Classifications

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  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
  • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
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  • H01M4/381—Alkaline or alkaline earth metals elements
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  • 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
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  • B22F2301/00—Metallic composition of the powder or its coating
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  • B22F2301/054—Alkali metals, i.e. Li, Na, K, Rb, Cs, Fr
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  • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
  • B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
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  • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
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  • H01M6/40—Printed batteries, e.g. thin film batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a method for applying a printable lithium composition suitable for formation of electrodes suitable for use in a wide variety of energy storage devices, including batteries and capacitors.
• 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.
• secondary lithium batteries were produced using non-lithiated compounds having high specific capacities such as TiS2, M0S2, Mn02, and V 2 O 5 , as the cathode active materials. These cathode active materials were coupled with a lithium metal anode. When the secondary battery was discharged, lithium ions were transferred from the lithium metal anode to the cathode through the electrolyte. Unfortunately, upon cycling, the lithium metal developed dendrites that ultimately caused unsafe conditions in the battery. As a result, the production of these types of secondary batteries was stopped in the early 1990s in favor of lithium-ion batteries.
• Lithium-ion batteries typically use lithium metal oxides such as UC0O2 and LiNiC>2 as cathode active materials coupled with an active anode material such as a carbon-based material. It is recognized that there are other anode types based on silicon oxide, silicon particles and the like. In batteries utilizing carbon-based anode systems, the lithium dendrite formation on the anode is substantially avoided, thereby making the battery safer. However, the lithium, the amount of which determines the battery capacity, is totally supplied from the cathode. This limits the choice of cathode active materials because the active materials must contain removable lithium. Also, delithiated products corresponding to Li x CoC>2, Li x NiC>2 formed during charging and overcharging are not stable. In particular, these delithiated products tend to react with the electrolyte and generate heat, which raises safety concerns.
• 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. Patent 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 methods for depositing lithium on a substrate to form an electrode by applying a printable lithium composition to the substrate.
• the printable lithium composition may be applied by various means, including printing, extruding, spraying, and coating.
• the printable lithium composition of the present invention comprises a lithium metal powder, a polymer binder, wherein the polymer binder is compatible with the lithium powder, and a rheology modifier compatible with the lithium powder and the polymer binder.
• a solvent may be included in the printable lithium composition, wherein the solvent is compatible with the lithium powder and compatible with (e.g., able to form suspension or to dissolve in) the polymer binder.
• the solvent may be included as a component during the initial preparation of the printable lithium composition, or added later after the printable lithium composition is prepared.
• FIG. 1 is a schematic of one embodiment of a printable lithium composition coated onto a substrate
• FIG. 2 is a schematic of one embodiment of a printable lithium composition extruded onto a substrate
• FIG. 3 is a schematic of one embodiment of a printable lithium composition printed onto a substrate using a slot die
• FIG. 4 is a plan view of a printable lithium composition printed onto a substrate
• FIG. 5 is a temperature and pressure profile for the reactivity testing of SLMP/styrene butadiene/toluene printable lithium composition
• FIG. 6 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.
• compositions/methods may contain additional components so long as the additional
• composition/method 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 method for applying a printable lithium composition is provided.
• the printable lithium composition is
• the printable lithium composition comprises 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 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 battery may be comprised of liquid electrolytes.
• the battery may be comprised of solid electrolytes to form a solid-state battery.
• the printable lithium composition may be used applied or deposited to form a monolithic lithium metal anode for use in conventional and solid- state batteries.
• 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 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 applied to a substrate or a preformed anode by coating the substrate with a roller.
• a gravure coating device such as one described in US Patent No. 4,948,635 herein incorporated by reference in its entirety.
• a pair of spaced rollers 12, 12’ support the substrate 10 as it advances toward a gravure roller 14.
• a nozzle is utilized to apply the coating material to the gravure roller 14 while a doctor blade 16 is utilized to remove excess coating from the gravure roller 14.
• the gravure roller 14 contacts the substrate 10 as it travels through the gravure roller to apply the ink composition.
• the gravure roller can be designed to print various patterns on the surface of the substrate; for example, lines or dots.
• the printable lithium composition may be applied to a substrate by extruding the printable lithium composition onto the substrate from an extruder.
• an extruder is described in US Patent No. 5,318,600 herein incorporated by reference in its entirety.
• high pressure forces the printable lithium composition through an extrusion nozzle to coat the exposed surface area of the substrate.
• the ink composition 20 is contained within a container 22.
• a high pressure forces the ink composition 20 through an extrusion nozzle 24 to coat the exposed surface area of the substrate 10.
• One example of such an extruding apparatus may be mounted upon a suitable table and includes the hydraulic cylinder having a high pressure oil feed inlet and an oil outlet.
• the hydraulic cylinder typically contains a piston that drives the piston head into engagement with the upper end of the extrusion plunger 26.
• the printable lithium composition may be applied to a substrate by printing the printable lithium composition onto the substrate.
• Slot die print heads may be used to print monolithic, stripe or other patterns of the printable lithium composition onto the substrate.
• a compatible printer utilizing a slot die print head is described in US Patent No. 5,494,518 herein incorporated by reference in its entirety.
• a slot coating die typically comprises a slot coating die head 30 through which the ink composition 20 is extruded onto the substrate 10, as the substrate 10 is moved past the slot coating die head 30.
• Figure 4 illustrates one example of a slot coating wherein the ink composition 20 having a coating width C w and gaps between each strip designated as C G . Both C w and C G may vary depending on the configuration of the slot coating die head 30.
• a conventional carbon anode may be prelithiated by depositing the printable lithium composition on the carbon anode. This will obviate the problem associated with carbon anodes in which upon initial charging of the cell when lithium is intercalated into the carbon some irreversibility occurs due to some lithium and cell electrolyte being consumed resulting in an initial capacity loss.
• 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 may be incorporated within the anode as described in US Publication No. 2018/0269471 herein incorporated by reference in its entirety.
• the anode can comprise an active anode composition and the printable lithium composition, and any electrically conductive powder if present.
• the printable lithium composition is placed along the surface of the electrode.
• the anode can comprise an active layer with an active anode composition and a printable lithium composition source layer on the surface of active layer.
• the printable lithium composition source layer is between the active layer and a current collector.
• the anode can comprise printable lithium composition source layers on both surfaces of the active layer.
• 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.
• 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 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.
• Anodes prelithiated using the printable lithium composition may be incorporated into various types of batteries.
• the prelithiated anodes may be incorporated into batteries as disclosed in US Patent Nos. 7,851 ,083, 8,088,509, 8,133,612, 8,276,695, and 9,941 ,505, which are incorporated herein by reference in their entireties.
• Printing the printable lithium composition on an anode material may be an alternative to smearing lithium as disclosed in US Patent No. 7,906,233 incorporated herein 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,
• the printable lithium composition may be used to prelithiate a capacitor, such as an anode in a lithium-ion capacitor as described in US Publication No.
• the anode can be constructed using hard carbon, soft carbon or graphite.
• the anode may then be attached to a current collector before or during having a printable lithium composition layer coated on the top surface of the anode.
• the printable lithium composition may also be used to prelithiate an energy storage device such as a lithium-ion capacitor as described in US Patent No. 9,711 ,297 herein incorporated by reference in its entirety.
• the printable lithium composition may be used to prelithiate a hybrid battery/capacitor as described in US Publication No. 2018/0241079 herein incorporated by reference in its entirety.
• the term “hybrid electrode” refers to an electrode that includes both battery electrode materials and capacitor electrode materials.
• the hybrid cathode may comprise a blend of higher energy materials, such as battery cathode materials, and high power materials, such as capacitor cathode materials.
• lithium-ion battery cathode materials may be combined with ultracapacitor or supercapacitor cathode materials.
• the hybrid cathode may be disposed against an anode electrode with a polyolefin separator in between the electrodes and is placed in a confined packaging, such as an energy storage device container, e.g. housing.
• a suitable electrolyte such as a solvent containing a lithium-ion electrolyte salt and optionally including an electrolyte additive.
• the energy storage device package can be sealed.
• the anode used in combination with the hybridized cathode can comprise elemental metal, such as elemental lithium.
• a method for prelithiation is direct addition of the printable lithium composition to the electrode formulation.
• This printable lithium composition uniformly integrated into the electrode formulation can then be used to form an electrode film, in a dry process, which can then be laminated onto a current collector, such as a metal foil, to form the electrode, such as an anode.
• the printable lithium composition can be also applied to the current collector prior to the lamination with the dry electrode.
• Embodiments herein can allow for a homogenous, and in some embodiments, dry, and/or particulate material, to be used as a raw material in the anode and hybridized cathode.
• the pre-doped electrode is a hybrid cathode. It will be understood that the elemental metal and related concepts described herein with respect to an energy storage device with lithium may be implemented with other energy storage devices, and other metals.
• the printable lithium composition comprises a lithium metal powder, one or more polymer binders, one or more rheology modifiers and may further include a solvent or co-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.
• 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). 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, copper, 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, nickel, 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 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 carbon black, carbon nanotubes, graphene, silicon nanotubes, graphite, hard carbon and mixtures, fumed silica, titanium dioxide, zirconium dioxide and other Group 11 A, IIIA, IVB, VB and VIA elements/compounds and mixtures or blends thereof.
• electrochemical device electrolyte salts such as lithium perchlorate (UCIO4), lithium hexafluorophosphate (LiPFe), lithium nitrate (UNO3), lithium bis(oxalate) borate (LiBOB), and lithium
• LiTFSI trifluoromethanesulfonimide
• 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 crystalline 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 in accordance with the present invention can accommodate higher binder ratios, including up to 20 percent on 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 printing.
• the printable lithium composition comprises about 70% lithium metal powder and about 30% polymer binder and rheology modifiers.
• the printable lithium composition may comprise about 85% lithium metal powder and about 15% 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 can be achieved by designing compositions with very high zero shear viscosity in the range of 1 x 10 4 cps to 1 x 10 7 cps. It is however very important to the application process that the compositions, when exposed to shear, exhibit viscosity characteristics in the ranges claimed.
• the resulting printable lithium composition preferably may have a viscosity at 10s _1 about 20 to about 20,000 cps, and often a viscosity of about 100 to about 10,000 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 10 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.
• the printable lithium composition may be applied or deposited to prelithiate an anode or cathode of a solid-state battery.
• the printable lithium composition may be used to form a monolithic lithium metal anode for use in a solid-state battery, including solid-state batteries as described in US Patent Nos. 8,252,438 and 9,893,379 and incorporated herein by reference in their entireties.
• the printable lithium composition may be used to form or in conjunction with a solid electrolyte for use in a solid-state battery.
• the printable lithium composition 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 an active material layer 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 printable lithium composition into contact with a surface of the active material layer of the negative electrode; and thereafter combining the negative electrode with the positive electrode to form an electrode assembly.
• 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 LMP with printable lithium derived thin lithium film as the anode vs. commercial thin lithium foil.
• EPDM 135,000 molecular weight ethylene propylene diene terpoiymer
• p-xylene 95,000 molecular weight ethylene propylene diene terpoiymer
• 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. 5 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 CV 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 LiPF 6 /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.

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