[go: up one dir, main page]

US20200024153A1 - Precursors of cathode materials for a rechargeable lithium ion battery - Google Patents

Precursors of cathode materials for a rechargeable lithium ion battery Download PDF

Info

Publication number
US20200024153A1
US20200024153A1 US16/488,717 US201816488717A US2020024153A1 US 20200024153 A1 US20200024153 A1 US 20200024153A1 US 201816488717 A US201816488717 A US 201816488717A US 2020024153 A1 US2020024153 A1 US 2020024153A1
Authority
US
United States
Prior art keywords
cobalt
compound
precursor
hydroxide carbonate
cobalt based
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US16/488,717
Other languages
English (en)
Inventor
Dae-Hyun Kim
Jens Paulsen
JinDoo OH
Maxime Blangero
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Umicore NV SA
Umicore Korea Ltd
Original Assignee
Umicore NV SA
Umicore Korea Ltd
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 Umicore NV SA, Umicore Korea Ltd filed Critical Umicore NV SA
Assigned to UMICORE KOREA, LTD., UMICORE reassignment UMICORE KOREA, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PAULSEN, JENS, BLANGERO, MAXIME, OH, JinDoo, KIM, DAE-HYUN
Publication of US20200024153A1 publication Critical patent/US20200024153A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/06—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/80—Compounds containing cobalt, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G51/82—Compounds containing cobalt, with or without oxygen or hydrogen, and containing two or more other elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • C01P2002/30—Three-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • 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
    • 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
    • C01P2006/12—Surface area
    • 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
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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

  • This invention relates to a powderous cobalt based compound, applicable as a precursor of a cathode material in a rechargeable lithium ion battery, and to a process to use this precursor to prepare a cathode material for rechargeable lithium ion batteries.
  • the precursor compound is a cobalt based hydroxide carbonate based compound which is prepared by a precipitation process using sodium carbonate.
  • the precursor compound is additionally doped with elements such as Al, Mg, Mn, Ni etc. and, preferably the compound has a spherical morphology, which provides benefits for improved electrochemical performance and higher energy density.
  • Lithium cobalt oxide LiCoO 2 ; referred to as LCO hereafter—doped or un-doped—has been used as a cathode material in the rechargeable batteries of most commercial portable electronic applications, such as a mobile phone, tablet PC, laptop computer, and digital camera, due to its high energy density and good cycle life.
  • LCO has a hexagonal ⁇ -NaFeO 2 type structure (space group of R-3 m), where layers of lithium ions are located between slabs of CoO 6 octahedron. Since the demand for smaller and lighter batteries which have a high energy density and good electrochemical properties has increased, lots of R&D groups are working on developing or improving cathode materials, especially LCO.
  • the packing density of a cathode material mainly depends on two components:
  • LCO is synthesized using a lithium (Li) precursor (generally, Li 2 CO 3 ) and a cobalt (Co) precursor (typically, Co 3 O 4 ).
  • Li lithium
  • Co cobalt
  • the way to get the preferred morphology of LCO is to start a synthesis from shaped cobalt precursors that have a high D50 and narrow span. Having a high density and low porosity is a benefit as it further enhances the packaging density of the final LCO and reduces the sintering efforts. Shaped cobalt precursor should also have enough mechanical hardness not to be broken during processing, such as blending with the lithium precursor.
  • a cathode material is one of the most critical components which determine the electrochemical properties of lithium ion batteries.
  • One way to increase the energy density of a lithium ion battery is to increase its working voltage by applying a higher charge voltage.
  • the state of charge increases by increasing the charge voltage, less lithium ions remain in the crystal structure, resulting in a thermodynamically unstable CoO 2 .
  • cobalt can slowly be dissolved in the electrolyte at high voltage, which is referred to as cobalt dissolution, resulting in the failure of the battery.
  • cobalt dissolution there have been tremendous efforts to reduce cobalt dissolution by means of doping LCO.
  • the dopant is already present and well distributed in the cobalt precursor before sintering, such as in CN102891312 A, CN105731551 A and CN102583585 B.
  • the dopant is already present and well distributed in the cobalt precursor before sintering, such as in CN102891312 A, CN105731551 A and CN102583585 B.
  • Full diffusion of dopant into the shaped particles of LCO requires a long sintering time or very high sintering temperatures. This especially applies for a synthesis process if the particle size is big, e.g. >10 ⁇ m, where the dopant is added during blending of lithium and cobalt precursors.
  • Cobalt precursors for LCO can be prepared by a precipitation process.
  • a solution having a certain concentration of a CoSO 4 and a solution having a certain concentration of NaOH are mixed in a reactor under controlled pH, where an impeller is rotating with a certain RPM. Consequently, solid cobalt hydroxide (Co(OH) 2 ) will be precipitated, which can be a cobalt source of LCO.
  • Co(OH) 2 there is a drawback when using Co(OH) 2 in that it is difficult to achieve a large D50 hydroxide because of certain particle growth limitations.
  • CoCO 3 precipitation allows more easily to obtain large, spherical and dense cobalt precursors.
  • cobalt salts can be chosen from CoSO 4 , CoCl 2 , Co(NO 3 ) 2 or other water soluble cobalt salts, while bases can be selected from Na 2 CO 3 , K 2 CO 3 , NaHCO 3 , KHCO 3 , NH 4 HCO 3 or other soluble carbonate or bicarbonate.
  • bases can be selected from Na 2 CO 3 , K 2 CO 3 , NaHCO 3 , KHCO 3 , NH 4 HCO 3 or other soluble carbonate or bicarbonate.
  • Na 2 CO 3 , NaHCO 3 and NH 4 HCO 3 are the three most widely used precipitation agents for CoCO 3 .
  • CoCO 3 is typically produced through a co-precipitation of a bicarbonate solution with a cobalt salt solution. If CoSO 4 is chosen as cobalt salt, a typical reaction equation is:
  • This invention aims to provide an improved cobalt based precursor compound for a cathode material, and a manufacturing method to obtain a low impurity content in the final cathode material, which improves the electrochemical stability and increases the energy density of the cathode material, with a cheaper process cost.
  • the invention can provide the use of a cobalt based hydroxide carbonate compound having a malachite-rosasite mineral structure as a precursor of a lithium cobalt based oxide usable as an active positive electrode material in lithium ion batteries.
  • the compound may have the general formula [Co 1-a A a ] 2 (OH) 2 CO 3 , A being either one or more of Ni, Mn, Al, Zr, Ti and Mg, with a0.05.
  • A is Al or Mg, with 0.002 ⁇ a ⁇ 0.020, and Al or Mg is homogeneously doped in the compound.
  • the same values for P can also be reached if the compound is part of a mixture comprising also cobalt carbonate.
  • the cobalt carbonate may have a rhombohedral structure.
  • the compound in the previous embodiments may further comprise Na as an impurity of up to 0.3wt %.
  • the compound may have a particle size distribution with D50 between 15 and 25 ⁇ m or between 20 and 25 ⁇ m, and a span ⁇ 0.80. Another PSD related characteristic may be that D99/D50 ⁇ 2.
  • the cobalt based hydroxide carbonate compound may have a spherical morphology and a tap density >1.8 g/cm 3 .
  • the invention can provide a method for manufacturing the cobalt based hydroxide carbonate compound of the first aspect of the invention, comprising the steps of:
  • the invention can also provide a method to manufacture a lithiated cobalt based oxide, comprising the steps of any one of the previous method embodiments, and subsequently comprising the steps of:
  • the precipitated cobalt based hydroxide carbonate compound may comprise Na as an impurity between 0.1 and 0.3 wt %, and wherein either:
  • a sulfate compound is added, whereby the molar quantity of SO 4 is equal to or higher than the molar content of Na, and subsequently comprising the step of washing the lithiated cobalt based oxide with water, and drying the lithiated cobalt based oxide.
  • the sulfate compound may be either one of Li 2 SO 4 , NaHSO 4 , CoSO 4 and Na 2 S 2 O 8 .
  • FIG. 1 Typical result of floating test
  • FIG. 2 Schematic illustration of Na 2 CO 3 based co-precipitation set-up
  • FIG. 3 The XRD patterns of cobalt hydroxide carbonate based cobalt precursors
  • FIG. 4 Relation between the proportion of Co 2 (OH) 2 CO 3 phase and amount of sodium impurity
  • FIGS. 5 a & b EDS mapping of EX3-P-3
  • the current invention discloses a cobalt compound useful as cobalt precursor of a cathode material for a rechargeable lithium ion battery. More specifically, this precursor is a cobalt hydroxy (or hydroxide) carbonate based compound.
  • this precursor is a cobalt hydroxy (or hydroxide) carbonate based compound.
  • This invention provides:
  • ammonia is added as chelating agent (for example to prepare M(OH) 2 ) or as part of the precursor salts (for example ammonium bicarbonate in the case of CoCO 3 ).
  • Ammonia containing solutions are not stable, and especially at higher temperatures and higher pH they decompose rapidly and NH 3 gas evolves. Therefore it is standard practice to (1) use closed reactors and (2) avoid high temperatures to avoid a contamination of the air in the plant by ammonia.
  • New strategies need to be applied to solve the sodium impurity problem in CoCO 3 precursor products. Besides impurities in general, a particular issue is that in a standard precipitation, no high quality precipitate is achieved. Typically the precipitate of a CoSO 4 +Na 2 CO 3 precipitation has a poor morphology and a very low density.
  • the invention discloses that a cobalt based hydroxide carbonate compound can be produced by using a Na 2 CO 3 precipitation process that is performed at high temperature under agitation, and ensuring that any CO 2 that is formed is evacuated from the reactor mixture.
  • the invention combines the following aspects:
  • a spherical dense cobalt compound which has narrow span can be prepared: the median particle size (D50) of the precipitated cobalt hydroxide carbonate can be easily above 20 ⁇ m with a span below 0.8. Due to the feature of a spherical dense cobalt compound which has a narrow span, the cathode material (LCO) can have also have a higher density and narrower span.
  • D50 median particle size of the precipitated cobalt hydroxide carbonate
  • a dopant (Ni, Mn, Nb, Al, Mg, Ti, Zr, and etc.) can be homogeneously distributed in the crystal structure of the cobalt precursor compound with atomic scale distribution, since the dopant is added during the precipitation process.
  • doping of 3-valent aluminum into the structure of the cobalt compound is possible.
  • doping of Mg is possible as well.
  • nano-particle doping can be applied as well (for example for TiO 2 ).
  • As aluminum suppresses the structural changes at high voltage, the influence of cobalt dissolution on the electrochemical properties of the final lithiated cobalt based oxide can be mitigated.
  • Doping of manganese in a cobalt precursor can stabilize the crystal structure of LCO resulting in the improved cycleability as well as the power performance of LCO.
  • Nickel doping can increase the capacity of LCO.
  • the sodium impurity can be generally suppressed in the cobalt hydroxide carbonate compound. However, in some conditions, a Na impurity remains after the precipitation, which can be removed by an intermediate washing step after addition of sulfur or chlorine compounds, followed by a drying step.
  • a precipitate of high quality can be achieved, related to the surprising discovery that the high quality precipitate is not a cobalt based carbonate but rather a cobalt hydroxide carbonate.
  • CO 2 is evaporated continuously from the solution. CO 2 only evaporates if the temperature during precipitation is sufficiently high and when an appropriate evacuation of CO 2 is foreseen, such as by working with an open reactor. If the CO 2 evaporation rate is insufficient cobalt carbonate precipitates instead of the desired cobalt hydroxide carbonate, and high quality precursors are not achieved.
  • a flow comprising Na 2 CO 3 , a flow comprising CoSO 4 or CoCl 2 , and another flow of dopant source are fed into a reactor under normal to strong agitation.
  • the agitation is achieved by a rotating impeller or circulating flows.
  • the precipitation reaction can be a batch process or a continuous process where the overflow is circulated back into the reactor. Under normal agitation, the precipitation process is mainly controlled by the following parameters:
  • the obtained cobalt bearing precursor is separated from the liquid by a suitable separation technique such as filtering, then washed by deionized water. Washing with deionized water can remove a fraction of the sodium impurity from the obtained cobalt baring precursor, but still a quite high amount of impurities remain even after washing with large amounts of deionized water.
  • the precipitated material comprises a cobalt hydroxide carbonate that may be represented by the general formula Co 2 (OH) 2 CO 3 , according to the reaction:
  • the precipitated material can also contain CoCO 3 , according to the theoretical reaction mentioned before (EQ 6). Nucleation and growth of the precipitated particles is related to the precipitation reaction kinetics. Since large spherical particles having a narrow span can be obtained in this process, it implies that during precipitation, existing particles grow and no or only a small number of new particles are created. Thus the main process is the precipitation of Co 2 (OH) 2 CO 3 onto existing Co 2 (OH) 2 CO 3 particles, resulting in the desired particle growth. The inventors speculate that the precipitation reaction happens in two steps. CoCO 3 could precipitate as an intermediate, metastable compound, which then reacts with liquid, and by an ion exchange process results in the hydroxide carbonate compound, according to the following reaction schemes:
  • the rate limiting step is the ion exchange reaction (EQ 8).
  • the ion exchange reaction (EQ 8).
  • the ion exchange kinetics are negatively influenced and residual CoCO 3 remains.
  • the residual CoCO 3 exceeds 50% by weight, the sodium impurity level increases severely and the preferred morphology is not obtained anymore. Only if the cobalt hydroxide carbonate phase dominates, a precursor of high quality is obtained.
  • the reaction in (EQ 7) is promoted by a high temperature during the precipitation process, preferably in a well agitated open-type reactor, so that generated CO 2 can easily be removed from the system. It has thus been found that if the base is Na 2 CO 3 , the precipitation needs to be performed at a temperature of at least 70° C., preferably at around 90° C., preferably in an open reactor, to allow the evolution of CO 2 .
  • the flow of base comprises a solution of Na 2 CO 3 .
  • the base can be a mixture of Na 2 CO 3 and NaOH, where up to 50% of the Na present in Na 2 CO 3 can be replaced by NaOH.
  • a 50% molar solution (Na 2 CO 3 +2NaOH) does not require the evolution of CO 2 , following the reaction:
  • the ratio of base to acid is larger than 1. If it is too low, unreacted cobalt remains in the solution. For example, if 100% Na 2 CO 3 is used, the molar ratio of CO 3 to Co should be at least 1. If a 50/50% Na 2 CO 3 /NaOH mixture is used, the ratio of (CO 3 +2OH) to Co should be at least 1. The Na 2 CO 3 content in the base should not be below 50% (CO 3 >2OH). In this case, too much NaOH is present and some of the precipitate will be Co(OH) 2 which is undesired.
  • the base and acid concentration may be sufficient high to achieve a low nucleation rate and a high reactor throughput. If Na 2 CO 3 is used, a typical concentration is at least 2N, which corresponds to 1 mol Na 2 CO 3 /L, preferably it is at least 3N and most preferably at least 4N.
  • the acid solution is typically at least 2N, corresponding to 1 mol CoSO 4 /L, more preferably at least 3N and most preferably at least 4N.
  • the residence time is the time needed to fill the reactor: it is the reactor volume divided by the sum of the feed flow rates.
  • the residence time should be sufficiently high to allow particles to grow into the desired shape. It should not be too high because this would cause a low reactor throughput and more carbonate type precursor formed instead of the desired hydroxy-carbonate.
  • Homogeneously distributed dopants may play an important role in a cathode material.
  • aluminum significantly suppresses changes in crystal structure of a cathode material when charged to a high voltage, resulting in better stability at such high voltage.
  • the invention discloses that dopants can be co-precipitated during the Na 2 CO 3 based process by using sulfate solutions such as aluminum sulfate and magnesium sulfate, or suspensions of nano-sized powder. Doping is preferably applied during the precipitation reaction.
  • One embodiment applies nano particle doping. Nano particles can be added as a powder or dispersed into the reactor in a separate feed flow. Alternatively nano particles can be dispersed within the acid or base feed flows. Suitable nano particles are embedded within the growing precipitate particles.
  • nano particles doping are TiO 2 , Al 2 O 3 , MgO, etc.
  • a typically doping by nano particles is at least 500 mol ppm (amount of metal dopant/transition metal) and not more than 2 mol %.
  • doping is performed by adding a dopant solution to the reactor. Salts of Ni, Mn, Mg or Al can be added as separate feed flows, or they can be part of the acid feed.
  • Typical dopant salts are sulfates, nitrates, etc.
  • Typical doping amounts are at least 0.2 mol % (amount of metal dopant/transition metal) and not more than 5 mol %.
  • Mg solution doping is difficult or impossible using a bicarbonate process because of the high solubility of Mg 2+ at low pH
  • the cobalt precursor compound obtained by the Na 2 CO 3 based process under industrial precipitation process conditions contains a high sodium impurity level of 1000 ppm to 3000 ppm. This sodium impurity cannot be removed from the precursor, even not by excessive washing with water. As a high sodium impurity in a cobalt precursor may create undesired phases which are not electrochemically active, this may be a cause of bad electrochemical properties of the cathode material in the final lithium ion battery.
  • LCO—doped or un-doped —which is the cathode material in the lithium ion battery, can be synthesized by a lithiation process of the cobalt hydroxide carbonate based precursor.
  • the precursor is mixed with a lithium source—such as lithium carbonate or lithium hydroxide—and certain additives, followed by heating at elevated temperature in an oxygen containing atmosphere, with a suitable heating profile. Finally the sintered material is crushed and sieved. It is expected that the charge and discharge capacities—which are amongst the most important electrochemical properties in a lithium ion battery—decrease as the level of sodium impurity increases.
  • a sodium impurity can be effectively removed by adding a specific additive before or during lithiation, followed by a heating and washing step.
  • additives may be sulfates, such as sodium bisulfate, lithium sulfate, cobalt sulfate, ammonium sulfate, etc.
  • NaHSO 4 can remove 1 mol of Na by washing away Na 2 SO 4 .
  • 1 mol of Na can be removed as LiNaSO 4 by adding 1 mol of Li 2 SO 4 .
  • 2 mols of Na can be removed as Na 2 SO 4 when adding CoSO 4 , etc.
  • lithium sodium sulfate is thermodynamically stable, it is formed during lithiation at elevated temperature if a sulfate is added to the cobalt compound, followed by a heat treatment. Therefore, the sulfate can be added during the blending step of the cobalt precursor and the lithium source, and the lithium sodium sulfate is removed by a washing step after firing.
  • lithium sulfate and cobalt sulfate are preferred because lithium and cobalt are the main elements in the cathode material, other sulfates such as aluminum sulfate and magnesium sulfate or bisulfates, peroxisulfates etc. can also be a good choice, since some additives deliver positive effects in a cathode material.
  • a sodium sulfate compound is formed it is water-soluble and can be easily removed by a simple washing step with water.
  • PSD particle size distribution
  • D50, D99, and span Data about the particle size distribution (PSD) such as D50, D99, and span are preferably obtained by a laser PSD measurement method.
  • the laser PSD is measured using a Malvern Mastersizer 2000 with Hydro 2000MU wet dispersion accessory, after dispersing the powder in an aqueous medium.
  • sufficient ultrasonic irradiation and stirring are applied and an appropriate surfactant is introduced.
  • the value of the span is used in the Examples to measure sphericity.
  • the specific surface area is measured with the Brunauer-Emmett-Teller (BET) method using a Micromeritics Tristar 3000. 3 g of powder sample is vacuum dried at 300° C. for 1 h prior to the measurement in order to remove adsorbed species before measurement.
  • BET Brunauer-Emmett-Teller
  • the inductively coupled plasma (ICP) method is used to measure the content of elements such as lithium, cobalt, sodium, aluminum and magnesium by using an Agillent ICP 720-ES.
  • ICP inductively coupled plasma
  • 2 g of powder sample is dissolved in 10 mL high purity hydrochloric acid in an Erlenmeyer flask.
  • the flask is covered by glass and heated on a hot plate for complete dissolution of the precursor. After being cooled to room temperature, the solution is moved to a 100 mL volumetric flask that was 3 ⁇ 4 times rinsed with distilled (DI) water. After filling the flask with the solution, the volumetric flask is filled with DI water up to the 100 mL mark, followed by complete homogenization.
  • DI distilled
  • the TD measurement is carried out on an ERWEKA® instrument.
  • the XRD measurement is performed with a Rigaku X-Ray Diffractometer (D/MAX-2200/PC) using Cu K ⁇ .
  • the scan speed is set at continuous scanning at 1 degree per minute.
  • the step-size is 0.02 degree. Scans are performed between 15 and 85 degree.
  • Quantitative phase analysis is carried out using a TOPAS software.
  • the peak intensity P1 is defined as the maximum intensity at 34 ⁇ 35 degree (corresponding to the (021) peak of the Co 2 (OH) 2 CO 3 structure) without background subtraction
  • Peak intensity P2 is defined as the maximum intensity at 32 ⁇ 33 degree (corresponding to the (104) peak of the CoCO 3 structure) without background subtraction.
  • the peak ratio P is the ratio of P1 to P2.
  • Cross section analysis is done by a focus ion beam instrument, which is a JEOL (IB-0920 CP).
  • the instrument uses an argon gas as a beam source.
  • a small amount of powder is mixed with a resin and hardener, then the mixture is heated for 10 minutes on a hot plate. After heating, it is placed into the ion beam instrument and the settings are adjusted in a standard procedure, which a voltage is set as 6 kV for 3 hours duration.
  • Scanning Electron Microscopy (SEM) is carried out using a JEOL JSM 7100 F scanning electron microscope. The electron microscope is fitted with a 50 mm 2 X-MaxN EDS (Energy-dispersive X-ray spectroscopy) sensor from Oxford instruments.
  • Step 1) preparation of a positive electrode: a slurry that contains the solids: electrochemical active material, conductor (Super P, Timcal) and binder (KF#9305, Kureha) in a weight ratio 90:5:5; and a solvent (NMP, Sigma-Aldrich) is prepared in a high speed homogenizer.
  • the homogenized slurry is spread on one side of an aluminum foil using a doctor blade coater with a 230 ⁇ m gap. It is dried in an oven at 120° C., pressed using a calendaring tool, and dried again in a vacuum oven to remove the solvent completely.
  • argon an inert gas
  • a separator (Celgard) is located between the positive electrode and a piece of lithium foil used as negative electrode.
  • two pieces of separator are located between the positive electrode and the negative material, which consists of graphite.
  • 1M LiPF6 in EC/DMC ratio 1:2 is used as electrolyte and dropped between separator and electrodes. Then, the coin cell is completely sealed to prevent leakage of electrolyte.
  • the floating test analyses the stability of cathode materials at high voltage charging at elevated temperature.
  • the maximum current is 1 mA.
  • the current of the coin cell reaches the maximum current (1 mA) and the voltage drops due to short circuiting, where this time is recorded as “failure time” (indicated by FT on the Figure) which is a measure of the high voltage stability and the degree of cobalt dissolution of cathode material.
  • the coin cell is disassembled.
  • the anode and separator close to the anode are analyzed by ICP (inductively coupled plasma) for a metal dissolution analysis, since the prior art described that if metal dissolution happens, the dissolved metal will be deposited on the surface of the anode in metal or metal alloy form.
  • the measured cobalt content is normalized by failure time and total amount of active material in the electrode so that the specific cobalt dissolution value can be obtained.
  • the general electrochemical test of coin cells comprises two parts as follows: (see also Table 1). Part I is the evaluation of rate performance at 0.1C, 0.2C, 0.5C, 1C, 2C and 3C in the 4.3 ⁇ 3.0V/Li metal window range.
  • the first charge and discharge capacity (CQ1 and DQ1) are measured by constant current mode with 0.1C rate, where 1C is defined as 160 mAh/g.
  • a relaxation time of 30 minutes for the first cycle and 10 minutes for all subsequent cycles is allowed between each charge and discharge.
  • the irreversible capacity Q irr. is expressed in % as:
  • nC ⁇ ⁇ rate DQn DQ ⁇ ⁇ 1 ⁇ 100 ⁇ ( % )
  • Part II is the evaluation of cycle life.
  • the charge cutoff voltage is set as 4.6V/Li metal.
  • the discharge capacity at 4.6V/Li metal is measured at 0.1C at cycles 7 and 31 and 1C at cycles 8 and 32.
  • Capacity fadings at 0.1C and 1C are calculated as follows and are expressed in % per 100 cycles:
  • Example 1 is explanatory and discusses the benefits of a well-shaped precursor.
  • the advantages of using large cobalt precursors that have a narrow span are that: 1) a simplified lithiation process is possible, 2) the final cathode material can have a high packing density, and 3) there will be less problems when making a positive electrode using the final cathode material such as less electrode crushing and scratching.
  • LCO is generally made from a cobalt precursor that has a small particle size—the median particle size being around 5 ⁇ m—and wide span.
  • the particle size of LCO is directly linked to the electrode density, and a median particle size of 15 to 20 ⁇ m is a most popular range in conventional LCO.
  • Table 2 shows the physical property of LCO as a function of the choice of cobalt precursors having different PSD.
  • CEX1-P is a conventional cobalt precursor (battery grade Co 3 O 4 from Umicore) which has a small particle size and wide span, while EX1-P is a cobalt precursor (Co 3 O 4 from Yacheng New Materials) which has a large particle size with narrow span.
  • EX1-C-1, EX1-C-2, CEX1-C-1, and CEX1-C-2 are synthesized in a lithiation process by blending the different cobalt precursors with lithium carbonate for different Li/Co ratios, heating at 980° C. for 10 hours in air atmosphere, crushing by a milling tool, and sieving by an ASTM standard 270 mesh sieve.
  • a low surface area of LCO can indicate that the internal porosity of LCO is smaller for a comparable PSD.
  • the internal porosity of LCO should be as small as possible to get the highest density of LCO. This is achieved by the long sintering time and high sintering temperature of the lithiation process. It is observed that a higher Li/Co (1.055 for CEX1-C-2) is required to get a similar D50 and surface area when CEX1-P is used, compared to 1.015 for EX1-C-1 using precursor EX1-P. Since it is expected that the electrochemical property of CEX1-C-2—more particularly cycle life—is much worse than that of EX1-C-1, CEX1-C-2 requires the additional high temperature heating step with extra cobalt precursor to decrease Li/Co.
  • D99 is a good parameter to estimate the maximum particle size.
  • the ratio D99/D50 of LCO is very important since a lower D99 can limit the need to increase D50, even though a higher D50 is preferable to increase the electrode density.
  • CEX1-C-2 has a much higher D99 than EX1-C-1 in spite of having a similar D50. Therefore, shaped narrow span cobalt precursors—thus having a low D99/D50 —can have a high D50 without concerns about the absolute value of D99, resulting in having the possibility to increase the electrode density further by increasing the particle size.
  • Example 2 illustrates the Na 2 CO 3 based co-precipitation process.
  • a schematic illustration of the process is shown in FIG. 2 .
  • the following is shown:
  • F1 dopant
  • F2 CoSO 4
  • F3 Na 2 CO 3
  • F4 Slurry
  • F5 Clear filtrate out
  • F6 thickening slurry
  • R1 precipitation reactor
  • R2 settlement reactor
  • R3 peristaltic pump
  • Na 2 CO 3 and CoSO 4 solutions with a concentration of 2 mol/L are separately prepared.
  • the precipitation is carried out in a 4L reactor at elevated temperature (referred to as T1 hereafter) with an impeller stirring speed of 1000 RPM.
  • the CoSO 4 solution is pumped first in the reactor for 20 minutes without adding Na 2 CO 3 solution.
  • more CoSO 4 solution is continuously pumped in the precipitation reactor together with the Na 2 CO 3 solution at double flow rate for 20 minutes. After that (40 minutes in total), the flow rate of CoSO 4 and Na 2 CO 3 solution is kept constant with a CO 3 /Co molar ratio of 1.08.
  • Two different methods to introduce dopants are used in the invention.
  • DM1 One way (referred to as DM1 hereafter) is to dissolve a sulfate—such as aluminum sulfate and magnesium sulfate—in a CoSO 4 solution with a certain molar ratio so that the dopant can be injected together with CoSO 4 .
  • the other way (referred to as DM2 hereafter) is to manually inject a suspension of the dopant directly in the reactor during the precipitation, and a certain amount of the suspension is injected once an hour to get a certain molar ratio of dopant to cobalt.
  • a first slurry containing precipitated cobalt hydroxide carbonate precursor is discharged from the precipitation reactor through overflow and goes to a second 3L settlement reactor.
  • the solid precipitate settles down to the bottom since the stirring speed is mild (less than 200 RPM), resulting in a solid-liquid separation.
  • the settled thick slurry at the bottom of the settlement reactor is pumped back into the precipitation reactor.
  • the precipitation is stopped once the particle size of the precipitates in the reactor reaches the target particle size or once the span of the precipitate starts increasing (whichever is first), where the “precipitation time” is defined as the time between starting to inject any solution into the reactor and stopping the precipitation.
  • the precursor is collected by emptying both the precipitation and settlement reactors. Then, a solid-liquid separation of the obtained precursor slurry takes place in a press filter, where the obtained solid is washed with deionized water several times. Finally, the precursor is dried at an elevated temperature to remove any remaining deionized water.
  • Example 3 describes the doped cobalt hydroxide carbonate precursor compound.
  • Table 3 and FIGS. 3 and 4 show the physical and chemical properties of the precursors, precipitated as described in Example 2, except for EX3-P-6 to 8, CEX3-P-2 and CEX3-P-3. Each precursor is precipitated with different resident and/or total precipitation times to show the influence on the particle size.
  • CEX3-P-3 is a pure cobalt carbonate precipitated by a NH 4 HCO 3 process without dopant as a control product, where 1.2 mol/L CoCl 2 and 2.5 mol/L NH 4 HCO 3 are used in a 10 L reactor and filtered precipitates are dried at 75° C.
  • the precipitation temperature T1 for CEX3-P-2 and CEX3-P-3 is 60° C. while for the other products it is 90° C.
  • the target dopant content for EX3-P-2 to 5, EX3-P-7 to 8, and CEX3-P-1 is 1.0 mol % for Al and Mg, and 0.5 mol % for Ti.
  • the obtained contents (from ICP or EDS analysis) are close to the target, with marginal deviations that can easily be adjusted. It is confirmed that both methods for introducing dopants—dissolving aluminum or magnesium sulfate in the cobalt sulfate solution (DM1) and injecting a suspension of nano-sized dopant into the precipitation reactor periodically (DM2)—work well. All products have a narrow span except CEX3-P-2.
  • EX3-P-6 and EX3-P-7 are precipitated using 90 vol % of 2 mol/L Na 2 CO 3 solution and 10 vol % of 4 mol/L NaOH solution as a base, and the other process parameters according to Example 2.
  • EX3-P-8 is precipitated using 60 vol % of 2 mol/L Na 2 CO 3 solution and 40 vol % of 4 mol/L NaOH solution as a base, and the other process parameters according to Example 2. It is observed that EX3-P-6 to 8 which are precipitated by mixtures of Na 2 CO 3 and NaOH as a base solution have relatively low Na contents compared to other products.
  • Each product EX3-P-1 to 8 can be used as a cobalt precursor of LCO depending on the characteristic of these products such as PSD, dopants concentration, and tap density.
  • a small fraction of EX3-P-5 which has smaller particle size can be blended as a “filler precursor” with a large fraction of EX3-P-3 as a “coarse precursor” to increase the volumetric powder density of LCO.
  • CEX3-P-2 precipitated at a too low temperature, results in a span and Na content that is too high, and a tap density that is too low.
  • CEX3-P-3 made by the traditional ammonium bicarbonate process results in a very low Na content, low span and high D50, but the morphology of the obtained pure CoCo 3 is not good, and this has a negative impact on the final LCO.
  • the cobalt content and quantitative phase analysis by XRD indicate that all products obtained by the Na 2 CO 3 based process are composed of cobalt hydroxide carbonate (Co 2 (OH) 2 CO 3 ), which belongs to the malachite-rosasite mineral group, and some additionally contain cobalt carbonate.
  • the XRD peak ratio (021) over (104) can be used as a criteria to quantify the relative amount the different crystal structures.
  • the malachite-rosasite mineral group is a monoclinic or triclinic metal hydroxide carbonates with the general formula A 2 (OH) 2 CO 3 or AB(OH) 2 CO 3 , where A and B is either cobalt, magnesium, copper, nickel or zinc, as described in “Fleischer's Glossary of Mineral Species” (J. A. Mandarino, The Mineralogical Record Inc., Arlington, 1999).
  • the crystallography of the cobalt hydroxide carbonate in this invention shows good agreement with that of Pokrovskite as described in “The malachite-rosasite group: crystal structures of Glaukosphaerite and Pokrovskite” (Perichiazzi. N et al., European Journal of Mineralogy, 2006).
  • FIG. 4 shows the relation between the proportion of the cobalt hydroxide carbonate phase in the precipitate, and the amount of sodium impurity (Na content in wt % obtained by ICP versus Co 2 (OH) 2 CO 3 content in wt % obtained by Rietveld XRD analysis). It is observed that the sodium impurity decreases as the proportion of cobalt hydroxide carbonate phase increases.
  • EX3-P-2 and CEX-P-1 are prepared with the same general process parameters (the base/acid molar ratio is the same as the CO 3 /Co ratio), except for the residence (RT) and precipitation time, where it can be observed that when increasing these times the hydroxy-carbonate phase is converted to the carbonate phase, and the obtained precursor does not permit to achieve the objectives of the invention.
  • the treatment of a high sodium content precursor is described.
  • an EDS (Energy dispersive X-ray spectroscopy) analysis is performed after cutting particles by using the cross section method as described in “Description of analysis methods”.
  • the upper left figure in FIG. 5 a is a SEM image of a cross section of EX3-P-3 and the upper right figure shows the EDS mapping result of EX3-P-3, where white points indicate a homogeneous presence of Al.
  • An enlarged view of this EDS map is repeated in FIG. 5 b . Since there is a clear Al peak in the spectrum, the white points in upper right figure and FIG. 5 b are not caused by noise.
  • Three different zones (Z1, Z2, and Z3), as shown in the upper left figure in FIG. 5 a are separately measured by EDS measurements and Table 4 shows the analysis result. Based on the Al contents of these zones and the result of the EDS mapping, it is clear that Al is homogeneously distributed in a particle of EX3-P-3.
  • Example 4 describes the synthesis of LCO with the precursors of Example 3: EX3-P-3 and CEX3-P-3 are lithiated to form lithium cobalt oxides. These cobalt compounds are blended with lithium carbonate with different lithium to metal (Li/M) ratios, where M is the sum of cobalt and aluminum. Each blend is heated at 1000° C. for 12 hours. Then, the sintered materials are crushed. For improving the electrochemical properties, titanium oxide is blended with the obtained materials and the resulting “second” blends are heated at 750° C. for 6 hours. Table 5 shows the failure time and specific cobalt dissolution from floating test as a function of the type of cobalt precursor and the Li/M molar ratio.
  • Li/M lithium to metal
  • the failure time increases as the Li/M ratio increases. This is because the cobalt dissolution is less due to the presence of more lithium, resulting in a better high voltage stability.
  • the example shows that LCO products made from an aluminum doped cobalt hydroxide carbonate precursor (EX3-P-3) have a much longer failure time and less cobalt dissolution than those from non-doped pure cobalt carbonate produced by the NH 4 HCO 3 process.
  • Working with a cobalt hydroxide carbonate precursor is thus not only interesting from a cost perspective, but also this Example indicates that the presence of aluminum in LCO is beneficial to have a better high voltage stability.
  • two LCO products are synthesized by using 1) an aluminum doped cobalt hydroxide carbonate based precursor (being EX3-P-3) mixed with 15 wt % of EX3-P-5 as a filler material before lithiation and 2) 1 mol % aluminum oxide coated Co 3 O 4 precursor (from Yacheng New Materials) mixed with 15 wt % of EX3-P-5 as a filler material before lithiation.
  • EX3-P-3 aluminum doped cobalt hydroxide carbonate based precursor
  • 1 mol % aluminum oxide coated Co 3 O 4 precursor from Yacheng New Materials
  • Table 6 shows the floating test results of the LCO products, where EX5-C is produced from an aluminum doped hydroxide carbonate based cobalt precursor and CEX5-C is produced by an alumina coated Co 3 O 4 precursor. It is observed that EX5-C has a much higher failure time and lower specific cobalt dissolution compared to CEX5-C, indicating that when Al is added, it should be homogeneously distributed in LCO by means of doping, instead of surface coating, to be able to benefit from the positive influence of the dopant on the structural stability of LCO. The difference in Co dissolution is not caused by the difference in nature of the precursor itself (hydroxy-carbonate versus cobalt oxide) since without doping or coating both of these have a similar Co dissolution problem.
  • Example 6 the removal of the sodium impurity is illustrated.
  • Example 3 it was shown that the sodium content of the precursor can be from 0.10% to 0.33%, which may be detrimental for the LCO application.
  • EX4-C-1 and EX4-C-3 are produced from EX3-P-3 which contains 0.23% of sodium.
  • Table 7 shows the sodium content and electrochemical property of EX4-C-1 and 3, measured by the general electrochemical test of coin cells described before. It is observed that the sodium content of LCO products is the same as that of cobalt compounds, indicating that sodium remains after lithiation. Due to the high sodium content, the charge and discharge capacities (CQ1 and DQ1) are lower than expected.
  • Heating and post treatment conditions are same as the conditions of EX4-C-1 and 3, described in Example 4.
  • the obtained LCO products are washed with water, followed by drying in an oven at elevated temperature after filtering.
  • two LCO products EX6-CW-1 and EX6-CW-2—are obtained.
  • EX6-CW-1 and 2 have a significantly reduced sodium content, resulting in improved electrochemical property such as CQ1, Q irr , DQ1, and 3C rate, and keeping the same cycle stability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Secondary Cells (AREA)
US16/488,717 2017-03-08 2018-02-07 Precursors of cathode materials for a rechargeable lithium ion battery Abandoned US20200024153A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP17159775.0 2017-03-08
EP17159775 2017-03-08
EP17167192 2017-04-20
EP17167192.8 2017-04-20
PCT/EP2018/053051 WO2018162165A1 (fr) 2017-03-08 2018-02-07 Précurseurs de matériaux de cathode pour une batterie à ions lithium rechargeable

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/053051 A-371-Of-International WO2018162165A1 (fr) 2017-03-08 2018-02-07 Précurseurs de matériaux de cathode pour une batterie à ions lithium rechargeable

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US16/568,756 Continuation US11189832B2 (en) 2017-03-08 2019-09-12 Precursors of cathode materials for a rechargeable lithium ion battery
US16/568,647 Continuation US20200006771A1 (en) 2017-03-08 2019-09-12 Precursors of cathode materials for a rechargeable lithium ion battery

Publications (1)

Publication Number Publication Date
US20200024153A1 true US20200024153A1 (en) 2020-01-23

Family

ID=61157223

Family Applications (3)

Application Number Title Priority Date Filing Date
US16/488,717 Abandoned US20200024153A1 (en) 2017-03-08 2018-02-07 Precursors of cathode materials for a rechargeable lithium ion battery
US16/568,647 Abandoned US20200006771A1 (en) 2017-03-08 2019-09-12 Precursors of cathode materials for a rechargeable lithium ion battery
US16/568,756 Active US11189832B2 (en) 2017-03-08 2019-09-12 Precursors of cathode materials for a rechargeable lithium ion battery

Family Applications After (2)

Application Number Title Priority Date Filing Date
US16/568,647 Abandoned US20200006771A1 (en) 2017-03-08 2019-09-12 Precursors of cathode materials for a rechargeable lithium ion battery
US16/568,756 Active US11189832B2 (en) 2017-03-08 2019-09-12 Precursors of cathode materials for a rechargeable lithium ion battery

Country Status (9)

Country Link
US (3) US20200024153A1 (fr)
EP (1) EP3592706B1 (fr)
JP (4) JP6920455B2 (fr)
KR (3) KR102327114B1 (fr)
CN (3) CN110475752B (fr)
FI (1) FI3592706T3 (fr)
HU (1) HUE063153T2 (fr)
PL (1) PL3592706T3 (fr)
WO (1) WO2018162165A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102327114B1 (ko) * 2017-03-08 2021-11-16 유미코아 충전식 리튬 이온 배터리용 캐소드 물질의 전구체
WO2020128714A1 (fr) * 2018-12-19 2020-06-25 Umicore Oxyde de cobalt en tant que précurseur de matériaux d'électrode positive pour batteries au lithium-ion rechargeables
US11670769B2 (en) 2019-07-23 2023-06-06 Umicore Powderous lithium cobalt-based oxide compound for rechargeable lithium ion batteries and a method for making thereof
FI4077217T3 (fi) * 2019-12-18 2023-11-09 Umicore Nv Jauhemainen litiumkobolttipohjainen oksidikatodiaktiivimateriaalijauhe uudelleenladattavia litiumioniakkuja varten ja menetelmä sen valmistamiseksi
CN113054186B (zh) * 2019-12-26 2022-07-15 惠州比亚迪实业有限公司 一种三元材料及其制备方法和锂离子电池
CN113292110B (zh) * 2020-02-24 2023-08-15 荆门市格林美新材料有限公司 一种超细且高度分散的球形碳酸钴的制备方法
CN114122378B (zh) * 2020-08-27 2024-05-14 宁波金山双鹿电池有限公司 一种电池正极材料及其制备方法和制备的碱性锌锰电池
CN113233516B (zh) * 2021-05-28 2023-01-06 金川集团股份有限公司 一种单晶小粒度四氧化三钴的制备方法
CN113675009A (zh) * 2021-07-06 2021-11-19 浙江工业大学 碱式碳酸钴@镍钴mof核壳阵列复合材料及其制备与应用
CN114516664B (zh) * 2022-03-31 2024-04-02 高点(深圳)科技有限公司 碳酸盐接枝碳酸盐型正极材料前驱体及其制备方法和应用
WO2025013281A1 (fr) * 2023-07-13 2025-01-16 日本化学産業株式会社 Procédé de fabrication d'un matériau actif d'électrode positive pour batterie secondaire au lithium-ion
CN117810428B (zh) * 2024-01-10 2025-10-24 井冈山大学 一种碳包覆具有褶皱纳米片状锌-钴金属化合物的制备方法
CN120127149B (zh) * 2025-05-12 2025-07-15 兴储世纪科技股份有限公司 高压实磷酸焦磷酸铁钠正极材料、极片及其制备方法和应用

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA975568A (en) * 1972-09-11 1975-10-07 David A. Huggins Precipitation of nickel carbonate
US4567031A (en) * 1983-12-27 1986-01-28 Combustion Engineering, Inc. Process for preparing mixed metal oxides
TW412505B (en) * 1995-05-26 2000-11-21 Starck H C Gmbh Co Kg Process for producing spheroidally agglomerated basic cobalt (II) carbonate
DE19519329C1 (de) * 1995-05-26 1996-11-28 Starck H C Gmbh Co Kg Kobaltmetallagglomerate, Verfahren zu ihrer Herstellung sowie deren Verwendung
JP4174887B2 (ja) * 1998-05-21 2008-11-05 堺化学工業株式会社 ニッケル、コバルト又は銅の炭酸塩又は水酸化物の微細な球状の粒子の製造方法
JP2002003222A (ja) * 2000-06-16 2002-01-09 Sumitomo Metal Mining Co Ltd 塩基性炭酸コバルトおよびその製造方法
CN1184137C (zh) * 2000-12-14 2005-01-12 长沙矿冶研究院 一种制备锂钴氧化合物的湿化学方法
JP2003313030A (ja) * 2002-04-23 2003-11-06 Sumitomo Metal Mining Co Ltd 高タップ密度塩基性炭酸コバルト粉及びその製造方法
JP4240982B2 (ja) * 2002-10-03 2009-03-18 住友金属鉱山株式会社 マンガン濃度の低いコバルト溶液の製造方法
CN1302999C (zh) * 2004-06-03 2007-03-07 曾福兴 一种高密度四氧化三钴的制造方法
KR101419097B1 (ko) 2007-06-29 2014-07-16 유미코르 2차 전지용 고밀도 리튬 코발트 옥사이드
JP2012528773A (ja) 2009-06-05 2012-11-15 ユミコア ソシエテ アノニム 安定なリチウムカソード材料のためのナノ粒子ドープ前駆体
CN101708868B (zh) * 2009-11-20 2011-06-15 江西核工业兴中科技有限公司 碱式碳酸镍或碱式碳酸钴快速生产工艺
CN101786673B (zh) * 2010-03-18 2011-11-02 武汉理工大学 一种碱式碳酸钴铁纳米材料的合成方法
CN102568833B (zh) * 2010-12-24 2014-03-05 同济大学 一种介孔四氧化三钴作正极的混合电化学电容器
CN102139929A (zh) * 2011-03-28 2011-08-03 浙江理工大学 一种制备Co3O4纳米片的方法
CN102583585B (zh) 2012-01-09 2014-04-09 安徽亚兰德新能源材料股份有限公司 一种掺杂Ti、Mg、Al的球形钴酸锂的制备工艺
CN102891312A (zh) 2012-09-25 2013-01-23 上海锦众信息科技有限公司 一种锂离子电池钴酸锂正极材料的制备方法
TWI521778B (zh) * 2013-09-05 2016-02-11 烏明克公司 用於含高鋰和錳的陰極材料之碳酸鹽先質
KR102185125B1 (ko) 2014-02-06 2020-12-01 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
HUE042152T2 (hu) 2014-10-08 2019-06-28 Umicore Nv Szennyezõanyagot tartalmazó, preferált morfológiájú katód anyag és módszer, szennyezõanyagot tartalmazó fém-karbonátból történõ elõállításra
CN105731551B (zh) * 2014-12-09 2018-01-16 荆门市格林美新材料有限公司 掺杂碳酸钴、掺杂四氧化三钴及其制备方法
KR102368975B1 (ko) * 2015-08-24 2022-03-03 삼성전자주식회사 양극 활물질, 이를 포함하는 양극 및 리튬 이차 전지, 및 상기 양극 활물질의 제조방법
CN105118991B (zh) * 2015-08-27 2017-06-16 北大先行科技产业有限公司 一种锂离子二次电池正极材料及其制备方法
KR102327114B1 (ko) * 2017-03-08 2021-11-16 유미코아 충전식 리튬 이온 배터리용 캐소드 물질의 전구체

Also Published As

Publication number Publication date
KR20190122847A (ko) 2019-10-30
EP3592706B1 (fr) 2023-06-14
JP2020510975A (ja) 2020-04-09
KR102327118B1 (ko) 2021-11-17
US20200006771A1 (en) 2020-01-02
FI3592706T3 (fi) 2023-08-11
JP2021054717A (ja) 2021-04-08
HUE063153T2 (hu) 2024-01-28
PL3592706T3 (pl) 2023-09-04
CN110475752A (zh) 2019-11-19
KR20190122257A (ko) 2019-10-29
WO2018162165A1 (fr) 2018-09-13
KR102327114B1 (ko) 2021-11-16
KR20190122846A (ko) 2019-10-30
JP2020077613A (ja) 2020-05-21
CN110734098A (zh) 2020-01-31
US11189832B2 (en) 2021-11-30
JP6940568B2 (ja) 2021-09-29
CN110475752B (zh) 2022-08-09
CN110844943A (zh) 2020-02-28
CN110734098B (zh) 2022-08-09
JP2020109048A (ja) 2020-07-16
JP6920455B2 (ja) 2021-08-18
US20200017370A1 (en) 2020-01-16
KR102327120B1 (ko) 2021-11-17
EP3592706A1 (fr) 2020-01-15
JP7500447B2 (ja) 2024-06-17

Similar Documents

Publication Publication Date Title
US11189832B2 (en) Precursors of cathode materials for a rechargeable lithium ion battery
JP7349109B2 (ja) リチウムニッケル含有複合酸化物の製造方法
EP2749537B1 (fr) Hydroxyde composite à base de nickel et son procédé de production, matière active d'électrode positive et procédé permettant de le préparer et cellule secondaire électrolytique non aqueuse
KR101644258B1 (ko) 니켈 복합 수산화물과 그의 제조 방법, 비수계 전해질 이차 전지용 정극 활물질과 그의 제조 방법, 및 비수계 전해질 이차 전지
US11973223B2 (en) Manganese composite hydroxide and process for producing same, positive electrode active material and process for producing same, and non-aqueous electrolyte secondary battery
JP6985406B2 (ja) 改善された二次電池性能を有するカソード材料の前駆体及び前駆体を調製する方法
WO2016055910A1 (fr) Précurseurs de carbonate pour matériau de cathode oxyde de lithium-nickel-manganèse-cobalt et leur procédé de fabrication
JP2012155916A (ja) リチウム二次電池用正極活物質とその製造方法および該正極活物質の前駆体とその製造方法
EP3561925B1 (fr) Précurseur de matériau actif d'électrode positive à électrolyte non aqueux
US20250079546A1 (en) Direct Upcycling of Lithium-ion Battery Cathodes to Single-Crystal Nickel-rich NCMs
JPWO2017033894A1 (ja) 非水系電解質二次電池用正極活物質及びその製造方法、非水系電解質二次電池
JP6020700B2 (ja) 正極活物質及びその製造方法、並びに非水系電解質二次電池
KR20250114534A (ko) 양극 활물질 입자들을 처리하기 위한 방법, 및 이를 채용한 양극 활물질 및 비수계 전해질 이차 배터리

Legal Events

Date Code Title Description
AS Assignment

Owner name: UMICORE KOREA, LTD., KOREA, REPUBLIC OF

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KIM, DAE-HYUN;PAULSEN, JENS;OH, JINDOO;AND OTHERS;SIGNING DATES FROM 20190917 TO 20190920;REEL/FRAME:050455/0961

Owner name: UMICORE, BELGIUM

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KIM, DAE-HYUN;PAULSEN, JENS;OH, JINDOO;AND OTHERS;SIGNING DATES FROM 20190917 TO 20190920;REEL/FRAME:050455/0961

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION