[go: up one dir, main page]

WO2025125540A1 - Particule pour matériau actif d'électrode positive - Google Patents

Particule pour matériau actif d'électrode positive Download PDF

Info

Publication number
WO2025125540A1
WO2025125540A1 PCT/EP2024/086157 EP2024086157W WO2025125540A1 WO 2025125540 A1 WO2025125540 A1 WO 2025125540A1 EP 2024086157 W EP2024086157 W EP 2024086157W WO 2025125540 A1 WO2025125540 A1 WO 2025125540A1
Authority
WO
WIPO (PCT)
Prior art keywords
particle
ratio
active material
positive electrode
electrode active
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.)
Pending
Application number
PCT/EP2024/086157
Other languages
English (en)
Inventor
Shinichi Kumakura
TaeHyeon YANG
KunWoo YOO
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
Original Assignee
Umicore NV SA
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 filed Critical Umicore NV SA
Publication of WO2025125540A1 publication Critical patent/WO2025125540A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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 particle for a positive electrode active material comprising lithium, oxygen, nickel, cobalt and optionally manganese having an enriched amount of aluminum and cobalt in the surface layer of the particle.
  • the invention also relates to a positive electrode active material comprising said particle and a battery comprising said positive electrode active material and the use of said battery.
  • lithium ions are removed from the cathode, transported through the electrolyte and are inserted into the anode while electrons are removed from the cathode and injected into the anode through an external circuit (charger).
  • lithium ions are removed from the anode, transported through the electrolyte, and are inserted into the cathode, while electrons flow through an external circuit to provide electric work.
  • cathode active materials are lithium transition metal oxides.
  • the delithiated cathode active material can slowly react with the non-aqueous electrolyte or the solid electrolyte leading to a gradual degradation of the electrochemical performance of lithium batteries using such cathode active materials.
  • WO 2022/096473 Al contemplates a positive electrode active material obtained after mixing and heating a Lii.oi(Nio.63Mno.22Coo.15)0.9902 compound with CO3O4 and AI2O3.
  • a positive electrode active material having an improved electrochemical performance.
  • an object of the invention is achieved by providing a particle for a positive electrode active material comprising lithium, oxygen, nickel, cobalt and optionally manganese having an enriched amount of aluminum and cobalt in the surface layer of the particle.
  • the invention provides a positive electrode active material comprising said particle.
  • the invention provides a battery comprising said positive electrode active material.
  • the invention provides a use of said battery.
  • Figure 1 is a cross-sectional SEM image of EXI wherein A is the position of the center of a particle, where Cocenter, Alcenter, Fcenter, N i center, and M ncenter are measured, and B is the position of the edge of a particle, where Coedge, Ale ge, and Fe ge are measured.
  • compositions comprising components A and B
  • the scope of the expression "a composition comprising components A and B” should not be limited to compositions consisting only of components A and B. It means that with respect to the present invention, the only relevant components of the composition are A and B. Accordingly, the terms “comprising” and “including” encompass the more restrictive terms “consisting essentially of” and “consisting of”.
  • solid-state battery refers to a cell or a battery that includes only solid or substantially solid-state components such as solid electrodes (e.g. anode and cathode) and a solid electrolyte.
  • a positive electrode active material (also known as cathode active material) as used herein and in the claims is defined as a material which is electrochemically active in a positive electrode or cathode.
  • active material it must be understood to be a material capable to capture and release Li ions when subjected to a voltage change over a predetermined period of time.
  • a positive electrode as used herein is defined as a material comprising a positive electrode active material also in addition to other components added to the positive electrode active material, which are not electrochemically active, in particular conductivity agents or binders.
  • solid and liquid shall be considered to be a solid and liquid in standard conditions for temperature and pressure as defined by the IUPAC, unless defined otherwise.
  • boiling point and the melting point shall be considered to be the boiling point and the melting point at standard atmospheric pressure, i.e. at 101325 Pa, unless specified otherwise.
  • the contents of the elements in positive electrode active material as described herein are measured by the Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES) method, for example (but not limiting to the invention) by using an Agillent ICP 720-OES.
  • ICP-OES Inductively Coupled Plasma - Optical Emission Spectrometry
  • the particle size distribution (PSD) of the positive electrode active material described herein is defined, in particular the D50 values, as the particle size at 50% of the cumulative volume % distribution for example (but not limiting to the invention) by using a Malvern Mastersizer 3000 with Hydro MV wet dispersion accessory.
  • X-ray photoelectron spectroscopy is used to analyze the surface of positive electrode active material powder particles.
  • the signal is acquired from the first few nanometers (/.e., 1 nm to 10 nm) of the uppermost part of a sample, i.e. surface layer.
  • the penetration depth is the distance along an axis perpendicular to a virtual line tangent to said external edge and passing trough said first point.
  • a wide survey scan to identify elements present at the surface is conducted at 200 eV pass energy.
  • Cis peak having a maximum intensity (or centered) at a binding energy of 284.8 eV is used as a calibrate peak position after data collection.
  • accurate narrow scans are performed afterwards at 50 eV for at least 10 scans for each identified element to determine the precise surface composition.
  • XPS measurement is carried out using a Thermo Ka+ spectrometer.
  • curve fitting is done with CasaXPS Version2.3.19PR1.0 using a Shirley-type background treatment and Scofield sensitivity factors, wherein preferably line shape GL(30) is the Gaussian/Lorentzian product formula with 70% Gaussian line and 30% Lorentzian line.
  • cross-sectional SEM-EDS is used to obtain the concentrations of the relevant elements such as Ni, Mn, Co, Al, and F from the edge to the center of the positive electrode active material particles are analyzed by energy-dispersive X-ray spectroscopy (EDS).
  • EDS energy-dispersive X-ray spectroscopy
  • An EDS analysis of the positive electrode active material particles provides the quantitative element analysis of the cross-section wherein it is assumed that particles are spherical or approximately spherical. So that the center point of a particle's cross-section is approximately the center point of the particle. Typically, the cross-sections geometric center may be taken as their center.
  • Cross-sections of the positive electrode active material as described herein are prepared by an ion beam cross-section polisher (CP) instrument JEOL (IB-19530CP).
  • the instrument uses argon gas as beam source.
  • a small amount of a positive electrode active material powder is mixed with a resin and hardener, then the mixture is heated for 10 minutes on a hot plate; and after heating, it is placed into the ion beam instrument for cutting and the settings are adjusted in a standard procedure, with a voltage of 6.5 kV for a 3 hours duration.
  • a particle with a diameter around D50 value as measured by PSD is selected for analysis for each sample.
  • the EDS is performed by JEOL JSM 7100F SEM equipment with a 50 mm 2 X-MaxN EDS sensor from Oxford instruments.
  • a straight line is set from an edge to the center point of the particle and Ni, Mn, Co, Al, and F concentrations are measured at edge and center and expressed as an at% relative to the sum of Ni, Mn, and Co content at each point.
  • At% signifies atomic percentage.
  • the at% or "atomic percent" of a given element expression of a concentration means how many percent of all atoms in the concerned compound are atoms of said element. Further in the framework of the present invention the designation at% is equivalent to mol% or "molar percent”.
  • the present invention concerns a particle for a positive electrode active material comprising lithium, nickel, cobalt, aluminium, oxygen and optionally manganese having a ratio Coedge / Cocenter > 1. 1 and a ratio Ale ge / Alcenter > 20.0, wherein Coedge is an atomic ratio of Co to the total amount of Ni, Co, and Mn at an edge of the particle,
  • Cocenter is an atomic ratio of Co to the total amount of Ni, Co, and Mn at a center of the particle
  • Aledge is an atomic ratio of Al to the total amount of Ni, Co, and Mn at an edge of the particle
  • Alcenter is an atomic ratio of Al to the total amount of Ni, Co, and Mn at a center of the particle, wherein Coedge, Cocenter, Aledge, and Alcenter are measured by cross-sectional SEM-EDS.
  • a highly preferred embodiment is the particle for the positive electrode active material for rechargeable batteries, preferably for solid-state batteries.
  • a preferred embodiment is the particle of the invention having a layered structure, preferably a layered structure of the a-NaFeO2 type, preferably a layered structure of the a-NaFeO2 type having a R-3m space group.
  • the particle is according to the invention, wherein the ratio Coedge / Cocenter > 1.2, preferably the ratio Coedge / Cocenter > 1.35, more preferably the ratio Coedge / Cocenter > 1.5.
  • the particle is according to the invention, wherein the ratio Coedge / Cocenter ⁇ 50.0, preferably the ratio Coedge / Cocenter ⁇ 10.0, more preferably the ratio Coedge / Cocenter ⁇ 5.0, most preferably the ratio Coedge / Cocenter ⁇ 3.0.
  • the particle is according to the invention, wherein the ratio Coedge / Cocenter is between 1.2 and 50.0, preferably the ratio Coedge / Cocenter is between 1.2 and 10.0, more preferably the ratio Coedge / Cocenter is between 1.35 and 5.0, most preferably the ratio Coedge / Cocenter is between 1.5 and 3.0.
  • the particle is according to the invention, wherein the ratio Coedge / Cocenter > 1.6, preferably the ratio Coedge / Cocenter > 1.65, more preferably the ratio Coedge / Cocenter > 1.7.
  • the positive electrode active material is according to the invention, wherein the ratio Coedge / Cocenter ⁇ 50.0, preferably the ratio Coedge / Cocenter ⁇ 10.0, more preferably the ratio Coedge / Cocenter ⁇ 5.0, most preferably the ratio Coedge / Cocenter ⁇ 3.0.
  • the particle is according to the invention, wherein the ratio Aledge / Alcenter is between 20.0 and 200.0, preferably the ratio Aledge / Alcenter is between 30.0 and 150.0, more preferably the ratio Aledge / Alcenter is between 35.0 and 100.0, most preferably the ratio Aledge / Alcenter is between 40.0 and 75.0.
  • the particle is according to the invention, wherein the ratio Aledge / Alcenter is between 20.0 and 100.0, preferably the ratio Aledge / Alcenter is between 30.0 and 75.0, more preferably the ratio Aledge / Alcenter is between 35.0 and 60.0.
  • the particle is according to the invention, wherein the ratio Fedge / Fcenter > 1.2, preferably the ratio Fedge / Fcenter > 1.3, more preferably the ratio Fedge / Fcenter > 1.4.
  • the positive electrode active material is according to the invention, wherein the ratio Fedge / Fcenter ⁇ 50.0, preferably the ratio Fedge / Fcenter ⁇ 10.0, more preferably the ratio Fedge / Fcenter ⁇ 5.0, most preferably the ratio Fedge / Fcenter ⁇ 3.0.
  • the positive electrode active material is according to the invention, wherein the ratio Fedge / Fcenter is between 1.1 and 50.0, preferably the ratio Fedge / Fcenter is between 1.2 and 10.0, more preferably the ratio Fedge / Fcenter is between 1.4 and 5.0, most preferably the ratio Fedge / Fcenter is between 1.4 and 3.0.
  • the particle is according to the invention, wherein the ratio Fedge / Fcenter > 1.5, preferably the ratio Fedge / Fcenter > 1.55, more preferably the ratio Fedge / Fcenter > 1.6.
  • the positive electrode active material is according to the invention, wherein the ratio Fedge / Fcenter ⁇ 50.0, preferably the ratio Fedge / Fcenter ⁇ 10.0, more preferably the ratio Fedge / Fcenter ⁇ 5.0, most preferably the ratio Fedge / Fcenter ⁇ 3.0.
  • the positive electrode active material is according to the invention, wherein the ratio Fedge / Fcenter is between 1.4 and 50.0, preferably the ratio Fedge / Fcenter is between 1.5 and 10.0, more preferably the ratio Fedge / Fcenter is between 1.55 and 5.0, most preferably the ratio Fedge / Fcenter is between 1.65 and 3.0.
  • the particle is according to the invention, wherein
  • the ratio Coedge / Cocenter is between 1.55 and 50.0, preferably the ratio Coedge /
  • Cocenter is between 1.6 and 10.0, more preferably the ratio Coedge / Cocenter is between 1.65 and 5.0, most preferably the ratio Coedge / Cocenter is between 1.7 and 3.0;
  • the ratio Ale ge / Alcenter is between 20.0 and 100.0, preferably the ratio Ale ge / Alcenter is between 30.0 and 75.0, more preferably the ratio Aledge / Alcenter is between 35.0 and 60.0; and
  • the ratio Fedge / Fcenter is between 1.4 and 50.0, preferably the ratio Fedge / Fcenter is between 1.5 and 10.0, more preferably the ratio Fedge / Fcenter is between 1.55 and 5.0, most preferably the ratio Fedge / Fcenter is between 1.65 and 3.0.
  • the particle is according to the invention havings a N icenter value > 45.0 at%, wherein N icenter is an atomic ratio of N i to the sum of N i , Co and Mn at a center of the particle, and wherein N icenter is measured by cross-sectional SEM-EDS.
  • the particle is according to the invention, wherein the N icenter value > 50.0 at%, preferably the N icenter value > 55.0 at%, more preferably the N icenter value > 60.0 at%. In a more preferred embodiment the particle is according to the invention, wherein the N icenter value ⁇ 75.0 at%, preferably the N icenter value ⁇ 70.0 at%, more preferably the N icenter value ⁇ 65.0 at%. In a more preferred embodiment the particle is according to the invention, wherein the N icenter value is between 50.0 and 75.0 at%, preferably the N icenter value is between 55.0 and 70.0 at%, more preferably the N icenter value is between 60.0 and.65.0 at%.
  • the particle is according to the invention having a Mn C enter value > 10.0 at%, wherein Mn C enter is an atomic ratio of Mn to the sum of Ni, Co and Mn at a center of the particle, and wherein Mn C enter is measured by cross-sectional SEM-EDS.
  • the particle is according to the invention, wherein the Mncenter value > 15.0 at%, preferably the Mn C enter value > 18.0 at%, more preferably the M ncenter value > 20.0 at%. In a more preferred embodiment the particle is according to the invention, wherein the M ncenter value ⁇ 35.0 at%, preferably the M ncenter value ⁇ 30.0 at%, more preferably the M ncenter value ⁇ 25.0 at%. In a more preferred embodiment the particle is according to the invention, wherein the M ncenter value is between 15.0 and 35.0 at%, preferably the Mncenter value is between 18.0 and 30.0 at%, more preferably the M ncenter value is between 20.0 and 25.0 at%.
  • the particle is according to the invention, wherein at least one of the primary particles has a Cocenter value > 5.0 at%, wherein Cocenter is an atomic ratio of Co to the sum of Ni, Co and Mn at a center of the primary particle, and wherein Cocenter is measured by cross-sectional SEM-EDS.
  • the particle is according to the invention, wherein the Cocenter value > 10.0 at%, preferably the Cocenter value > 12.0 at%, more preferably the Cocenter value > 15.0 at%.
  • the particle is according to the invention, wherein the Cocenter value ⁇ 30.0 at%, preferably the Cocenter value ⁇ 25.0 at%, more preferably the Cocenter value ⁇ 20.0 at%.
  • the positive electrode active material is according to the invention, wherein the Cocenter value is between 10.0 and 35.0 at%, preferably the Cocenter value is between 18.0 and 30.0 at%, more preferably the Cocenter value is between 20.0 and 25.0 at%.
  • the Nicenter value is between 50.0 and 75.0 at%, preferably the Nicenter value is between 55.0 and 70.0 at%, more preferably the N icenter value is between 60.0 and 65.0 at%;
  • the M ncenter value is between 15.0 and 35.0 at%, preferably the M ncenter value is between 18.0 and 30.0 at%, more preferably the M ncenter value is between 20.0 and 25.0 at%;
  • the Cocenter value is between 10.0 and 35.0 at%, preferably the Cocenter value is between 18.0 and 30.0 at%, more preferably the Cocenter value is between 20.0 and 25.0 at%.
  • the particle of the invention is a single particle consisting of one primary particle.
  • the particle of the invention is a secondary particle consisting of at least two primary particles and at most 20 primary particles.
  • primary particles are distinguished from each other in a SEM image by observing grain boundaries between the primary particles.
  • a grain boundary is defined as the interface between two primary particles, preferably wherein the atomic planes of the two primary particles are aligned to different orientations and meet as a crystalline discontinuity.
  • the primary particle constituting the single particle and/or secondary particle is observed in a SEM image.
  • the invention provides a positive electrode active material of the invention comprising the particle according to the first aspect of the invention.
  • the positive electrode active material of the invention is a powder comprising a plurality of the particles according to the invention, wherein at least one of the particles is the single particle as defined herein and/or the secondary particle as defined herein.
  • the positive electrode active material is according to the invention having an atomic content of Ni, relative to the total amount of Ni, Co, and Mn, of at least 45.0 at%, preferably at least 50.0 at%, more preferably at least 55.0 at%, as determined by ICP-OES.
  • a preferred embodiment is the positive electrode active material of the invention having an atomic content of Ni, relative to the total amount of Ni, Co, and Mn, of at most 95.0 at%, preferably at most 90.0 at%, more preferably at most 85.0 at%, as determined by ICP-OES.
  • a preferred embodiment is the positive electrode active material of the invention having an atomic content of Ni, relative to the total amount of Ni, Co, and Mn, of 45.0 to 95.0 at%, preferably 50.0 to 90.0 at%, more preferably 55.0 to 85.0 at%, as determined by ICP-OES.
  • a certain preferred embodiment is the positive electrode active material of the invention having an atomic content of Ni, relative to the total amount of Ni, Co, and Mn, of 45.0 to 75.0 at%, preferably 50.0 to 70.0 at%, more preferably 55.0 to 65.0 at%, as determined by ICP-OES.
  • a preferred embodiment is the positive electrode active material according to the invention having an atomic content of Co, relative to the total amount of Ni, Co, and Mn, of at least 3.0 at%, preferably at least 5.0 at%, more preferably at least 10.0 at%, as determined by ICP-OES.
  • a preferred embodiment is the positive electrode active material according to the invention having an atomic content of Co, relative to the total amount of Ni, Co, and Mn, of at most 30.0 at%, preferably at most 25.0 at%, more preferably at most 22.0 at%, as determined by ICP-OES.
  • a preferred embodiment is the positive electrode active material according to the invention having an atomic content of Co, relative to the total amount of Ni, Co, and Mn, of 3.0 to 30.0 at%, preferably 5.0 to 25.0 at%, more preferably 10.0 to 22.0 at%, as determined by ICP-OES.
  • a preferred embodiment is the positive electrode active material according to the invention having an atomic content of Mn, relative to the total amount of Ni, Co, and Mn, of at least 3.0 at%, preferably at least 5.0 at%, more preferably at least 10.0 at%, as determined by ICP-OES.
  • a preferred embodiment is the positive electrode active material according to the invention having an atomic content of Mn, relative to the total amount of Ni, Co, and Mn, of at most 35.0 at%, or of at most 30.0 at%, preferably at most 25.0 at%, more preferably at most 20.0 at%, as determined by ICP-OES.
  • a preferred embodiment is the positive electrode active material according to the invention having an atomic content of Mn, relative to the total amount of Ni, Co, and Mn, of 3.0 to 30.0 at%, preferably 5.0 to 25.0 at%, more preferably 10.0 to 20.0 at%, as determined by ICP-OES.
  • a preferred embodiment is the positive electrode active material according to the invention having an atomic content of Al, relative to the total amount of Ni, Co, and Mn, of 0.3 to 3.0 at%, preferably of 0.4 to 2.0 at%, more preferably of 0.6 to 1.0 at%, as determined by ICP-OES.
  • a preferred embodiment is the positive electrode active material of the invention having a Li/(Ni + Mn+Co) ratio (mol/mol), > 0.90, preferably > 0.92, more preferably > 0.95.
  • a preferred embodiment is the positive electrode active material of the invention having a Li/(Ni + Mn+Co) ratio (mol/mol), ⁇ 1.10, preferably ⁇ 1.08, more preferably ⁇ 1.05.
  • a preferred embodiment is the positive electrode active material of the invention having a Li/(Ni + Mn+Co) ratio (mol/mol), in the range of 0.90 -1.10, preferably in the range of 0.92 - 1.08, more preferably in the range of 0.95 - 1.05.
  • a more preferred embodiment is the positive electrode active material of the invention having
  • Ni an atomic content of Ni, relative to the total amount of Ni, Co, and Mn, of 45.0 to 95.0 at%, preferably 50.0 to 90.0 at%, more preferably 55.0 to 85.0 at%, as determined by ICP-OES;
  • Ni an atomic content of Ni, relative to the total amount of Ni, Co, and Mn, of 45.0 to 75.0 at%, preferably 50.0 to 70.0 at%, more preferably 55.0 to 65.0 at%, as determined by ICP-OES;
  • a certain preferred embodiment is the positive electrode active material of the invention comprising Li, M', F and oxygen, wherein M' comprises:
  • a more certain preferred embodiment is the positive electrode active material of the invention comprising Li, M', F and oxygen, wherein M' comprises:
  • the positive electrode active material of the invention can comprise impurities or be doped or contain metals on the surface resulting in an overall positive electrode active material comprising one or more elements other than Li, Ni, Mn, Co, F and O, which is reflected in the parameter "D" used herein.
  • a preferred embodiment is the positive electrode active material according to the invention comprising D, wherein D is at least one element selected from the group consisting of B, Ba, Ca, Ce, Cr, Fe, La, Mg, Mo, Nb, S, Sr, Ti, V, W, Y, Zn, and Zr; preferably Ti, Cr, Nb, S, Y, W, and Zr; more preferably Ti, Nb, W, and Zr.
  • the content d is 0.0 at% ⁇ d ⁇ 1.75 at%, preferably 0.25 at% ⁇ d ⁇ 1.5 at%, more preferably 0.5 at% ⁇ d ⁇ 1.25 at%, relative to M'.
  • the positive electrode active material consists of Li, M', F and oxygen.
  • the positive electrode active material comprises F and a lithium transition metal oxide according to formula (I):
  • the positive electrode active material of the invention can comprise impurities or be doped or contain metals on the surface resulting in an overall positive electrode active material comprising one or more elements other than Li, Ni, Mn, Co, Al and 0, which is reflected in the parameter "D2" used herein.
  • a preferred embodiment is the positive electrode active material according to the invention comprising D2, wherein D2 is at least one element selected from the group consisting of B, Ba, Ca, Ce, Cr, Fe, La, Mg, Mo, Nb, S, Sr, Ti, V, W, Y, Zn, and Zr; preferably Ti, Cr, Y, W, and Zr; more preferably Ti, W, and Zr.
  • D2 is at least one element selected from the group consisting of B, Ba, Ca, Ce, Cr, Fe, La, Mg, Mo, Nb, S, Sr, Ti, V, W, Y, Zn, and Zr; preferably Ti, Cr, Y, W, and Zr; more preferably Ti, W, and Zr.
  • the amount of Li, Ni, Mn, Co, Al and D in the positive electrode active material is measured by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES).
  • ICP-OES Inductively Coupled Plasma Optical Emission Spectroscopy
  • an Agilent ICP 720-ES is used in the ICP-OES analysis.
  • the positive electrode active material is according to the invention, wherein the positive electrode active material comprises aluminum and has an atomic ratio of Al to the total amount of Ni, Co, and Mn of 1.0 to 7.0, as determined by XPS analysis.
  • the atomic ratio of Al to the total amount of Ni, Co, and Mn of 1.5 to 6.0, preferably 2 to 5, more preferably 2.5 to 3.0, as determined by XPS analysis.
  • the positive electrode active material of the invention comprises cobalt and has an atomic ratio of Co to the total amount of Ni, Co, and Mn of 0.25 to 0.45, as determined by XPS analysis.
  • the positive electrode active material is according to the invention wherein the positive electrode active material comprises:
  • the positive electrode active material of the invention has the atomic ratio of Co to the total amount of Ni, Co, and Mn of 0.30 to 0.44, preferably 0.32 to 0.42, as determined by XPS analysis.
  • the positive electrode active material of the invention has a ratio COXPS/COICP of 1.50 to 2.30, wherein COXPS is the atomic ratio of Co to the total amount of Ni, Co, and Mn of 0.25 to 0.45, as determined by XPS analysis; and COICP is the atomic ratio of Co to the total amount of Ni, Co, and Mn of 0.25 to 0.45, as determined by ICP-OES.
  • the positive electrode active material is according to the invention wherein the positive electrode active material comprises:
  • COXPS is the atomic ratio of Co to the total amount of Ni, Co, and Mn of 0.25 to 0.45, as determined by XPS analysis
  • COICP is the atomic ratio of Co to the total amount of Ni, Co, and Mn of 0.25 to 0.45, as determined by ICP-OES.
  • the positive electrode active material is according to the invention wherein the positive electrode active material comprises:
  • COXPS is the atomic ratio of Co to the total amount of Ni, Co, and Mn of 0.25 to 0.45, as determined by XPS analysis
  • COICP is the atomic ratio of Co to the total amount of Ni, Co, and Mn of 0.25 to 0.45, as determined by ICP-OES.
  • the positive electrode active material is according to the invention having the ratio COXPS/COICP of 1.60 to 2.25, preferably 1.70 to 2.20, more preferably 1.75 to 2.15.
  • the positive electrode active material is according to the invention further comprises F and has an atomic ratio of F to the total amount of Ni, Co, and Mn of 0.5 to 6.0, as determined by XPS analysis.
  • the positive electrode active material is according to the invention having an atomic ratio of F to the total amount of Ni, Co, and Mn of 1.0 to 5.0, preferably 1.5 to 4.0, more preferably 1.8 to 3.0, as determined by XPS analysis.
  • the present invention provides the positive electrode active material according to the invention, wherein said positive electrode active material is a powder comprising said single particles and/or said secondary particles, wherein each of the single particles consists of only one primary particle and each of the secondary particles consists of at least two primary particles and at most twenty primary particles as observed in a SEM image.
  • At least 30% of the particles, more preferably at least 50% of the particles, constituting the powder observed in a SEM image are the single particles and/or the secondary particles.
  • the number of primary particles constituting the single particles and/or the secondary particles are determined in a field of view of at least 45 pm x at least 60 pm (i.e. of at least 2700 pm 2 ), preferably of: at least 100 pm x 100 pm (i.e. of at least 10,000 pm 2 ).
  • the particles in the image should be well distributed therefore avoiding overlap between particles. This can be achieved by pouring a small amount of powder sample to the adhesive attached on the SEM sample holder and blowing air to remove the excess powder.
  • primary particles are distinguished from each other in a SEM image by observing grain boundaries between the primary particles.
  • a grain boundary is defined as the interface between two primary particles, preferably wherein the atomic planes of the two primary particles are aligned to different orientations and meet as a crystalline discontinuity.
  • Certain preferred embodiments concern the positive electrode active material of the invention being said powder comprising the single particles and/or the secondary particles, wherein said powder has a median particle size D50 value of less than 15 .m, preferably less than 10 .m, more preferably less than 8 p.m.
  • Certain preferred embodiments concern the positive electrode active material of the invention , wherein said powder has a median particle size D50 value of more than 1 .m, preferably more than 2 .m, more preferably more than 4 .m. Certain preferred embodiments concern the positive electrode active material of the invention, wherein said powder has a median particle size D50 value between 1 and 15 .m, preferably between 2 and 10 .m, more preferably between 4 and 8 p.m.
  • the particle size distribution (PSD) D50 of the positive electrode active material powder is measured by laser diffraction particle size analysis.
  • the D50 is defined as a volume median particle size, more preferably the particle size at 50% of the cumulative volume% distributions obtained from the Malvern Mastersizer 3000 with Hydro MV measurements.
  • the particle median D50 can be measured using a Malvern Mastersizer 3000.
  • the invention concerns a battery comprising the positive electrode active material according to the second aspect of the invention.
  • the battery is a solid-state battery.
  • the solid-state battery comprises a polymer-based electrolyte, preferably a polymer-based solid electrolyte, more preferably the polymer-based solid electrolyte is polymer comprising oxyethylene units, most preferably the polymer-based solid electrolyte is polyethylene oxide.
  • the present invention is not limited to a particular polyethylene oxide having a specific weight average molecular weight M w . Such polymers are commercially available in a variety of different number average molecular weight.
  • the polyethylene oxide has a weight average molecular weight M w of less than 5,000,000 g/mol and more than 50,000 g/mol, preferably a weight average molecular weight M w of less than 3,000,000 g/mol and more than 100,000 g/mol, more preferably a weight average molecular weight M w of less than 2,000,000 g/mol and more than 500,000 g/mol, most preferably a weight average molecular weight M w of about 1,000,000 g/mol.
  • the battery is a polymer solid-state battery.
  • the solid-state battery further comprises an anode comprising anode active material.
  • anode comprising anode active material.
  • Suitable electrochemically active anode materials are those known in art.
  • the anode may comprise graphitic carbon, metallic lithium or a metal alloy comprising lithium, such as Li-In alloy, as the anode active material.
  • the battery according to the invention has a DCR.2-DCR.1 value of less than 400 Q, preferably less than 300 Q, more preferably less than 200 Q, most preferably less than 150 Q.
  • DCR.1 and DR.C2 value is determined as explained under point E2) of the examples described below
  • the present invention concerns a use of the positive electrode active material according to the second aspect of the invention in a battery.
  • a preferred embodiment is the use of the positive electrode active material in a battery, preferably a solid-state-battery, more preferably a polymer solid-state- battery, to reduce the DCR. value of the battery.
  • the present invention concerns a use of the battery according to invention in either one of a portable computer, a tablet, a mobile phone, an energy storage system, an electric vehicle or in a hybrid electric vehicle, preferably in an electric vehicle or in a hybrid electric vehicle.
  • ICP-OES Inductively coupled plasma - optical emission analysis
  • the contents of the elements in positive electrode active material examples and comparative example as described herein below are measured by the Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES) method using an Agillent ICP 720-OES.
  • ICP-OES Inductively Coupled Plasma - Optical Emission Spectrometry
  • the volumetric flask is filled with DI water up to the 250 mL mark, followed by complete homogenization.
  • An appropriate amount of solution is taken out by pipette and transferred into a 250 mL volumetric flask for the 2 nd dilution, where the volumetric flask is filled with internal standard and 10% hydrochloric acid up to the 250 mL mark and then homogenized. Finally, this solution is used for ICP-OES measurement.
  • the contents of Ni, Mn, Co, and Al are expressed as wt.% of the total of these contents.
  • the PSD is measured using a Malvern Mastersizer 3000 with Hydro MV wet dispersion accessory after dispersing examples as described herein below of positive electrode active material powders in an aqueous medium.
  • D50 is defined as the particle size at 50% of the cumulative volume % distribution.
  • X-ray photoelectron spectroscopy is used to analyze the surface of positive electrode active material powder particles.
  • the signal is acquired from the first few nanometers (e.g., 1 nm to 10 nm) of the uppermost part of a sample, i.e., surface layer. Therefore, all elements measured by XPS are contained in the surface layer.
  • XPS measurement is carried out using a Thermo K-o+ spectrometer.
  • a wide survey scan to identify elements present at the surface is conducted at 200 eV pass energy.
  • Cis peak having a maximum intensity (or centered) at a binding energy of 284.8 eV is used as a calibrate peak position after data collection.
  • Accurate narrow scans are performed afterwards at 50 eV for at least 10 scans for each identified element to determine the precise surface composition.
  • Curve fitting is done with CasaXPS Version2.3.19PR1.0 using a Shirley-type background treatment and Scofield sensitivity factors.
  • the fitting parameters are according to Table la.
  • Line shape GL(30) is the Gaussian/Lorentzian product formula with 70% Gaussian line and 30% Lorentzian line.
  • constraints are set for each defined peak according to Table lb.
  • Al and F surface contents as determined by XPS are expressed as atomic fractions of Al and F, respectively, in the surface layer of the particles divided by the total content of Ni, Mn, and Co, in said surface layer.
  • Cross-sections of the positive electrode active material examples and comparative examples as described herein below are prepared by an ion beam cross-section polisher (CP) instrument JEOL (IB-19530CP).
  • the instrument uses argon gas as beam source.
  • a small amount of a positive electrode active material 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 for cutting and the settings are adjusted in a standard procedure, with a voltage of 6.5 kV for a 3 hour duration.
  • EDS Energy-dispersive X-ray spectroscopy
  • the concentrations of Ni, Mn, Co, Al, and F from the edge to the center of the positive electrode active material particles are analyzed by energy- dispersive X-ray spectroscopy (EDS).
  • EDS energy- dispersive X-ray spectroscopy
  • a particle with a diameter around D50 value as measured by PSD according to Section B) is selected for analysis for each sample.
  • the EDS is performed by JEOL JSM 7100F SEM equipment with a 50 mm 2 X-MaxN EDS sensor from Oxford instruments.
  • An EDS analysis of the positive electrode active material particles provides the quantitative element analysis of the cross-section wherein it is assumed that particles are spherical. A straight line is set from the edge to the center point of the particle and Ni, Mn, Co, Al, and F concentrations are measured at edge and center and expressed as an at% relative to the sum of Ni, Mn, and Co content at each point.
  • a solid polymer electrolyte is prepared according to the process as follows: Step 1) Mixing polyethylene oxide (PEO, 1,000,000 g/mol, Alfa Aesar) with lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI, > 98.0 %, TCI) in acetonitrile anhydrous 99.8 wt% (Aldrich), using a mixer for 30 minutes at 2,000 revolutions per minute (rpm). The mass ratio of polyethylene oxide to LiTFSI is 3.0.
  • PEO polyethylene oxide
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide salt
  • Step 2 Pouring the mixture from Stepl) into a Teflon dish and drying at 25 °C for 12 hours.
  • Step 3) Detaching the dried SPE from the dish and punching the dried SPE in order to obtain SPE disks having a thickness of 300 pm and a diameter of 19 mm.
  • a positive electrode is prepared according to the process as follows:
  • Step 1) Preparing a polymer electrolyte mixture comprising polyethylene oxide (PEO, 100,000 g/mol, Alfa Aesar) solution in anisole anhydrous 99.7 wt% (Sigma-Aldrich) and Lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI, > 98.0 %, TCI) in acetonitrile.
  • PEO polyethylene oxide
  • LiTFSI Lithium bis(trifluoromethanesulfonyl)imide salt
  • the mixture has a ratio of PEO : LiTFSI of 74 : 26 by weight.
  • Step 2 Mixing the polymer electrolyte mixture prepared from Step 1) with a positive electrode active material and a conductor powder (Super P, Timcal) in acetonitrile solution with a ratio of 21 : 75 : 4 by weight so as to prepare a slurry mixture.
  • the mixing is performed by a homogenizer for 45 minutes at 5,000 rpm.
  • Step 3) Casting the slurry mixture from Step 2) on one side of a 20 pm-thick aluminum foil with 100 pm coater gap.
  • Step 4) Drying the slurry-casted foil at 30 °C for 12 hours followed by punching in order to obtain catholyte electrodes having a diameter of 14 mm.
  • a Li foil (diameter 16 mm, thickness 500 pm) is prepared as a negative electrode.
  • the coin-type polymer cell is assembled in an argon-filled glovebox with an order from bottom to top: a 2032 coin cell can, a positive electrode prepared from section Cl.2, a SPE prepared from section Cl.l, a gasket, a negative electrode prepared from section Cl.3, a spacer, a wave spring, and a cell cap. Then, the coin cell is completely sealed to prevent leakage of the electrolyte.
  • Each cell is cycled at 80 °C using a Toscat-3100 computer-controlled galvanostatic cycling stations (Toyo).
  • the coin cell testing procedure uses a 1C current definition of 160 mA/g in the 4.4-3.0 V/Li metal window range according to the schedule below: Step 1) Charging in a constant current mode with C-rate of 0.05 with an end condition of 4.4 V followed by 10 minutes rest.
  • Step 2 Discharging in a constant current mode with C-rate of 0.05 with an end condition of 3.0 V followed by 10 minutes rest.
  • the DCR. is calculated by following equation:
  • Step 4) Switching to a constant voltage mode and keeping 4.4 V for 60 hours.
  • Step 5) Discharging in a constant current mode with C-rate of 0.05 with an end condition of 3.0 V.
  • a positive electrode active material powder labelled as CEX1 was obtained through a solid-state reaction between a lithium source and a nickel-based transition metal source. The process was running as follows:
  • Step 1) A transition metal oxidized-hydroxide powder having a metal composition Ni0.63Mn0.22Co0.15 was prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.
  • CSTR continuous stirred tank reactor
  • Step 3) First firing: The first mixture from Step 2) was fired at 900°C for 10 hours in dry air atmosphere so as to obtain a first fired cake. The first fired cake was grinded so as to obtain a first fired powder.
  • Step 4) Second mixing: the first fired powder from Step 3) was mixed with LiOH in an industrial blender so as to obtain a second mixture having a lithium to metal ratio of 1.05.
  • Step 5 Second firing: the second mixture from Step 4) was fired at 930°C for 10 hours in dry air, followed by a crushing (bead milling) and sieving process so as to obtain a second fired powder.
  • Step 6) Third mixing: the second fired powder from Step 5) was mixed with 2 mol% of Co from CO3O4 powder and 5 mol% of LiOH with respect to the total molar contents of Ni, Mn, and Co in an industrial blender so as to obtain a third mixture.
  • Step 7) Third firing: the third mixture from Step 6) was fired at 775°C for 12 hours in dry air so as to produce a third fired powder labelled as CEX1.
  • the powder has a D50 of 6.4 pm, as determined by laser diffraction.
  • CEX1 comprises single particles and secondary particles, wherein each of the single particles consists of only one primary particle and each of the secondary particles consists of at least two primary particles and at most twenty primary particles as observed in a SEM image. Comparative Example 2
  • a positive electrode active material CEX2 was prepared according to the following process:
  • Step 1) Mixing 1 kg of the CEX1 powder with 2 grams of alumina (AI2O3) nano-powder for 30 minutes at 1000 rpm.
  • Step 2 Firing the mixture obtained from Step 1) in a furnace under the flow of an oxidizing atmosphere at 750°C for 10 hours.
  • Step 3) Mixing 1 kg powder from Step 2) with 2 grams of alumina (AI2O3) nanopowder and 3 grams of polyvinylidene fluoride (PVDF) powder for 30 minutes at 1000 rpm.
  • AI2O3 alumina
  • PVDF polyvinylidene fluoride
  • Step 4) Firing the mixture obtained from Step 3) in a furnace under the flow of oxidizing atmosphere at 375°C for 5 hours to produce a fired powder labelled as CEX2.
  • the powder has a D50 of 6.4 pm, as determined by laser diffraction.
  • CEX2 comprises single particles and secondary particles, wherein each of the single particles consists of only one primary particle and each of the secondary particles consists of at least two primary particles and at most twenty primary particles as observed in a SEM image.
  • a positive electrode active material CEX3 was prepared according to the following process:
  • Step 1) Mixing CEX1 with 1 mol% of Co from CO3O4 powder and 5 mol% of LiOH with respect to the total molar contents of Ni, Mn, and Co in an industrial blender so as to obtain a mixture.
  • Step 2) Firing the mixture from Step 1) was fired at 750°C for 12 hours in dry air so as to produce a fired powder labelled as CEX3.
  • the powder has a D50 of 6.4 pm, as determined by laser diffraction.
  • CEX3 comprises single particles and secondary particles, wherein each of the single particles consists of only one primary particle and each of the secondary particles consists of at least two primary particles and at most twenty primary particles as observed in a SEM image. Comparative Example 4
  • a positive electrode active material CEX4 was prepared according to the following process:
  • Step 1) Mixing CEX1 with 2 mol% of Co from CO3O4 powder and 5 mol% of LiOH with respect to the total molar contents of Ni, Mn, and Co in an industrial blender so as to obtain a mixture.
  • Step 2) Firing the mixture from Step 1) was fired at 750°C for 12 hours in dry air so as to produce a fired powder labelled as CEX4.
  • the powder has a D50 of 6.4 pm, as determined by laser diffraction.
  • CEX4 comprises single particles and secondary particles, wherein each of the single particles consists of only one primary particle and each of the secondary particles consists of at least two primary particles and at most twenty primary particles as observed in a SEM image.
  • a positive electrode active material CEX5 was prepared according to the following process:
  • Step 1) Mixing CEX1 with 3 mol% of Co from CO3O4 powder and 5 mol% of LiOH with respect to the total molar contents of Ni, Mn, and Co in an industrial blender so as to obtain a mixture.
  • Step 2) Firing the mixture from Step 1) was fired at 750°C for 12 hours in dry air so as to produce a fired powder labelled as CEX5.
  • the powder has a D50 of 6.4 pm, as determined by laser diffraction.
  • CEX5 comprises single particles and secondary particles, wherein each of the single particles consists of only one primary particle and each of the secondary particles consists of at least two primary particles and at most twenty primary particles as observed in a SEM image.
  • CEX6 A positive electrode active material CEX6 was prepared according to the same method as CEX2, except that CEX5 is used in step 1) instead of CEX1.
  • the powder has a D50 of 6.4 pm, as determined by laser diffraction.
  • CEX6 comprises single particles and secondary particles, wherein each of the single particles consists of only one primary particle and each of the secondary particles consists of at least two primary particles and at most twenty primary particles as observed in a SEM image.
  • a positive electrode active material EXI was prepared according to the same method as CEX2, except that CEX3 is used in step 1) instead of CEX1.
  • the powder has a D50 of 6.4 pm, as determined by laser diffraction.
  • EXI comprises single particles and secondary particles, wherein each of the single particles consists of only one primary particle and each of the secondary particles consists of at least two primary particles and at most twenty primary particles as observed in a SEM image.
  • a positive electrode active material EX2 was prepared according to the same method as CEX2, except that CEX4 is used in step 1) instead of CEX1.
  • the powder has a D50 of 6.2 pm, as determined by laser diffraction.
  • EX2 comprises single particles and secondary particles, wherein each of the single particles consists of only one primary particle and each of the secondary particles consists of at least two primary particles and at most twenty primary particles as observed in a SEM image.
  • Table 2 summarizes the cross sectional SEM-EDS analysis of examples and comparative examples with main variation in concentration of elements especially for Co, Al and F.
  • the edge/center values higher than 1 indicates that element is enriched on surface than center and with higher value, elements enriched more.
  • Table 3 summarizes the properties of examples and comparative examples.
  • Composition of contents measured by ICP-OES indicates contents of entire particles.
  • Al or F value higher than 0 indicates that Al or F present on the surface of the positive electrode active material as associated with the XPS measurement which signal is acquired from the first few nanometers (e.g. lnm to lOnm) of the uppermost part of a sample, i.e. surface layer.
  • the battery performance was measured with the DCR (Direct Current internal Resistant) analysis. This provides information about internal state of battery, and it is known as that with smaller value, it has better performance.
  • DCR Direct Current internal Resistant
  • EXI and EX2 are positive electrode active materials having higher value of Coedge/Cocenter than the comparative examples. As confirmed by XPS, the EXs simultaneously have Al and/or F enriched surface. Comparing with other CEXs, they exhibit improved electrochemical properties as indicated by lower DCR1 and DCR2 values.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une particule pour un matériau actif d'électrode positive comprenant du lithium, du nickel, du cobalt, de l'aluminium, de l'oxygène et du manganèse ayant un rapport Cobord/Cocentre ≥ 1,1 et un rapport Albord/Alcentre ≥ 20,0, Cobord représentant un rapport atomique de Co à la quantité totale de Ni, de Co et de Mn au niveau d'un bord de la particule, Cocentre représentant un rapport atomique de Co à la quantité totale de Ni, de Co et de Mn au centre de la particule, Albord représentant un rapport atomique de Al à la quantité totale de Ni, de Co et de Mn au niveau d'un bord de la particule, Alcentre représentant un rapport atomique de Al à la quantité totale de Ni, de Co et de Mn au centre de la particule, et Cobord, Cocentre, Albord et Alcentre étant mesurés par MEB-EDS en coupe transversale.
PCT/EP2024/086157 2023-12-15 2024-12-13 Particule pour matériau actif d'électrode positive Pending WO2025125540A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23217293.2 2023-12-15
EP23217293 2023-12-15

Publications (1)

Publication Number Publication Date
WO2025125540A1 true WO2025125540A1 (fr) 2025-06-19

Family

ID=89223319

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2024/086157 Pending WO2025125540A1 (fr) 2023-12-15 2024-12-13 Particule pour matériau actif d'électrode positive

Country Status (1)

Country Link
WO (1) WO2025125540A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103715424B (zh) * 2014-01-06 2016-06-08 中国科学院宁波材料技术与工程研究所 一种核壳结构正极材料及其制备方法
US20180034045A1 (en) * 2015-01-23 2018-02-01 Umicore Lithium Metal Oxide Cathode Powders for High Voltage Lithium-Ion Batteries
US20180123187A1 (en) * 2016-10-31 2018-05-03 Grst International Limited Battery module for starting a power equipment
US10790510B2 (en) * 2016-03-31 2020-09-29 Umicore Lithium ion battery for automotive application
WO2022096473A1 (fr) 2020-11-04 2022-05-12 Umicore Matériau actif d'électrode positive pour batteries rechargeables

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103715424B (zh) * 2014-01-06 2016-06-08 中国科学院宁波材料技术与工程研究所 一种核壳结构正极材料及其制备方法
US20180034045A1 (en) * 2015-01-23 2018-02-01 Umicore Lithium Metal Oxide Cathode Powders for High Voltage Lithium-Ion Batteries
US10790510B2 (en) * 2016-03-31 2020-09-29 Umicore Lithium ion battery for automotive application
US20180123187A1 (en) * 2016-10-31 2018-05-03 Grst International Limited Battery module for starting a power equipment
WO2022096473A1 (fr) 2020-11-04 2022-05-12 Umicore Matériau actif d'électrode positive pour batteries rechargeables

Similar Documents

Publication Publication Date Title
EP3728129B1 (fr) Matériau d'électrode positive pour batteries lithium-ion rechargeables
US11522186B2 (en) Positive electrode material for rechargeable lithium ion batteries
KR102886386B1 (ko) 재충전 가능한 리튬-이온 배터리용 양극 활물질
US20250046807A1 (en) A positive electrode active material for rechargeable solid-state batteries
KR102872794B1 (ko) 충전식 배터리용 양극 활물질
WO2025125540A1 (fr) Particule pour matériau actif d'électrode positive
EP4347499A1 (fr) Oxyde composite à base de lithium-nickel en tant que matériau actif d'électrode positive pour batteries au lithium-ion rechargeables
WO2025125543A1 (fr) Matériau actif d'électrode positive et son procédé de fabrication
JP2023553656A (ja) 充電式リチウムイオン電池のための正極活物質
JP7727732B2 (ja) リチウムイオン充電式電池用正極活物質
EP4380898B1 (fr) Matériau actif d'électrode positive pour batterie rechargeable au lithium-ion
WO2023118257A1 (fr) Matériau actif d'électrode positive pour batteries rechargeables à électrolyte solide
WO2024079307A1 (fr) Matériau actif d'électrode positive et procédé de fabrication d'un matériau actif d'électrode positive
EP4347495A1 (fr) Oxyde composite à base de nickel-lithium utilisé en tant que matériau actif d'électrode positive pour batteries rechargeables au lithium-ion à l'état solide
WO2025056522A1 (fr) Matériau actif d'électrode positive et méthode de fabrication d'un matériau actif d'électrode positive
WO2024121287A1 (fr) Oxyde composite à base de lithium-nickel en tant que matériau actif d'électrode positive pour batteries rechargeables à l'état solide au sulfure
WO2024126691A1 (fr) Matériau actif d'électrode positive et méthode de fabrication d'un matériau actif d'électrode positive

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: 24829089

Country of ref document: EP

Kind code of ref document: A1