WO2024008636A1 - Matériau actif de cathode pour une cathode dans un élément de batterie, ensemble cathode pour élément de batterie et élément de batterie - Google Patents

Matériau actif de cathode pour une cathode dans un élément de batterie, ensemble cathode pour élément de batterie et élément de batterie Download PDF

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Publication number
WO2024008636A1
WO2024008636A1 PCT/EP2023/068213 EP2023068213W WO2024008636A1 WO 2024008636 A1 WO2024008636 A1 WO 2024008636A1 EP 2023068213 W EP2023068213 W EP 2023068213W WO 2024008636 A1 WO2024008636 A1 WO 2024008636A1
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WO
WIPO (PCT)
Prior art keywords
cathode
active material
battery cell
cathode active
assembly
Prior art date
Application number
PCT/EP2023/068213
Other languages
English (en)
Inventor
Prasad Mangesh KORDE
Original Assignee
Northvolt Ab
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Filing date
Publication date
Application filed by Northvolt Ab filed Critical Northvolt Ab
Publication of WO2024008636A1 publication Critical patent/WO2024008636A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • 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

  • a cathode active material for a cathode in a battery cell a cathode assembly for a battery cell and a battery cell
  • the present disclosure relates to a cathode active material for a cathode in a battery cell, a cathode assembly for a battery cell and a battery cell.
  • lithium ion batteries Li-ion batteries
  • a Li-ion battery cell typically comprises a cathode and an anode, with an electrolyte and a separator arranged between the electrodes.
  • the cathode comprises an intercalation material, which is a solid host network capable of reversibly storing lithium guest ions.
  • Most commercialised cathode materials are based on transition metal oxides, such as the lithium cobalt oxide used in the first commercial lithium ion batteries, where cobalt contributes to stability and performance in the cathode material.
  • the anode typically comprises a carbon material such as graphitic or hard carbon, which is capable of intercalating lithium between its graphene planes.
  • the separator may typically be a single- or multi-layer porous polyolefin membrane, sometimes coated with one or more ceramic layers.
  • Electrolytes for lithium ion batteries may typically be based on organic carbonates such as ethylene carbonate, with additives such as lithium salts used to optimise the electrolyte properties.
  • the inventors have identified a number of shortcomings with prior art lithium ion batteries.
  • Some appropriate performance metrics that are desirable to be improved include, but are not limited to, charge rate, discharge rate, energy density, specific energy, power density, and specific power of the batteries.
  • Some of the raw materials used in the manufacture of Li-ion batteries are relatively scarce and thus expensive, particularly some of the transition metals used in cathode manufacture, and there is a desire to transition to the use of cheaper, more abundant materials.
  • NMC is a commonly used intercalation material in cathode active materials for lithium ion batteries, and cobalt may typically be added to the cathode active material to obtain stability in the cathode active material and to obtain improved performance.
  • cobalt is both scarce and toxic, and it would therefore be desirable to be able to reduce the cobalt content in the cathode active material, while maintaining stability and performance and avoiding cathode corrosion.
  • the presence of the dopants in combination with magnesium in the cathode active material allows the cobalt content to be reduced, without compromising the performance of the cathode active material and the battery cell.
  • the present disclosure also relates to a cathode assembly for a battery cell, the cathode assembly comprising a current collector and a cathode layer, wherein the cathode layer comprises the cathode active material as described above, and to a battery cell comprising the cathode assembly, an anode assembly comprising a current collector and at least one anode active material layer, a separator, and an electrolyte.
  • the anode active material may preferably comprise graphite, or graphite and a silicon-based material.
  • the electrolyte may comprise one or more lithium salts, preferably LiPF 6 or LiPO 2 , or combinations thereof, and/or one or more additives, preferably vinylene carbonate or fluoroethylene carbonate, or combinations thereof.
  • a lithium ion battery cell comprises at least one cathode assembly, at least one anode assembly, an electrolyte, and optionally a separator.
  • the electrolyte is arranged in contact with the cathode and anode in order to provide ion transport within the cell.
  • the separator if present, is primarily intended to provide a physical barrier between the cathode and anode, whilst still permitting ion transport.
  • the cell may comprise a single cathode assembly and single anode assembly, or multiple cathodes, i.e. two or more cathodes, and/or multiple anodes, i.e. two or more anodes.
  • the contents of the cell may be housed in a casing.
  • the cell may be of any design known in the art, such as a cylindrical, prismatic or pouch cell, and is preferably a cylindrical cell.
  • single battery cells may be used, or the cells may be arranged into battery packs comprising a plurality of battery cells, i.e. two or more battery cells, such as from about two to about 20 000 cells.
  • a battery pack may comprise a plurality of cells arranged in series and/or parallel, and may comprise further components such as a battery management system and a pack housing to enclose the battery pack components.
  • a cathode assembly comprises a current collector and at least one cathode layer, and the current collector may comprise a metal foil, such as an aluminium foil, a copper foil, a stainless steel foil, or combinations thereof.
  • the current collector may preferably be aluminium foil.
  • a cathode layer is arranged on at least one surface of the current collector, alternatively on both surfaces of the current collector.
  • the cathode layer comprises cathode active material, binder, and optionally further additives such as conductive additive, for example a carbon material such as graphitic particles, carbon black, carbon nanotubes (single- or multi-walled) or graphite particles.
  • NMC is among the most popular cathode materials for lithium ion batteries, due in part to it having a specific energy comparable to lithium cobalt oxide (LCO) despite lower cost.
  • LCO lithium cobalt oxide
  • Increasing the proportion of nickel in the NMC provides further improved energy/power density and may therefore be desirable, but may result in capacity degradation with repeated use.
  • Cobalt is often added to the cathode material in an amount of about 10 mole% to obtain stability in the cathode material and obtain improved performance by balancing magnetic frustration.
  • the cobalt content is normally 10 mol%.
  • cobalt is both scarce and toxic, and it would therefore be desirable to be able to reduce the cobalt content in the cathode active material, while maintaining stability and performance and avoiding cathode corrosion.
  • the cathode active material for a cathode in a battery cell comprises an NMC metal oxide intercalation material, preferably wherein nickel constitutes 5-98 mol%, preferably at least 83 mol%, of the total of non-lithium metals in the NMC metal oxide intercalation material.
  • the Mn content of the cathode active material may suitably be 0.005 ⁇ b ⁇ 0.02, and the Co content may preferably be 0.03 ⁇ c ⁇ 0.09.
  • Inclusion of magnesium in the cathode active material can contribute to thermal stability and delay oxygen release, prolonging cycling stability of cathode materials having high Ni content, such as Ni>80 mol%.
  • Battery cells containing Mg-substituted materials with high Ni content have been found to exhibit superior discharge capacities when charged to 4.5 V. While cycle life and thermal stability can be significantly improved by the inclusion of Mg in the cathode active material, it may reduce the initial capacities and specific energies, due to Mg being electrochemically inactive and occupying Li sites in the layered crystal structure.
  • the Mg content should therefore be in the range 0,5-2 mol% based on the total of non-lithium metals in the NMC metal oxide intercalation material.
  • the selected dopants Ti 4+ , Ta 5+ ,Ru 8+ , Os 8+ and Mo 6+ can contribute to highly oriented, elongated grain microstructures formation due to proper orientation of crystal structure, and reduce the risk of formation of micro-cracks. This can reduce the risk of collapse in structure in a high charge state, and can improve balancing of magnetic moment in case of high nickel content, thus improving stability.
  • the metal dopants may preferably have an oxidation state of 5 or more, for example Ta 5+ ,Ru 8+ , Os 8+ and/or Mo 6+ , preferably Ta 5+ and/or Mo 6+ , as this gives and improved effect due to improved stabilization of magnetic frustration.
  • Ta2Os or MoC are easily available and less expensive compared to the other dopants, and may thus be preferred.
  • the present disclosure also relates to a cathode assembly for a battery cell, the cathode assembly comprising a current collector and a cathode layer, wherein the cathode layer comprises the cathode active material as described above.
  • the cathode assembly may be prepared by coating the current collector with a slurry comprising the cathode active material, binder and optional additives in a suitable solvent.
  • a suitable solvent may be a polar aprotic solvent such as NMP (N-methyl-2-pyrrolidone). Any suitable coating methods known in the art may be used.
  • the cathode assembly may be further processed as is conventional in the art, such as by drying and calendaring.
  • This disclosure further relates to a battery cell comprising a cathode assembly as mentioned above, an anode assembly comprising a current collector and at least one anode active material layer, a separator, and an electrolyte.
  • the current collector may comprise, consist essentially of, or consist of a metal foil, such as a copper foil, an aluminium foil, a stainless steel foil, or combinations thereof.
  • the current collector may preferably be copper.
  • An anode layer is arranged on at least one surface of the current collector, alternatively on both surfaces of the current collector.
  • the anode layer comprises anode active material, binder, and optionally further additives such as conductive additive.
  • the binder may be any binder known in the art, such as for example SBR (styrene-butadiene rubber), CMC (carboxymethylcellulose), PVDF (polyvinylidene fluoride), or combinations thereof.
  • the binder preferably consists essentially of a combination of SBR and CMC.
  • the anode active material may comprise, consist essentially of, or consist of any anode active material known in the art, including but not limited to graphite particles, graphitic carbon particles, amorphous carbon particles, silicon, silicon monoxide, germanium, tin, LTO (lithium titanium oxide), and combinations or composites thereof.
  • the anode active material may consist essentially of graphite and/or graphitic particles, such as carbon-coated natural graphite particles, or secondary synthetic graphite particles.
  • the anode active material may consist essentially of a composite of graphite and a silicon-based material, such as silicon oxide.
  • the electrolyte may preferably comprise one or more lithium salts, preferably LiPFe or LiPCh, and/or one or more additives, preferably vinylene carbonate (VC) or fluoroethylene carbonate (FEC), in order to increase the battery cell lifetime by supporting formation of an effective solid electrolyte interphase (SEI) at the anode.
  • LiPFe or LiPCh lithium salts
  • additives preferably vinylene carbonate (VC) or fluoroethylene carbonate (FEC)
  • SEI solid electrolyte interphase
  • SEI solid electrolyte interphase
  • Item IV The cathode active material of any one of items l-lll, wherein 0.83 ⁇ a ⁇ 0.98.
  • a cathode assembly for a battery cell comprising a current collector and a cathode layer, wherein the cathode layer comprises the cathode active material according to any one of items l-IV.
  • a battery cell comprising a cathode assembly according to item V, an anode assembly comprising a current collector and at least one anode active material layer, a separator, and an electrolyte.
  • Item VII The battery cell of item VI, wherein the anode active material comprises graphite, or graphite and a silicon-based material.
  • Item IX The battery cell of item VIII, wherein the electrolyte comprises one or more lithium salts, preferably LiPFe or Li PO2, or combinations thereof, and/or one or more additives, preferably vinylene carbonate (VC) or fluoroethylene carbonate (FEC), or combinations thereof.
  • the electrolyte comprises one or more lithium salts, preferably LiPFe or Li PO2, or combinations thereof, and/or one or more additives, preferably vinylene carbonate (VC) or fluoroethylene carbonate (FEC), or combinations thereof.
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un matériau actif de cathode pour une cathode dans un élément de batterie, le matériau actif de cathode ayant la formule LixNiaMnbCocMgdMeO2-yAy, où 0,95 < x < 1,05, et où a + b + c + d + e = 1, où 0,5 ≤ a ≤ 0,98, et où M est un ou plusieurs dopants métalliques choisis dans le groupe constitué par Ta5+, Ru8+ et Os8+ et c < 0,1, 0,005 ≤ d ≤ 0,02, 0,01 <_e <_0,05, et où A est un ou plusieurs éléments choisis dans le groupe constitué par S, N, F, Cl, Br, I, et P, et y ≤ 0,1. L'invention concerne un ensemble cathode pour un élément de batterie et un élément de batterie.
PCT/EP2023/068213 2022-07-06 2023-07-03 Matériau actif de cathode pour une cathode dans un élément de batterie, ensemble cathode pour élément de batterie et élément de batterie WO2024008636A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE2250851-9 2022-07-06
SE2250851A SE2250851A1 (en) 2022-07-06 2022-07-06 A cathode active material for a cathode in a battery cell, a cathode assembly for a battery cell and a battery cell

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WO2024008636A1 true WO2024008636A1 (fr) 2024-01-11

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110269018A1 (en) * 2009-06-17 2011-11-03 Satoshi Kono Electrode for electrochemical device and electrochemical device using the same
US20120282524A1 (en) * 2010-12-20 2012-11-08 Satoshi Kono Nonaqueous secondary battery
CN108767239A (zh) * 2018-06-07 2018-11-06 四川富骅新能源科技有限公司 一种高镍低钴三元正极材料及其制备方法
US20190115596A1 (en) * 2016-03-30 2019-04-18 Basf Toda Battery Materials Llc Positive electrode active material for nonaqueous electrolyte secondary batteries, method for producing same, and nonaqueous electrolyte secondary battery using same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101408043B1 (ko) * 2008-01-17 2014-06-17 삼성에스디아이 주식회사 캐소드 및 이를 채용한 리튬 전지
JP5978014B2 (ja) * 2012-06-07 2016-08-24 日立マクセル株式会社 非水二次電池
JP6353310B2 (ja) * 2014-07-30 2018-07-04 マクセルホールディングス株式会社 非水電解質二次電池
CN112582599B (zh) * 2020-12-10 2022-08-05 万华化学(四川)有限公司 一种无钴高镍四元正极材料、其制备方法及其应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110269018A1 (en) * 2009-06-17 2011-11-03 Satoshi Kono Electrode for electrochemical device and electrochemical device using the same
US20120282524A1 (en) * 2010-12-20 2012-11-08 Satoshi Kono Nonaqueous secondary battery
US20190115596A1 (en) * 2016-03-30 2019-04-18 Basf Toda Battery Materials Llc Positive electrode active material for nonaqueous electrolyte secondary batteries, method for producing same, and nonaqueous electrolyte secondary battery using same
CN108767239A (zh) * 2018-06-07 2018-11-06 四川富骅新能源科技有限公司 一种高镍低钴三元正极材料及其制备方法

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