WO2022189792A1 - Process for the preparation of nickel based hydroxide - Google Patents

Process for the preparation of nickel based hydroxide Download PDF

Info

Publication number
WO2022189792A1
WO2022189792A1 PCT/GB2022/050618 GB2022050618W WO2022189792A1 WO 2022189792 A1 WO2022189792 A1 WO 2022189792A1 GB 2022050618 W GB2022050618 W GB 2022050618W WO 2022189792 A1 WO2022189792 A1 WO 2022189792A1
Authority
WO
WIPO (PCT)
Prior art keywords
nickel
aqueous mixture
preferred
source
based hydroxide
Prior art date
Application number
PCT/GB2022/050618
Other languages
French (fr)
Inventor
Christian Bruenig
Jasmin BRUNNER
Original Assignee
Johnson Matthey Public Limited Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johnson Matthey Public Limited Company filed Critical Johnson Matthey Public Limited Company
Publication of WO2022189792A1 publication Critical patent/WO2022189792A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • 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 generally relates to lithium nickel composite oxide materials which have utility as cathode materials in secondary lithium-ion batteries, to nickel-based hydroxide powders which have utility as precursors for the preparation of such lithium nickel composite oxide materials, and to improved processes for making such nickel-based hydroxide powders.
  • Lithium nickel composite oxide materials having a layered structure find utility as cathode materials in secondary lithium-ion batteries.
  • lithium nickel composite oxide materials are produced by mixing nickel-based precursors, such as hydroxides, with a source of lithium, and then calcining the mixture at an elevated temperature, such as 700 to 1000 °C. During the calcination process, the nickel-based precursor is lithiated and oxidised and undergoes a crystal structure transformation via intermediate phases to form the desired layered LiNiC>2 structure.
  • the nickel-based precursors used to produce lithium nickel composite oxides are typically formed by co-precipitation of a mixed metal salt solution in the presence of ammonia at high pH. Such processes require careful control of complex crystallisation conditions, long reaction times, and produce significant amounts of industrial waste which can be difficult and expensive to safely dispose of.
  • Ser., 1153 012074 that a precursor with a molar ratio Ni:Co:Mn of 8:1:1 may be formed be hydrothermally treating a mixture of nickel sulphate hexahydrate, manganese sulphate monohydrate, cobalt sulphate heptahydrate, and ammonium bicarbonate in a mixture of ethylene glycol and water at 160 to 190 °C for a period of 12 hours.
  • nickel-based hydroxide precursors may be produced hydrothermally in a process which provides significant process efficiencies in comparison to prior art processes.
  • M is one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Mg, Sr, Ca, Ce, La, Mo,
  • a nickel-based hydroxide powder according to Formula 1 in the form of spherical agglomerates of primary particles and with a BET surface area 3 30 m 2 /g.
  • a process for preparing a lithium nickel composite oxide material comprising:
  • a lithium nickel composite oxide material obtained or obtainable by the process of the third aspect.
  • an electrode comprising a lithium nickel composite oxide material according to the fourth aspect.
  • an electrochemical call comprising an electrode according to the fifth aspect.
  • Figure 1 shows an SEM image of the material of Example 1.
  • Figure 2 shows an analysis of the particle size distribution of the material of Example 1.
  • Figure 3 shows an SEM image of the material of Example 2.
  • Figure 4 shows an analysis of the particle size distribution of the material of Example 1.
  • the present invention provides nickel-based hydroxide powders with a composition according to Formula 1 and a process for their preparation.
  • 0 ⁇ y £ 0.5 It may be preferred that 0 ⁇ y £ 0.45, 0 ⁇ y £ 0.40, 0 ⁇ y £ 0.35, 0 ⁇ y £ 0.30, 0 ⁇ y £ 0.25, 0 ⁇ y £ 0.20, or 0 ⁇ y £ 0.15. It may also be preferred that 0.01 £ y £ 0.2, 0.02 £ y £ 0.2, 0.03 £ y £ 0.2, 0.01 £ y £ 0.17, or 0.01 £ y £ 0.15.
  • 0 £ a £ 0.1 It may be preferred that a is greater than or equal to 0.001, 0.002, 0.003, 0.004, or 0.005. It may be preferred that a is less than or equal to 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, or 0.01. It may be preferred that 0 £ a £ 0.05, 0 £ a £ 0.04, 0 £ a £ 0.03, or 0 £ a £ 0.02.
  • 0.001 £ a £ 0.05, 0.002 £ a £ 0.05, 0.003 £ a £ 0.05, 0.004 £ a £ 0.05, 0.005 £ a £ 0.05, 0.005 £ a £ 0.04, 0.005 £ a £ 0.03, or 0.005 £ a £ 0.02. It may be further preferred that a 0.
  • b £ 0.1 0 £ b £ 0.1. It may be preferred that b is greater than or equal to 0.001, 0.002, 0.003, 0.004, or 0.005. It may be preferred that b is less than or equal to 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, or 0.01. It may be preferred that 0 £ b £ 0.05, 0 £ b £ 0.04, 0 £ b £ 0.03, or 0 £ b £ 0.02.
  • 0.001 £ b £ 0.05, 0.002 £ b £ 0.05, 0.003 £ b £ 0.05, 0.004 £ b £ 0.05, 0.005 £ b £ 0.05, 0.005 £ b £ 0.04, 0.005 £ b £ 0.03, or 0.005 £ b £ 0.02. It may be further preferred that b 0.
  • the nickel-based hydroxide powder is a pure metal hydroxide having the general formula [Ni x Co y Mn z Al a M b ][(OH)2] a .
  • some such materials may spontaneously partially oxidise in air to form an oxyhydroxide having the general formula [Ni x CoyMn z Al a M b ][Op(OH)q] a , where p > 0.
  • p may be greater than 0, and q may be less than 2.
  • a is selected such that the overall charge balance is 0.
  • a may therefore satisfy 0.5 £ a £ 1.5.
  • a may be 1.
  • M is selected from one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Mg, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W. It may be preferred that M is Mg and optionally one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W.
  • the nickel- based hydroxide powder may contain sulphur anions, generally in the form of sulphate anions.
  • the sulphur content of the nickel-based hydroxide powder may be less than 10000 ppm, less than 5000 ppm, less than 3000 ppm, or less than 1500 ppm.
  • the sulphate content of the nickel-based hydroxide powder may be less than 30000 ppm, less than 15000 ppm or less than 9000 ppm.
  • the sulphur content of the nickel-based hydroxide powder is preferably less than about 3000 ppm (about 9000 ppm or less of sulphate).
  • the particles of the nickel-based hydroxide are typically approximately spherical agglomerates of primary particles, each primary particle made up from one or more crystallites: these agglomerates are generally referred to as ‘secondary particles’.
  • secondary particles Such spherical morphology provides advantages associated with particle packing enabling high electrode density.
  • particles of the nickel-based hydroxide have a volume-based particle size distribution such that the D50 is in the range of and including 1 to 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. It may be preferred that the D50 is in the range of and including 1 to 12 pm. It may be further preferred that the D50 is in the range of and including 1 to 5 pm.
  • nickel-based hydroxide powders with a D50 in the range 1 to 5 pm facilitates conversion into lithium nickel composite oxide materials with a single crystal morphology through calcination in the presence of a lithium source. It may be further preferred that the D90-D10/D50 value is less than 1.5.
  • particles of the nickel-based hydroxide formed herein described process have a high surface area in comparison with prior art materials.
  • the nickel-based hydroxide powder has a BET surface area 3 30 m 2 /g.
  • the BET surface area may be determined by the measurement of the amount of physically adsorbed gas according to the Brunauer, Emmett and Teller (BET) method.
  • BET Brunauer, Emmett and Teller
  • a high BET surface area of the precursor materials offers electrochemical benefits when converted to a lithium nickel composite oxide cathode material, for example relating to high rate performance due to short lithium diffusion distances.
  • the nickel-based hydroxide powder may be produced by a process comprising the step of (i) producing an aqueous mixture comprising at least one source of nickel, at least one source of cobalt, optionally at least one source of manganese, optionally at least one source of aluminium, and optionally one or more source of element(s) M.
  • the source of nickel is a nickel (II) salt, such as an inorganic nickel (II) salt, for example nickel (II) sulphate or nickel (II) nitrate.
  • Nickel (II) sulphate may be particularly preferred.
  • the source of cobalt is a cobalt (II) salt, such as an inorganic cobalt (II) salt, for example cobalt (II) sulphate or cobalt (II) nitrate.
  • Cobalt (II) sulphate may be particularly preferred.
  • the source of manganese is a manganese (II) salt, such as an inorganic manganese salt (II), for example manganese (II) sulphate or manganese (II) nitrate.
  • Manganese (II) sulphate may be particularly preferred.
  • the source of aluminium is an aluminium salt, such as an inorganic aluminium salt, for example aluminium sulphate or aluminium nitrate.
  • the source of element(s) M are salts of M, such as inorganic M salts, such as oxides, hydroxides, sulphates, or nitrates.
  • the aqueous mixture is produced with a pH of at least 10.
  • the aqueous mixture comprises a base, such as a metal hydroxide, for example lithium hydroxide, sodium hydroxide or potassium hydroxide. Potassium hydroxide may be particularly preferred. It may be preferred that the aqueous mixture has a pH of greater than or equal to 11. It may be further preferred that the aqueous mixture has a pH of greater than or equal to 12.
  • the aqueous mixture is formed by a process comprises the steps of (a) forming an aqueous solution of a base; (b) forming an aqueous mixed metal solution comprising at least one source of nickel, at least one source of cobalt, optionally at least one source of manganese, optionally at least one source of aluminium, and optionally one or more source of element(s) M; (c) mixing the aqueous mixed metal solution with the aqueous solution of the base. It may be preferred that step (c) comprises adding the aqueous mixed metal solution to the aqueous solution of the base. This can enable enhanced control of pH within the reaction vessel.
  • the addition of the mixed metal solution to the aqueous base may be carried out under an inert atmosphere, such as nitrogen, argon or mixtures thereof.
  • the aqueous mixture is typically formed in a vessel suitable for hydrothermal treatment, such as an autoclave or other pressure vessel.
  • the aqueous mixture does not contain ammonia or an ammonium salt. This can provide advantages associated with simplification of the treatment of waste streams from the process.
  • the inclusion of ammonia or ammonium salts in the aqueous mixture can also introduce safety concerns during high pressure and temperature reactions.
  • does not contain it is meant herein that no ammonia or ammonia salts are intentionally added to the aqueous mixture and this does not exclude the presence of impurity levels present in the starting materials.
  • the aqueous mixture is formed with water as the only solvent, i.e. that the aqueous mixture is substantially free of organic solvents, such as alkyl alcohols, for example methanol, ethanol and ethylene glycol.
  • organic solvents such as alkyl alcohols, for example methanol, ethanol and ethylene glycol.
  • substantially free it is meant herein that no organic solvents are intentionally added to the aqueous mixture and this does not exclude the presence of impurity levels present in the starting materials.
  • the ability to carry out the reaction in water provides significant advantages associated with simplified industrial waste treatment.
  • the aqueous mixture is then treated under hydrothermal conditions at a temperature in the range of and including 100 to 180 °C.
  • Heating to at least 100 °C is required to generate the hydrothermal conditions which enable the rapid formation of the desired nickel-based hydroxide materials. Heating to greater than 180 °C can lead to high pressures incompatible with manufacturing equipment and such temperatures are not required for the formation of the desired materials.
  • treating under hydrothermal conditions is understood as treatment of the aqueous mixture at an elevated temperature and a steam pressure of above 1 bar. It may be preferred that the temperature is in the range of and including 100 to 160 °C, 100 to 155 °C, 100 to 150 °C 105 to 145 °C, 110 to 140 °C, 115 to 135 °C or 120 to 135 °C.
  • the hydrothermal treatment is carried out at a steam pressure of from 1 bar to 40 bar, in particular at a steam pressure from 1 bar to 10 bar.
  • the aqueous mixture is typically reacted in a tightly closed or pressure-resistant vessel.
  • the reaction preferably takes place in an inert or protective gas atmosphere.
  • suitable inert gases include nitrogen, argon, or mixtures thereof.
  • the hydrothermal treatment comprises a heating phase, a hold phase and a cooling phase.
  • the hold phase comprises holding at a temperature in the range of and including 100 to 150 °C for a period of greater than 1 hour, for example between 1 and 10 hours. Holding at a temperature in the range of and including 100 to 150 °C has been found by the current inventors to provide a good balance between rapid formation of the desired nickel- based hydroxide and process efficiency. It may be further preferred that the hold phase comprises holding at a temperature in the range of and including 100 to 150 °C for a period of between 1 and 6 hours, such as between 1 and 4 hours, or between 1 and 3 hours.
  • the following specific conditions may be selected: 1 h heat up time to 130° C, 2 h hydrothermal treatment at 130° C, 3 h cooling from 130° C to 25° C.
  • the nickel-based hydroxide power is then isolated.
  • the reaction mixture following the hydrothermal treatment is filtered and then dried.
  • the reaction mixture following the hydrothermal treatment is filtered and then spray dried. It is advantageous to utilise a spray drying step as this leads to a spherical morphology of the formed particles.
  • the spray dryer configuration in particular the nozzle size and the flow rate, may be used to control the particle size of the obtained nickel- hydroxide particle. It may be preferred that the spray dryer is configured such that the D50 of the isolated nickel-based hydroxide powder is in the range 1 to 5 pm.
  • the filtered material may also be washed prior to a drying step. Typically, the filtered material is washed with distilled water. It may be preferred that the filtered material is washed until the conductivity of the filtrate is less than 500 pS/cm at 25 °C, preferably less than 400 pS/cm at 25 °C. After the nickel-based hydroxide power is isolated the process may include one or more milling steps.
  • the nature of the milling equipment is not particularly limited.
  • it may be a ball mill, a planetary ball mill or a rolling bed mill.
  • the milling may be carried out until the particles reach the desired size.
  • the particles of the nickel-based hydroxide powder may be milled until they have a D50 particle size of less than 10 pm, for example in the range 1 to 10 pm.
  • the nickel-based hydroxide powder may advantageously be used to prepare lithium nickel composite oxide materials.
  • the materials have a composition according to Formula 2:
  • M is one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Mg, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W; x1 satisfying 0.5 £ x1 ⁇ 1 y1 satisfying 0 ⁇ y1 £ 0.5 z1 satisfying 0 £ z1 £ 0.5 a1 satisfying 0 £ a1 £ 0.1 b1 satisfying 0 £ b1 £ 0.1 c1 satisfying 0.9 £ d £ 1.1 d1 satisfying - 0.1 £ d1 £ 0.1
  • 0 ⁇ y1 £ 0.5 It may be preferred that 0 ⁇ y1 £ 0.45, 0 ⁇ y1 £ 0.40, 0 ⁇ y1 £ 0.35, 0 ⁇ y1 £ 0.30, 0 ⁇ y1 £ 0.25, 0 ⁇ y1 £ 0.20, or 0 ⁇ y1 £ 0.15. It may also be preferred that 0.01 £ y1 £ 0.2, 0.02 £ y1 £ 0.2, 0.03 £ y1 £ 0.2, 0.01 £ y1 £ 0.17, or 0.01 £ y1 £ 0.15. In Formula 2, 0 £ z1 £ 0.5.
  • 0 £ z1 £ 0.45, 0 £ z1 £ 0.40, 0 £ z1 £ 0.35, 0 £ z1 £ 0.30, 0 £ z1 £ 0.25, 0 £ z1 £ 0.20, 0 £ z1 £ 0.15. It may be further preferred that z1 0.
  • a1 is less than or equal to 0.09, 0.08,
  • b1 is less than or equal to 0.09, 0.08,
  • d1 is greater than or equal to -0.1. It may also be preferred that d1 is less than or equal to 0.1. It may be further preferred that -
  • M is selected from one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Mg, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W. It may be preferred that M is Mg and optionally one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W.
  • M Mg and optionally one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W.
  • 0.5 £ x1 ⁇ 1 , 0 ⁇ y1 £ 0.5, 0 ⁇ z1 £ 0.5, a1 0, 0 £ b1 £ 0.1 , 0.8 £ c1 £ 1.2, -0.2 £ d1 £ 0.2.
  • the nickel-based hydroxide powder may be used to prepare lithium nickel composite oxide materials according to Formula 2 by a process comprising the step of mixing the nickel-based hydroxide powder with a lithium source.
  • Suitable lithium-containing compounds include lithium salts, such as inorganic lithium salts, for example lithium hydroxide (e.g. LiOH or UOH.H2O), lithium carbonate (U2CO3), and hydrated forms thereof. Lithium hydroxide may be particularly preferred.
  • the mixture is then calcined to obtain a lithium nickel composite oxide material.
  • the calcination step is carried out at a temperature of at least 600 °C, or at least 650 °C.
  • the calcination step may be carried out at a temperature of 1000 °C or less, 900 °C or less, or 800 °C or less or 750 °C or less.
  • the material to be calcined may be held at a temperature of at least 600 °C or at least 650 °C for a period of at least 2 hours, at least 3 hours, at least 4 hours or at least 5 hours. The period may be less than 12 hours, or less than 8 hours.
  • the calcination step comprises heating to a temperature in the range of and including 600 °C and 1000 °C for a period of 2 to 12 hours.
  • the calcination step may be carried out under a CC free atmosphere.
  • CC>2-free air may be flowed over the materials to be calcined during calcination and optionally during cooling.
  • the CC>2-free air may, for example, be a mix of oxygen and nitrogen.
  • the CC>2-atmosphere comprises at least 90 vol% oxygen, or more preferably the CC>2-free atmosphere may be oxygen (e.g. pure oxygen).
  • the atmosphere is an oxidising atmosphere.
  • the term “CC>2-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 calcination may be carried out in any suitable furnace known to the person skilled in the art, for example a static kiln (such as a tube furnace or a muffle furnace), a tunnel furnace (in which static beds of material are moved through the furnace, such as a roller hearth kiln or push-through furnace), or a rotary furnace (including a screw-fed or auger-fed rotary furnace).
  • a static kiln such as a tube furnace or a muffle furnace
  • a tunnel furnace in which static beds of material are moved through the furnace, such as a roller hearth kiln or push-through furnace
  • a rotary furnace including a screw-fed or auger-fed rotary furnace.
  • the furnace used for calcination is typically capable of being operated under a controlled gas atmosphere. It may be preferred to carry out the calcination step in a furnace with a static bed of material, such as a static furnace or tunnel furnace (e.g. roller hearth kiln or push-through furnace).
  • the material is typically loaded into a calcination vessel (e.g. saggar or other suitable crucible) prior to calcination.
  • a calcination vessel e.g. saggar or other suitable crucible
  • 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 2.5 g/cm 3 , at least 2.8 g/cm 3 , at least 3 g/cm 3 , or at least 3.3 g/cm 3 . It may have an electrode density of 4.5 g/cm 3 or less, or 4 g/cm 3 or less.
  • 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 Production of a nickel-based hydroxide powder of formula N 10.83C00.11 M h o.o b (OH)2
  • a first mixture was prepared by mixing KOH (358.2 g) and deionized water (610 ml_) and stirring for a period of 10 minutes.
  • a second mixture was prepared by mixing NiSC> 4 * 6 H 2 O (218.2 g), COSC> 4 (31.02 g) and MnSCU ' khO (10.14 g) in deionized water (1.2 L) and stirring for a period of 30 minutes.
  • the first mixture was placed in an autoclave with a stirrer set at 800 rpm and the autoclave was flushed three times with nitrogen.
  • the second mixture was added to the autoclave over a period of 20 minutes.
  • the autoclave was then heated from 30 °C to 130 °C over a period of 1 hour, held at a temperature of 130 °C for 2 hours, and cooled to 25 °C over a period of 3 hours.
  • the resulting precipitate was filtered and the filter cake washed with distilled water until the conductivity was less than 200 pS/cm.
  • Powder x-ray diffraction analysis confirmed the desired Ni(OH)2 structure was present.
  • Figure 1 shows an SEM image of the powder indicating the material is on the form of spherical agglomerates of primary particles.
  • Figure 2 shows an analysis of the particle size distribution of the material of Example 1 using a Mastersizer 2000.
  • the material has a particle size distribution as follows: D5 1.24 pm,
  • the D90-D10/D50 value is 1.37.
  • a first mixture was prepared by mixing KOH (374.07 g) and deionized water (610 ml_) and stirring for a period of 10 minutes.
  • a second mixture was prepared by mixing NiS0 4 * 6 H2O (239.2 g), C0SO4 (22.56 g) and MgS04 * 7H20 (2.47g) in deionized water (1.2 L) and stirring for a period of 30 minutes.
  • the first mixture was placed in an autoclave with a stirrer set at 800 rpm and the autoclave was flushed three times with nitrogen.
  • the second mixture was added to the autoclave over a period of 20 minutes.
  • the autoclave was then heated from 30 °C to 130 °C over a period of 1 hour, held at a temperature of 130 °C for 2 hours, and cooled to 25 °C over a period of 3 hours.
  • the resulting precipitate was filtered and the filter cake washed with distilled water until the conductivity 200 pS/cm.
  • Figure 3 shows an SEM image of the powder formed in Example 2 indicating the material is in the form of spherical agglomerates of primary particles.
  • Figure 4 shows an analysis of the particle size distribution of the material of Example 2 using a Mastersizer 2000. The material has a particle size distribution as follows: D5 1.36 pm,
  • D10 1.59 pm, D503.11 pm, D906.17 pm.
  • the D90-D10/D50 value is 1.47.

Abstract

The present invention generally relates to lithium nickel composite oxide materials which have utility as cathode materials in secondary lithium-ion batteries, to nickel-based hydroxide powders which have utility as precursors for the preparation of such lithium nickel composite oxide materials, and to improved processes for making such nickel-based hydroxide powders.

Description

PROCESS FOR THE PREPARATION OF NICKEL BASED HYDROXIDE
Field of the Invention
The present invention generally relates to lithium nickel composite oxide materials which have utility as cathode materials in secondary lithium-ion batteries, to nickel-based hydroxide powders which have utility as precursors for the preparation of such lithium nickel composite oxide materials, and to improved processes for making such nickel-based hydroxide powders.
Background of the Invention
Lithium nickel composite oxide materials having a layered structure find utility as cathode materials in secondary lithium-ion batteries. Typically, lithium nickel composite oxide materials are produced by mixing nickel-based precursors, such as hydroxides, with a source of lithium, and then calcining the mixture at an elevated temperature, such as 700 to 1000 °C. During the calcination process, the nickel-based precursor is lithiated and oxidised and undergoes a crystal structure transformation via intermediate phases to form the desired layered LiNiC>2 structure.
The nickel-based precursors used to produce lithium nickel composite oxides are typically formed by co-precipitation of a mixed metal salt solution in the presence of ammonia at high pH. Such processes require careful control of complex crystallisation conditions, long reaction times, and produce significant amounts of industrial waste which can be difficult and expensive to safely dispose of.
It is known to use hydrothermal processes to produce precursors of lithium nickel composite oxide materials. For it is described in ‘Synthesis of LiNi0.8Mn0.1Co0.1O2 cathode material by hydrothermal method for high energy density lithium ion battery’ Hendri Widiyandari et al., 2019, J. Phys.: Conf. Ser., 1153 012074 that a precursor with a molar ratio Ni:Co:Mn of 8:1:1 may be formed be hydrothermally treating a mixture of nickel sulphate hexahydrate, manganese sulphate monohydrate, cobalt sulphate heptahydrate, and ammonium bicarbonate in a mixture of ethylene glycol and water at 160 to 190 °C for a period of 12 hours.
There remains a need for improved processes for making nickel-based hydroxide precursors and for making lithium nickel composite oxide materials. Summary of the Invention
The present inventors have found that nickel-based hydroxide precursors may be produced hydrothermally in a process which provides significant process efficiencies in comparison to prior art processes.
Accordingly, in a first aspect of the invention, there is provided a process for preparing a nickel-based hydroxide powder according to Formula 1:
[NixCoyMnzAlaMb][Op(OH)q]a
Formula 1 wherein:
M is one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Mg, Sr, Ca, Ce, La, Mo,
Nb, P, Sb, and W; x satisfying 0.5 £ x < 1 y satisfying 0 < y £ 0.5 z satisfying 0 £ z £ 0.5 a satisfying 0 £ a £ 0.1 b satisfying 0 £ b £ 0.1 wherein p is in the range 0 £ p < 1 ; q is in the range 0 < q £ 2; x + y + z + a + b = 1; and a is selected such that the overall charge balance is 0; the process comprising the steps of:
(i) producing an aqueous mixture with a pH of at least 10, the aqueous mixture comprising at least one source of nickel, at least one source of cobalt, optionally at least one source of manganese, optionally at least one source of aluminium, and optionally one or more source of element(s) M;
(ii) treating the aqueous mixture under hydrothermal conditions at a temperature in the range of and including 100 to 180 °C;
(iii) isolating the nickel-based hydroxide power. In a second aspect of the invention there is provided a nickel-based hydroxide powder with a composition according to Formula 1 and which is obtained or obtainable by a process according to the first aspect.
In a third aspect of the invention there is provided a nickel-based hydroxide powder according to Formula 1 in the form of spherical agglomerates of primary particles and with a BET surface area ³ 30 m2/g.
In a fourth aspect of the invention there is provided a process for preparing a lithium nickel composite oxide material the process comprising:
(i) mixing a nickel-based hydroxide powder according to the second aspect, or prepared according to the process of the first aspect, with a lithium source;
(ii) calcining the mixture to obtain a lithium nickel composite oxide material.
In a fifth aspect of the invention there is provided a lithium nickel composite oxide material obtained or obtainable by the process of the third aspect.
In a sixth aspect of the invention there is provided an electrode comprising a lithium nickel composite oxide material according to the fourth aspect.
In a seventh aspect there is provided an electrochemical call comprising an electrode according to the fifth aspect.
Brief Description of the Drawings
Figure 1 shows an SEM image of the material of Example 1.
Figure 2 shows an analysis of the particle size distribution of the material of Example 1. Figure 3 shows an SEM image of the material of Example 2.
Figure 4 shows an analysis of the particle size distribution of the material of Example 1.
Detailed Description
Preferred and/or optional features of the invention will now be set out. Any aspect of the invention may be combined with any other aspect of the invention unless the context demands otherwise. Any of the preferred and/or optional features of any aspect may be combined, either singly or in combination, with any aspect of the invention unless the context demands otherwise. The present invention provides nickel-based hydroxide powders with a composition according to Formula 1 and a process for their preparation.
In Formula I, 0.5 £ x < 1. It may be preferred that 0.60 £ x < 1 , 0.65 £ x < 1, 0.70 £ x < 1, 0.75 £ x < 1 , 0.80 £ x < 1 , 0.85 £ x < 1 , or that 0.90 £ x < 1. It may be preferred that x is less than or equal to 0.99, 0.98, 0.97, 0.96 or 0.95. It may be preferred that 0.80 £ x £ 0.99, for example 0.80 £ x £ 0.98, 0.80 £ x £ 0.97, 0.80 £ x £ 0.96 or 0.80 £ x £ 0.95.
In Formula 1 , 0 < y £ 0.5. It may be preferred that 0 < y £ 0.45, 0 < y £ 0.40, 0 < y £ 0.35, 0 < y £ 0.30, 0 < y £ 0.25, 0 < y £ 0.20, or 0 < y £ 0.15. It may also be preferred that 0.01 £ y £ 0.2, 0.02 £ y £ 0.2, 0.03 £ y £ 0.2, 0.01 £ y £ 0.17, or 0.01 £ y £ 0.15.
In Formula 1 , 0 £ z £ 0.5. It may be preferred that 0 £ z £ 0.45, 0 £ z £ 0.40, 0 £ z £ 0.35, 0 £ z £ 0.30, 0 £ z £ 0.25, 0 £ z £ 0.20, 0 £ z £ 0.15. It may be further preferred that z = 0.
In Formula I, 0 £ a £ 0.1. It may be preferred that a is greater than or equal to 0.001, 0.002, 0.003, 0.004, or 0.005. It may be preferred that a is less than or equal to 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, or 0.01. It may be preferred that 0 £ a £ 0.05, 0 £ a £ 0.04, 0 £ a £ 0.03, or 0 £ a £ 0.02. It may be further preferred that 0.001 £ a £ 0.05, 0.002 £ a £ 0.05, 0.003 £ a £ 0.05, 0.004 £ a £ 0.05, 0.005 £ a £ 0.05, 0.005 £ a £ 0.04, 0.005 £ a £ 0.03, or 0.005 £ a £ 0.02. It may be further preferred that a = 0.
In Formula I, 0 £ b £ 0.1. It may be preferred that b is greater than or equal to 0.001, 0.002, 0.003, 0.004, or 0.005. It may be preferred that b is less than or equal to 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, or 0.01. It may be preferred that 0 £ b £ 0.05, 0 £ b £ 0.04, 0 £ b £ 0.03, or 0 £ b £ 0.02. It may be further preferred that 0.001 £ b £ 0.05, 0.002 £ b £ 0.05, 0.003 £ b £ 0.05, 0.004 £ b £ 0.05, 0.005 £ b £ 0.05, 0.005 £ b £ 0.04, 0.005 £ b £ 0.03, or 0.005 £ b £ 0.02. It may be further preferred that b = 0.
In Formula 1 , p is in the range 0 £ p < 1 ; q is in the range 0 < q £ 2; and a is selected such that the overall charge balance is 0.
Preferably, p is 0, and q is 2. In other words, preferably the nickel-based hydroxide powder is a pure metal hydroxide having the general formula [NixCoyMnzAlaMb][(OH)2]a. However, without wishing to be bound by theory, it is understood that some such materials may spontaneously partially oxidise in air to form an oxyhydroxide having the general formula [NixCoyMnzAlaMb][Op(OH)q]a, where p > 0. Where the nickel-based hydroxide powder has partially or completely oxidised, p may be greater than 0, and q may be less than 2. As discussed above, a is selected such that the overall charge balance is 0. a may therefore satisfy 0.5 £ a £ 1.5. For example, a may be 1.
In Formula 1 , M is selected from one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Mg, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W. It may be preferred that M is Mg and optionally one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W.
It may be preferred that 0.5 £ x < 1 , 0 < y £ 0.5, z = 0, 0 £ a £ 0.1 and 0 £ b £ 0.1. It may be further preferred that 0.5 £ x < 1, 0 < y £ 0.5, z = 0, a = 0 and 0 £ b £ 0.1. It may further be preferred that 0.5 £ x < 1 , 0 < y £ 0.5, z = 0, a = 0 and 0 £ b £ 0.1 and M = Mg and optionally one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and Wor that 0.8 £ x < 1, 0 < y £ 0.2, z = 0, a = 0 and 0 £ b £ 0.1 and M = Mg and optionally one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W.
It may also be preferred that 0.5 £ x < 1 , 0 < y £ 0.5, 0 < z £ 0.5, a = 0 and 0 £ b £ 0.1. It may be further preferred that 0.75 £ x < 1 , 0 < y £ 0.25, 0 < z £ 0.25, a = 0 and 0 £ b £ 0.1 , that 0.75 £ x < 1 , 0 < y £ 0.25, 0 < z £ 0.25, a = 0 and b = 0, or that 0.80 £ x < 1 , 0 < y £ 0.20, 0 < z £ 0.20, a = 0 and b = 0.
It may be further preferred that 0.5 £ x < 1, 0 < y £ 0.2, 0.1 < z £ 0.4, a = 0, 0 £ b £ 0.1. It may be further preferred that 0.5 £ x £ 0.8, 0.05 £ y £ 0.15, 0.2 < z £ 0.4, a = 0, 0 £ b £ 0.05. It may also be further preferred that 0.5 £ x £ 0.8, 0.05 £ y £ 0.15, 0.2 < z £ 0.4, a = 0, 0 £ b £ 0.05 and M is Mg.
In some cases, for example where sulphate-based starting materials are used, the nickel- based hydroxide powder may contain sulphur anions, generally in the form of sulphate anions. The sulphur content of the nickel-based hydroxide powder may be less than 10000 ppm, less than 5000 ppm, less than 3000 ppm, or less than 1500 ppm. The sulphate content of the nickel-based hydroxide powder may be less than 30000 ppm, less than 15000 ppm or less than 9000 ppm. The sulphur content of the nickel-based hydroxide powder is preferably less than about 3000 ppm (about 9000 ppm or less of sulphate).
The particles of the nickel-based hydroxide are typically approximately spherical agglomerates of primary particles, each primary particle made up from one or more crystallites: these agglomerates are generally referred to as ‘secondary particles’. Such spherical morphology provides advantages associated with particle packing enabling high electrode density.
Typically, particles of the nickel-based hydroxide have a volume-based particle size distribution such that the D50 is in the range of and including 1 to 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. It may be preferred that the D50 is in the range of and including 1 to 12 pm. It may be further preferred that the D50 is in the range of and including 1 to 5 pm. It has been found that use of nickel-based hydroxide powders with a D50 in the range 1 to 5 pm facilitates conversion into lithium nickel composite oxide materials with a single crystal morphology through calcination in the presence of a lithium source. It may be further preferred that the D90-D10/D50 value is less than 1.5.
Typically, particles of the nickel-based hydroxide formed herein described process have a high surface area in comparison with prior art materials. Preferably the nickel-based hydroxide powder has a BET surface area ³ 30 m2/g. The BET surface area may be determined by the measurement of the amount of physically adsorbed gas according to the Brunauer, Emmett and Teller (BET) method. A high BET surface area of the precursor materials offers electrochemical benefits when converted to a lithium nickel composite oxide cathode material, for example relating to high rate performance due to short lithium diffusion distances.
The nickel-based hydroxide powder may be produced by a process comprising the step of (i) producing an aqueous mixture comprising at least one source of nickel, at least one source of cobalt, optionally at least one source of manganese, optionally at least one source of aluminium, and optionally one or more source of element(s) M.
Typically, the source of nickel is a nickel (II) salt, such as an inorganic nickel (II) salt, for example nickel (II) sulphate or nickel (II) nitrate. Nickel (II) sulphate may be particularly preferred.
Typically, the source of cobalt is a cobalt (II) salt, such as an inorganic cobalt (II) salt, for example cobalt (II) sulphate or cobalt (II) nitrate. Cobalt (II) sulphate may be particularly preferred.
Typically, the source of manganese is a manganese (II) salt, such as an inorganic manganese salt (II), for example manganese (II) sulphate or manganese (II) nitrate. Manganese (II) sulphate may be particularly preferred.
Typically, the source of aluminium is an aluminium salt, such as an inorganic aluminium salt, for example aluminium sulphate or aluminium nitrate. Typically, the source of element(s) M are salts of M, such as inorganic M salts, such as oxides, hydroxides, sulphates, or nitrates.
The aqueous mixture is produced with a pH of at least 10. Typically, the aqueous mixture comprises a base, such as a metal hydroxide, for example lithium hydroxide, sodium hydroxide or potassium hydroxide. Potassium hydroxide may be particularly preferred. It may be preferred that the aqueous mixture has a pH of greater than or equal to 11. It may be further preferred that the aqueous mixture has a pH of greater than or equal to 12.
Typically, the aqueous mixture is formed by a process comprises the steps of (a) forming an aqueous solution of a base; (b) forming an aqueous mixed metal solution comprising at least one source of nickel, at least one source of cobalt, optionally at least one source of manganese, optionally at least one source of aluminium, and optionally one or more source of element(s) M; (c) mixing the aqueous mixed metal solution with the aqueous solution of the base. It may be preferred that step (c) comprises adding the aqueous mixed metal solution to the aqueous solution of the base. This can enable enhanced control of pH within the reaction vessel.
It may be preferred that the addition of the mixed metal solution to the aqueous base may be carried out under an inert atmosphere, such as nitrogen, argon or mixtures thereof.
The aqueous mixture is typically formed in a vessel suitable for hydrothermal treatment, such as an autoclave or other pressure vessel.
It may be preferred that the aqueous mixture does not contain ammonia or an ammonium salt. This can provide advantages associated with simplification of the treatment of waste streams from the process. The inclusion of ammonia or ammonium salts in the aqueous mixture can also introduce safety concerns during high pressure and temperature reactions. By “does not contain” it is meant herein that no ammonia or ammonia salts are intentionally added to the aqueous mixture and this does not exclude the presence of impurity levels present in the starting materials.
Alternatively, or in addition it may be preferred that the aqueous mixture is formed with water as the only solvent, i.e. that the aqueous mixture is substantially free of organic solvents, such as alkyl alcohols, for example methanol, ethanol and ethylene glycol. By “substantially free” it is meant herein that no organic solvents are intentionally added to the aqueous mixture and this does not exclude the presence of impurity levels present in the starting materials. The ability to carry out the reaction in water provides significant advantages associated with simplified industrial waste treatment. The aqueous mixture is then treated under hydrothermal conditions at a temperature in the range of and including 100 to 180 °C. Heating to at least 100 °C is required to generate the hydrothermal conditions which enable the rapid formation of the desired nickel-based hydroxide materials. Heating to greater than 180 °C can lead to high pressures incompatible with manufacturing equipment and such temperatures are not required for the formation of the desired materials. In the context of the present invention treating under hydrothermal conditions is understood as treatment of the aqueous mixture at an elevated temperature and a steam pressure of above 1 bar. It may be preferred that the temperature is in the range of and including 100 to 160 °C, 100 to 155 °C, 100 to 150 °C 105 to 145 °C, 110 to 140 °C, 115 to 135 °C or 120 to 135 °C. It may also be preferred that the hydrothermal treatment is carried out at a steam pressure of from 1 bar to 40 bar, in particular at a steam pressure from 1 bar to 10 bar. The aqueous mixture is typically reacted in a tightly closed or pressure-resistant vessel. The reaction preferably takes place in an inert or protective gas atmosphere. Examples of suitable inert gases include nitrogen, argon, or mixtures thereof.
The hydrothermal treatment comprises a heating phase, a hold phase and a cooling phase. Preferably the hold phase comprises holding at a temperature in the range of and including 100 to 150 °C for a period of greater than 1 hour, for example between 1 and 10 hours. Holding at a temperature in the range of and including 100 to 150 °C has been found by the current inventors to provide a good balance between rapid formation of the desired nickel- based hydroxide and process efficiency. It may be further preferred that the hold phase comprises holding at a temperature in the range of and including 100 to 150 °C for a period of between 1 and 6 hours, such as between 1 and 4 hours, or between 1 and 3 hours.
Purely as a non-limiting example, the following specific conditions may be selected: 1 h heat up time to 130° C, 2 h hydrothermal treatment at 130° C, 3 h cooling from 130° C to 25° C.
The nickel-based hydroxide power is then isolated. Typically, the reaction mixture following the hydrothermal treatment is filtered and then dried. Preferably, the reaction mixture following the hydrothermal treatment is filtered and then spray dried. It is advantageous to utilise a spray drying step as this leads to a spherical morphology of the formed particles.
The skilled person will understand that the spray dryer configuration, in particular the nozzle size and the flow rate, may be used to control the particle size of the obtained nickel- hydroxide particle. It may be preferred that the spray dryer is configured such that the D50 of the isolated nickel-based hydroxide powder is in the range 1 to 5 pm. The filtered material may also be washed prior to a drying step. Typically, the filtered material is washed with distilled water. It may be preferred that the filtered material is washed until the conductivity of the filtrate is less than 500 pS/cm at 25 °C, preferably less than 400 pS/cm at 25 °C. After the nickel-based hydroxide power is isolated the process may include one or more milling 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 milling may be carried out until the particles reach the desired size. For example, the particles of the nickel-based hydroxide powder may be milled until they have a D50 particle size of less than 10 pm, for example in the range 1 to 10 pm.
The nickel-based hydroxide powder may advantageously be used to prepare lithium nickel composite oxide materials. Suitably the materials have a composition according to Formula 2:
Lid Nixi OOyi Mrizi Alai Mbi O2+ 11 Formula 2 wherein:
M is one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Mg, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W; x1 satisfying 0.5 £ x1 < 1 y1 satisfying 0 < y1 £ 0.5 z1 satisfying 0 £ z1 £ 0.5 a1 satisfying 0 £ a1 £ 0.1 b1 satisfying 0 £ b1 £ 0.1 c1 satisfying 0.9 £ d £ 1.1 d1 satisfying - 0.1 £ d1 £ 0.1
In Formula 2, 0.5 £ x1 < 1. It may be preferred that 0.60 £ x1 < 1 , 0.65 £ x1 < 1 , 0.70 £ x1 < 1 , 0.75 £ x1 < 1 , 0.80 £ x1 < 1 , 0.85 £ x1 < 1 , or that 0.90 £ x1 < 1. It may be preferred that x 1 is less than or equal to 0.99, 0.98, 0.97, 0.96 or 0.95. It may be preferred that 0.80 £ x1 £ 0.99, for example 0.80 £ x1 £ 0.98, 0.80 £ x1 £ 0.97, 0.80 £ x1 £ 0.96 or 0.80 £ x1 £ 0.95.
In Formula 2, 0 < y1 £ 0.5. It may be preferred that 0 < y1 £ 0.45, 0 < y1 £ 0.40, 0 < y1 £ 0.35, 0 < y1 £ 0.30, 0 < y1 £ 0.25, 0 < y1 £ 0.20, or 0 < y1 £ 0.15. It may also be preferred that 0.01 £ y1 £ 0.2, 0.02 £ y1 £ 0.2, 0.03 £ y1 £ 0.2, 0.01 £ y1 £ 0.17, or 0.01 £ y1 £ 0.15. In Formula 2, 0 £ z1 £ 0.5. It may be preferred that 0 £ z1 £ 0.45, 0 £ z1 £ 0.40, 0 £ z1 £ 0.35, 0 £ z1 £ 0.30, 0 £ z1 £ 0.25, 0 £ z1 £ 0.20, 0 £ z1 £ 0.15. It may be further preferred that z1 = 0.
In Formula 2, 0 £ a1 £ 0.1. It may be preferred that a1 is greater than or equal to 0.001,
0.002, 0.003, 0.004, or 0.005. It may be preferred that a1 is less than or equal to 0.09, 0.08,
0.07, 0.06, 0.05, 0.04, 0.03, 0.02, or 0.01. It may be preferred that 0 £ a1 £ 0.05, 0 £ a1 £ 0.04, 0 £ a1 £ 0.03, or 0 £ a1 £ 0.02. It may be further preferred that 0.001 £ a1 £ 0.05,
0.002 £ a1 £ 0.05, 0.003 £ a1 £ 0.05, 0.004 £ a1 £ 0.05, 0.005 £ a1 £ 0.05, 0.005 £ a1 £
0.04, 0.005 £ a1 £ 0.03, or 0.005 £ a1 £ 0.02. It may be further preferred that a1 = 0.
In Formula 2, 0 £ b1 £ 0.1. It may be preferred that b1 is greater than or equal to 0.001,
0.002, 0.003, 0.004, or 0.005. It may be preferred that b1 is less than or equal to 0.09, 0.08,
0.07, 0.06, 0.05, 0.04, 0.03, 0.02, or 0.01. It may be preferred that 0 £ b1 £ 0.05, 0 £ b1 £ 0.04, 0 £ b1 £ 0.03, or 0 £ b1 £ 0.02. It may be further preferred that 0.001 £ b1 £ 0.05,
0.002 £ b1 £ 0.05, 0.003 £ b1 £ 0.05, 0.004 £ b1 £ 0.05, 0.005 £ b1 £ 0.05, 0.005 £ b1 £
0.04, 0.005 £ b1 £ 0.03, or 0.005 £ b1 £ 0.02. It may be further preferred that b1 = 0.
In Formula 2, 0.8 £ d £ 1.2. It may be preferred that d is greater than or equal to 0.90, or greater than or equal to 0.95. It may be preferred that d is less than or equal to 1.10, or less than or equal to 1.05. It may be preferred that 0.90 £ d £ 1.10, for example 0.95 £ d £ 1.05. It may be preferred that d = 1.
In Formula 2, -0.2 £ d1 £ 0.2. It may be preferred that d1 is greater than or equal to -0.1. It may also be preferred that d1 is less than or equal to 0.1. It may be further preferred that -
O.1 £ d1 £ 0.1 , or that d1 is 0 or about 0.
In Formula 2, M is selected from one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Mg, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W. It may be preferred that M is Mg and optionally one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W.
It may be preferred that 0.5 £ x1 < 1 , 0 < y1 £ 0.5, z1 = 0, 0 £ a1 £ 0.1 , 0 £ b1 £ 0.1 , 0.8 £ d £ 1.2 and -0.2 £ d1 £ 0.2. It may be further preferred that 0.5 £ x1 < 1 , 0 < y1 £ 0.5, z1 = 0, a1 = 0, 0 £ b1 £ 0.1 , 0.8 £ d £ 1.2 and -0.2 £ d1 £ 0.2. It may further be preferred that 0.5 £ x1 < 1 , 0 < y1 £ 0.5, z1 = 0, a1 = 0, 0 £ b1 £ 0.1 , 0.8 £ d £ 1.2, -0.2 £ d1 £ 0.2 and M = Mg and optionally one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Sr, Ca, Ce, La, Mo, Nb,
P, Sb, and W, or that 0.8 £ x1 < 1 , 0 < y1 £ 0.2, z1 = 0, a1 = 0, 0 £ b1 £ 0.1 , 0.8 £ d < 1.2, - 0.2 £ d1 £ 0.2 and M = Mg and optionally one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W. It may also be preferred that 0.5 £ x1 < 1 , 0 < y1 £ 0.5, 0 < z1 £ 0.5, a1 = 0, 0 £ b1 £ 0.1 , 0.8 £ c1 £ 1.2, -0.2 £ d1 £ 0.2. It may be further preferred that 0.75 £ x1 < 1 , 0 < y1 £ 0.25, 0 < z1 £ 0.25, a1 = 0, 0 £ b1 £ 0.1 , 0.8 £ c1 £ 1.2, -0.2 £ d1 < 0.2; that 0.75 £ x1 < 1 , 0 < y1 £ 0.25, 0 < z1 £ 0.25, a1 = 0, b1 = 0, 0.8 £ d £ 1.2, -0.2 £ d1 £ 0.2; or that 0.80 £ x1 < 1 , 0 < y1 £ 0.20, 0 < z1 £ 0.20, a1 = 0, b1 = 0, 0.8 £ d £ 1.2 and -0.2 £ d1 £ 0.2.
The nickel-based hydroxide powder may be used to prepare lithium nickel composite oxide materials according to Formula 2 by a process comprising the step of mixing the nickel-based hydroxide powder with a lithium source. Suitable lithium-containing compounds include lithium salts, such as inorganic lithium salts, for example lithium hydroxide (e.g. LiOH or UOH.H2O), lithium carbonate (U2CO3), and hydrated forms thereof. Lithium hydroxide may be particularly preferred.
The mixture is then calcined to obtain a lithium nickel composite oxide material. Typically, the calcination step is carried out at a temperature of at least 600 °C, or at least 650 °C. The calcination step may be carried out at a temperature of 1000 °C or less, 900 °C or less, or 800 °C or less or 750 °C or less. The material to be calcined may be held at a temperature of at least 600 °C or at least 650 °C for a period of at least 2 hours, at least 3 hours, at least 4 hours or at least 5 hours. The period may be less than 12 hours, or less than 8 hours. Preferably, the calcination step comprises heating to a temperature in the range of and including 600 °C and 1000 °C for a period of 2 to 12 hours.
The calcination step may be carried out under a CC free atmosphere. For example, CC>2-free air may be flowed over the materials to be calcined during calcination and optionally during cooling. The CC>2-free air may, for example, be a mix of oxygen and nitrogen. Preferably the CC>2-atmosphere comprises at least 90 vol% oxygen, or more preferably the CC>2-free atmosphere may be oxygen (e.g. pure oxygen). Preferably, the atmosphere is an oxidising atmosphere. As used herein, the term “CC>2-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 calcination may be carried out in any suitable furnace known to the person skilled in the art, for example a static kiln (such as a tube furnace or a muffle furnace), a tunnel furnace (in which static beds of material are moved through the furnace, such as a roller hearth kiln or push-through furnace), or a rotary furnace (including a screw-fed or auger-fed rotary furnace). The furnace used for calcination is typically capable of being operated under a controlled gas atmosphere. It may be preferred to carry out the calcination step in a furnace with a static bed of material, such as a static furnace or tunnel furnace (e.g. roller hearth kiln or push-through furnace).
Where the calcination is carried out in a furnace with a static bed of material, the material is typically loaded into a calcination vessel (e.g. saggar or other suitable crucible) prior to calcination.
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. Typically, 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.
Typically, the electrode of the present invention will have an electrode density of at least 2.5 g/cm3, at least 2.8 g/cm3, at least 3 g/cm3, or at least 3.3 g/cm3. It may have an electrode density of 4.5 g/cm3 or less, or 4 g/cm3 or less. 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.
The present invention will now be described with reference to the following examples, which are provided to assist with understanding the present invention and are not intended to limit its scope.
Examples
Example 1 - Production of a nickel-based hydroxide powder of formula N 10.83C00.11 M ho.ob(OH)2
A first mixture was prepared by mixing KOH (358.2 g) and deionized water (610 ml_) and stirring for a period of 10 minutes. A second mixture was prepared by mixing NiSC>4 *6 H2O (218.2 g), COSC>4(31.02 g) and MnSCU'khO (10.14 g) in deionized water (1.2 L) and stirring for a period of 30 minutes. The first mixture was placed in an autoclave with a stirrer set at 800 rpm and the autoclave was flushed three times with nitrogen. The second mixture was added to the autoclave over a period of 20 minutes. The autoclave was then heated from 30 °C to 130 °C over a period of 1 hour, held at a temperature of 130 °C for 2 hours, and cooled to 25 °C over a period of 3 hours.
The resulting precipitate was filtered and the filter cake washed with distilled water until the conductivity was less than 200 pS/cm.
The filtered solid was then suspended in water and then spray dried to yield a solid (64g).
Powder x-ray diffraction analysis (PXRD) confirmed the desired Ni(OH)2 structure was present.
Figure 1 shows an SEM image of the powder indicating the material is on the form of spherical agglomerates of primary particles.
Figure 2 shows an analysis of the particle size distribution of the material of Example 1 using a Mastersizer 2000. The material has a particle size distribution as follows: D5 1.24 pm,
D10 1.47 pm, D502.89 pm, D90 5.43 pm. The D90-D10/D50 value is 1.37.
Example 2 - Production of a nickel-based hydroxide powder of formula N io.9i Coo.08 M go.oi (OH )å
A first mixture was prepared by mixing KOH (374.07 g) and deionized water (610 ml_) and stirring for a period of 10 minutes. A second mixture was prepared by mixing NiS04 *6 H2O (239.2 g), C0SO4 (22.56 g) and MgS04 * 7H20 (2.47g) in deionized water (1.2 L) and stirring for a period of 30 minutes.
The first mixture was placed in an autoclave with a stirrer set at 800 rpm and the autoclave was flushed three times with nitrogen. The second mixture was added to the autoclave over a period of 20 minutes. The autoclave was then heated from 30 °C to 130 °C over a period of 1 hour, held at a temperature of 130 °C for 2 hours, and cooled to 25 °C over a period of 3 hours.
The resulting precipitate was filtered and the filter cake washed with distilled water until the conductivity 200 pS/cm.
The filtered solid was then suspended in water and then spray dried to yield a solid (44g). Powder x-ray diffraction analysis (PXRD) confirmed the desired Ni(OH)2 structure was present.
Figure 3 shows an SEM image of the powder formed in Example 2 indicating the material is in the form of spherical agglomerates of primary particles. Figure 4 shows an analysis of the particle size distribution of the material of Example 2 using a Mastersizer 2000. The material has a particle size distribution as follows: D5 1.36 pm,
D10 1.59 pm, D503.11 pm, D906.17 pm. The D90-D10/D50 value is 1.47.

Claims

Claims
1. A process for preparing a nickel-based hydroxide powder according to Formula 1 :
[NixCoyMnzAlaMb][Op(OH)q]a
Formula 1 wherein:
M is one or more of V, Ti, B, Zr, Cu, Sn, Cr, Fe, Ga, Si, Zn, Mg, Sr, Ca, Ce, La, Mo, Nb, P, Sb, and W; x satisfying 0.5 £ x < 1 y satisfying 0 < y £ 0.5 z satisfying 0 £ z £ 0.5 a satisfying 0 £ a £ 0.1 b satisfying 0 £ a £ 0.1 wherein p is in the range 0 £ p < 1 ; q is in the range 0 < q £ 2; x + y + z + a + b = 1; and a is selected such that the overall charge balance is 0; the process comprising the steps of:
(i) producing an aqueous mixture with a pH of at least 10, the aqueous mixture comprising at least one source of nickel, at least one source of cobalt, optionally at least one source of manganese, optionally at least one source of aluminium, and optionally one or more source of element(s) M;
(ii) treating the aqueous mixture under hydrothermal conditions at a temperature in the range of and including 100 to 180 °C;
(iii) isolating the nickel-based hydroxide power.
2. A process according to claim 1 wherein the aqueous mixture comprises a base, such as an inorganic hydroxide, for example potassium hydroxide.
3. A process according to any one of claims 1 to 2 wherein the aqueous mixture is treated at a temperature in the range of and including 100 to 180 °C for a period of 1 to 6 hours.
4. A process according to any one of the preceding claims wherein the aqueous mixture is treated at a temperature in the range of and including 100 to 150 °C, preferably for a period of 1 to 6 hours.
5. A process according to any one of the preceding claims wherein the aqueous mixture does not contain ammonia or an ammonium salt.
6. A process according to any one of the preceding claims wherein treating the aqueous mixture under hydrothermal conditions is carried out in a pressure vessel.
7. A process according to any one of the preceding claims wherein the nickel-based hydroxide powder is isolated by filtration and subsequent spray-drying.
8. A process according to any one of the preceding claims wherein z = 0, and M is Mg.
9. A process according to any one of claims 1 to 7 wherein 0 < y £ 0.2 and 0 < z £ 0.2
10. A nickel-based hydroxide powder with a composition according to Formula 1 and obtained or obtainable by a process according to any one of claims 1 to 9.
11. A nickel-based hydroxide powder according to claim 10 which has a D50 in the range of and including 1 to 5 pm.
12. A nickel-based hydroxide powder according to claim 10 or claim 11 which has a BET surface area ³ 30 m2/g.
13. A process for preparing a lithium nickel composite oxide material the process comprising the steps of:
(iii) mixing a nickel-based hydroxide powder according to any one of claims 10 to 13, or prepared according to the process of any one of claims 1 to 9, with a lithium source;
(iv) calcining the mixture to obtain a lithium nickel composite oxide material.
14. A lithium nickel composite oxide material obtained or obtainable by a process according to claim 13.
15. An electrode comprising a lithium nickel composite oxide material according to claim 14.
16. An electrochemical call comprising an electrode according to claim 15.
PCT/GB2022/050618 2021-03-12 2022-03-10 Process for the preparation of nickel based hydroxide WO2022189792A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB2103475.6A GB202103475D0 (en) 2021-03-12 2021-03-12 Process
GB2103475.6 2021-03-12

Publications (1)

Publication Number Publication Date
WO2022189792A1 true WO2022189792A1 (en) 2022-09-15

Family

ID=75623156

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2022/050618 WO2022189792A1 (en) 2021-03-12 2022-03-10 Process for the preparation of nickel based hydroxide

Country Status (2)

Country Link
GB (1) GB202103475D0 (en)
WO (1) WO2022189792A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002023650A1 (en) * 2000-09-13 2002-03-21 Ovonic Battery Company, Inc. Method of making a nickel hydroxide material
CN109179518B (en) * 2018-07-16 2020-12-15 昆明理工大学 Preparation method of high-density doped nickel cobalt hydroxide precursor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002023650A1 (en) * 2000-09-13 2002-03-21 Ovonic Battery Company, Inc. Method of making a nickel hydroxide material
CN109179518B (en) * 2018-07-16 2020-12-15 昆明理工大学 Preparation method of high-density doped nickel cobalt hydroxide precursor

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
ASH BALADEV ET AL: "Perspectives on Nickel Hydroxide Electrodes Suitable for Rechargeable Batteries: Electrolytic vs. Chemical Synthesis Routes", NANOMATERIALS, vol. 10, no. 9, 19 September 2020 (2020-09-19), pages 1878, XP055929506, DOI: 10.3390/nano10091878 *
D. S. HALL ET AL: "Nickel hydroxides and related materials: a review of their structures, synthesis and properties", ROYAL SOCIETY OF LONDON. PROCEEDINGS. MATHEMATICAL, PHYSICAL AND ENGINEERING SCIENCES, vol. 471, no. 2174, 24 December 2014 (2014-12-24), GB, pages 1 - 65, XP055373108, ISSN: 1364-5021, Retrieved from the Internet <URL:http://rspa.royalsocietypublishing.org/content/royprsa/471/2174/20140792.full.pdf> DOI: 10.1098/rspa.2014.0792 *
HENDRI WIDIYANDARI ET AL., J. PHYS.: CONF. SER., vol. 1153, 2019, pages 012074
MARTINS PAULO ROBERTO ET AL: "Thermodynamic stabilization of nanostructured alpha-Ni1-xCox(OH)2 for high efficiency batteries and devices", RSC ADVANCES, vol. 3, no. 43, 1 January 2013 (2013-01-01), GB, pages 20261, XP055929832, ISSN: 2046-2069, DOI: 10.1039/c3ra42417k *
THAI DIEN KHUONG ET AL: "Agglomeration of Ni-rich hydroxide crystals in Taylor vortex flow", POWDER TECHNOLOGY, vol. 274, 1 April 2015 (2015-04-01), Basel (CH), pages 5 - 13, XP055895582, ISSN: 0032-5910, DOI: 10.1016/j.powtec.2015.01.008 *
WALLNER HARALD ET AL: "Growth of Pure Ni(OH)2 Single Crystals from Solution - Control of the Crystal Size", ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, vol. 628, no. 13, 19 December 2002 (2002-12-19), Hoboken, USA, pages 2818 - 2820, XP055929792, ISSN: 0044-2313, DOI: 10.1002/1521-3749(200213)628:13<2818::AID-ZAAC2818>3.0.CO;2-J *

Also Published As

Publication number Publication date
GB202103475D0 (en) 2021-04-28

Similar Documents

Publication Publication Date Title
JP5081731B2 (en) The manufacturing method of the raw material for positive electrode active materials for lithium secondary batteries.
EP1875537B1 (en) Method for preparing layered core-shell cathode active materials for lithium secondary batteries
JP4217712B2 (en) Lithium-nickel-cobalt-manganese-fluorine-containing composite oxide, method for producing the same, and lithium secondary battery using the same
EP2910528B1 (en) Li-Ni COMPLEX OXIDE PARTICLE POWDER AND NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY
EP1837937A1 (en) Lithium manganese-based composite oxide and method and method forpreparing the same
JP3922040B2 (en) Lithium manganese composite oxide, method for producing the same, and use thereof
JP5958926B2 (en) Lithium manganese composite oxide and method for producing the same
JP2003048718A (en) Lithium ferritic multiple oxide and production method therefor
CN111971822A (en) Production method of positive electrode material for lithium ion battery
Chang et al. Syntheses of LiCoO2 for cathode materials of secondary batteries from reflux reactions at 130–200 C
KR100679380B1 (en) Low temperature lithiation of cobalt, nickel and manganese containning hydroxides using a wet process
US20230092675A1 (en) Cathode material and process
WO2018096972A1 (en) Lithium-manganese complex oxide and method for producing same
WO2022189792A1 (en) Process for the preparation of nickel based hydroxide
JP2001126731A (en) Positive electrode material for lithium secondary cell, positive electrode for lithium secondary cell, and the lithium secondary cell
JP2000154022A (en) Lithium manganese double oxide, its production and its use
JP3914981B2 (en) Cubic rock salt type lithium ferrite oxide and method for producing the same
WO2018181967A1 (en) Manganese oxide, production method therefor, and lithium secondary battery
JP2002338246A (en) Method for manufacturing lithium/manganese compound oxide and lithium cell formed using lithium/manganese compound oxide
JPH1160244A (en) Lithium-containing compound metal oxide and its production and use
JP2002075358A (en) Positive electrode material for lithium ion secondary battery and manufacturing method of the material
JP7483987B1 (en) Lithium metal composite oxide, positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery, and lithium secondary battery
US20230219826A1 (en) Process
JP3968420B2 (en) Cubic rock salt type lithium ferrite complex oxide and method for producing the same
WO2022034329A1 (en) Process for preparing lithium nickel composite oxide, lithium nickel composite oxide, electrode material comprising it and method to prepare it

Legal Events

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

Ref document number: 22711588

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22711588

Country of ref document: EP

Kind code of ref document: A1