WO2023076011A1 - Traitement à sec de formation d'électrode - Google Patents

Traitement à sec de formation d'électrode Download PDF

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Publication number
WO2023076011A1
WO2023076011A1 PCT/US2022/045837 US2022045837W WO2023076011A1 WO 2023076011 A1 WO2023076011 A1 WO 2023076011A1 US 2022045837 W US2022045837 W US 2022045837W WO 2023076011 A1 WO2023076011 A1 WO 2023076011A1
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Prior art keywords
lithium
metal powder
dry
lithium metal
electrode
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PCT/US2022/045837
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English (en)
Inventor
Jian XIA
Kenneth Brian Fitch
Marina Yakovleva
Rebecca N. BLACK
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Livent USA Corp.
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Priority claimed from US17/702,154 external-priority patent/US20220328799A1/en
Priority claimed from US17/960,239 external-priority patent/US20240113274A1/en
Application filed by Livent USA Corp. filed Critical Livent USA Corp.
Publication of WO2023076011A1 publication Critical patent/WO2023076011A1/fr

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381Alkaline or alkaline earth metals elements
    • H01M4/382Lithium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0404Methods of deposition of the material by coating on electrode collectors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0407Methods of deposition of the material by coating on an electrolyte layer
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0411Methods of deposition of the material by extrusion
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/043Processes of manufacture in general involving compressing or compaction
    • H01M4/0435Rolling or calendering
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134Electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1393Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1395Processes of manufacture of electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • H01M4/622Binders being polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the present invention relates to processes for forming electrodes in a single processing step and provides dry processes for forming electrodes, namely the use of solvents is essentially or substantially eliminated, or reduced.
  • Lithium and lithium-ion secondary or rechargeable batteries have found use in certain applications such as in cellular phones, camcorders, and laptop computers, and even more recently, in larger power application such as in electric vehicles and hybrid electric vehicles. It is preferred in these applications that the secondary batteries have the highest specific capacity possible but still provide safe operating conditions and good cyclability so that the high specific capacity is maintained in subsequent recharging and discharging cycles.
  • each construction includes a positive electrode (or cathode), a negative electrode (or anode), a separator that separates the cathode and anode, an electrolyte in electrochemical communication with the cathode and anode.
  • a positive electrode or cathode
  • a negative electrode or anode
  • a separator that separates the cathode and anode
  • an electrolyte in electrochemical communication with the cathode and anode.
  • lithium ions are transferred from the anode to the cathode through the electrolyte when the secondary battery is being discharged, i.e. , used for its specific application.
  • electrons are collected from the anode and pass to the cathode through an external circuit.
  • the lithium ions are transferred from the cathode to the anode through the electrolyte.
  • New lithium-ion cells or batteries are initially in a discharged state.
  • lithium moves from the cathode material to the anode active material (e.g. graphite).
  • the lithium moving from the cathode to the anode reacts with an electrolyte material at the surface of the graphite anode, causing the formation of a passivation interface on the anode.
  • the passivation interface formed on the graphite anode is also called a solid electrolyte interface (SEI).
  • SEI solid electrolyte interface
  • lithium powder can be stabilized by passivating the metal powder surface with carbon dioxide such as described in U.S. Pat. Nos. 5,567,474, 5,776,369, and 5,976,403, the disclosures of which are incorporated herein in their entireties by reference.
  • the CO2 passivated lithium metal powder may not be ideal because it can be used only in air with low moisture levels for a limited period of time before the lithium metal content decays because of the reaction of the lithium metal and air.
  • Another solution is to apply a coating such as fluorine, wax, phosphorus or a polymer to the lithium metal powder such as described in U.S. Patent Nos.
  • lithium foil is used for pre-lithiation and directly laminated to the surface of the electrode, as a result of “short circuit” lithiation due to the lamination pressure applied, potentially, significant heat may be generated.
  • this pre-lithiation technique is performed in a roll to roll process, heat may build up in the center of the roll and might be difficult to dissipate. This heat buildup can potentially lead to for example, mechanical damage of the electrode and more importantly, to potential thermal runaway.
  • Electrodes are typically formed from a slurry and may consist of active materials, binder, conductive materials as well as solvents.
  • N-Methyl-2-pyrrolidone (NMP) is the most commonly used solvent for cathode slurry while water is becoming more widely used for graphite-based anode slurry.
  • NMP has a high boiling point (202°C) and thus the removal of NMP requires significant energy consumption.
  • NMP is reactive with lithium, may be toxic and requires a solvent recovery system to reduce potential environmental hazards, further adding costs to the battery electrode fabrication process. Water-based approaches are more environmentally friendly and eliminates the need of solvent recovery systems.
  • Interfaces 2017, 4, 1700570] reported the use of ESD, followed by a hot-rolling treatment, to create a 40-130 mm thick cathode containing a 90:5:5 ratio of LCO: carbon additive: PVDF with about 30% porosity, which delivers a specific capacity of 121 mAh g-1 at a charge rate of 0.1 C.
  • the present invention is directed to a one-step and dry process for forming electrodes that essentially or substantially eliminates the use of solvent, particularly solvents that are reactive with lithium, while incorporating a prelithiating agent. No additional solvent may be necessary except for what is present in the prelithiation agent.
  • the process also enables one step advanced electrode production in which irreversible capacity may be eliminated.
  • a stand-alone self-supported film or foil does not need to be formed first then laminated to the substrate (e.g., current collector or a pretreated current collector) in a separate step.
  • the dry electrode material layer or interface may be applied to the substrate as a non self-supported layer.
  • the dry electrode material may be a dry anode material in one embodiment.
  • the electrode is formed using a one-step and dry process.
  • the process may comprise preparing a dry active material comprising an active component comprising an active electrode material, (e.g. active anode material), a binder and a conductive material mixed with a prelithiation agent such as a printable lithium composition to form a dry electrode material mixture.
  • the printable lithium composition may include a lithium metal powder, a polymer binder compatible with the lithium metal powder, and a rheology modifier compatible with the lithium metal powder, and may be essentially solvent free.
  • the prelithiation agent in another embodiment may be a solvent-free stabilized lithium metal powder.
  • the dry electrode material mixture may be applied to a substrate to form the electrode.
  • the dry electrode material mixture may be applied to the substrate by directly depositing the dry electrode material mixture onto the substrate as a layer or interface without the need to form a standalone film or foil and with minimum use of a solvent, i.e. , the process is essentially solvent free.
  • the dry electrode material mixture may then be pressed onto the substrate to form the prelithiated electrode, for example using a roll to roll process.
  • the thusly form electrode may be used in a wide variety of lithium-ion and solid-state batteries particularly as an anode.
  • FIG. 1 is a schematic diagram of an exemplary process according to an embodiment of the invention.
  • FIG. 2 is a plot comparing the 1 st cycle voltage curve of a baseline cell versus a cell with an electrode incorporating printable lithium composition, both formed using dry electrode process according to Example 1 .
  • FIG. 3 is a plot comparing the voltage curve of a baseline cell versus a cell with printable lithium composition incorporated according to Example 1 .
  • FIG. 4 is a plot comparing differential capacity (dQ/dV) versus potential (V) during first charge between baseline and cells with a printable lithium composition incorporated according to Example 1.
  • FIG 5 is a plot comparing differential capacity (dQ/dV) versus potential (V) during first charge between baseline and cells with a printable lithium composition incorporated according to Example 2.
  • FIG. 6 is a plot comparing differential capacity (dQ/dV) versus potential (V) during first charge between baseline and cells with a printable lithium composition incorporated according to Example 3.
  • FIG. 7 is a plot comparing the voltage curve of a baseline cell versus a cell with an electrode incorporating printable lithium composition according to Example 4.
  • FIG. 8 is a plot comparing differential capacity (dQ/dV) versus potential (V) during first charge between baseline and cells with a printable lithium composition incorporated according to Example 4.
  • FIG. 9 is a plot comparing the voltage curve of a baseline cell versus a cell with an electrode incorporating solvent-free stabilized lithium metal powder incorporated according to Example 5.
  • FIG. 10 is a plot comparing differential capacity (dQ/dV) versus potential (V) during first change between baseline and cells with a solvent-free stabilized lithium metal powder according to Example 5.
  • FIG. 11 is a plot comparing the cycle life time of a baseline cell versus cells with an electrode incorporating printable lithium composition or stabilized lithium metal powder according to Examples 4 and 5 respectfully.
  • compositions/methods may contain additional components so long as the additional components do not materially alter the composition/method.
  • materially alter refers to an increase or decrease in the effectiveness of the composition/method of at least about 20% or more.
  • a process for forming an electrode comprises dry mixing an active component comprising an active electrode material, a binder and a conductive material with a prelithiation agent or reagent such as a printable lithium composition comprising a lithium metal powder, a polymer binder compatible with the lithium metal powder, and a rheology modifier compatible with the lithium metal powder to form a dry electrode material mixture.
  • a prelithiation agent or reagent such as a printable lithium composition comprising a lithium metal powder, a polymer binder compatible with the lithium metal powder, and a rheology modifier compatible with the lithium metal powder to form a dry electrode material mixture.
  • the prelithiation agent may be stabilized lithium metal powder.
  • Dry mixing is intended to mean that essentially or substantially no solvent or an essentially or substantially low amount of solvent is used in the mixing process.
  • the only solvent present is from the prelithiation agent such as the small amount of solvent in the printable lithium composition.
  • the dry electrode material mixture may then be applied to a substrate to form the electrode as a non self-supporting layer or interface.
  • a non self-supporting layer or interface is a layer or interface or coating that cannot standalone and is in contrast to a standalone film or foil.
  • the substrate may be a substrate for an anode (e.g., a current collector), a cathode or a solid electrolyte for a solid-state battery.
  • Batteries having a cathode and an anode formed from the process may have a first cycle efficiency greater than about 80%, and in some instances, may be greater than 90%.
  • Dry mixing may be carried out using conventional techniques known in the art. For example, dry mixing may be performed with high sear mixers, planetary mixers, ribbon mixers, drum mixers, screw mixers, conical mixers, multi-shaft mixers and static mixers.
  • the dry electrode material mixture may be applied to the substrate using a variety of techniques.
  • the dry electrode material mixture may be deposited onto the substrate as a non self-supported layer using a dry powder application technique.
  • Methods for depositing dry powder are disclosed in US Publication No. 2021/0050584 incorporated herein by reference in its entirety.
  • Methods for depositing the dry electrode material mixture to the substrate may include sieving, spraying, extruding, roll compaction, electrostatic deposition and combinations thereof.
  • the deposited dry electrode material mixture may then be pressed onto the substrate; for example, at a temperature between about 20° and 180°C and at a pressure between about 500 and 50000 PSI.
  • the substrate may be a current collector such as a foil, film mesh or foam of copper, nickel, zinc, aluminum, silver, graphene and the like with or without a coating (e.g., a polymer coating such as polyisobutylene).
  • a current collector such as a foil, film mesh or foam of copper, nickel, zinc, aluminum, silver, graphene and the like with or without a coating (e.g., a polymer coating such as polyisobutylene).
  • the substrate may be for a solid electrolyte for a solid- state battery.
  • exemplary solid electrolytes may include polymer films derived from polystyrene, polyethylene, polyethylene oxide, polyester, polyvinylidene fluoride, polypropylene and the like.
  • the solid electrolyte may be a ceramic in the form of oxides, sulfides and phosphates.
  • the active material may be mixed with a prelithiation agent such as a printable lithium composition as described in US Application Nos. 16/359,707 and 16/573,587, which are incorporated herein by reference in their entireties or with a solvent-free stabilized lithium metal powder.
  • a printable lithium composition may comprise a lithium metal powder, a polymer binder, a rheology modifier and may or may not further include a solvent.
  • the dry electrode material mixture may contain no solvents, particularly solvents that are reactive to lithium.
  • solvents that are reactive with lithium and are to be avoided are polar solvents such as N-methyl 1 , 2 pyrrolidone (NMP) and gamma-butyrolactone (GBL).
  • NMP N-methyl 1 , 2 pyrrolidone
  • GBL gamma-butyrolactone
  • the active material may be mixed with a the prelithiation agent (printable lithium composition) without additional solvent namely the prelithiation agent is essentially free of solvent.
  • the resulting dry electrode material mixture may be formed from the printable lithium composition that may include a small amount of solvent that is mixed with a dry active material. Such amount of solvent aids processability while not substantially adversely affecting other properties.
  • the amount of solvent in the printable lithium composition may depend on properties of the active material/component (e.g., properties such as silicon content or irreversible capacity) and the amount of lithium metal powder in the printable formulation. Thus, the amount of solvent may be controlled. As shown in Table 1 , the solvent ratio (weight %) in the dry electrode material mixture may vary and be controlled based on the amount of the lithium powder present in the prelithiation agent of the dry electrode mixture and the active material. Table 1
  • the resulting dry electrode mixture may have a solvent content from the printable lithium composition of less than about 20 percent, often less than about 10 percent, sometimes less than about 1 percent, and may be essentially or substantially solvent free.
  • the mixture may have a solvent content of less than about 19 percent, less than about 18 percent, less than about 17 percent, less than about 16 percent, less than about 15 percent, less than about 14 percent, less than about 13 percent, less than about 12 percent, less than about 11 percent, less than about 10 percent, less than about 9 percent, less than about 8 percent, less than about 7 percent, less than about 6 percent, less than about 5 percent, less than about 4 percent, less than about 3 percent, less than about 2 percent, less than about 1 percent, less than about 0.5 percent, and less than about 0.1 percent.
  • the dry electrode mixture once it is applied to the substrate (e.g., current collector), may have less than 1 percent, often less than 0.5 percent solvent and preferably about 0 percent and essentially free of solvent.
  • the once applied dry electrode mixture may have a solvent level of less than about 0.9 percent, less than about 0.8 percent, less than about 0.7 percent, less than about 0.6 percent, less than about 0.5 percent, less than about 0.4 percent, less than about 0.3 percent, less than about 0.2 percent, less than about 0.1 percent, less than about 0.05 percent, and less than about 0.01 percent.
  • the substrate may be treated with an adhesion promoting agent, e.g., as a polymer coating.
  • adhesion promoters may include unsaturated elastomers, saturated elastomers, thermoplastics, polyacrylic acid, polyvinylidene chloride, and polyvinyl acetate.
  • exemplary active electrode materials for the active component may include active anode materials such as graphite, carbon black, hard carbon, carbon alloys and combinations thereof.
  • the active anode material may be graphite - SiOx composites, SiO, SiC>2, Si powder, SiC, SiC composites, Si-based alloys, graphite - SNO, SN C Composites and combinations thereof.
  • the active electrode material may be an active cathode material that may be lithiated such as non-lithiated materials including MnO2, V2O5, M0S2, metal fluorides, sulfur, sulfur composites, tin and combinations thereof.
  • lithiated materials such as LiMn2O4 and LiMC wherein M is Ni, Co or Mn that can be further lithiated may also be used.
  • the non-lithiated active materials are preferred because they generally have higher specific capacities, lower cost and broader choice of cathode materials in this construction that can provide increased energy and power over conventional secondary batteries that include lithiated active materials.
  • the lithium metal powder may be in the form of a finely divided and stabilized powder that is essentially solvent-free, namely there may be less than 1 percent solvent present, and often 0 percent solvent present.
  • the once applied dry electrode mixture may have a solvent level of less than about 0.9 percent, less than about 0.8 percent, less than about 0.7 percent, less than about 0.6 percent, less than about 0.5 percent, less than about 0.4 percent, less than about 0.3 percent, less than about 0.2 percent, less than about 0.1 percent, less than about 0.05 percent, and less than about 0.01 percent.
  • the lithium metal powder typically has a median particle size of less than about 80 microns, often less than about 40 microns and sometimes less than about 20 microns.
  • the lithium metal powder may be non- pyrophoric stabilized lithium metal power (SLMP®) available from Livent USA Corp.
  • the lithium metal powder may also include a substantially continuous layer or coating of fluorine, wax, phosphorus or a polymer or the combination thereof (as disclosed in U.S. Pat. Nos. 5,567,474, 5,776,369, and 5,976,403 and incorporated herein by reference in their entireties).
  • Stabilized lithium metal powder has a significantly reduced reaction with moisture and air and may be used in the active component or as the prelithiation agent.
  • the lithium metal powder may also be alloyed with a metal.
  • the lithium metal powder may be alloyed with a Group l-VIII element.
  • Suitable elements from Group IB may include, for example, silver or gold.
  • Suitable elements from Group I IB may include, for example, zinc, cadmium, or mercury.
  • Suitable elements from Group HA of the Periodic Table may include beryllium, magnesium, calcium, strontium, barium, and radium.
  • Elements from Group I HA that may be used in the present invention may include, for example, boron, aluminum, gallium, indium, or thallium.
  • Elements from Group IVA that may be used in the present invention may include, for example, carbon, silicon, germanium, tin, or lead.
  • Elements from Group VA that may be used in the present invention may include, for example, nitrogen, phosphorus, or bismuth.
  • Suitable elements from Group VHIB may include, for example, palladium, or platinum.
  • the polymer binder for the printable lithium composition is selected so as to be compatible with the lithium metal powder. “Compatible with” or “compatibility” is intended to convey that the polymer binder does not violently react with the lithium metal powder resulting in a safety hazard.
  • the lithium metal powder and the polymer binder may react to form a lithium-polymer complex, however, such complex should be stable at various temperatures. It is recognized that the amount (concentration) of lithium and polymer binder contribute to the stability and reactivity.
  • the polymer binder may have a molecular weight of about 1 ,000 to about 8,000,000, and often has a molecular weight of 2,000,000 to 5,000,000.
  • Suitable polymer binders may include one or more of polyethylene oxide), polystyrene, polyisobutylene, natural rubbers, butadiene rubbers, styrene-butadiene rubber, polyisoprene rubbers, butyl rubbers, hydrogenated nitrile butadiene rubbers, epichlorohydrin rubbers, acrylate rubbers, silicon rubbers, nitrile rubbers, polyacrylic acid, polyvinylidene chloride, polyvinyl acetate, ethylene propylene diene termonomer, ethylene vinyl acetate copolymer, ethylene-propylene copolymers, ethylene-propylene terpolymers, polybutenes.
  • the binder may also be a wax.
  • the binder is added as a dry powder. It is noted that the polymer binder may also function as a rheology modifier.
  • the rheology modifier is selected so as to be compatible with the lithium metal powder and the polymer binder and dispersible in the composition.
  • the rheology modifier is carbon-based.
  • the rheology modifier may be comprised of carbon nanotubes to provide a structure for a coated electrode.
  • carbon black may be added as a rheology modifier.
  • a preferred embodiment of the printable lithium composition includes a carbonbased rheology modifier such as carbon nanotubes.
  • a carbonbased rheology modifier such as carbon nanotubes.
  • Use of carbon nanotubes may also provide a three-dimensional support structure and conductive network for a lithium anode when coated with the printable lithium composition and increase its surface area.
  • Another support structure may be one as described by Cui et al. [Science Advances, Vol. 4, no. 7, page 5168, DOI: 10.1126/sciadv.aat5168], incorporated herein by reference in its entirety, which uses a hollow carbon sphere as a stable host that prevents parasitic reactions, resulting in improved cycling behavior.
  • Yet another support structure may be a nanowire as described in US Patent No. 10,090,512 incorporated herein by reference in its entirety.
  • Other compatible carbon-based rheology modifiers include carbon black, graphene, graphite, hard carbon and mixtures or blends thereof.
  • Suitable rheology modifiers may include non-carbon-based materials, including titanium oxides and silicon oxides.
  • silicon nanostructures such as nanotubes or nanoparticles may be added as a rheology modifier to provide a three-dimensional structure and/or added capacity.
  • the rheology modifiers may also increase the durability of the layer (i.e., coating, foil or film) formed from the printable lithium composition or the stabilized lithium metal powder by preventing mechanical degradation and allow for faster charging.
  • Additional rheology modifiers may be added to the composition to modify properties such as viscosity and flow under shear conditions.
  • the rheology modifier may also provide conductivity, improved capacity and/or improved stability/safety depending on the selection of the rheology modifier.
  • the rheology modifier may be the combination of two or more compounds so as to provide different properties or to provide additive properties.
  • Exemplary rheology modifiers may include one or more of silicon nanotubes, fumed silica, titanium dioxide, zirconium dioxide and other Group HA, IIIA, IVB, VB and VIA elements/compounds and mixtures or blends thereof.
  • electrochemical device electrolyte salts such as lithium perchlorate (l_iCIO4), lithium hexafluorophosphate (LiPFe), lithium difluoro(oxalate)borate (LiDFOB), lithium tetrafluoroborate (LiBF4), lithium nitrate (LiNOs), lithium bis(oxalate) borate (LiBOB), lithium trifluoromethanesulfonimide (LiTFSI), lithium bis(fluorosulfonyl) imide (LiFSI).
  • electrochemical device electrolyte salts such as lithium perchlorate (l_iCIO4), lithium hexafluorophosphate (LiPFe), lithium difluoro(oxalate)borate (LiDFOB), lithium tetrafluoroborate (LiBF4), lithium nitrate (LiNOs), lithium bis(oxalate) borate (LiBOB), lithium trifluoromethanesulf
  • the lithium metal powder in the printable lithium composition may be dispersed uniformly with the dry electrode active and inactive components using dispersion/mixing techniques known to those skilled in the art.
  • the lithium metal powder is brought into intimate contact with the active anode material.
  • the lithium metal powder will react with the anode active producing a lithiated compound.
  • the space where the lithium metal powder particle once resided will become partially vacant resulting in a porous structure.
  • Higher concentration of lithium metal powder will result in a more porous structure.
  • Rheology modifiers may be included in the printable lithium formulation to modify the porosity and overall three-dimensional support structure as desired. Examples of such modifiers may include carbon nanotubes (CNTs), graphene or polyacrylate as described in Electrochemical and Solid-State Letters, 12, 5, A107- Al 10, 2009.
  • suitable acyclic and cyclic hydrocarbons include n-hexane, n-heptane, cyclohexane, and the like.
  • suitable aromatic hydrocarbons include toluene, ethylbenzene, xylene, isopropylbenzene (cumene), and the like.
  • Suitable symmetrical, unsymmetrical, and cyclic ethers include di-n-butyl ether, methyl t-butyl ether, tetrahydrofuran, glymes and the like.
  • Commercially available isoparaffinic synthetic hydrocarbon solvents with tailored boiling point ranges such as Shell Sol® (Shell Chemicals) or Isopar® (Exxon) are also suitable.
  • the polymer binder and solvents are selected to be compatible with each other and with the lithium metal powder.
  • the binder or solvent should be non- reactive with the lithium metal powder or in amounts so that any reaction is kept to a minimum and violent reactions are avoided.
  • the binder and solvent should be compatible with each other at the temperatures at which the printable lithium composition is made and will be used.
  • the solvent is low in hygroscopicity in that there is a minimum attraction of moisture in the air. Non-polar solvents are thus well-suited for the invention.
  • polar solvents have a high hygroscopicity and have reactivity and non-compatibility with the binder, and particularly with the lithium metal.
  • Polar solvents like N-methyl 1 ,2 pyrrolidone (NMP) and gammabutyrolactone (GBL) should be avoided due to their being highly reactive with lithium leading to run away and potentially catastrophic pyric reactions.
  • the solvent (or co-solvent) will have sufficient volatility to readily evaporate from the printable lithium composition (e.g., in slurry form) to provide drying of the printable lithium composition (slurry) after application and to provide the electrode material in dry form.
  • a mixture of the polymer binder, rheology modifier, coating reagents, and other potential additives for the lithium metal powder may be formed and introduced to contact the lithium droplets during dispersion at a temperature above the lithium melting point, or at a lower temperature after the lithium dispersion has cooled such as described in U.S. Patent No. 7,588,623 the disclosure of which is incorporated by reference in its entirety.
  • the thusly modified lithium metal may be introduced in a dry powder form or in a solution form in a solvent of choice. It is understood that combinations of different process parameters could be used to achieve specific coating and lithium powder characteristics for particular applications.
  • the components of the printable lithium composition may be mixed together as a slurry or paste to have a high concentration of solid.
  • Dry lithium powder may be dispersed by standard techniques, the selection of which may be made by one skilled in the art.
  • the slurry/paste may be in the form of a concentrate with not all of the solvent necessarily added prior to the time of depositing or applying.
  • the lithium metal powder may be uniformly suspended along with any rheology modifiers in the solvent so that when applied or deposited a substantially uniform distribution of lithium metal powder is deposited or applied.
  • the powder may be suspended in the solvent such that there is no qualitative variation in lithium metal powder content from top to bottom of the suspension
  • Embodiments of the printable lithium composition in accordance with the present invention may accommodate high binder ratios, including up to 20% on a dry basis.
  • Various properties of the printable lithium composition such as viscosity and flow, may be modified by increasing the binder and modifier content up to 50% dry basis without loss of electrochemical activity of lithium.
  • Increasing the binder content facilitates the loading of the printable lithium composition and the flow during the dry application (coating) process.
  • the printable lithium composition may comprise between about 50% to about 98% by weight of lithium metal powder and about 2% to about 50% by weight of polymer binder and rheology modifiers on a dry weight basis.
  • the printable lithium composition comprises between about 60% to about 90% by weight lithium metal powder and between about 10% to about 40% by weight of polymer binder and rheology modifiers.
  • An important aspect of printable lithium compositions is the rheological stability of the suspension. Because lithium metal has a low density of 0.534 g/cc, it is difficult to prevent lithium powder from separating from solvent suspensions.
  • viscosity and rheology may be tailored to create the stable suspension of the invention.
  • a preferred embodiment shows no separation at greater than 90 days. This may be achieved by designing compositions with zero shear viscosity in the range of 1 x 10 4 cps to 1 x 10 7 cps, wherein such zero shear viscosity maintains the lithium in suspension particularly when in storage. When shear is applied, the suspension viscosity decreases to levels suitable for use in printing or coating applications.
  • the resulting printable lithium composition preferably may have a viscosity at 10s’ 1 about 20 to about 20,000 cps, and sometimes a viscosity of about 100 to about 2,000 cps, and often a viscosity of about 700 to about 1 ,100 cps. At such viscosity, the printable lithium composition is a flowable suspension or gel.
  • the printable lithium composition preferably has an extended shelf life at room temperature and is stable against metallic lithium loss at temperatures up to 60°C, often up to 120°C, and sometimes up to 180°C.
  • the printable lithium composition may separate somewhat over time but can be placed back into suspension by mild agitation and/or application of heat.
  • the lithium metal powder of the prelithiation agent prior to mixing with the active component comprises on a solution basis about 0.5 to about 100%, preferably about 0.5% to about 50%, more preferably about 10 to about 30%.
  • the lithium metal powder may be added to the active component by itself with no other additives.
  • the printable lithium composition prior to mixing with the active component comprises on a solution basis about 0.0 to about 20% polymer binder, preferably about from 0.1 % to about 10%, most preferably from about 0.1 % to about 5%.
  • the printable lithium composition prior to mixing with the active component comprises on a solution basis about 0.0 to about 20% rheology modifier, preferably about from 0.1% to about 10%, most preferably from about 0.5% to about 5%.
  • the printable lithium composition prior to mixing with the active component comprises on a solution basis about 0% to about 95% solvent, preferably from about 40% to about 95%, most preferably from about 65% to about 90%.
  • the process for manufacturing an electrode may entail depositing the dry electrode mixture 10 of the active component (active electrode material, a binder and conductive material) and the printable lithium composition via a nozzle 15.
  • the thickness of the deposited dry electrode mixture on the substrate 20 e.g. shown as a current collector
  • the dry electrode mixture 10 may be pressed onto the substrate 20 using rollers 30 followed by a calendar 35 to form the electrode 40.
  • the active anode material and the printable lithium composition are provided together and deposited onto the current collector (e.g., copper, nickel, etc.).
  • the active anode material and printable lithium composition may be mixed and deposited together.
  • a Buhler continuous mixer may be employed.
  • the active anode material and the printable lithium composition are co-extruded to form a layer of the printable lithium composition on the substrate (e.g., the current collector for an anode or on the solid electrolyte of a solid-state battery).
  • the deposition of the dry electrode mixture including the above extrusion technique may include depositing as wide variety patterns (e.g., dots, stripes), thicknesses, widths, etc.
  • the printable lithium composition and active anode material may be deposited as a series of stripes, such as described in US Publication No. 2014/0186519 incorporated herein by reference in its entirety.
  • the stripes would form a 3D structure that would account for expansion of the active anode material during lithiation.
  • silicon may expand by 300 to 400 % during lithiation.
  • Such swelling potentially adversely affects the anode and its performance.
  • the dry electrode mixture as a thin stripe in the Y-plane as an alternating pattern between the silicon anode stripes
  • the silicon anode material may expand in the X-plane alleviating electrochemical grinding and loss of particle electrical contact.
  • the printing method may provide a buffer for expansion.
  • the printable lithium composition may be supplied to the anode active material prior to the formation process of the battery.
  • the dry electrode mixture may be incorporated within an anode as described in US Publication No. 2018/0269471 herein incorporated by reference in its entirety.
  • the anode may comprise an active anode composition and the dry anode mixture, and any electrically conductive powder if present.
  • the dry electrode mixture may be placed along the surface of the electrode.
  • the anode may comprise an active layer with an active anode composition and a dry electrode mixture source layer on the surface of active layer.
  • the printable lithium composition source layer may be between the active layer and a current collector.
  • the anode may comprise printable dry electrode mixture source layers on both surfaces of the active layer.
  • the dry anode mixture may be incorporated into a three-dimensional electrode structure as described in US Publication No. 2018/0013126 herein incorporated by reference in its entirety.
  • the mixture may be incorporated into a three-dimensional porous anode, porous current collector or porous polymer or ceramic film, wherein the dry anode mixture may be deposited therein.
  • an electrode prelithiated with the printable lithium composition may be assembled into a cell with the electrode to be preloaded with lithium. A separator may be placed between the respective electrodes. Current may be allowed to flow between the electrodes.
  • an anode prelithiated with the prelith iation agent of the present invention may be formed into a battery such as described in U.S. Patent No. 6,706,447 herein incorporated by reference in its entirety.
  • the dry electrode mixture may be used to form a composite lithium metal anode for use in a solid-state battery, including solid-state batteries as described in U.S. Provisional No. 63/349,742 filed June 7, 2022 and U.S. Patent Nos. 7,914,930, 8,252,438 and 9,893,379 and incorporated herein by reference in their entireties.
  • the dry electrode mixture may be deposited on a variety of solid- state electrolytes as described in US Patent No. 7,914,930 herein incorporated by reference in its entirety.
  • a solid-state secondary battery may include a positive electrode capable of electrochemically absorbing and desorbing lithium; a negative electrode capable of electrochemically absorbing and desorbing lithium, the negative electrode including a dry electrode mixture that comprises an active material, the active material layer being carried on a current collector; and a non-aqueous electrolyte.
  • a method includes the steps of: reacting lithium with the active material of the negative electrode by bringing the dry electrode mixture into contact with a surface of the substrate of the negative electrode(anode); and thereafter combining the negative electrode with the positive electrode(cathode) to form an electrode.
  • the electrolyte may be a solid electrolyte, and more particularly a hybrid solid electrolyte(HSE).
  • the hybrid solid electrolyte may include the combination of a polyethylene oxide(PEO), tantalum-doped lithium lanthanum zirconate(LLTZO), and lithium bis(trifluoromethanesulfonyl)imide(LiTSFI).
  • hybrid solid electrolytes include PEO, Lii+ x Al x Ti2- x (PO4)3 (LATP) or Lii+ x AlxGe2- x (PO4)3 (LAGP) and LiTFSI, and LiTFSI, PEO and SiO2 or TiO2 or AI2O3 and LiTFSI, described, for example, in “Recent Developments and Challenges in Hybrid Solid Electrolytes for Lithium Ion Batteries” Han et al, Frontiers in Energy Research. September 2020, Vol.
  • ionic liquids such as butylmethylimidazolium (Bmim), ethylmethylimidazolium (Emim) and dimethylimidazolium (Dmim) units or similar.
  • the LLZTO portion of the HSE may also be doped or replaced with an anion (oxygen) site doped garnet, Nasicon (sodium super ionic conductor) type solid electrolytes or Lisicon (lithium super ionic conductor) type solid electrolytes.
  • the doping elements could be chlorine, fluorine, or sulfur to improve the grain boundary conductivity and decrease the interfacial resistance thereby improving cell performance.
  • the dry anode material may be utilized in a lithium ion battery comprising a negative sheet comprising the dry electrode (anode) material, a current collector, a positive active material layer or negative active material layer arranged on a surface of the current collector, a lithium supplemental layer arranged on the surface of the current collector, preferably at intervals with the positive or negative active material such as described in CN 113823849A and CN 113823851 A, the disclosures of which are incorporated by reference in their entireties.
  • the dry electrode (anode) material may be incorporated as a supplemental lithium source associated with an anode.
  • the anode may comprise an active layer with an active anode composition and a supplemental lithium source layer on the surface of the active layer such as described in U.S. Patent No. 11 ,387,440 B2, the disclosure of which is incorporated by reference in its entirety.
  • the preferred Examples and Comparative Examples of the present invention will be described. However, the following Examples are only a preferred exemplary embodiment of the present invention and the present invention is not limited thereto. The Examples provide illustration of the formation of coin cells and larger pouch cells.
  • TH INKY ARE 250 planetary centrifugal mixer at 1000 rpm for 5 minutes.
  • a 10% printable lithium composition from Livent USA Corp, as Liovix® and having a lithium equivalence of about 20% of the total anode capacity is added in, and mixed for another 1 minute in the THINKY ARE 250 planetary centrifugal mixer.
  • the resulting dry mixture is deposited on a polymer-coated copper substrate and pressed at 160 °C, 15000 PSI.
  • 85% of a Graphite 1 10% silicon oxide mixture, 5% carbon black and 10% PVDF are dry mixed in a THINKY ARE 250 planetary centrifugal mixer at 1000 rpm for 5 minutes.
  • a 10% printable lithium composition available from Livent USA Corp, as Liovix® and having a lithium equivalence of about 20% of the total anode capacity is added in and mixed for another 1 minute in the THINKY ARE 250 planetary centrifugal mixer.
  • the resulting dry mixture is deposited on a polymer-coated copper substrate and pressed at 160 °C, 15000 PSI.
  • 85% of a Graphite 125% silicon oxide mixture, 5% carbon black and 10% PVDF are dry mixed in a THINKY ARE 250 planetary centrifugal mixer at 1000 rpm for 5 minutes.
  • a 10% printable lithium composition available from Livent USA Corp, as Liovix® and having a lithium equivalence of about 20% of the total anode capacity is added in and mixed for another 1 minute in the THINKY ARE 250 planetary centrifugal mixer.
  • the resulting dry mixture is deposited on a polymer-coated copper substrate and pressed at 160 °C, 15000 PSI.
  • the dry anode of Examples 1-3 are assembled into a half cell in the coin cell format with a lithium metal counter electrode (Graphite/Celgard 3501/Li half-cell) using 1 M LiPFe in EC:FEC:DEC:DMC 1 :1 :2:6 (volume ratio) electrolyte.
  • the cell is tested with the following protocol on a Maccor series 4000 cycler: 1 ) rest 24hrs @ 45°C, 2) discharge at 1 .50 to 0.005V, 3) a constant voltage step until current drop to 0.01 C, and 4) charge at 0.1 C to 1 ,5V.
  • FIGS. 2 and 3 illustrate the voltage curves for baseline cells and cells with a printable lithium composition incorporated according to Examples 1-3.
  • the voltage curves demonstrate that cells with a printable lithium composition incorporated have a lower starting open circuit voltage, which indicates the electrode is partially lithiated by the printable lithium composition.
  • the difference between the average charge and discharge voltage is lower for cells with a printable lithium composition incorporated compared to baseline cells and indicates lower DC resistance.
  • FIGS. 4-6 are plots comparing the differential capacity (dQ/dV) versus potential (V) between baseline and cells with a printable lithium composition incorporated according to Examples 1 to 3 respectively during the first charge. Electrochemical results are similar to results for electrodes produced using the conventional approach. As seen in FIGS. 4-6, incorporation of a printable lithium composition eliminates the electrolyte solvent reduction peak since formation of the solid electrolyte interface has taken place within 24 hours of applying the dry electrode material mixture to the substrate.
  • Table 2 provides a comparison of first cycle efficiencies between baseline cells and cells with a printable lithium composition incorporated according to Example 1 .
  • the first cycle efficiency (CE) for baseline cells averages about 84.0% whereas the first CE for cells with a printable lithium composition is about 95.8% on average, representing about a 12% increase.
  • Table 3 provides a comparison of first cycle efficiencies between baseline cells and cells with a printable lithium composition incorporated according to Example 2.
  • the first cycle efficiency (CE) for baseline cells averages about 78.0% whereas the first CE for cells with a printable lithium composition incorporated is about 86.3% on average, representing about an 8.3% increase.
  • Table 4 Performance Comparison Between Baseline Cells and Cells with Printable Lithium Composition in Graphite-25%SiO/Li half cells (Example 3) Table 4 provides a comparison of first cycle efficiencies between baseline cells and cells with a printable lithium composition incorporated according to Example 3.
  • the first cycle efficiency (CE) for baseline cells averages about 64.6% whereas the first CE for cells with a printable lithium composition incorporated is about 76.4% on average, representing about a 11.8% increase.
  • pouch cells were made.
  • the dry mixture of Example 1 was deposited on the polymer- coated copper substrate and pressed at 160°C, 15000 PSI to form an electrode for the pouch cell having the dimension of 4.6 cm by 4.3 cm.
  • Example 4 After drying and calendaring, the electrode of Example 4 is assembled into a half cell in the pouch cell format with a lithium metal counter electrode (Graphite/Celgard 3501/Li half-cell) and with 1 M LiPFe in EC:FEC:DEC:DMC 1 :1 :2:6 (volume ratio) electrolyte.
  • the cell is tested with the following protocol on a Maccor series 4000 cycler: 1 ) rest 24hrs @ 45°C, 2) discharge at 1 .50 to 0.005V, 3) a constant voltage step until current drop to 0.01 C, and 4) charge at 0.1 C to 1 ,5V.
  • FIG. 7 illustrates the voltage curve for baseline pouch cells and cells with the printable lithium position incorporated according to Example 4.
  • FIG. 8 is a plot comparing the differential capacity (dQ/dV) versus potential (V) between baseline and cells with a printable lithium composition incorporated according to Example 4.
  • the voltage curve demonstrates that cells with a printable lithium composition incorporated have a lower starting open circuit voltage, which indicates the electrode is partially lithiated by the printable lithium composition.
  • Table 5 Performance Comparison Between Baseline Cells and Cells with Printable Lithium Composition (Example 4)
  • Example 5 After calendaring the electrodes of Example 5 are assembled into a half cells in the coin cell format with a lithium metal counter electrode (Graphite/Celgard 3501 /Li) using 1 M LiPFe in EC:FEC:DEC:DMC 1 :1 :2:6 (volume ratio) electrolyte.
  • the cells are tested with the following protocol on a Maccor series 4000 cycler: 1 ) rest 24hrs @ 45°C, 2) discharge at 1 ,5C to 0.005V, 3) a constant voltage step until current drop to 0.01 C, and 4) charge at 0.1 C to 1 ,5V.
  • FIG. 9 illustrates the voltage curve for baseline pouch cells and cells with a SLMP® according to Example 5.
  • FIG. 10 is a plot comparing the differential capacity (dQ/dV) versus potential (V) between baseline and cells with SLMP® incorporated according to Example 5.
  • Table 6 Performance Comparison Between Baseline Cells and Cells with SLMP® (Example s)
  • the first cycle efficiency (CE) for baseline cells averages about 76.0% whereas, the first CE for cells with stabilized lithium metal powder incorporated is about 36.0 percent on average, representing about a 10.0% increase.
  • SLMP® provides improvement over the baseline cells. SLMP® may have a slightly less improvement than a printable lithium composition due to the better processability of the printable lithium formulation because of a small amount of solvent being present.
  • FIG. 11 is a plot comparing the cycle life time between baseline cell and cells with LIOVIX® incorporated and SLMP® incorporated according to Examples 4 and 5.

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Abstract

L'invention concerne un procédé en une étape et à sec pour former une première anode à haut rendement de cycle. Le procédé peut consister à mélanger à sec un constituant actif comportant un matériau d'anode actif, un liant et un matériau conducteur avec un agent de prélithiation pour former un mélange de matériau d'anode sec. L'agent de prélithiation peut être une composition de lithium imprimable et peut comprendre une poudre de lithium métallique, un liant polymère compatible avec la poudre de lithium métallique, et un modificateur de rhéologie compatible avec la poudre de lithium métallique. L'agent de prélithiation peut également être une poudre de lithium métallique stabilisée exempte de solvant. Le mélange de matériau d'anode sec est appliqué à un substrat sous la forme d'une couche non autoportante pour former l'électrode qui peut être utilisée dans une grande variété de batteries comprenant des batteries au lithium-ion, des condensateurs au lithium-ion et des batteries tout solide.
PCT/US2022/045837 2021-10-29 2022-10-06 Traitement à sec de formation d'électrode WO2023076011A1 (fr)

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US202263349742P 2022-06-07 2022-06-07
US63/349,742 2022-06-07
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