, e.g. 2.3 to 2.7 wt% Co.
  • approximately 45% of the cobalt included in the particle is in the enriched surface layer of the particle.
  • the content of a given element in the surface enriched layer is calculated by determining the wt% of that element in the particulate lithium nickel oxide material prior to surface enrichment (sometimes referred to herein as the first calcined material or the core material) by ICP to give value A, determining the wt% of that element in the final particulate lithium nickel oxide material after surface enrichment (and optional further calcination) by ICP to give value B, and subtracting value A from value B.
  • the content of a given element in the core may be determined by determining the wt% of that element in the particulate lithium nickel oxide material prior to surface enrichment (sometimes referred to herein as the first calcined material or the core material) by ICP.
  • 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 Al in the particle is in the enriched surface layer, this means that all or substantially all of the Al is added in the surface enrichment step, but does not preclude materials where some of the Al added in the surface enrichment step has migrated into the core.
  • the surface modification comprises immersion in a solution comprising aluminium and/or cobalt species (for example in the form of an aluminium- containing compound and/or a cobalt-containing compound), followed by drying of the surface-modified material and optionally calcination.
  • the solution may additionally contain lithium species (for example in the form of a lithium-containing compound).
  • the solution is heated, for example to a temperature of at least 50 °C, for example at least 55 °C or at least 60 °C.
  • the surface-modified material is spray-dried after being contacted with the solution.
  • the surface-modified material is calcined after spray drying.
  • the lithium, aluminium and cobalt- containing compounds may independently be the respective metal nitrates.
  • the particulate lithium nickel oxide material typically has a D50 particle size of at least 4 ⁇ m, e.g. at least 5 ⁇ m, at least 5.5 ⁇ m, at least 6.0 ⁇ m or at least 6.5 ⁇ m.
  • the particles of lithium nickel oxide e.g. secondary particles typically have a D50 particle size of 20 ⁇ m or less, e.g. 15 ⁇ m or less or 12 ⁇ m or less.
  • the D50 particle size is from about 5 ⁇ m to about 20 ⁇ m, for example about 5 ⁇ m to about 19 ⁇ m, for example about 5 ⁇ m to about 18 ⁇ m, for example about 5 ⁇ m to about 17 ⁇ m, for example about 5 ⁇ m to about 16 ⁇ m, for example about 5 ⁇ m to about 15 ⁇ m, for example about 5 ⁇ m to about 12 ⁇ m, for example about 5.5 ⁇ m to about 12 ⁇ m, for example about 6 ⁇ m to about 12 ⁇ m, for example about 6.5 ⁇ m to about 12 ⁇ m, for example about 7 ⁇ m to about 12 ⁇ m, for example about 7.5 ⁇ m to about 12 ⁇ m.
  • the D50 particle size refers to Dv50 (volume median diameter) and may be determined by using the method set out in ASTM B822 of 2017 under the Mie scattering approximation, for example using a Malvern Mastersizer 3000.
  • the D10 particle size of the material is from about 0.1 ⁇ m to about 10 ⁇ m, for example about 1 ⁇ m to about 10 ⁇ m, about 2 ⁇ m to about 8 ⁇ m, or from about 5 ⁇ m to about 7 ⁇ m.
  • the D10 particle size refers to Dv10 (10% intercept in the cumulative volume distribution) and may be determined by using the method set out in ASTM B822 of 2017 under the Mie scattering approximation, for example using a Malvern Mastersizer 3000.
  • the D90 particle size of the material is from about 10 ⁇ m to about 40 ⁇ m, for example from about 12 ⁇ m to about 35 ⁇ m, about 12 ⁇ m to about 30 ⁇ m, about 15 ⁇ m to about 25 ⁇ m or from about 16 ⁇ m to about 20 ⁇ m.
  • the D90 particle size refers to Dv90 (90% intercept in the cumulative volume distribution) and may be determined by using the method set out in ASTM B822 of 2017 under the Mie scattering approximation, for example using a Malvern Mastersizer 3000.
  • the tapped density of the particulate lithium nickel 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 2.4 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 oxide typically comprises less than 1 wt% of surface Li 2 CO 3 . It may comprise less than 0.8 wt% of surface Li 2 CO 3 , e.g. less than 0.6 wt%, less than 0.5 wt%, less than 0.3 wt%, less than 0.2 wt% or less than 0.15 wt%. It may have 0 wt% surface Li 2 CO 3 , but in some embodiments there may be at least 0.01 wt% , 0.02 wt% or 0.05 wt% of surface Li 2 CO 3.
  • the amount of surface Li 2 CO 3 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 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 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 92% after 50 cycles.
  • 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.
  • 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 material may have a capacity retention (after 50 cycles in a half cell coin cell vs Li, at an electrode loading of 9.0 mg/cm 2 and an electrode density of 3.0 g/cm 3 , tested at 23 °C and a 1C charge/discharge rate and voltage window of 3.0-4.3V) of at least 92%.
  • the capacity retention is at least 93% or at least 93.5%.
  • the materials of the present invention are also characterised by high capacity retention when tested with a large voltage window, in particular a high retention of capacity after 50 cycles.
  • high capacity retention when tested with a large voltage window, in particular a high retention of capacity after 50 cycles.
  • materials according to the invention may provide a capacity retention of greater than 90% after 50 cycles.
  • 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 material may have a capacity retention (after 50 cycles in a half cell coin cell vs Li, at an electrode loading of 9.0 mg/cm 2 and an electrode density of 3.0 g/cm 3 , tested at 23 °C and a 1C charge/discharge rate and voltage window of 2.5-4.4V) of at least 90%.
  • the capacity retention is at least 91%, at least 91.5% or at least 92%.
  • Materials of the invention are also characterised by a high specific capacity. It has been found that materials according to the invention when tested in a cell at 23 °C, a 1C discharge rate and a voltage window of 3.0-4.3V, with an electrode loading of 9.0 mg/cm 2 and an electrode density of 3.0 g/cm 3 in a half call coin cell vs Li metal, provide a specific capacity of at least 160 mAh/g, in some cases as high as 190 mAh/g.
  • This high specific capacity in combination with the high capacity retention on cycling provides a cell or battery of improved performance with an extended usable lifetime which is useful in high performance applications such as in electric vehicles.
  • the material may have a specific capacity when tested in a cell at 23 °C, a 1C discharge rate and a voltage window of 3.0-4.3V, with an electrode loading of 9.0 mg/cm 2 and an electrode density of 3.0 g/cm 3 in a half call coin cell vs Li metal of at least 190 mAh/g, e.g. at least 200 mAh/g, at least 205 mAh/g or at least 208 mAh/g.
  • the lithium nickel oxide materials of the present invention are typically made by calcining a mixture of lithium compound and a mixed metal hydroxide, for example in CO 2 -free air. CO 2 - free air can be prepared using a CO 2 scrubber.
  • the materials include an enriched surface layer
  • this is typically provided by performing a surface modification step on a core lithium nickel oxide material.
  • the particles may be milled to achieve the desired size.
  • the mixed metal hydroxide may be prepared by co-precipitation from a solution of metal salts by methods known in the art.
  • 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.
  • Comparative Example 1 Preparation of base materials Comparative Example 1A
  • Base 1 and 26.36 g LiOH were dry mixed in a poly-propylene bottle for 30 mins.
  • the LiOH was pre-dried at 200 °C under vacuum for 24 hours and kept dry in a purged glovebox filled with dry N 2 .
  • the powder mixture was loaded into 99%+ alumina crucibles and calcined under an artificial CO 2 -free air mix which was 80:20 N 2 :O 2 . Calcination was performed as follows: to 450 °C (5 °C/min) with 2 hours hold, ramp to 700 °C (2 °C/min) with a 6 hour hold and cooled naturally to 130 °C. The artificial air mix was flowing over the powder bed throughout the calcination and cooling. The title compound was thereby obtained.
  • the samples were then removed from the furnace at 130 °C and transferred to a high- alumina lined mill pot and milled on a rolling bed mill until D 50 was between 12.0 and 12.5 ⁇ m.
  • D 5 O was measured according to ASTM B822 of 2017 using a Malvern Mastersizer 3000 under the Mie scattering approximation and was found to be 9.5 ⁇ m.
  • the chemical formula of the material was determined by ICP analysis to be Lii o 3 oNio .953 Coo . o 3 oMgo . oioO 2.
  • Example 1 Preparation of surface-modified materials
  • Example 1A Compound 1
  • Comparative Example 1 A The product of Comparative Example 1 A was sieved through a 53 ⁇ m sieve and transferred to a N 2 -purged glovebox. An aqueous solution containing 5.91 g Co(NO 3 )2.6H 2 O, 0.47 g LiNO 3 and 2.44 g AI(NO 3 )3.9H 2 O in 100 mL water was heated to between 60 and 65 °C.
  • the sample was milled in a high-alumina lined mill pot on a rolling bed mill.
  • the target end point of the milling was when D 50 was between 10 and 11 ⁇ m; D 50 was measured after milling and found to be 9.5 ⁇ m.
  • the sample was passed through a 53 ⁇ m sieve and stored in a purged N 2 filledglove-box.
  • the water content of the material was 0.18 wt%.
  • the chemical formula of the material was determined by ICP analysis to be
  • Comparative Example 1 B The product of Comparative Example 1 B was subjected to the procedure set out under Example 1A, except that the aqueous solution contained 5.90 g Co(NO 3 )2.6H 2 O, 0.47 g LiNO 3 and 2.43 g AI(NO 3 ) 3 .9H 2 O in 100 mL water. The title compound was thereby obtained. D 50 was found to be 8.5 ⁇ m. The water content of the material was 0.28 wt%.
  • Comparative Example 1C The product of Comparative Example 1C was subjected to the procedure set out under Example 1A, except that the aqueous solution contained 5.89 g Co(NO 3 )2.6H 2 O, 0.46 g LiNO 3 and 2.43 g AI(NO 3 )3.9H 2 O in 100 mL water. The title compound was thereby obtained. D 50 was found to be 7.61 ⁇ m. The water content of the material was 0.2 wt%.
  • Example 1D The product of Comparative Example 1 D was subjected to the procedure set out under Example 1A, except that the aqueous solution contained 3.94 g Co(NO 3 ) 2 .6H 2 O and 2.43 g AI(NO 3 ) 3 .9H 2 O in 100 mL water, but did not contain any LiNO 3 . The title compound was thereby obtained. D 50 was found to be 11.7 ⁇ m. The water content of the material was 0.26 wt%. The chemical formula of the material was determined by ICP analysis to be L Example 1E - Compound 5
  • Comparative Example 1E The product of Comparative Example 1E was subjected to the procedure set out under Example 1A, except that the aqueous solution contained 3.93 g Co(NO 3 ) 2 .6H 2 O and 2.42 g AI(NO 3 ) 3. 9H 2 O in 100 mL water, but did not contain any LiNO 3 . The title compound was thereby obtained. D 50 was found to be 10.7 ⁇ m. The water content of the material was 0.09 wt%. The chemical formula of the material was determined by ICP analysis to be
  • Comparative Example 1 F The product of Comparative Example 1 F was subjected to the procedure set out under Example 1A, except that the aqueous solution contained 2.43 g AI(NO 3 ) 3 .9H 2 O in 100 mL water, but did not contain any Co(NO 3 ) 2 .6H 2 O or LiNO 3 . The title compound was thereby obtained. D 50 was found to be 7.5 ⁇ m. The water content of the material was 0.18 wt%.
  • Comparative Example 1G The product of Comparative Example 1G was subjected to the procedure set out under Example 1A, except that the aqueous solution contained 2.44 g AI(NO 3 ) 3 .9H 2 O in 100 mL water, but did not contain any Co(NO 3 ) 2 .6H 2 O or LiNO 3 . The title compound was thereby obtained. D 50 was found to be 7.9 ⁇ m. The water content of the material was 0.29 wt%. The chemical formula of the material was determined by ICP analysis to be
  • Comparative Example 1 H The product of Comparative Example 1 H was subjected to the procedure set out under Example 1A, except that the aqueous solution contained 11.82 g Co(NO 3 ) 2 .6H 2 O, 1.88 g UNO 3 and 2.44 g AI(NO 3 ) 3 .9H 2 O in 100 mL water. The title compound was thereby obtained. D 50 was found to be 8.2 ⁇ m. The water content of the material was 0.29 wt%. The chemical formula of the material was determined by ICP analysis to be
  • Comparative Example 1 J The product of Comparative Example 1 J was subjected to the procedure set out under Example 1A, except that the aqueous solution contained 11.77 g Co(NO 3 ) 2. 6H 2 O, 1.87 g LiNO 3 and 2.44 g AI(NO 3 ) 3. 9H 2 O in 100 mL water. The title compound was thereby obtained. D 50 was found to be 10.0 ⁇ m. The water content of the material was 0.08 wt%. The chemical formula of the material was determined by ICP analysis to be
  • Comparative Example 1 K The product of Comparative Example 1 K was subjected to the procedure set out under Example 1 A, except that the aqueous solution contained 3.93 g Co(NO 3 ) 2. 6H 2 O and 2.42 g AI(NO 3 ) 3. 9H 2 O in 100 mL water, but did not contain any UNO3. The title compound was thereby obtained. D 50 was found to be 9.4 ⁇ m. The water content of the material was 0.17 wt%. The chemical formula of the material was determined by ICP analysis to be
  • the powder mixture was loaded into 99%+ alumina crucibles and calcined under an artificial CO 2 free air mix which was 80:20 N 2 :O 2 . Calcination was performed as follows: to 450 °C (5 °C/min) with 2 hours hold, ramp to 700 °C (2°C/min) with a 6 hour hold and cooled naturally to 130 °C. The artificial air mix was flowing over the powder bed throughout the calcination and cooling.
  • the samples were then removed from the furnace at 130 °C and transferred to a purged N 2 filled glove-box.
  • the sample was transferred to a high-alumina lined mill pot and milled on a rolling bed mill until D 50 was between 12.0 - 12.5 ⁇ m.
  • the product was sieved through a 53 ⁇ m sieve and transferred to a purged N 2 filled glovebox.
  • An aqueous solution containing 11.83 g Co(NO 3 )2.6H 2 O, 1.88 g L1NO3 and 2.44 g AI(NO 3 )3.9H 2 O in 100 mLwater was heated to between 60 and 65 °C.
  • 100 g of the sieved powder was added rapidly while stirring vigorously.
  • the slurry was stirred at a temperature between 60 and 65 °C until the supernatant was colourless.
  • the slurry was then spray-dried.
  • the sample was milled in a high-alumina lined mill pot on a rolling bed mill. The end point of the milling was when D50 was between 10 and 11 ⁇ m; D 50 was measured after milling and found to be 8.8 ⁇ m.
  • the sample was passed through a 53 ⁇ m sieve and stored in a purged N 2 filled glove-box.
  • the water content of the material was 0.4 wt%.
  • the chemical formula of the material was determined by ICP analysis to be Compounds 12 to 20, listed in Table 3 below, were made by an analogous process to Compounds 1 to 10, using the following bases:
  • the total magnesium and cobalt contents (weight % based on the total particle weight) in the Comparative and Inventive materials was determined by ICP and is given in Table 3 below.
  • the surface cobalt content was calculated by subtracting the ICP wt% Co in the base material from the ICP wt% Co in the final material.
  • the core cobalt content is taken as the ICP wt% Co in the base material.
  • the elemental composition of the compounds was measured by ICP-OES. For that, 0.1 g of material are digested with aqua regia (3:1 ratio of hydrochloric acid and nitric acid) at ⁇ 130°C and made up to 100 ml_.
  • the ICP-OES analysis was carried out on an Agilent 5110 using matrix matched calibration standards and yttrium as an internal standard. The lines and calibration standards used were instrument-recommended.
  • Electrochemical Testing Electrodes were made in a 94:3:3 active:carbon:binder formulation with an ink at 65 % solids. 0.6 g of SuperC65 carbon was mixed with 5.25 g of N-methyl pyrrolidone (NMP) on a Thinky® mixer. 18.80 g of active material was added and further mixed using the Thinky® mixer. Finally, 6.00 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 125 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 LiPF 6 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 first cycle efficiency (FCE), 0.1 C specific capacity, 1.0 C specific capacity, capacity retention and DCIR growth using a 10s pulse.
  • Capacity retention and DCIR growth were determined based on performance after 50 cycles at 1C.
  • Table 3 includes details of the materials tested. Capacity retention was also determined using a voltage window of 2.5-4.4 V, with all other conditions kept the same for some of the samples. The results are shown in Table 4 below.

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Abstract

L'invention concerne des matériaux d'oxyde de lithium-nickel particulaires améliorés qui sont utiles en tant que matériaux de cathode dans des batteries secondaires au lithium. L'invention concerne également des procédés de préparation de tels matériaux d'oxyde de lithium-nickel et des électrodes et des cellules comprenant ces matériaux.
PCT/GB2021/050730 2020-03-27 2021-03-25 Matériau de cathode et procédé WO2021191617A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6921609B2 (en) 2001-06-15 2005-07-26 Kureha Chemical Industry Co., Ltd. Gradient cathode material for lithium rechargeable batteries
US20120119167A1 (en) * 2009-08-04 2012-05-17 Panasonic Corporation Positive electrode active material, method for producing same, and non-aqueous electrolyte secondary battery using same
WO2013025328A2 (fr) 2011-08-16 2013-02-21 Tiax Llc Oxyde métallique polycristallin, procédés de fabrication de celui-ci et articles le comprenant
EP3315638A1 (fr) * 2016-07-11 2018-05-02 Ecopro Bm Co., Ltd. Oxyde complexe de lithium pour batterie secondaire au lithium, matériau actif positif et son procédé de préparation
US20190140276A1 (en) * 2016-04-27 2019-05-09 Camx Power, Llc. Polycrystalline layered metal oxides comprising nano-crystals

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6921609B2 (en) 2001-06-15 2005-07-26 Kureha Chemical Industry Co., Ltd. Gradient cathode material for lithium rechargeable batteries
US20120119167A1 (en) * 2009-08-04 2012-05-17 Panasonic Corporation Positive electrode active material, method for producing same, and non-aqueous electrolyte secondary battery using same
WO2013025328A2 (fr) 2011-08-16 2013-02-21 Tiax Llc Oxyde métallique polycristallin, procédés de fabrication de celui-ci et articles le comprenant
US20190140276A1 (en) * 2016-04-27 2019-05-09 Camx Power, Llc. Polycrystalline layered metal oxides comprising nano-crystals
EP3315638A1 (fr) * 2016-07-11 2018-05-02 Ecopro Bm Co., Ltd. Oxyde complexe de lithium pour batterie secondaire au lithium, matériau actif positif et son procédé de préparation

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