Classifications

• • 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
  • H01M4/134—Electrodes based on metals, Si or alloys
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  • 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
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
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  • 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0421—Methods of deposition of the material involving vapour deposition
  • H01M4/0423—Physical vapour deposition
  • H01M4/0426—Sputtering
• • H—ELECTRICITY
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  • 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
  • H01M4/139—Processes of manufacture
  • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
• • 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
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
• • 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
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/381—Alkaline or alkaline earth metals elements
  • H01M4/382—Lithium
• • 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
  • H01M4/58—Selection 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
  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
  • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
• • H—ELECTRICITY
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
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  • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
  • H01M4/625—Carbon or graphite
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0068—Solid electrolytes inorganic
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0088—Composites
  • H01M2300/0091—Composites in the form of 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
• • 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
• • 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
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/40—Printed batteries, e.g. thin film batteries

Definitions

• the present invention relates to a battery which utilizes a printable lithium composition.
• 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.
• 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 film on the anode.
• the passivation film formed on the graphite anode is a solid electrolyte interface (SEI).
• SEI solid electrolyte interface
• the lithium consumed by the formation of the SEI is not returned to the cathode. This results in a lithium-ion cell having a smaller capacity compared to the initial charge capacity because some of the lithium has been consumed by the formation of the SEI.
• the partial consumption of the available lithium on the first cycle reduces the capacity of the lithium-ion cell. This phenomenon is called irreversible capacity and is known to consume about 10% to more than 20% of the capacity of a lithium ion cell. Thus, after the initial charge of a lithium-ion cell, the lithium-ion cell loses about 10% to more than 20% of its capacity.
• 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 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. 7,588,623,
• the present invention provides a solid-state battery with one or more components prelithiated, or lithiated with a printable lithium composition.
• a solid-state battery comprising the printable lithium composition will have increased energy density and improved safety and manufacturability.
• the battery may comprise a cathode and a composite anode.
• the composite anode may comprise a lithium metal anode and at least one interface layer between the lithium metal anode and a solid electrolyte.
• the lithium metal anode and/or interface layer may be formed of a printable lithium composition comprised of lithium metal powder, a polymer binder compatible with the lithium metal powder, a rheology modifier compatible with the lithium metal powder, and a solvent compatible with the lithium metal powder and with the polymer binder.
• the interface layer may be added to a surface of the solid electrolyte to improve the uniformity of its surface and optimize contact between the surface of the lithium metal anode and the surface of the solid electrolyte leading to better battery performance.
• the anode may formed from a printable lithium formulation and serve as an interface layer.
• the lithium metal anode and/or interface layer may be comprised of a foil or film formed from a printable lithium composition comprising lithium metal powder, a polymer binder compatible with the lithium metal powder, and a rheology modifier compatible with the lithium metal powder and the polymer binder, wherein the rheology modifier provides a three-dimensional support structure for preventing the degradation and increasing the durability of the foil or film when coated with the printable lithium composition.
• the cathode may be a composite of non-lithiated cathode materials and printable Li metal; for example, a sulfur cathode can be prelithiated with printable Li and this composite cathode can paired with non-lithiated or prelithiated anode in solid-state batteries.
• FIG. 1 is a schematic of a solid-state battery according to one embodiment of the present invention.
• FIG. 2 is a temperature and pressure profile for the reactivity testing of SLMP/styrene butadiene/toluene printable lithium composition
• FIG. 3 is a plot showing the cycle performance for a pouch cell with printable lithium derived thin lithium film as the anode vs. commercial thin lithium foil;
• FIG. 4A is a plot showing the cycling voltage of a coin-type all solid-state battery with a LiFeP0 4 (LFP) cathode, a Lii 0 GeP 2 Si 2 (LGPS) solid electrolyte and an anode comprising a printable lithium composition; and
• LFP LiFeP0 4
• LGPS Lii 0 GeP 2 Si 2
• FIG. 4B is a plot showing the charge capacity and discharge capacity versus cycle number for one embodiment at 70°C.
• compositions/methods may contain additional components so long as the additional
• composition/method does 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 solid-state battery 10 comprising an anode 12, a cathode 14 and a solid electrolyte 16 is provided in accordance with one embodiment of the present invention.
• the solid-state battery may further include an anode current collector 20 and a cathode current collector 22.
• a printable lithium composition may be applied or deposited to a current collector, electrode and/or solid electrolyte of the solid-state battery.
• the printable lithium composition may be used to form a monolithic lithium metal anode of various thicknesses and widths for use in a solid-state battery, including solid- state batteries as described in US Patent Nos.
• the printable lithium composition may be applied or deposited so as to form a solid electrolyte for a solid-state battery, and includes combining the printable lithium composition with a polymer or ceramic material to form a solid electrolyte.
• the printable lithium composition may comprise a lithium metal powder, one or more polymer binders, one or more rheology modifiers and may further include a solvent or co-solvent.
• the printable lithium composition may be applied to a current collector, electrode or solid electrolyte by various methods, including extruding, coating, printing, painting, dipping, and spraying as disclosed in US Application No. 16/359,725 and hereby incorporated by reference in its entirety.
• the anode may be lithiated or prelithiated by printing the printable lithium composition onto the anode or a current collector, where the thin lithium film with controlled thickness and width could be formed, or coating the anode with the printable lithium composition.
• the surfaces of typical solid electrolytes may be rough depending on the solid electrolyte selection and therefore may not form good contacts between the solid electrolyte and the lithium (foil) anode, leading to a sub-optimal interface and reduced battery performance.
• the printable lithium composition may be used to prelithiate a solid electrolyte, forming an interface layer that improves the solid electrolyte surface and therefore provides for improved adhesion with a lithium anode.
• the interface layer may comprise a foil or film formed from a printable lithium composition. The printable lithium composition forming the interface layer may be applied to various types of solid electrolytes, including polymer, glass, and ceramic electrolytes.
• Having a modified solid electrolyte surface optimizes contact between the solid electrolyte and a lithium anode, resulting in an improved interface between the solid electrolyte and lithium anode and leading to better battery performance by lessening the impedance growth caused by loss of contact between lithium and the electrolyte that occurs because of volume increase of the lithium during cycling.
• a solid-state secondary battery may include a cathode capable of electrochemically absorbing and desorbing lithium; an anode capable of electrochemically absorbing and desorbing lithium, the anode including an active material layer that comprises an active material, the active material layer being carried on a current collector; and a non-aqueous electrolyte as described in US Patent No. 7,914,930 herein incorporated by reference in its entirety.
• a method includes the steps of: reacting lithium with the active material of the anode by bringing the printable lithium composition into contact with a surface of the active material layer of the anode; and thereafter combining the anode with the cathode to form an electrode assembly.
• the printable lithium composition comprises a lithium metal powder, a polymer binder, a rheology modifier and may further include a solvent.
• the polymer binder may be compatible with the lithium metal powder.
• the rheology modifier may be compatible with the lithium metal powder and the polymer binder.
• the solvent may be compatible with the lithium metal powder and with the polymer binder.
• the lithium metal powder may be in the form of a finely divided powder.
• the lithium metal powder typically has a mean 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 a low pyrophoricity stabilized lithium metal power (SLMP®) available from FMC Lithium 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.
• Lithium metal powder has a significantly reduced reaction with moisture and air.
• 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 MB may include, for example, zinc, cadmium, or mercury.
• Suitable elements from Group IIA of the Periodic Table may include beryllium, magnesium, calcium, strontium, barium, and radium.
• Elements from Group IIIA 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 VIIIB may include, for example, palladium, or platinum.
• the polymer binder 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
• 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 poly(ethylene 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 rheology modifier is selected to be compatible with the lithium metal powder and the polymer binder.
• the rheology modifier provides rheology properties such as viscosity.
• the rheology modifier may also be multi-functional and 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 carbon black, carbon nanotubes, graphene, silicon nanotubes, graphite, hard carbon and mixtures, fumed silica, titanium dioxide, zirconium dioxide and other Group IIA, IIIA, IVB, VB and VIA elements/compounds and mixtures or blends thereof.
• Solvents compatible with lithium may include acyclic hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, symmetrical ethers, unsymmetrical ethers, cyclic ethers, alkanes, sulfones, mineral oil, and mixtures, blends or cosolvents thereof.
• 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 (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.
• the components of the printable lithium composition may be mixed together as a slurry or paste to have a high concentration of solid.
• 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 should be uniformly suspended in the solvent so that when applied or deposited a substantially uniform distribution of lithium metal powder is deposited or applied. Dry lithium powder may be dispersed such as by agitating or stirring vigorously to apply high sheer forces.
• 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 the 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 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. In one embodiment, 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. In another embodiment the printable lithium composition comprises between about 75% to about 85% by weight of lithium metal powder and between about 15% to about 30% 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 printable lithium composition comprises on a solution basis about 5 to 50 percent lithium metal powder, about 0.1 to 20 percent polymer binder, about 0.1 to 30 percent rheology modifier and about 50 to 95 percent solvent. In one embodiment, the printable lithium composition comprises on a solution basis about 15 to 25 percent lithium metal powder, about 0.3 to 0.6 percent polymer binder having a molecular weight of 4,700,000, about 0.5 to 0.9 percent rheology modifier, and about 75 to 85 percent solvent. Typically, the printable lithium composition is applied or deposited to a thickness of about 50 microns to 200 microns prior to pressing. After pressing, the thickness can be reduced to between about 1 to 50 microns. Examples of pressing techniques are described, for example, in US Patent Nos.
• a current collector, electrode and/or solid electrolyte of the solid-state battery may comprise a substrate coated with a printable lithium composition as described in U.S. Provisional
• the printable lithium composition comprises lithium metal powder, a polymer binder compatible with the lithium metal powder, and a rheology modifier compatible with the lithium metal powder and the polymer binder, wherein the rheology modifier is dispersible within the composition and provides a three-dimensional support structure for preventing degradation and increasing the durability of the anode when made with the printable lithium 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.
• the carbon-based rheology modifier may also provide a conductive network between lithium particles after pressing effectively increasing areal surface area and lowering areal current density during device operation and giving lithium ions a pathway to deposit in the bulk rather than just on the surface of the foil as occurs with regular lithium foil.
• 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 by preventing mechanical degradation and allow for faster charging.
• the printable lithium composition may be applied onto a substrate, such as an energy storage device substrate.
• a substrate such as an energy storage device substrate.
• examples may include a current collector, an anode, a cathode, and an electrolyte.
• electrolytes may include a solid electrolyte, a polymer electrolyte, a glass electrolyte, and a ceramic electrolyte.
• the printable lithium composition may be applied or deposited to prelithiate an anode or cathode. The prelithiated anode or cathode may be incorporated into an energy storage device such as a capacitor or battery.
• the substrate may be a lithium anode.
• the lithium anode may be a flat lithium metal anode, or may be a lithium-carbon anode such as an amine functionalized lithium-carbon film as described in Niu et al. [Nature Nanotechnology, Vol. 14, pgs. 594-201 (2019); DOI: 10.1038/s41565-019-0427-9] and herein incorporated by reference in its entirety.
• the printable lithium composition may be applied or deposited so as to form a solid electrolyte for a solid-state battery, and includes combining the printable lithium composition with a polymer, glass or ceramic material to form a solid electrolyte or a composite solid electrolyte.
• the printable lithium composition and polymer material may be extruded together to create a solid electrolyte film, and optionally may include other active electrolyte materials.
• the substrate may comprise an electrode coated with a printable lithium composition, and further include a protective layer between the lithium layer and an electrolyte; for example, the protective layer described in US Patent No. 6,214,061 herein incorporated by reference in its entirety.
• the protective layer may be a glassy or amorphous material capable of conducting lithium ions and is adapted to prevent contact between the lithium surface and an electrolyte.
• suitable protective layers include lithium silicates, lithium borates, lithium aluminates, lithium phosphates, lithium phosphorous oxynitrides, lithium silicosulfides, lithium borosulfides, lithium aminosulfides and lithium phosphosulfides.
• the protective layer may be applied onto an electrode surface by a physical or chemical deposition process.
• the printable lithium composition may be applied onto the protective layer as a coating, foil or film.
• the protective layer may be separating a lithium layer and electrolyte wherein the electrolyte may be comprised of a substrate coated with the printable lithium composition.
• the formulation may employ use of a semi-solid polymer binder, such as described by Li et al. [Joule, Vol. 3, No. 7, pgs. 1637-1646 (2019), DOI: 10.1016/j.joule.2019.05.022] and herein incorporated by reference in its entirety, in order to increase contact of lithium metal with the solid-state electrolyte and maintain contact during charge/discharge cycling.
• One embodiment may comprise a battery with a scalable three-dimensional (3D) lithium metal anode; for example, as disclosed by Liu et al. [Energy Storage Materials, Vol. 16, pgs. 505-511 (2019), DOI: 10.1016/j.ensm.2018.09.021] and herein incorporated by reference in its entirety, wherein a cathode, electrolyte, 3D lithium metal anode, or a combination thereof may each comprise a substrate coated with a printable lithium composition.
• 3D lithium metal anode for example, as disclosed by Liu et al. [Energy Storage Materials, Vol. 16, pgs. 505-511 (2019), DOI: 10.1016/j.ensm.2018.09.021] and herein incorporated by reference in its entirety, wherein a cathode, electrolyte, 3D lithium metal anode, or a combination thereof may each comprise a substrate coated with a printable lithium composition.
• Another embodiment may comprise a battery having a cathode, electrolyte and a lithium anode modified with Znl 2 such as disclosed by Kolensikov et al. [Journal of the Electrochemical Society, vol. 166, no. 8, pages A1400-A1407 (2019), DOI: 10.1149/2.0401908jes] and herein incorporated by reference in its entirety.
• the lithium anode may be prepared by applying the printable lithium composition onto a copper foil and modified by placing the foil in contact with a Znl 2 in tetrahydrofuran (THF) solution.
• the substrate may comprise a silicon-nanotube anode such as described by Forney et al. [Nanoletters, Vol. 13, no. 9, pages 4158-4163 (2013), DOI:
• the silicon-nanotube anode thereof may further include a lithium layer, such as a coating, foil or film, formed from the printable lithium composition.
• the polymer binder 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
• 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 poly(ethylene 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 rheology modifier is selected so as to be compatible with the lithium metal powder and the polymer binder and dispersible in the composition.
• a preferred embodiment of the printable lithium composition includes a carbon-based 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.
• 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 IIA, IIIA, IVB, VB and VIA
• electrochemical device electrolyte salts such as lithium perchlorate (UCIO4), lithium hexafluorophosphate (LiPFe), lithium
• LiDFOB difluoro(oxalate)borate
• Li1BF4 lithium tetrafluoroborate
• LiNO3 lithium nitrate
• LiBOB lithium bis(oxalate) borate
• LiTFSI lithium trifluoromethanesulfonimide
• LiFSI bis(fluorosulfonyl) imide
• 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 printable lithium composition may be in the form of a foil or a film as described in U.S. Provisional Application No. 62/864,739 and herein incorporated by reference in its entirety.
• the foil or film formed from the printable lithium composition may be applied to a substrate for use in one or more components in a battery.
• the battery may include a cathode, an electrolyte and an anode with a substrate coated with the printable lithium composition.
• the electrolyte may have a concentration of above 1 M, often equal to about 3 M or higher, and sometimes above 5 M.
• Suitable electrolytes include lithium perchlorate (UCIO4), lithium hexafluorophosphate (LiPF 6 ), lithium difluoro(oxalate)borate (LiDFOB), lithium tetrafluoroborate (LiBF 4 ), lithium nitrate (L1NO3), lithium bis(oxalate) borate (LiBOB), lithium bis(fluorosulfonyl) imide (LiFSI) and lithium trifluoromethanesulfonimide (LiTFSI) and mixtures or blends thereof.
• UCIO4 lithium perchlorate
• LiPF 6 lithium hexafluorophosphate
• LiDFOB lithium difluoro(oxalate)borate
• LiBF 4 lithium tetrafluoroborate
• LiBF 4 lithium nitrate
• LiBOB lithium bis(oxalate) borate
• LiFSI lithium bis(fluorosulfonyl) imide
• LiTFSI lithium tri
• One exemplary example is a battery having a cathode and an anode with a substrate coated with the printable lithium composition and a high concentration electrolyte, wherein LiFSI is the major salt of the high concentration electrolyte.
• Another example is a battery having a cathode and an anode with a substrate coated with the printable lithium composition and a dual-salt liquid electrolyte as described by Weber et al
• the dual salt liquid electrolyte may be comprised of lithium difluoro(oxalate)borate (LiDFOB) and L1BF4, and may have a concentration of about 1 M. Dual-salt electrolytes may provide increased initial capacity retentions and improved cycle performance.
• the printable lithium composition is deposited or applied to an active anode material on a current collector namely to form a prelithiated anode.
• active anode materials include graphite and other carbon-based materials, alloys such as tin/cobalt, tin/cobalt/carbon, silicon-carbon, variety of silicone/tin based composite compounds, germanium-based composites, titanium-based composites, elemental silicon, and germanium.
• the anode materials may be a foil, mesh or foam. Application may be via spraying, extruding, coating, printing, painting, dipping, and spraying, and are described in co-pending US Patent Publication No. 16/359,725, and incorporated herein by reference in its entirety.
• the active anode material and the printable lithium composition are provided together and extruded onto the current collector (e.g., copper, nickel, etc.).
• the active anode material and printable lithium composition may be mixed and co extruded together.
• active anode materials include graphite, graphite-SiO, graphite- SnO, SiO, hard carbon and other lithium ion battery and lithium ion capacitor anode materials.
• the active anode material and the printable lithium composition are co extruded to form a layer of the printable lithium composition on the current collector.
• the deposition of the printable lithium composition 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 percent during lithiation. Such swelling potentially adversely affects the anode and its performance.
• the silicon anode material can expand in the X-plane alleviating electrochemical grinding and loss of particle electrical contact.
• the printing method can provide a buffer for expansion.
• the printable lithium formulation is used to form the anode, it could be co-extruded in a layered fashion along with the cathode and separator, resulting in a solid-state battery.
• the printable lithium composition may be used to pre-lithiate an anode as described in US Patent No. 9,837,659 herein incorporated by reference in its entirety.
• the method includes disposing a layer of printable lithium composition adjacent to a surface of a pre-fabricated/pre-formed anode.
• the pre-fabricated electrode comprises an electroactive material.
• the printable lithium composition may be applied to the carrier/substrate via a deposition process.
• a carrier substrate on which the layer of printable lithium composition may be disposed may be selected from the group consisting of: polymer films (e.g., polystyrene, polyethylene, polyethyleneoxide, polyester, polypropylene,
• thermodynamics by way of non limiting example.
• Heat may then be applied to the printable lithium composition layer on the substrate or the pre-fabricated anode.
• the printable lithium composition layer on the substrate or the pre-fabricated anode may be further compressed together, under applied pressure.
• the heating, and optional applied pressure facilitates transfer of lithium onto the surface of the substrate or anode.
• pressure and heat can result in mechanical lithiation, especially where the pre-fabricated anode comprises graphite. In this manner, lithium transfers to the electrode and due to favorable thermodynamics is incorporated into the active material.
• the printable lithium composition can be supplied to the anode active material prior to the formation process of the battery.
• the anode can comprise a partially lithium-loaded silicon-based active material as described in US Publication No. 2018/0269471 herein incorporated by reference, in which the partially loaded active material has a selected degree of loading of lithium through
• the battery may utilize a composite cathode.
• the battery may include a sulfur cathode, such as described in US Patent Nos. 9,882,238 and 9,917,303 and herein incorporated by reference in their entireties.
• the printable lithium composition 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 printable lithium composition may be incorporated into a three-dimensional porous anode, porous current collector or porous polymer or ceramic film, wherein the printable lithium composition may be deposited therein.
• the printable lithium composition may be incorporated into a solid electrolyte, wherein the solid electrolyte may be combined with or applied to a lithium metal anode to form a composite anode.
• the solid electrolyte may be applied as one or more interface ion conductive electrolyte layers or interfaces to the lithium metal anode.
• One example is described in US Patent No. 8,182,943 herein incorporated by reference in its entirety.
• the printable lithium composition 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 three-dimensional electrode may be a permeable composite material comprised of a support defining pores and an alkali metal deposit on the support, wherein the alkali metal is deposited using a printable lithium composition.
• the three- dimensional electrode may have a porosity between about 1 % by volume to about 95% by volume, and may have a mean flow pore size in the range of from about 1 nm to about 300 pm.
• Another embodiment of the battery may include a composite anode formed using a pulsed electron beam as described in US Patent No. 10,047,432 herein incorporated by reference in its entirety.
• the pulsed electron beam may be used as a virtual cathode deposition (VCD) process applied to an anode material, wherein a three-dimensional porous anode structure is created using the electron beam.
• VCD virtual cathode deposition
• the three-dimensional structure formed from the pulsed electron beam may be a carbon allotrope for lithium ion batteries (CALIB).
• the CALIB structure may be deposited with lithium using a printable lithium composition to form a carbon polymorph.
• an electrode prelithiated with the printable lithium composition can be assembled into a cell with the electrode to be preloaded with lithium.
• a separator can be placed between the respective electrodes.
• Current can be allowed to flow between the electrodes.
• an anode prelithiated with the printable lithium composition of the present invention may be formed into a second battery such as described in U.S. Patent No. 6,706,447 herein incorporated by reference in its entirety.
• the cathode is formed of an active material, which is typically combined with a carbonaceous material and a binder polymer.
• the active material used in the cathode is preferably a material that can be lithiated.
• non-lithiated materials such as MnC>2, V2O5 , M0S2, metal fluorides or mixtures thereof, Sulphur and sulfur composites can be used as the active material.
• lithiated materials such as LiM ⁇ C and UMO2 wherein M is Ni, Co or Mn that can be further lithiated can 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.
• S-SBR Europrene Sol R 72613 10g of solution styrene butadiene rubber (S-SBR Europrene Sol R 72613) is dissolved in 90g toluene (99% anhydrous, Sigma Aldrich) by stirring at 21 °C for 12 hours. 6g of the 10wt% SBR (polymer binder) in toluene (solvent) is combined with 0.1g carbon black (Timcal Super P) (rheology modifier) and 16g of toluene and dispersed in a Thinky ARE 250 planetary mixer for 6 minutes at 2000 rpm.
• S-SBR Europrene Sol R 72613 10g of solution styrene butadiene rubber (S-SBR Europrene Sol R 72613) is dissolved in 90g toluene (99% anhydrous, Sigma Aldrich) by stirring at 21 °C for 12 hours. 6g of the 10wt% SBR (polymer binder) in tolu
• FIG. 1 is a plot showing the cycle performance for a pouch cell with printable lithium derived thin 20 micron lithium film as the anode vs. commercial 50 micron lithium foil.
• EPDM 135,000 molecular weight ethylene propylene diene terpolymer
• p-xylene 95,000 molecular weight ethylene propylene diene terpolymer
• 6g of the 10wt% EPDM (polymer binder) in p-xylene (solvent) is combined with 0.1g Ti02 (Evonik Industries) (rheology modifier) and 16g of toluene and dispersed in a Thinky ARE 250 planetary mixer for 6 minutes at 2000 rpm.
• printable lithium components must be selected to ensure chemical stability for long shelf life at room temperature and stability at elevated temperature for shorter durations such as during transport or during the drying process.
• the printable lithium composition stability was tested using calorimetry. 1.5g SLMP was added to a 10ml volume Hastelloy ARC bomb sample container. 2.4g of 4% SBR binder solution was added to the container. The container was fitted with a 24-ohm resistance heater and a thermocouple to monitor and control sample temperature. The bomb sample set-up was loaded into a 350ml containment vessel along with insulation. An Advance Reactive Screening Systems Tool calorimeter by Fauske Industries was used to assess the compatibility of the printable lithium solutions during a constant rate temperature ramp to 190°C.
• FIG. 1 shows the temperature and pressure profiles for the reactivity testing of a SLMP/styrene butadiene/toluene printable lithium composition.
• the quality of the printable lithium composition with regard to printability is measured by several factors, for example, consistency of flow which directly impact one’s ability to control lithium loading on a substrate or an electrode surface.
• An effective means of measuring flow is Flow Conductance which is an expression of the loading per square centimeter in relation to the factors which control the loading - the pressure during extrusion and the speed of the printer head. It can most simply be thought of as the inverse of flow resistance.
• the expression is used to allow comparisons between prints of varying pressures and speeds, and changes in Flow Conductance can alert one to non-linear relationships of flow with pressure. These are important for scaling the loading for a printable lithium up or down depending on the need of the anode or cathode. An ideal printable lithium composition would behave in a linear fashion to changes in extrusion pressure.
• a printable lithium composition is filtered through 180pm opening stainless steel mesh and loaded into a Nordson EFD 10ml syringe. The syringe is loaded into a Nordson EFD HP4x syringe dispenser and attached to a slot die print head.
• the slot die print head is equipped with a 100pm - 300pm thick shim with channel openings designed to deliver the desired printable lithium composition loading.
• the slot die head is mounted on a Loctite 300 Series robot.
• the print head speed is set to 200 mm/s and the printing pressure is between 20 and 200 psi argon, depending on shim and channel design.
• the print length is 14cm.
• the printable lithium composition was printed 30 times from a single syringe at dispenser settings ranging from 80psi to 200psi.
• the flow conductance average was 0.14 with standard deviation of 0.02.
• mAh loading of lithium can be controlled very consistently. For example, for a print of 0.275 lithium metal, the coefficient of variance is about 5%.
• the pre-lithiation effect of printable lithium composition can be evaluated by printing the required amount of printable lithium onto the surface of prefabricated electrodes.
• the pre- lithiation lithium amount is determined by testing the anode material in half-cell format and calculating the lithium required to compensate for the first cycle losses due to formation of SEI, or other side reactions.
• the capacity as lithium metal of the composition must be known and is approximately 3600mAh/g dry lithium basis for the compositions used as examples.
• the pre-lithiation effect is tested using Graphite-SiO/NCA pouch cells.
• the Graphite- SiO anode sheet has the following formulation: artificial graphite (90.06%) + SiO (4.74%) + carbon black (1.4%) + SBR/CMC (3.8%).
• the capacity loading of the electrode is 3.59 mAh/cm 2 with 87% first cycle CE (columbic efficiency).
• the printable lithium is applied onto a Graphite-SiO anode at 0.15 mg/cm 2 lithium metal.
• the electrode is dried at 80°C for 100 min followed by lamination at a roller gap approximately 75% of the thickness of the electrode. A 7 cm x 7 cm electrode is punched from the printable lithium treated anode sheet.
• the positive electrode has the following formulation: NCA (96%) + carbon black (2%) + PVdF (2%).
• the positive electrode is 6.8 cm x 6.8 cm with capacity loading of 3.37 mAh/cm 2 .
• the NCA cathode has 90% first cycle CE.
• the anode to cathode capacity ratio is 1.06 and the baseline for full cell first cycle CE is 77%.
• Single layer pouch cells are assembled and 1M LiPFe /EC+DEC (1 :1) is used as the electrolyte.
• the cells are pre-conditioned for 12 hours at 21°C and then the formation cycle is conducted at 40°C.
• the formation protocol is 0.1 C charge to 4.2V, constant voltage to 0.01 C and 0.1C discharge to 2.8V. In the described test 89% first cycle CE was demonstrated.
• the printable Li anode is tested in coin type all-solid state batteries.
• the printed lithium anode electrode in Example 3 is dried at 110 °C for 2 min in a dry room (RH ⁇ 1 % at 21 °C) and is cut into 12mm disks.
• This powder is then pressed into a solid electrolyte film using the same pressure (50,000 psi).
• the Li anode is then placed on top of a solid electrolyte film and pressed using a pressure of 25,000 psi.
• the all solid state battery is then tested in a pressure-controlled (up to 20 MPa) Split Coin cell (MTI Corp, part number : EQ-PSC) at 70°C at a current density of C/10 with cycling between 2.8 and 3.8 V.
• Fig. 4A shows the cycling voltage of the coin-type all solid-state battery with LFP cathode, LGPS solid electrolyte and printable Li as the anode.
• Fig 4A shows the all solid-state battery has the typical LFP charging voltage plateau of 3.5 V and discharge voltage plateau of about 3.4V.
• Figure 4B shows the charge capacity and discharge capacity versus cycle number for the all solid state batteries cycle at 70°C. The all solid-state batteries cycled well during the first 12 cycles.

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