Classifications

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  • 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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• • 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
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  • 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 solid-state battery which includes 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.
• secondary lithium batteries were produced using non-lithiated compounds having high specific capacities such as T1S2, 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. 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 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 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.
• 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 is 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
• 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 ink composition with a polymer or ceramic material to form a solid electrolyte.
• 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 a current collector, electrode or solid electrolyte by various methods, including extruding, coating, printing, painting, dipping, and spraying as disclosed in US Application No. _ (Attorney Matter ID 073396.1183, filed concurrently with this application 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 printable lithium composition may be used to prelithiate a solid electrolyte 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.
• 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, 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 IMA 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.
• the rheology modifier may also provide conductivity, improved capacity and/or improved
• 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 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 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. 3,721 ,113 and 6,232,014 which are incorporated herein by reference in their entireties.
• 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
• 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 assembly of the battery.
• the anode can comprise partially lithium-loaded silicon-based active material, in which the partially loaded active material has a selected degree of loading of lithium through intercalation/alloying or the like.
• 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 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 Mn0 2 , V 2 O 5, M0S 2 , metal fluorides or mixtures thereof, Sulphur and sulfur composites can be used as the active material.
• lithiated materials such as uMh 2 0 4 and L1MO 2 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 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. 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 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 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.

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