WO2020041767A1 - Architectures de batterie hybride et à semi-conducteurs à charge élevée et leurs procédés de fabrication - Google Patents

Architectures de batterie hybride et à semi-conducteurs à charge élevée et leurs procédés de fabrication Download PDF

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WO2020041767A1
WO2020041767A1 PCT/US2019/048025 US2019048025W WO2020041767A1 WO 2020041767 A1 WO2020041767 A1 WO 2020041767A1 US 2019048025 W US2019048025 W US 2019048025W WO 2020041767 A1 WO2020041767 A1 WO 2020041767A1
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solid
state
electrolyte
electrochemically
hybrid
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PCT/US2019/048025
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English (en)
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John Chmiola
Lawrence A. RENNA
Vincent Giordani
Sean Barrett
Sam KEENE
Fabio Albano
Martin Welch
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Fisker Inc.
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Publication of WO2020041767A1 publication Critical patent/WO2020041767A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • 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
    • H01M2300/0071—Oxides
    • 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 bulk hybrid or solid-state batteries consisting of a plurality of composite electrodes with high loading of electrochemically- active materials into an ionically and/or electronically conducting solid-state or hybrid scaffold, a dendrite-blocking separator placed between the anode and the cathode, a secondary phase between the electrochemically-active materials to facilitate low interfacial impedance and the solid-state or hybrid electrolyte and methods thereof
  • the electric vehicle (EV) battery pack performs the same function as the gasoline tank in a conventional vehicle; it stores the energy needed to operate the vehicle.
  • Gasoline tanks can store the energy to drive the vehicle 300-500 miles before refilling; however, current generation batteries only offer capacities of 50-200 miles in affordable vehicles and up to a maximum of 335 miles in expensive large luxury vehicles. [0004] Thus, EVs require 30-40 kWh battery packs for a reasonable mileage range and must possess a long cycle life. This imposes practical needs for high energy density and cycle lifetime. United States Advanced Battery Consortium LLC (USABC) targets for
  • Lithium-ion batteries LIBs
  • Li-metal polymer batteries LMPBs
  • LIBs Li-metal polymer batteries
  • LMPBs Li-metal polymer batteries
  • LIBs are the most promising technology for the widespread use of EVs.
  • SEI solid-electrolyte interphase
  • Li metal anodes offer very high energy densities, 3860 mAh/g; however, safety and cyclability remain limitations that must be addressed for them to be deployed in any practical systems. In general, traditional LiBs are limited in energy density largely for 3 reasons.
  • Thickness of electroactive layers is limited to less than 100 pm due to low electrical conductivity cathode materials which results in a higher fraction of nonelectroactive materials in the cell.
  • Solvent oxidation and Aluminum current collector corrosion occur when using cathodes with electrochemical potentials higher than approximately 4.5V vs. Li/Li* electrochemical potentials substantially above (cathodes) or below (anodes) the standard hydrogen potential [Ma, T., 2017, J. Phys. Chem. Lett., 8, 5, 1072-1077].
  • thick electrodes are desirable because they result in higher energy density cells due to a lower fraction of electrochemically inactive materials required for the battery to function.
  • thick electrodes manufactured with traditional particulate slurry coating methods result in high resistance that limits the amount of power that a battery can output.
  • manufacturers have to design thin electrodes - limiting the coating thickness to below
  • the first also develops due to Li + gradients that develop within the electrolyte and can be minimized through increasing Li + concentrations greater than 1.0M, increasing ionic conductivity or a combination.
  • the underutilization of active materials in thick electrodes could be addressed by increasing solid-state diffusion in the active materials, improving electronic conductivity through the electrode thickness, reducing Li + gradients in the electrolyte phase.
  • thick electrodes >100 pm
  • standard powder processing methodologies have concerns with delamination from the current collector, electrochemically-active particles becoming loose and mobile within the cell, and lithium plating at the anode during charge at even moderate rates of C/10 [Singh, M., 2016, Batteries, 2, 35, 1 -11].
  • Lithium plating at the anode during charge would not be problematic if lithium plated smoothly, however Lithium tends to plate as long filaments even at low current densities which can grow across the cell and cause short circuiting [Xu, W., 2014, Energy & Environmental Science, 7, 513-537]. This short circuiting causes rapid discharge of the cell, excessive heating, and could cause thermal runaway and cell fires. Seminal work by Newman showed that if the electrolyte was a solid with sufficient stiffness, dendrite growth and propagation could be retarded, giving birth to a substantial body of work on solid-polymer electrolytes.
  • Solid-polymer batteries were introduced by Sony and Bellcore in the late 1990’s, but suffered a number of issues, with the predominant one being very high impedance to do the low conductivity polymer electrolytes being used. Operating at elevated temperature or adding a solvent to“gel" the polymer served to aid in reducing the cell impedance, allowing thicker active material layers, but increased safety concerns because of the reduced critical current density for dendrite growth and increased concerns with thermal runaway.
  • Solid-state Li-ion Batteries in which the organic liquid electrolyte is replaced by a ceramic electrolyte eliminate thermal management systems and allow use of lithium metal anodes, providing batteries with higher specific energy, as well as the ability to safely operate at higher temperatures.
  • Current limitations impeding the development of solid-state batteries are related to poor interfacial behavior of the solid-state electrolyte with the electrode materials.
  • The“solid-solid” interface leads to high interfacial resistance and poor charge transfer kinetics thus limiting the power output of the battery, with C- rates as low as C/100 at room temperature, which makes solid-state batteries non suitable for automotive application.
  • Engineering secondary phase electrolyte interfaces is therefore key to enabling the development of high power all solid-state and hybrid Li-ion batteries.
  • the solid-state or hybrid battery disclosed herein is directed to overcoming one or more of the problems set forth above and/or other problems of the prior art.
  • a solid-state or hybrid battery comprising: a cathode- side and an anode-side; at least one electrolyte; at least one active material; and at least one composite electrode located on the cathode-side or the anode side, or both, wherein the composite electrode comprises a three-dimensional porous scaffold that exhibits ionic conductivity, electronic conductivity, or both, wherein the three-dimensional porous scaffold, electrolyte and active material are configured to provide ion and electron conductivity that enables electrochemically-active material loadings in excess of 2.5 mAh/cm 2 .
  • the three-dimensional composite electrode which has ionic conductivity, electronic conductivity, or both consists of a plurality of ion-conducting regimes and electron-conducting regimes.
  • FIG. 1A shows a graph demonstrating the high ionic conductivity of two doped solid-state electrolyte samples prepared by casting and sintering at 1000 °C a c- LLZO nanoparticle slurry, according to the present disclosure, having a D50 average nanoparticle size of 400 nanometers (nm);
  • FIG. 1 B shows a charge-discharge curve of a solid state battery cell according to the present disclosure by infiltrating a nickel-manganese-cobalt (NMC) cathode material into a c-LLZO electrolyte scaffold and laminating a lithium metal anode onto it;
  • NMC nickel-manganese-cobalt
  • FIG. 2 shows one exemplary cylindrical cell monoblock and an enlarged view of the stack prepared using the solid-state electrolytes and arranged in a bipolar configuration according to the present disclosure and having a 14.8 Volt capacity;
  • FIG. 3A is a pie chart showing the relative distribution (in mass) of materials comprising a typical Li ion battery;
  • FIG. 3B is a pie chart showing the relative distribution (in mass) of materials comprising a Li-ion battery produced according to the present disclosure
  • FIG. 4 is cross-sectional representation of the architecture of a unit cell of the solid-state battery according to the present disclosure
  • FIG. 5 is a flow diagram showing an inventive process used in cell assembly of the batteries according to the present disclosure
  • FIG. 6 is an inventive device used to insert materials into the three- dimensional porous scaffolds described in the present disclosure
  • FIGS. 7A and 7B show comparisons between two liquid electrolyte formulations tested in symmetric Li-Li cell using a plastic separator.
  • FIG. 8 is a Scanning Electron Microscope (SEM) image of a three- dimensional porous scaffold and dendrite-blocking separator, both produced from LLZO according to the present disclosure
  • FIG. 9 is a graph showing potential (V) versus cell areal capacity (mAh/cm 2 ) for a hybrid pouch cell according to the present disclosure
  • FIG. 10 is a graph comparing two catholyte binder systems for a hybrid solid-state battery showing reduced interfacial resistance (consistent with enhanced electrode kinetics) measured by complex electrochemical impedance spectroscopy;
  • FIG. 11 is a schematic representation of a planarization jig used to produce three-dimensional composite scaffolds of precise thickness;
  • FIG. 12A is a complex electrochemical impedance spectroscopy (EIS) spectrum of the PEO separator obtained using a SS/PEO/SS blocking electrode conductivity cell at room temperature.
  • EIS electrochemical impedance spectroscopy
  • FIG. 12B displays the calculated room temperature Li + ionic conductivity of thin PEO separators as a function of EO to Li + molar ratio
  • FIG. 13 displays a chronoamperogram recorded at an aluminum foil working electrode using a liquid electrolyte made of LiFSI and Sulfolane.
  • the chronoamperogram demonstrates high anodic stability of the electrolyte up to 4.6 V vs Li + /Li°;
  • FIG. 14 is a schematic representation of carbon deposited inside of the pores of the three-dimensional composite scaffold
  • FIG. 15A is a SEM micrograph of a carbon-coated c-LLZO bilayer showing a thin layer of conducting amorphous carbon deposited on the surface and within the pores of the porous c-LLZO scaffold;
  • FIG. 15B is an elemental mapping of carbon using energy dispersive X-ray spectroscopy on Hie c-LLZO bilayer showing successful carbon deposition
  • FIG. 15C is a photograph of an as-prepared c-LLZO bilayer following calcination and containing a carbon coating within the porous scaffold;
  • FIG. 16 is an SEM micrograph of an of a microscopically-ordered porous ionically-conductive c-LLZO scaffold in contact with electrochemically-active LiNio.6MnO.2Coo.2O2.
  • the dashed line highlights the interface between the ceramic electrolyte and the cathode active material;
  • FIG. 17 is a schematic representation of a heated uniaxial press to attach current collectors with a conductive thermoplastic adhesive
  • FIG. 18 is a bar graph showing the through-plane resistance of various inventive thermoplastic electronically conductive current collectors
  • FIG. 19 shows a schematic of a composite hybrid solid-state cell using adhesive current collector
  • FIG. 20 displays a cell voltage profile as function of areal capacity (mAh/cm 2 ) for a hybrid solid-state battery using a conductive binder within the cathode- infiltrated c-LLZO porous scaffold.
  • the term“Anolyte” is intended to mean that portion of the electrolyte in the immediate vicinity of the electrode with lower electrochemical potential in an electrochemical cell including a battery cell, opposite to the electrode with higher electrochemical potential.
  • the term“Catholyte” is intended to mean that portion of the electrolyte in the immediate vicinity of the electrode with higher electrochemical potential in an electrochemical cell including a battery cell, opposite to the electrode with lower electrochemical potential.
  • the term“Electrolyte” is intended to mean a solid, liquid, or gel that contains mobile ions.
  • Solid electrolyte is intended to mean a solid material (as opposed to a liquid or gel) that contains mobile ions.
  • a solid-state battery typically encompasses battery technology that uses solid electrodes and a solid electrolyte, instead of liquid or gel electrolytes.
  • Bulk Density is intended to mean, the mass of a divided solid, such as powders or particles, divided by the total volume they occupy.
  • the total volume includes particle volume, inter-particle void volume, and internal pore volume.
  • Bulk density can also be referred to as apparent density or volumetric density.
  • the term“Dendrites” is intended to mean branching crystals that grow from an electroplated surface when the current passed is above the threshold where the reaction rate is governed purely by electrode kinetics.
  • the term“Slurry” is intended to mean a mixture of solids suspended and/or dissolved in a liquid.
  • solute is intended to mean a liquid mixture comprising a minor component (the solute) that is uniformly distributed within a major component (the solvent).
  • Dispossion is intended to mean the act of separating solids homogenously into a liquid.
  • Low-energy ball milling is intended to mean a process whereby milling media is added to a slurry or solution, and the plurality is agitated by rotating around one or more axes but at a speed not sufficient to reduce the particle size of the solids or cause any chemical or mechanical distortion
  • the term“High-energy ball milling” is intended to mean a process whereby milling media is added to a slurry or solution, and the plurality is agitated by rotating around one or more axes at a speed sufficient to reduce the particle size of the solids and/or cause chemical or mechanical distortion.
  • a“Hybrid Electrode” is intended to mean a plurality of a solid-electrolyte scaffold and electrochemically-active material.
  • Shear mixing is intended to mean dispersing or transporting one phase or ingredient into a main (and typically immiscible) continuous phase by causing one area of fluid to travel at a different velocity relative to an adjacent area.
  • LLZO is intended to mean the cubic garnet-type structure LiyLaaZraO ⁇ .
  • Emboss is intended to mean putting patterns, typically raised patterns, on a material, such as fabric, by passing it through rollers with patterns.
  • Pore-former is intended to mean a material used to fabricate a material with controlled or defined porosity, such as with distinct features including pore size, distribution and/or morphology.
  • the term “Current collectors” is intended to mean the component of a battery that delivers electrons from to and from the electroactive materials
  • the term“Wetting” is intended to mean the ability of a liquid to penetrate into and maintain contact with a porous surface.
  • Hybrid Electrode is intended to mean an electrode containing a plurality of at least two of the following, solid electrolytes, gel electrolytes, and liquid electrolytes.
  • a solid-state or hybrid Li-ion battery comprising a ceramic, solid-state electrolyte having a lithium-conducting oxide composition selected from the group consisting of perovskite-type oxides, NASICON-structured lithium electrolytes, and garnet-type structures containing transition metal oxides and the manufacturing methods to make them.
  • NASICON generally refers to sodium super ionic conductors.
  • a perovskite is any material with the same type of crystal structure as calcium titanium oxide (CaTi03). They have the general chemical formula of ABX3, wherein A and B are cations having very different sizes from each other and X is an anion that binds to both A and B.
  • NASICON generally refers to sodium super ionic conductors.
  • a perovskite is any material with the same type of crystal structure as calcium titanium oxide (CaTIOa). They have the general chemical formula of ABXa, wherein A and B are cations having very different sizes from each other and X is an anion that binds to both A and B.
  • the garnet-type structures containing transition metal oxides comprise .
  • M a transition metal.
  • the garnet-type structures containing transition metal oxides comprise amorphous UPON or LiSi-CON.
  • the garnet-type structures containing transition metal oxides comprise lithium ion-conducting sulfides selected from the group consisting of glass, glass, Li 2 S-SiS 2 glass, 2 glass,
  • the precursor ceramic nanoparticle powder has a composition with a general formula ABO a with“A” representing an alkaline or rare earth metal ion and“B" representing a transition metal ion, e.g. (perovskite).
  • the precursor nanoparticle compounds have a general formula of AM2(P04>3 where“A” represents an alkali metal ion and
  • M represents a tetravalent metal ion
  • the precursor nanoparticle compounds have a general formula where“A” represents an eight coordination cation and“B”
  • the solid-state electrolyte may be a metal substituted c-LLZO with a general formula of (garnet), wherein the
  • metal M is selected from the group but not limited to Al, Ga, Ta, W, and elements in group
  • x can be a whole number or any fraction thereof.
  • the solid-state electrolyte may be a metal substituted o-LLZO with a general formula of 2 (garnet), wherein the
  • metal M is selected from the group but not limited to Sc, Y, Ti, or another transition meta
  • the precursor materials are crystalline or amorphous nanoparticles of solid sulfide-based electrolytes, such as those of the Li 2 S-SiS system or those having compositions of the format
  • x is a number between 0 and 1.
  • the anode, cathode or electrolyte material can be formed into a film and the films can include a thin-film coating interfacial layer applied to their surface before or after sintering and interfacing one or all of the individual layers.
  • This facilitates lithium ionic mobility between layers and reduces or prevents layer-to-layer contact resistance, a hindrance that typically plagues solid state lithium batteries.
  • an interfacial layer may prevent anode, cathode and electrolyte material interdiffusion and promote adhesion between layers of dissimilar composition, crystal structure and mechanical properties.
  • Suitable materials for such a buffer layer may be selected from, without limitation, compounds from the group including and
  • the thin-film coating interfacial layer applied to anode, cathode or electrolyte layers consists of a polymeric material or a polymer electrolyte material based on a material selected from the group consisting of polyethylene oxide (PEO), poly(vinyl alcohol) (PVA), aramids, and polyaramid polyparaphenylene terephthalamide.
  • any of the solid-state electrolyte precursor nanoparticles or the sintered film, the cathode precursor nanoparticles or the sintered film, and the anode precursor nanoparticles or the sintered film may be infiltrated or pre-coated with, respectively, an intermediate phase between the electrolyte and a secondary or tertiary compound, a catholyte, or an anolyte selected from, without limitation, the group consisting of Li, Li 2 0, lithium
  • LiPON phosphorous oxy-nitride
  • LaTi0 3 LaTi0 3
  • the electrolyte film prepared according to the present disclosure includes a polymer coating applied after sintering and before anode or cathode layers are bonded to the electrolyte or the electrolyte scaffold.
  • Li is melt-infiltrated or electrodeposited into the solid-state electrolyte prepared according to the present disclosure.
  • Further embodiments comprise a composite electrolyte film with lithium infiltrated between the composite grains or as an intermediate electrolyte phase acting as an anolyte or a catholyte infiltrated in between the composite grains or the active material grains, e.g. in the cathode.
  • Such an intermediate electrolyte phase comprises at least two components resulting from the reaction of the lithium or the cathode materials with the electrolyte forming a binary or tertiary intermediate phase.
  • a lithium or lithium alloy ribbon, foil or other suitable metallic film form is laminated onto the electrolyte layer to form the anode.
  • an intermediate layer interposed made of, but not limited to, compounds from the group including
  • the thin-film intermediate layer consists of a polymeric material or a polymer electrolyte material based on a material selected from the group consisting of PEO, PVA, aramids, and polyaramid polyparaphenylene terephthalamide.
  • the solid-state electrolyte may be a metal substituted c-LLZO with a general formula of (garnet), wherein the metal M is
  • x has a value of from 0 to 3.
  • the solid-state electrolyte may be a metal substituted c-LLZO with a general formula of (garnet), wherein the metal M is
  • x has a value of from 0 to 2.
  • the battery designed according to the present disclosure may be a 12V (nominal voltage) LIB made with such electrolytes, wherein the electrolytes are made using scalable casting and sintering methods based on metal-oxide nanoparticle powders.
  • the solid-state electrolyte membranes e.g. ⁇ 30pm thick
  • the solid-state electrolyte membranes may be fabricated using nanoparticle powders that have sizes ranging from 20-900 nanometers synthesized by flame-spray pyrolysis, co-precipitation or other solid-state or wet chemistry nanoparticle (“NPs”) fabrication routes.
  • Nanoparticles that can be used for the invention can be synthesized by any of a variety of methods including, without limitation, plasma spray, ultrasonic assist spray synthesis, fluidized bed reaction, atomic layer deposition (ALD) assisted synthesis, direct laser writing (DLW), chemical vapor deposition (CVD), low pressure chemical vapor deposition (LPCVD), microwave plasma enhanced chemical vapor deposition
  • NPECVD pulsed laser deposition
  • PLD pulsed laser deposition
  • PVD physical vapor deposition
  • gas phase decomposition detonation
  • flame spray pyrolysis co-precipitation
  • sol-gel synthesis sol- gel dipping, spinning or sintering.
  • they preferably have an average particle size of from 20 to 900 nm, more preferably from 200 to 600 nm.
  • nanoparticles that can be used for preparing the solid-state electrolytes according to the present disclosure in certain embodiments can be coated, treated at the surface or throughout the bulk or in any open porosity by one or multiple layers of solid electrolyte materials or intermediate phases between solid electrolyte and anode or cathode active materials, e.g.
  • a catholyte or anolyte suitable compound using one or more sequential deposition processes selected from, without limitation, plasma treatment, ultrasonic assist spray, fluidized bed reaction, atomic layer deposition (ALD), direct laser writing (DLW), chemical vapor deposition (CVD), low pressure chemical vapor deposition (LPCVD), microwave plasma enhanced chemical vapor deposition (NPECVD), pulsed laser deposition (PLD), physical vapor deposition (PVD), gas phase decomposition, detonation, flame spray pyrolysis, co-precipitation, sol-gel synthesis, sol-gel dipping, spinning or sintering, sputtering, radio frequency magnetron sputtering, nanoimprint, ion implantation, laser ablation, spray deposition.
  • sequential deposition processes selected from, without limitation, plasma treatment, ultrasonic assist spray, fluidized bed reaction, atomic layer deposition (ALD), direct laser writing (DLW), chemical vapor deposition (CVD), low pressure chemical vapor deposition (LPCVD
  • nanoparticles having a spherical aspect ratio and bell-shaped size distributions that improve the packing density of the green films formed and result in lower sintering temperatures with final film densities above 95% for incorporation into a LIB design.
  • Suitable precursor nanoparticle materials include, for instance, ionic conductors with garnet, olivine, perovskite, or NASICON crystal structures, or sulfide or phosphate based glasses and having enhanced ionic conductivities, e.g. c-LLZO or lithium phosphate as described herein.
  • the precursor ceramic nanoparticle powder has a composition with a general formula ABOa with“A” representing an alkaline or rare earth metal ion and ⁇ " representing a transition metal ion, e.g. with a perovskite
  • the precursor compounds have a general formula of AM 2 (P0 4 ) 3 where“A” represents an alkali metal ion (Li*, Na*, K*) and“M” represents a tetravalent metal ion (NASICON structured
  • the precursor compounds have a general formula where“A” represents an eight coordination cation and ⁇ ” represents a six
  • coordination cation e.g. a garnet type structure including a transition metal oxide. Ionic conductivity of these materials could be further enhanced by substitution of
  • the precursor materials are crystalline or amorphous nanoparticles of solid sulfide-based electrolytes, such as those of the LfeS- SiS system or those having compositions of the format Li4_ x Ge.,_ x P x S 4 where x has a value between 0 and 1.
  • the batteries produced using the approaches disclosed in the present invention will have superior performance to any of the existing lithium ion or other battery chemistries.
  • the batteries produced with the methods disclosed herein will have gravimetric energy density between 350 and 650 Wh/kg and will also have volumetric energy density between 750 and 1 ,200 Wh/L.
  • the anode, cathode or electrolyte films may include a thin-film coating interface layer applied to their surface before or after sintering and interfacing one or all of the individual layers. This facilitates Lithium ionic mobility between layers and reduces or prevents layer-to-layer contact resistance, a hindrance that typically plagues solid-state
  • Such an interface layer may prevent anode, cathode and electrolyte materials interdiffusion and promote adhesion between layers of dissimilar composition, crystal structure and mechanical properties.
  • Suitable materials for such a interface layer may be selected from, without limitation, compounds from the group including
  • the solid-state electrolyte includes a lithium phosphorous oxy-nitride (“LiPON”) coating applied to the surface of the films pre-sintering or, alternatively, after sintering and before calendering.
  • LiPON lithium phosphorous oxy-nitride
  • the present invention also comprehends several avenues to improve c-
  • LLZO films to enable Li cycling without shorting, to generate solid ion conductors that can prevent dendrite growth, self-discharge, and to promote safety, power and cycle life.
  • Hybrid solid-state ion conductors e.g. newly-developed c-LLZO combined with high energy density cathodes and Li anodes according to the present disclosure represent innovations that remove the tradeoffs between energy and cycle life.
  • Novel, composite c-Li7La 3 Zr20 12 ion-conducting solid-state films made by freeze-casting and low-pressure-sintering of nanoparticles according to the present disclosure can overcome most of the existing technical gaps in solid-state electrolytes and can attain ionic conductivities comparable to liquid electrolytes see FIG. 1 A.
  • freeze cast films sintered according to the present invention show significant conductivity even at temperatures below 0 °C and even below -30 °C.
  • the A-substituted film was formed from LiyLaa-xMxZraOi? wherein M was aluminum; the B-substituted film was formed using gallium as the metal.
  • These materials prepared according to the present disclosure are uniform, thin £ 30 pm, 95+% dense with Li+ conductivity comparable to traditional ICMs with liquid electrolytes.
  • the slope of the curves is constant and linear, prior art systems demonstrate a hockey stick shaped curve wherein the conductivity at temperatures of 0 °C or lower are equal to nearly 0.
  • solid-state electrolyte materials well- known in the field of thin-film batteries, are costly, produced through unscalable techniques and difficult to integrate in existing battery systems.
  • FIG. 1 B demonstrates the benefits of solid-state ionic conductors according to the present disclosure like the ones reported in FIG. 1 A when integrated into a full solid-state battery cell system constructed using freeze casting methods outlined in the present invention.
  • the cell was constructed by infiltrating a nickel-manganese-cobalt (NMC) cathode material into an LLZO scaffold and laminating a lithium metal anode onto it.
  • NMC nickel-manganese-cobalt
  • FIG. 2 shows one exemplary cylindrical cell monoblock and an enlarged view of the stack prepared using the solid-state electrolytes according to the present disclosure and having a 14.8Volt voltage.
  • the cathode can be formed from a nickel- manganese-cobalt (NMC) compound, LNMO, LIS and other known materials.
  • the solid- state electrolyte such as a c-LLZO is shown located between the cathode and the anode.
  • the cell monoblock consists of four 3.7 V cells situated in series.
  • the stack is jelly rolled to form the cylindrical cell as shown.
  • the present invention comprehends fabricating electrolyte/anode composite layers as an alternative approach to increase interfacial areas in order to reduce the interfacial resistance on the cathode side.
  • the present invention comprehends several avenues to either mechanically block Li dendrites or maximize distribution of the Li+ current by increasing Li/electrolyte interfacial areas to enhance tolerable current densities with a target performance >2.5 mA/cm 2 at ambient temperature.
  • cathode layer is only several tens of pm thick, limiting the attainable energy density.
  • thicker (several hundreds of pm) cathode layers are required.
  • the present invention comprehends cathode/electrolyte or anode/electrolyte composite layers formed by infiltrating cathode or anode active materials into the solid-state electrolyte scaffolds to maximize the utilization of the active materials (cathode and anode) and to accelerate the ionic and electronic conductance on charge/discharge. See FIG. 4, FIG. 14 and FIG. 19 which show schematic figures of such structures.
  • the present invention comprehends: purchasing from commercial suppliers nanoparticles of c-LLZO or other solid-state electrolytes and cathode materials, with
  • NMC532 6:2:2 (NMC622), and 8:1 :1 (NMC81 1 ) cathode NPs or using one of the described high-throughput methods to synthesizing these NPs materials at rates higher than 100 g/h.
  • LiPON and LiBO x for these fabricated layers.
  • Such all-solid-state LIBs as disclosed hereinabove eliminate thermal management systems and allow use of Li-metal anodes, providing batteries with higher volumetric/gravimetric energy densities, as well as the ability to safely operate at higher temperatures with faster charge/discharge rates that enable further flexibility in LIB designs.
  • composite cathodes having at least one unique chemical, mechanical or physical make-up.
  • the solid-state or hybrid battery electrode disclosed herein has a thickness that is substantially greater than the current state of the art slurry-cast electrodes.
  • the methods described herein are effective at producing composite electrode thicknesses of >100 pm.
  • electrodes with thicknesses in the range of 200-500 pm which provides a good balance between energy and power.
  • the present invention also describes methods that enable electrode loadings in excess of 2.5 mAh/cm2 as shown in FIG. 9, in some cases greater than 5 mAh/cm2 and even in excess of 8 mAh/cm2.
  • the maximization of porosity of the three-dimensional solid- state or hybrid scaffold is desired and is accompanied with the minimization of the interparticle porosity of the cathode.
  • the reason for this is to minimize the fraction of non- electrochemically active materials, with the inter-particle porosity of the cathode becoming filled with non-electrochemically active liquid in the realized hybrid device.
  • the solid-state or hybrid cell disclosed herein describes steps to obtain a three-dimensional solid-state or hybrid electrolyte scaffold ceramic electrolyte with porosity in excess of 30% that houses electrochemically active materials with a porosity of less than 30%.
  • the three-dimensional solid-state or hybrid electrolyte scaffold has a porosity of greater than 60% and more typically 85% and the electrochemically active materials that are housed within it have a porosity less than 30% and more typically 15-
  • a number of conductive additives can be used to enhance the electrical conductivity of the composite electrodes disclosed within, as depicted in FIG. 10 and in FIG. 20.
  • the requirements for selection of conductive additives include but are not limited to: 1 ) electrochemical compatibility, 2) chemical compatibility,
  • materials from the carbon family are chosen to meet the foregoing properties. These include but are not limited to carbons from the families of carbon black, vapor-grown nanofibers, graphite, mesocarbon microbeads (MCMB), nanocrystalline graphite, single-wall carbon nanotubes, double-wall carbon nanotubes, multi-wall carbon nanotubes, carbon fullerenes, carbon nanodiamond, polymers from the families including but not limited to polyaniline, polypyrrole, polyacetylene, polythiophene, poly(3,4-ethylenedioxythiophene), poly(p-phenyl sulfide), poly(p-phenylene vinylene) and a number of conductive metal oxides including but not limited to WO3, Re02, Ru02, Ir02,
  • the conductive polymer can be polymerized within the porous network of the composite electrode.
  • aniline can be electrochemically oxidized in-situ to polyaniline inside of the porous structure of the composite cathode structure.
  • conductive polymers such as polythiophene, or polypyrrole which can be electrochemically or chemically oxidized to their conductive polymeric forms.
  • conductive polymers can be polymerized in-situ during operation of the battery through proper selection of liquid electrolyte additives.
  • An additional embodiment of the present disclosure is the use of polymers with both ionically conductive and electronically conductive domains.
  • One particular embodiment of the present invention is the use of poly-4-vinylpyridine (P4VP) polymers as binders in the cathode material slurry.
  • P4VP is a polymer of interest due to its high electrical conductivity, though it suffers from low thermal and mechanical stability.
  • electronic conductivity can be added to the composite electrodes, which for the sake of this disclosure can be described as the plurality of the three-dimensional solid-state or hybrid scaffold, the electrochemically- active electrode material, and any additional binders, and ionically and/or electronically conductive additives or coatings by using a conductive coating within the scaffold porosity.
  • electrical conductivity can be added to porous Al- doped LLZO by depositing carbon on the surface.
  • a dilute solution of sucrose, an organic compound, typically in the range of 1 wt.% to 20 wt.% and more typically 5 wt.%, is produced in a solvent, then introduced into the pores of the three-dimensional solid-state or hybrid scaffold.
  • This can be accomplished by any number of techniques, with the simplest being the use of a pipette or similar.
  • the solution is then evaporated by heating at a temperature in the range of 50°C to 100°C to produce a coating of the organic compound, in this case sucrose, on the surface of the pore walls of the three-dimensional solid-state or hybrid scaffold.
  • FIG. 15A shows a SEM micrograph of one particular example of this embodiment.
  • 15B shows an elemental mapping of carbon using energy dispersive X-ray spectroscopy on the c-LLZO bilayer showing successful carbon deposition.
  • a hydrocarbon gas is introduced into an environment that contains the three-dimensional solid-state or hybrid scaffold at a temperature above the temperature where the hydrocarbon gas is thermodynamically stable. In general, these temperatures are greater than 400°C.
  • Numerous materials disclosed herein that comprise the three-dimensional solid-state or hybrid scaffold are catalytic to growing low dimensionality (zero-dimensional, one-dimensional and/or two- dimensional) carbon nanostructures at a temperature in the range of 500°C to 900°C.
  • An additional and exemplary embodiment of this disclosure is the purposeful inclusion of carbonization catalysts that both encourage the growth of highly conductive and low dimensionality carbon nanostructures and become incorporated into the crystal lattice on the lithium site of LLZO, which reduces the effects of high temperature lithium loss and encourages the stabilization of the cubic phase of LLZO.
  • One choice for this would be iron.
  • 2.5% acetylene in 97.5% argon when used as the precursor gas with iron oxide nanoparticles with diameter in the range of 1 nm to 100 nm, such as 5 nm at a temperature of 600°C results in a structure with facile electron and ion transport.
  • carbon-forming polymers such as polyacrylonitrile
  • PAN poly(1 ,3-diethnylbenzene)
  • PAB poly(1 ,3-diethnylbenzene)
  • the polyacrylonitrile is then slowly heated to 400°C to carbonize the polyacrylonitrile.
  • the polyacrylonitrile can be further graphitized to increase the electronic conductivity by heating to temperatures of approximately 1000°C.
  • iron can be advantageously added to reduce the temperature at which carbon graphitizes or becomes low dimensional structures in the form of iron oxide nanoparticles, or, in the case of polyacrylonitrile, a metal organic compound containing iron such as ferrocene.
  • a solid and fully-dense separator of LLZO with a thickness in the range of 1 pm to 100 pm, such as 15 pm is thermally sintered to a porous LLZO film with a thickness in the range of 50 pm to 1 ,000 pm, such as 300 pm to 500 pm and porosity in the range of 50% to 95%.
  • Further embodiments include the removal any carbon that becomes deposited on the dense LLZO separator to prevent electrical shorting of the positive electrochemically active material to the negative electrochemically active material. This is achieved through a number of methods, though the most exemplary methods disclosed here include but are not limited to using pulsed laser ablation, mechanical ablation, sanding, lapping, polishing, sandblasting, use of a water jet or combinations thereof.
  • the manufacture of a high-quality slurry from electrochemically-active materials is essential to delivering high performance.
  • These slurries are similar to traditional but state of the art lithium ion battery slurries in that they contain a plurality of active material, binder, conductive additive and other additives that provide functionality in some solvent.
  • the identity of the solvent, ratio of the constituent parts and addition of alternative additives is novel, however.
  • the active material slurry contains 60-95 wt.% electrochemically active material, 1-20 wt.% conductive additive, 1-20 wt.% binder and a solvent with solids loading in the range of 5% to 40%.
  • the slurry comprises the one or more electrochemically-active materials, selected depending on the balance of energy, power, lifetime, cost or other considerations desired, the solvent or mixtures of solvent, the binder or combination of binders, the conductive additives, as well in some embodiments solids state, polymer, liquid, or gel electrolyte components.
  • the total solids loadings of is typically greater than about 55% and less than about 70% and more typically the total solids loadings are from about 10% to about 40%.
  • the slurry suspension has a nanopowder concentration greater than or equal to about 1 vol% to less than or equal to about 70 vol.% and that nanopowder can be a plurality of but not limited to solid electrolyte powder, electrochemically active materials, inorganic fillers, or combinations thereof
  • Exemplary solvents consist of dimethylformamide (DMF), n-methyl-pyrrolidone (NMP), cyclohexyl-2-pyrrolidone (CHP), chloroform, toluene, aniline, dimethyl acetamide
  • DMF dimethylformamide
  • NMP n-methyl-pyrrolidone
  • CHP cyclohexyl-2-pyrrolidone
  • chloroform toluene
  • aniline dimethyl acetamide
  • an embodiment provides at least one solvent containing conjugated carbon ring structures and amine functionality.
  • electrochemically- active materials can be used as the three-dimensional ionically and/or electronically conductive scaffold that can be subsequently used as-is with a liquid-, polymer-, gel-, or solid-electrolyte, or have further functionality added such as enhanced conductivity as described elsewhere herein.
  • the methods described elsewhere for producing the three-dimensional ionically and/or electronically conductive hybrid or solid- state scaffold can be utilized.
  • a further step of sintering could be used to improve the inter particle connection in such a three-dimensional and electrochemically active scaffold, though this technique is not necessarily compatible with all electrochemically-active electrode materials.
  • binders of the family including but not limited to poly(ethylene oxide) poly(vinylidene fluoride), styrene-co-butadiene, and poly(ethylene carbonate), would enable the 3-dimensional electrochemically-active scaffold to be used without sintering, enabling a host of other electrochemically-active cathode materials.
  • the last method disclosed could also involve casting directly onto the current collector.
  • a cathode slurry containing a material of the olivine or sulfide family, an anode of the titanate family and a suitable solid-state electrolyte, hybrid-electrolyte, polymer-electrolyte, gel electrolyte, or combinations thereof can be used in conjunction with the three-dimensional ionically and/or electronically conductive solid-state or hybrid scaffold.
  • a cathode slurry containing a material of the NMC family, a lithium metal anode and a suitable electrolyte can be used in conjunction with the three-dimensional ionically and/or electronically conductive solid-state or hybrid scaffold. If high operation temperatures are desired, utilizing lithium iron phosphate in the cathode, lithium titanate in the anode and a solid polymer electrolyte consisting of polyethylene oxide with a salt of the family lithium bis(fluorosulfonyl)imide can be successfully used.
  • additional cathode materials can be considered, including but not limited to the lithium- containing oxides of lithium cobalt oxide, lithium manganese oxide, lithium nickel oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium nickel manganese oxide, lithium titanium oxide, the lithium-containing silicates including but not limited to lithium iron silicate, the lithium-containing phosphates including but not limited to lithium iron phosphate, lithium cobalt phosphate, combinations thereof.
  • additional anode materials can be considered, including but not limited to graphite, silicon, tin, antimony, magnesium, aluminum, and combinations thereof.
  • the three-dimensional ionically and/or electronically conductive solid-electrolyte or hybrid scaffold is a gel.
  • the three-dimensional ionically and/or electronically conductive solid state or hybrid scaffold is purposefully designed to be a different state of matter under different fabrication temperatures and pressures and operational temperatures and pressures.
  • the three-dimensional structure of the three-dimensional ionically and/or electronically conductive solid state or hybrid scaffold is characterized by a thickness of no less than about 50 pm and no greater than about
  • the pores of the three-dimensional ionically and/or electronically conductive solid state or hybrid scaffold have an acicular or elliptical structure with a long axis of 10 pm - 1000 pm and a short axis of 1 pm to 20 pm.
  • the ionically conductive materials selected for the three-dimensional ionically and/or electronically conductive solid-state or hybrid scaffold can come from the class of solid ceramic electrolyte materials, either used individually or in combination, of but not limited to garnet materials, perovskites, anti-perovskites, lithium-containing halide materials, LISICON-type structures, argyondite materials, and combinations thereof.
  • the ionically conductive ceramic material selected for the three-dimensional ionically and/orelectronically conductive solid-state or hybrid scaffold comes from the class of lithium garnets (LLZO) with the chemical formula Li7La3Zr2012.
  • the ionically conductive ceramic material selected for the three-dimensional ionically and/or electronically conductive solid-state or hybrid electrolyte scaffold come from the class of doped lithium garnets with the chemical formula Li7-2xAxLa3Zr2012.
  • A is a metal that can substitute for Li in the structure and x > 0.05 and can be selected from but not limited to AI3+, Ga3+, Be2+, Fe3+, Br3+, B3+, Zn2+, or combinations thereof.
  • the ionically conductive ceramic material selected for the three-dimensional ionically and/or electronically conductive solid-state or hybrid electrolyte scaffold come from the class of doped lithium garnets with the chemical formula Li7-xBxLa3Zr2-x012.
  • B is a metal that can substitute for Zr in the cubic structure and x > 0.05 and can be selected from but not limited to T
  • the ionically conductive ceramic material selected for the three-dimensional ionically and/or electronically conductive solid-state or hybrid electrolyte scaffold come from the class of doped lithium garnets with the chemical formula Li7-xBxLa3Zr2-x012.
  • B is a metal that can substitute for Zr in the cubic structure and x > 0.05 and can be selected from but not limited to or combinations thereof.
  • transition metals are generally not suitable for electrolytes because they can be reduced against a lithium anode.
  • 3d transition metals are particularly interesting because of their low molar mass.
  • a physical barrier that is nonconductive to electrons but highly conductive to Li+ can be inserted between the anode active material and the transition metal-doped LLZO.
  • AI3+ can be reduced at the lithium anode and therefore is governed by the same concerns.
  • the three dimensional ionically and/or electronically conductive solid-state or hybrid scaffold that is comprised of metal-doped LLZO is separated from the anode active material using undoped LLZO, or LLZO doped with dopants having a greater affinity for the LLZO lattice than their base metal form.
  • this separation can be created in-situ during operation of the battery.
  • the undoped and/or cation-doped LLZO selected to form the three dimensional ionically and/or electronically conductive solid-state or hybrid scaffold can be isolated from the anode active material by using a porous polymer separator impregnated with a liquid containing Li+ and with an appropriately large ionic conductivity that is stable both at the undoped and/or cation- doped LLZO and the anode electrochemically active material.
  • An exemplary form of this embodiment is the usage of polyethylene with 45% porosity and thickness of 16 pm in conjunction with electrolytes containing carbonate solvents.
  • the cation-doped LLZO selected to form the three dimensional ionically and/or electronically conductive solid- state or hybrid scaffold can be isolated from the anode active material by using a porous glass that is nonconductive to electrons and may or may not be conductive to ions that is wetted by an electrolyte solution containing lithium ions.
  • An exemplary form of this embodiment is the usage of borosilicate glass fiber mats.
  • the cation-doped LLZO selected to form the three dimensional ionically and/or electronically conductive solid- state or hybrid scaffold can be isolated from the anode active material by using a fully dense ceramic solid electrolyte that is nonconductive to electrons and highly conductive to ions.
  • electronic conductivity less than 1 E-4 S/cm and ionic conductivity >1 E-4 S/cm has been achieved and is desired.
  • the cation-doped LLZO selected to form the three dimensional ionically and/or electronically conductive solid- state or hybrid scaffold can be isolated from the anode active material by using a fully dense glass solid electrolyte that is nonconductive to electrons and highly conductive to ions. Glass electrolytes from the sulfide family, particularly Li2S-P2S5, Li7P3S11 , LiPON, U3P04, Li3N, Li10GeP2S12, Li1.3AI0.3Ti1.7(PO4)3, Li1.5AI0.5Ge1.5(P04)3 and combinations thereof.
  • the ionically conductive ceramic material selected for the three-dimensional ionically and/or electronically conductive solid-state or hybrid scaffold comes from the family of solid electrolyte polymers including but not limited to polyethylene oxide), polypropylene oxide), poly(butylene oxide) or their mixtures, polyimide, polyamide, poly(vinyl pyridine), Li- exchanged Nafion or similar cation exchange polymers, polyacrylonitrile, polyvinylpyrrolidone, poly(methyl methacrylate), poly(vinylidene fluoride), poly(vinylidene fluoride-co-hexafluoropropylene) and combinations thereof.
  • solid electrolyte polymers including but not limited to polyethylene oxide), polypropylene oxide), poly(butylene oxide) or their mixtures, polyimide, polyamide, poly(vinyl pyridine), Li- exchanged Nafion or similar cation exchange polymers, polyacrylonitrile, polyvinylpyrrolidone, poly(methyl me
  • the three-dimensional ionically and/or electronically conductive solid-state or hybrid scaffold aspect of this disclosure it may be beneficial to combine the polymers, ceramics, and/or glasses into a hybrid configuration to increase the ionic conductivity, improve the electrochemical stability, enhance the mechanical properties or some combination of all of those improvements.
  • a liquid is added in addition to any ceramics, polymers, or glasses to improve the ionic conductivity, reduce the interfacial impedance, enhance the electrochemical stability or some combination of all of these properties.
  • the hybrid solid state battery comprises a secondary electrolyte phase that enable a conducting interface with the anode and the cathode active materials.
  • the secondary electrolyte phase is a conducting interface made
  • the liquid secondary electrolyte phase comprises one or multiple solvents, in which one of more conducting lithium salts can be dissolved in appreciable molarities.
  • the electrolyte introduced into the composite cathode pores to improve the charge transfer between the electrodes and lower any interfacial resistance is a liquid at slightly elevated temperature, which for the sake of this disclosure is of the range 40°C to 100°C, with the embodiment being in the range of 60°C to 80°C.
  • a liquid electrolyte is introduced between the anode material and the ceramic electrolyte to lower interfacial impedance and achieve high discharging/charging rates for the hybrid lithium-ion battery.
  • the liquid electrolyte comprises one or more solvents selected from the group consisting of but not limited to carbonates, esters, ethers, sulfones, ketones, amides, nitriles, imides and combinations thereof.
  • a hybrid lithium ion battery comprising a liquid electrolyte composition at the interface between the cathode and/or the anode and the ceramic electrolyte, wherein the nonaqueous electrolyte composition comprises at least one electrolyte salt and at least one fluorinated acyclic carboxylic acid ester and/or at least one fluorinated acyclic carbonate.
  • the liquid electrolyte contains at least one electrolyte salt.
  • Suitable electrolyte salts include without limitation lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(perfluoroethanesulfonyl)imide, lithium (fluorosulfonyl) (nonafluorobutanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium tris(trifluoromethanesulfonyl)methide, lithium bis(oxalato)borate, lithium difluoro(oxalato)borate and combinations thereof.
  • the electrolyte lithium salt can be contained in the liquid secondary electrolyte phase in an amount of about 0.1 to about 4 mol/L, and more preferably of about 1 to about 3.mol/L.
  • the liquid electrolyte is made of a room temperature ionic liquid comprising an organic cation and an organic anion.
  • the organic cation is a hydrocarbon comprising at least one charged atom selected from the group of N+, P+, C+, S+ and combinations thereof.
  • the organic anion is selected from a halide ion, a polyhalide ion, a complex anion containing at least one halide ion CF3S03,
  • the thickness and planarity of the three-dimensional electronically and/or ionically conductive solid-state or hybrid electrolyte scaffold and/or the electronically insulating and ionically conducting solid-electrolyte separator can be controlled by using mechanical techniques including but not limited to sanding, polishing, lapping, chemical etching, plasma etching, laser ablation, photoablation, milling and combinations thereof.
  • the porosity of the three-dimensional electronically and/or ionically conductive solid-state or hybrid electrolyte scaffold can additionally be controlled by using mechanical techniques including but not limited to chemical etching, plasma etching, laser ablation, photoablation, milling and combinations thereof.
  • the geometry of the three-dimensional electronically and/or ionically conductive solid-state or hybrid electrolyte scaffold can additionally be controlled by using mechanical techniques including but not limited to sanding, polishing, lapping, chemical etching, plasma etching, laser ablation, photoablation, milling, milling and combinations thereof.
  • FIG. 1 1 discloses schematically one particular invention suitable for producing 275 urn thickness parts, whereby an electrolyte scaffold is placed into a cavity of fully-dense LLZO that is 275 urn in thickness and is polished using diamond lapping paper on a rotating polishing wheel.
  • the method described herein further comprises the step of infiltrating the pores of the three-dimensional ionically and/or electronically conductive solid-state or hybrid electrolyte scaffold with one or more components selected from but not limited to a liquid electrolyte, anode active material, a cathode active material, a solid electrolyte, conductive additive, polymer electrolyte, gel electrolyte, surfactant, inorganic filler, corrosion inhibiter, film former, electrolyte salts, and combinations thereof.
  • FIG. 16 shows a SEM micrograph of a cathode slurry infiltrated into the pores of a c-LLZO scaffold.
  • the three-dimensional ionically and/or electronically conductive solid-state or hybrid scaffold can be infiltrated with electrochemically active cathode or anode materials by producing a slurry of the electrochemically-active materials, depositing said slurry onto the porous surface of the of the three-dimensional ionically and/or electronically conductive solid-state or hybrid scaffold and allowing capillary action and gravity to insert the electrochemically-active material into the porous structure.
  • Loadings in terms of mass of electrochemically active material per unit surface area can be controlled by modulating the solids loading of the electrochemically-active material slurry, or the amount of electrochemically-active material slurry deposited.
  • the tool used to deposit the electrochemically-active material slurry has resolution of ⁇ 10 pm and in the x-y direction.
  • the tool used to deposit the electrochemically-active material slurry can deposit quantities of electrochemically-active material slurry as low as 10 pL and as high as 1 ,000 pL.
  • the electrochemically- active material slurry is deposited in one location on top of the three-dimensional ionically and/or electronically conductive solid state or hybrid electrolyte scaffold and bedaubed across the entire surface. [0172] Per an additional embodiment of this disclosure, the electrochemically- active material slurry is deposited over the entirety of the part.
  • excess electrochemically- active slurry is removed from the surface of the electrochemically-active material slurry using techniques including but not limited to: wiping with an absorbent cloth, using a rubberized squeegee, using a jet of gas, and combinations thereof.
  • excess electrochemically- active slurry is allowed to remain on top of the surface of the three-dimensional ionically and/or electronically conductive solid-state or hybrid electrolyte scaffold.
  • the electrochemically-active slurry can either have the solvent removed and current collectors can be attached following a drying step, or the slurry can be allowed to have some amount of solvent remaining, up to 100% of the original solvent loading to aid in current collector attachment.
  • the overiayer of electrochemically- active slurry can have thickness when dried of 0 pm to 300 pm.
  • insertion of the electrochemically-active slurry into the pores of the three-dimensional ionically and/or electronically conductive solid-state or hybrid scaffold can be further assisted by applying the slurry over the entire surface of the three-dimensional ionically and/or electronically conductive solid-state or hybrid electrolyte scaffold using the methods described herein under a pressure lower than atmospheric pressure, but above the solvent boiling point, followed by a gas pressurization step.
  • insertion of the electrochemically-active slurry into the pores of the three-dimensional ionically and/or electronically conductive solid-state or hybrid scaffold can be further assisted by applying vibration following the application of slurry over the entire surface of the three-dimensional ionically and/or electronically conductive solid-state or hybrid electrolyte scaffold.
  • insertion of the electrochemically-active slurry into the pores of the three-dimensional ionically and/or electronically conductive solid-state or hybrid scaffold can be further assisted by applying a magnetic field following the application of slurry over the entire surface of the three- dimensional ionically and/or electronically conductive solid-state or hybrid electrolyte scaffold.
  • the electrochemically- active slurry does not contain a liquid and is infiltrated into the pores of the threedimensional solidr-state or hybrid electrolyte scaffold in its dry state.
  • the dry mixture of solids and components thereof contains but is not limited to anode active material, a cathode active material, a solid electrolyte, conductive additive, polymer electrolyte, gel electrolyte, surfactant, inorganic filler, corrosion inhibiter, film former, electrolyte salts.
  • insertion of the dry mixture of electrochemically-active and inactive materials into the pores of the three-dimensional ionically and/or electronically conductive solid-state or hybrid scaffold can be further assisted by applying vibration following the application of slurry over the entire surface of the three-dimensional ionically and/or electronically conductive solid-state or hybrid electrolyte scaffold.
  • one or more of bar coating, wire wound rod coating, drop casting, freeze tape casting, freeze casting, casting, spin casting doctor blading, dip coating, spray coating, microgravure, screen printing, ink jet printing, 3D printing, slot die casting, reverse comma casting, acoustive sonocasting, acoustic field patterning, magnetic field patterning, electric field patterning, photolithography, etching, and self-assembly may be used.
  • a conductive polymer may be additionally inserted into the electrochemically- active material interstitial porosity by adding a polymer monomer using one many, or all of the methods detailed herein and polymerizing using cationic polymerization, anionic polymerization, free-radical polymerization, condensation polymerization, emulsion polymerization, solution polymerization, suspension polymerization, precipitation polymerization, photopolymerization, plasma polymerization, and/or electrochemical polymerization.
  • polymers including but not limited to polyaniline, polypyrrole, polyacetylene, polythiophene, poly(3,4- ethylenedioxythiophene), poly(p-phenyl sulfide), poly(p-phenylene vinylene) can be used according to the methods disclosed herein.
  • a conductive carbon may be additionally inserted into the electrochemically- active material interstitial porosity by utilizing general methods of carbon deposition which can be generally grouped into catalytic hydrocarbon gas decomposition, organic compound decomposition and thermal oxidation of polyacrylonitrile.
  • FIG. 14 shows schematically what such a hybrid structure would look like. A thin, single-digit nanometer coating of carbon is left on the surface of the porous scaffold. Numerous routes can be utilized to produce the desired conductive carbon that would be obvious to someone skilled in the art and the exemplary embodiments are disclosed herein.
  • a dilute solution of sucrose, an organic compound typically in the range of
  • 1 wt.% to 20 wt.% and more typically 5 wt.% is produced in an appropriate solvent, then is introduced into the pores of the three-dimensional solid-state or hybrid scaffold.
  • This can be accomplished by any number of techniques, with the simplest being the use of a pipette or similar.
  • the solution is then evaporated by heating at a temperature in the range of 50°C to 100°C to produce a coating of the organic compound, in this case sucrose, on the surface of the pore walls of the three-dimensional solid-state or hybrid scaffold.
  • the coated three-dimensional solid-state or hybrid scaffold is then placed into an oven containing an inert atmosphere and heated to a temperature of 400°C to 900°C which causes decomposition of the organic compound into an amorphous carbon that provides electronic conductivity while still enabling access of lithium ions to the ionically-conducting three-dimensional solid-state or hybrid scaffold.
  • a hydrocarbon gas is introduced into an environment that contains the three-dimensional solid-state or hybrid scaffold at a temperature above the temperature where the hydrocarbon gas is thermodynamically stable. In general, these temperatures are greater than 400 e C.
  • a hydrocarbon gas is introduced into an environment that contains the three-dimensional solid-state or hybrid scaffold at a temperature above the temperature where the hydrocarbon gas is thermodynamically stable. In general, these temperatures are greater than 400 e C.
  • numerous materials disclosed herein that comprise the three- dimensional solid-state or hybrid scaffold would be catalytic to growing low dimensionality
  • An additional and exemplary embodiment of this disclosure is the purposeful inclusion of carbonization catalysts that both encourage the growth of highly conductive and low dimensionality carbon nanostructures and become incorporated into the crystal lattice on the lithium site of LLZO, which reduces the effects of high temperature lithium loss and encourages the stabilization of the cubic phase of LLZO.
  • iron is used as an exemplary example of the present disclosure.
  • 2.5% acetylene in 97.5% argon when used as the precursor gas with iron oxide nanoparticles with diameter in the range of 1 nm to 100 nm, such as 5 nm at a temperature of 600°C results in a structure with facile electron and ion transport.
  • carbon-forming polymers such as polyacrylonitrile (PAN) or poly(1 ,3- diethnylbenzene) (PAB), which someone skilled in the art would recognize as being the predominant carbon fiber precursor, is introduced into the pores of the tree-dimensional solid-state or hybrid scaffold through either solution deposition, as was previously disclosed for the embodiment concerning organic material decomposition, or through direct polymerization of acrylonitrile monomers using a radical initiator.
  • the polyacrylonitrile is then slowly heated to 400°C to carbonize the polyacrylonitrile.
  • the polyacrylonitrile can be further graphitized to increase the electronic conductivity by heating to temperatures of approximately 1000°C.
  • iron can be advantageously added to reduce the temperature at which carbon graphitizes or becomes low dimensional structures in the form of iron oxide nanoparticles, or, in the case of polyacrylonitrile, a metal organic compound containing iron such as ferrocene.
  • the present disclosure teaches using aluminum, either carbon coated or not, woven mesh, perforated sheet, expanded sheets, foams, honeycombs, wool or similar non-solid material to improve electrolyte wetting of the cathode. Additionally, the present invention discloses using uncoated copper woven mesh, perforated sheet, expanded sheets, foams, honeycombs, wool or similar non-solid material to improve electrolyte wetting of the anode. Additionally, when lithium metal is used as the anode electrochemically-active material, using a higher dimensionality copper current collector provides physical space to accommodate the shrinkage and growing of the lithium without requiring excessive cell pressures on the stack. In the present disclosure, there is a change in lithium thickness in each cell pair of electrodes by 10pm to 50pm during each full charge/discharge cycle that needs to be accommodated.
  • the previously disclosed embodiment addresses electrolyte wetting in single-layer pouch cells and the composite electrodes at the top and bottom of a prismatic stack but is not effective for ensuring good electrolyte wetting for multi-layer prismatic cell stacks.
  • the present invention addresses this by disclosing the methods and materials to produce current collectors that can be attached to the hybrid solid-state battery architecture following the addition of any liquid to the infiltrated three-dimensional composite solid-state or hybrid solid state electrodes. This is shown schematically in FIG. 18 and is accomplished by providing current collectors with conductive adhesive, either pressure sensitive adhesive or hot melt adhesive, filled with an appropriate amount of carbon.
  • FIG. 18 shows through-plate electrical resistance of 12 such thermoplastic current collectors.
  • a hot melt adhesive is formed by combining a blend of polymers from the families of polyethylene, ethylene-vinyl acetate ethylene-coethyl acetate, and combinations thereof in a ratio to produce a substantial softening at 80°C to 150°C.
  • the addition of carbon lowers the softening temperature, but also reduces the tackiness.
  • a mass fraction of carbon in the range of 1 wt% to 20 wt% is most desirable and that carbons with more conjugation produce substantially higher conductivities.
  • current collectors manufactured using this protocol produce through plane conductivities of >1 E1 S/m.
  • pressure sensitive adhesives can be produced using a very similar procedure.
  • the pressure sensitive adhesive is produced from a mixture of acrylics and short chain styrene butadiene rubbers with carbon being added in a mass fraction of 1 % to 10% and has a thickness less than 10 pm.
  • polymeric materials to the current collector to enhance the conductivity. These materials fall into the broad families of but not limited to polyanilines, polypyrroles, polyacetylenes, polylthiophenes, poly(3,4- ethylenethiophosphene), poly(p-phenylene sulfide), poly(p-phenylene vinylene). When these materials are added in a range of 1 wt.% to 50 wt.% conductivity is enhanced. It is of particular interest to combine polypyrroles and carbon nanotubes for both tack and conductivity.
  • liquid electrolytes with different thermal stabilities may be desired.
  • solvents with low boiling points such as the ethers, or formulations with numerous unstable or marginally stable additives such as vinylene carbonate
  • using current collectors coated with a pressure sensitive conductive adhesive is the preferred embodiment.
  • high boiling point or nonvolatile liquids such as the solvent N-butyl-N-methyl bis(fluorosulfonyl)imide, or carbonate-based solvents with larger linear carbonate molecules
  • the hot melt adhesive is the preferred embodiment. In both embodiments, it is preferable to introduce the liquid into the composite electrode structure prior to attaching the current collectors.
  • the producing the three-dimensional porous scaffold with ionic and/or electronic conductivity filled with electrochemically-active material comprises casting a plurality of the solid-state electrolyte and/or hybrid electrolyte slurry, the electrochemically-active material slurry, and the separator with sufficient mechanical properties to retard dendrite growth and combinations thereof directly onto a current collector.
  • an anode or negative electrode consists in 100 microns thick lithium metal coated onto a 10 microns thick copper foil current collector (MTI Corporation).
  • a 16 microns thick microporous separator (SK innovation) comprising 75 mI/cm 2 of a Li+ conducting non-aqueous electrolyte was used as interface between the lithium anode and the solid electrolyte containing c-LLZO.
  • the liquid electrolyte consisted in a mixture of lithium bis(fluorosulfonyl)imide (LiFSI, 99+%, Fluolyte) 1.2M dissolved in ethylene carbonate (EC) : ethyl methyl carbonate (EMC) (3/7 v/v) (SoulBrain Ml) with 5wt.% lithium hexafluorophosphate (LiPF6, Sigma-Aldrich), 5wt.% fluoroethylene carbonate (FEC, Sigma-Aldrich), and 5wt.% lithium difluoro(oxalato)borate (LiDFOB, Sigma-Aldrich).
  • the liquid electrolyte formulation comprised additives improving cycle life of lithium metal anodes.
  • the liquid electrolyte water content was measured by Karl
  • a polymer mixture comprising polyvinylidene difluoride (PVdF, Solvay) was prepared by mixing 0.25 grams of the polymer in 2.25 grams of N-methylpyrrolidinone (NMP, 99%, anhydrous, Sigma-Aldrich). The mixture was stirred for about 12 hours in a milling jar.
  • a cathode mixture comprising 0.25 grams of conducting carbon black (SGP- 5, Imerys), 0.25 grams of another conducting carbon black (Super-C, Timcal), and 4.25 grams of cathode active material LiNi0.6Mn0.2Co0.202 (NMC622, Umicore) was then added to the polymer mixture.
  • the mixture was then be vigorously mixed in the high shear mixer until a substantially homogeneous blend was obtained.
  • the cathode slurry containing the active material was then infiltrated within the porous c-LLZO scaffold using a vacuum apparatus inside an Ar-filled glovebox.
  • the porous c-LLZO scaffold had a thickness of about 100-500 pm. In various examples, the thickness was 300-400 pm, such as 350 pm.
  • the 16 microns thick carbon-coated aluminum current collector (MTI Corporation) was attached onto the cathode containing the electro-active material and c- LLZO porous scaffold.
  • the cathode/current collector was vacuum dried at 120 °C for 24 hours to remove the NMP.
  • the cathode has an active material areal loading of about 20 to about 60 mg/cm2 and more preferably at about 50 mg/cm2.
  • a cathode current collector which was a sheet of expanded aluminum metal with a thickness of 25 pm and an open area of 50%. It was available from Dexmet Corporation (Wallingford, CT,
  • a 3 cm by 3 cm square with a 0.4 cm by 0.4 cm square tab can be cut using scissors forming the cathode current collector for the current example.
  • the composite electrode can be allowed to sit for a period of 15 minutes subsequent to slurry deposition at a temperature between 20°C and 50°C.
  • the cut current collector can be positioned on top of the 3 cm by 3 cm bulk composite cathode and the NMP allowed to evaporate.
  • An additional drying step of 12h at 120°C at a pressure of -10 kPa can be employed.
  • a cathode current collector can be employed which was a solid sheet of aluminum of 16 pm thickness with a 1 pm coating of acrylate adhesive containing a conductive carbon available from MTI Corporation (Richmond, CA, USA).
  • a polymer solution comprising 0.25 g polyvinylidene difluoride in 2.25 g n-methyl-2-pyrrolidone, 4.5 g of LiNi0.6Mn0.2Co0.202 available from Umicore (Brussels, Belgium), 0.25 g SGP-5 synthetic graphite from (SEC Carbon, Hyogo Japan) and 0.25g Super C65 from Imerys Graphite & Carbon (Paris, France) was added into a borosilicate mixing vessel.
  • the mixture was gently mixed using an overhead mixer while 9.4 g additional n-methyl-2- pyrrolidone was added for 10 minutes.
  • a suitable mixer was from IKA, Model Eurostar 20. The slurry was then vigorously mixed using a high shear mixer for 30 minutes at about 10,000 RPM.
  • a suitable mixer was from Lanyo model AD500S-H.
  • the cathode slurry was deposited on top of a square bulk composite electrode of width 3 cm and length 3 cm having a co-sintered bilayer of 95% bulk density
  • Li6.75AI0.25La7Zr3O12 with 25 pm thickness and Li6.75AI0.25La7Zr3O12 of approximately 20% bulk density and 350 pm thickness by pipetting 400 uL of the cathode slurry evenly across the surface using a micropipette.
  • a suitable one was an Eppendorf
  • a 3 cm by 3 cm square with a 0.4 cm by 0.4 cm square tab was cut using scissors forming the cathode current collector for the current example.
  • the composite electrode was allowed to sit for a period of 15 minutes subsequent to slurry deposition at a temperature between 20°C and 50°C. Following this, the cut current collector was positioned on top of the 3 cm by 3 cm bulk composite cathode and the NMP allowed to evaporate. An additional drying step of 12h at 120°C at a pressure of -10 kPa was employed.
  • a cathode slurry was made using poly(4-vinylpyridine), available from Sigma Aldrich.
  • poly(4-vinylpyridine) available from Sigma Aldrich.
  • a polymer solution comprising 0.25 g poly(4- vinylpyridine) in 2.25 g dimethylformamide, 4.5 g of LiNi0.6Mn0.2Co0.202 available from Sigma Aldrich.
  • Umicore (Brussels, Belgium), 0.25 g SGP-5 synthetic graphite from (SEC Carbon, Hyogo Japan), and 0.25g Super C65 from Imerys Graphite & Carbon (Paris, France) was added into a borosilicate mixing vessel. The mixture was gently mixed using an overhead mixer while and additional 9.4 g dimethylformamide was added for 10 minutes. A suitable mixer was from IKA, Model Eurostar 20. The slurry was then vigorously mixed using a high shear mixer for 30 minutes at about 10,000 RPM. A suitable mixer was from Lanyo model
  • a carbon coating was done to the bulk composite electrode scaffold prior to filling with electroactive material.
  • methanol heated to 60°C
  • sucrose was added to a stirring 20 mL solution of methanol heated to 60°C
  • the sucrose/ethanol solution was stirred for a further 15 minutes before 0.2 mL deionized water was added dropwise, waiting 90 seconds between successive additions, until the solution was no longer turbid.
  • sucrose/methanol solution was deposited on top of a rectangular bulk composite electrode of width 2 cm and length 3 cm having a co-sintered bilayer of 95% bulk density Li6.75AI0.25La7Zr3O12 with 25 pm thickness and Li6.75AI0.25La7Zr3O12 of approximately 20% bulk density and 350 pm thickness by pipetting 250 uL of the cathode slurry evenly across the surface using a micropipette.
  • a suitable one is an
  • the rectangular bulk composite electrode was dried in a drying oven at 50°C for 2h.
  • a suitable one was an American
  • FIG. 15A shows a SEM micrograph of the composite c-LLZO scaffold with carbon deposited on the surface.
  • FIG. 15B shows an elemental mapping of carbon using energy dispersive X-ray spectroscopy on the c-LLZO bilayer showing successful carbon deposition. Note the color is grey, compared to the brilliant white of the as-sintered c-LLZO scaffold.
  • FIG. 15C is a photograph of the as-prepared c-LLZO solid state electrolyte coated with carbon within the pores.
  • a bulk composite electrode scaffold having a 300 pm thickness layer with porosity >50% and a 25 pm thickness layer with porosity ⁇ 5% that are physically attached through co-sintering was further improved by mechanical planarization.
  • a planarization jig which consists of a 275 pm thickness deep cavity where the bulk composite electrode scaffold was housed (FIG 1 1 ) was employed along with a lapping film.
  • a suitable one for the latter was
  • PEO polyethylene oxide
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • the materials are previously vacuum dried at 50 °C for 3 days inside an Ar-filled glovebox.
  • PEO and LiTFSI are then added to 7.86 g of anhydrous acetonitrile (AON, Sigma-Aldrich) and stirred for 24 hours to form a homogenized solution.
  • the solution was tape cast using a doctor blade with 200 microns gap height and vacuum dried for 12 hours into a thin film in an argon filled glove box at 80 °C.
  • a series of solid electrolytes are formed using the above process with various amounts of PEO and LiTFSI.
  • a first series of electrolytes are formed having a EO:Li molar ratio of 30:1 , 15:1 , 10:1 , and 4:1.
  • a second series of polymer electrolytes are also formed having a c-LLZO concentration of 5 to 15 wt % incorporated within the PEO:LiTFSI separator.
  • the c-LLZO“additive" was added to the mixture in order to promote Li+ ionic conductivity at room temperature.
  • the electrochemical properties of the polymer electrolytes are measured using an electrochemical instrument (Ivium Technologies).
  • the free-standing PEO separator has a thickness of ca.
  • the free-standing PEO separator acts as a hybrid interface and/or anolyte between lithium metal anode and c-LLZO solid electrolyte.
  • a bulk composite electrode was produced by filling a bulk composite scaffold with 300 pm thickness layer with porosity >50% and 25 pm thickness layer with porosity ⁇ 5% that are physically attached by co-sintering with a cathode slurry consisting of 0.25 g polyvinylidene difluoride in 2.25 g n-methyl-2-pynOlidone, 4.5 g of
  • LiNi0.6MnQ.2Co0.2O2 available from Umicore (Brussels, Belgium), 0.25 g SGP-5 synthetic graphite from SEC Carbon (Hyogo, Japan), and 0.25 g Super C65 from Imerys
  • the bulk composite scaffold filled with cathode slurry was placed on a wire drying rack and excess cathode slurry was removed from the surface of the 300 pm thickness layer using a delicate task wipers.
  • the solvent was partially evaporated by allowing the bulk composite scaffold filled with cathode slurry to sit on the drying rack at room temperature for 24h.
  • the excess cathode slurry on the 25 pm thickness layer side was removed by flipping the bulk composite scaffold filled with cathode slurry over onto a flat glass plate so the 25 pm thickness layer was facing upwards and wiping away any excess cathode slurry with a solvent-soaked delicate task wiper.
  • a catholyte containing a liquid electrolyte having high oxidative stability and high chemical compatibility with aluminum-based cathode current collector was used to enhance the performance of a hybrid solid-state battery that comprises a porous c-LLZO 3D scaffold with thickness of 300 pm and porosity > 50%.
  • the liquid electrolyte consists in dissolving lithium bis(fluorosulfonyl)imide (LiFSI, 99+%, Fluolyte) in Sulfolane (Alfa Aesar, >98+%) at 2 mol/L inside an Ar-filled glovebox. Sulfolane was dried over molecular sieves until water content was below 50 ppm. LiFSI salt was vacuum dried at 100 °C for
  • FIG. 13 shows a chronoamperogram illustrating high electrochemical stability of the liquid electrolyte up to 4.6 V. It also demonstrates chemical stability of the aluminum current collector at high voltage using LiFSI-based liquid electrolyte.
  • FIG. 17 shows a schematic of a uniaxial press that was used to press current collectors onto three-dimensional composite electrodes such as shown schematically in FIG. 19.
  • a three-dimensional composite electrode (8,9), with attached dendrite-blocking separator (7), and lithium (5) physically bonded was placed on top of an Al current-collector (11 ) with a conductive thermoplastic coating (10). Additionally, a copper current collector (5) was placed on top of the lithium. 5, 6, 7, 8, 9, 10 and 11 was placed in between the heated plates (4). Pressure (14) was applied.
  • thermoplastics with 5% carbon black (Super C65,
  • porous scaffolds comprised of Al-doped c-LLZO of 300 pm thickness, dendrite-blocking separator comprised of Al-doped c-LLZO, 90%
  • Li0.6Ni0.2Co0.202 active cathode material 5% PVDF binder, 2.5% SGP-5 (SEC Carbon,
  • 150 Pa and 80 °C for 5 minutes can produce good adhesion of the current collector to the three dimensional composite electrode.
  • FIG. 19 following the addition of a liquid electrolyte into the pores of the three-dimensional composite electrode by the application isostatic pressure at slightly elevated temperature.
  • a cell was produced using For polyethylene (MW 10,000, Sigma) conductive thermoplastics with 5% carbon black (Super C65, Imerys, Switzerland), and porous scaffolds comprised of Al-doped c-LLZO of 300 pm thickness, dendrite-blocking separator comprised of Al-doped c-LLZO, 90% Li0.6Ni0.2Co0.202 active cathode material, 5% PVDF binder, 2.5% SGP-5 (SEC Carbon, Hyogo, Japan), 2.5% Super C65 (Imerys, Switzerland), and 100 pm Li on 10 pm Cu foil, was used to produce the bond between the current collector and the three-dimensional composite electrode.
  • a 3 cm wide by 3 cm long electrode stack shown schematically in FIG. 19 was produced and have Ni tabs ultrasonically welded to the Cu current collector on the anode side and the
  • the electrode stack was sealed into a standard pouch along with an electrolyte comprising 2 M LiFSI in sulfolane. Following the final vacuum sealing step, the chamber was heated to 80 °C and pressurized to 5 psi for 15 minutes.
  • the hybrid solid state electrochemical cell comprising the c-LLZO solid electrolyte incorporates a nanofiber separator at the interface between the lithium metal anode and c-LLZO.
  • This separator enables the use of a stable anolyte that reduces the interfacial impedance of the electrochemical cell.
  • the microporous separator has a thickness of 20 microns and was made of aramid nanofibers
  • the separator was filled with the anolyte at 75 pL/cm 2 loading.
  • the liquid electrolyte was composed of lithium bis(fluorosulfonyl)imide
  • the hybrid solid state electrochemical cell comprising the c-LLZO solid electrolyte incorporates a microporous film at the interface between the lithium metal anode and c-LLZO.
  • This separator enables the use of a stable anolyte that reduces the interfacial impedance of the electrochemical cell.
  • the microporous separator has a thickness of 5 microns and was made of polyolefin (SK Innovation). During cell assembly the separator was filled with the anolyte at 75 pL/cm 2 loading.
  • the liquid electrolyte was composed of lithium bis(fluorosulfonyl)imide (LiFSI, 99+%, Fluolyte) dissolved at a 2 molar concentration in 3-methylsulfolane (TCI America,
  • the hybrid solid state electrochemical cell comprising the c-LLZO solid electrolyte incorporates a microporous film at the interface between the lithium metal anode and c-LLZO.
  • This separator enables the use of a stable anolyte that reduces the interfacial impedance of the electrochemical cell.
  • the microporous separator has a thickness of 5 microns and was made of polyolefin (SK Innovation). During cell assembly the separator was filled with the anolyte at 75 pL/cm 2 loading.
  • the liquid electrolyte was composed of lithium bis(fluorosulfonyl)imide (LiFSI, 99+%, Fluolyte) dissolved at a 4 molar concentration in 1 ,2-dimethoxyethane (DME,

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Abstract

Des batteries hybrides à l'état solide ou en volume comprennent une pluralité d'électrodes composites à charge élevée de matériaux électrochimiquement actifs, un séparateur de blocage de dendrites placé entre l'anode et la cathode, une phase secondaire entre les matériaux électrochimiquement actifs et l'électrolyte solide ou hybride et des procédés associés. L'invention concerne également des procédés de fabrication et d'utilisation correspondants.
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