EP3411914A1 - Séparateurs d'électrolyte à grenat recuit - Google Patents

Séparateurs d'électrolyte à grenat recuit

Info

Publication number
EP3411914A1
EP3411914A1 EP16888407.0A EP16888407A EP3411914A1 EP 3411914 A1 EP3411914 A1 EP 3411914A1 EP 16888407 A EP16888407 A EP 16888407A EP 3411914 A1 EP3411914 A1 EP 3411914A1
Authority
EP
European Patent Office
Prior art keywords
la3zr
electrolyte
examples
lithium
separator
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP16888407.0A
Other languages
German (de)
English (en)
Other versions
EP3411914A4 (fr
Inventor
Lei Cheng
Sriram Iyer
Will Gardner
Tim Holme
Shuang Li
Cheng-Chieh Chao
Niall DONNELLY
Arnold Allenic
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Quantumscape Battery Inc
Original Assignee
Quantumscape Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Quantumscape Corp filed Critical Quantumscape Corp
Publication of EP3411914A1 publication Critical patent/EP3411914A1/fr
Publication of EP3411914A4 publication Critical patent/EP3411914A4/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H01M50/406—Moulding; Embossing; Cutting
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • 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

  • Li + ions move from a negative electrode to a positive electrode during discharge and in the opposite direction during charge.
  • An electrolyte physically separates and electrically insulates the positive and negative electrodes while also providing a medium for Li + ions to conduct between the electrodes.
  • the electrolyte ensures that electrons, produced when Li metal oxidizes at the negative electrode during discharge of battery (e.g., Li ⁇ Li + + e " ), conduct between the electrodes by way of an external and parallel electrical pathway to the pathway taken by the Li + ions.
  • electrolytes may be used in combination with, or intimately mixed with, cathode (i.e., positive electrode) active materials to facilitate the conduction of Li + ions within the cathode region, for example, from the electrolyte-cathode interface and into and/or with the cathode active material.
  • cathode i.e., positive electrode
  • liquid-based electrolytes which include lithium salts dissolved in organic solvents (e.g., 1M solutions of LiPF 6 salts in 1 : 1 ethylene carbonate:di ethylene carbonate solvents).
  • organic solvents e.g., 1M solutions of LiPF 6 salts in 1 : 1 ethylene carbonate:di ethylene carbonate solvents.
  • solid state ion-conducting ceramics such as lithium-stuffed garnet oxide materials, have been proposed as next generation electrolyte separators in a variety of electrochemical devices including Li + ion rechargeable batteries.
  • Solid state electrolytes solid state electrolytes are attractive for safety reasons, such as not being flammable, as well as for economic reasons which include low processing costs.
  • Solid state lithium-stuffed garnet electrolyte membranes and separators are well suited for electrochemical devices because of their high Li + ion conductivity, their electric insulating properties, as well as their chemical compatibility with Li metal anodes (i.e., negative electrodes).
  • solid state lithium-stuffed garnet electrolyte membranes can be prepared as thin films, which are thinner and lighter than conventional electrolyte separators. See, for example, US Patent Application Publication No.
  • the resulting electrochemical cells are thought to achieve higher volumetric and gravimetric energy densities because of the volume and weight reduction afforded by the solid state separators.
  • lithium-stuffed garnet electrolytes Some of the contributors to bulk and interfacial resistance and/or impedance in lithium-stuffed garnet electrolytes are impurities in the lithium-stuffed garnet oxide, which include but are not limited to secondary phases other than a pure lithium-stuffed garnet oxide which can be found at either or all of the electrolyte's bulk, surface and/or interface with other materials. Resistive secondary phases, e.g., Li 2 C0 3 on the surface or interface of a lithium-stuffed garnet solid electrolyte are also a source of high impedance and poor cycling performance in lithium-stuffed garnet electrolytes. Previously, researchers mechanically processed lithium-stuffed garnet electrolytes to remove secondary phases from its surfaces.
  • the present disclosure relates generally to components for lithium rechargeable batteries as well as to lithium-stuffed garnet electrolyte membranes and separators for lithium rechargeable batteries.
  • Some of the electrolytes disclosed herein have low interfacial impedance, a reduced tendency for lithium dendrites to form therein or thereupon when used as electrolyte separators in electrochemical cells, and/or have advantageous surface chemical compositions and features.
  • methods of making these solid-state electrolyte membranes and separators including certain annealing methods for producing the aforementioned advantageous surface chemical compositions and features.
  • the instant disclosure includes, in some examples, intermediate temperature annealing methods, in inert or reducing environments, for removing surface species, e.g., Li 2 C0 3 , which otherwise result in high impedance and poor electrochemical performance in the electrolyte if not removed.
  • the instant disclosure includes, in some examples, serial heat treatment steps, in inert or reducing environments, for removing surface species, e.g., Li 2 C0 3 , which otherwise result in high impedance and poor electrochemical performance in the electrolyte if not removed.
  • the instant disclosure sets forth a thin electrolyte membrane or separator, having top and bottom surfaces, wherein the length or width of either the top or bottom surfaces is at least 10 times the membrane or separator thickness, and wherein the membrane or separator thickness is from about 10 nm to about 100 ⁇ ; wherein the electrolyte bulk is characterized by the chemical formula Li x La 3 Zr 2 0i 2 y(Al 2 0 3 ), wherein 3 ⁇ x ⁇ 8 and 0 ⁇ y ⁇ l; and wherein either the top or bottom surface is characterized as having less than 1 ⁇ layer thereupon which includes a lithium carbonate, lithium hydroxide, lithium oxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • the thickness of the layer on the membrane or separator is only as thick or is thinner than the thickness of the membrane or separator, not including any layers thereupon.
  • x and y are rational numbers.
  • having less than 1 ⁇ layer thereupon refers to a surface coating, or surface adhered or bonded layer, which is chemically distinct from the bulk material on which the surface coating is present.
  • this layer is a native oxide or an oxide which spontaneously forms on the surface of the materials described herein post- synthesis and upon exposure to air.
  • the instant disclosure sets forth a method of making a thin electrolyte membrane or separator , having top and bottom surfaces, wherein the length or width of either the top or bottom surfaces is at least 10 times the membrane or separator thickness, and wherein the membrane or separator thickness is from about 10 nm to about 100 ⁇ ; wherein the electrolyte bulk is characterized by the chemical formula Li x La 3 Zr 2 0i 2 y(Al 2 0 3 ), wherein 3 ⁇ x ⁇ 8 and 0 ⁇ y ⁇ l; and wherein either the top or bottom surface is characterized as having less than 1 ⁇ layer thereupon which includes a lithium carbonate, lithium hydroxide, lithium oxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • the thickness of the layer on the membrane or separator is only as thick or is thinner than the thickness of the membrane or separator, not including any layers thereupon.
  • the method includes preparing a thin film lithium-stuffed garnet electrolyte by calcining lithium-stuffed electrolyte garnet electrolyte precursors in the presences of binders and or dispersants to prepare calcined thin films of lithium-stuffed garnet electrolytes and subsequently sintering and annealing the thin films by heating the films a second or third time in a reducing or inert atmosphere and at elevated temperatures.
  • the instant disclosure sets forth methods of reducing the area- specific resistance (ASR) of a lithium-stuffed garnet electrolyte membrane or separator , wherein the method includes annealing the membrane or separator by heating it after it is sintered in a reducing atmosphere and at elevated temperatures.
  • the heating is between 500 and 750°C and the reducing atmosphere is Ar:H 2 or Ar or an inert atmosphere.
  • the instant disclosure sets forth an electrochemical device which includes the electrolyte membranes and/or separators set forth herein.
  • electrochemical devices which include the electrolyte membranes and/or separators set forth herein, wherein the methods include bonding lithium metal to a surface of the electrolyte membrane or separator using a formation cycle.
  • the instant disclosure sets forth methods of laminating, depositing, or bonding lithium metal onto an electrolyte membranes and/or separators set forth herein.
  • Figure 1 shows a transmission electron microscopy (TEM) image of Sample A (untreated) - a lithium-stuffed garnet prepared according to Example 2.
  • the scale bar in the image is 0.5 ⁇ .
  • Figure 2 shows a TEM image of Sample B (treated - annealed) - a lithium-stuffed garnet prepared according to Example 2.
  • the scale bar in the image is 1.0 ⁇ .
  • Figure 3 shows an overlaid x-ray photoelectron spectroscopy (XPS) spectra for lithium-stuffed garnet electrolyte membranes, Sample A and Sample B, prepared according to Example 2.
  • XPS x-ray photoelectron spectroscopy
  • FIG 4 shows an electron paramagnetic resonance (EPR) spectrum for Sample B prepared according to Example 2.
  • Figure 5 shows a scanning electron micrograph (SEM) of Sample B prepared according to Example 2.
  • Figure 6 shows overlaid electrical impedance spectra for Samples (untreated) A and B (treated - annealed).
  • Figure 7 shows a reduced magnification of Figure 6.
  • Figure 8A shows electrochemical cycling data for a lithium-stuffed garnet electrolyte membrane of Sample B, in a symmetric Li-metal cell, which was cycled at 2mA/cm 2 , for the first three cycles (Fig 8 A), and then 2mA/cm 2 , for forty-six (46 days) at 130 ° C (Fig 8B). Each cycle passes 20 ⁇ of lithium in both directions (i.e. a half cycle is approximately
  • Figure 9 shows an overlaid FT-IR spectra for Sample A (untreated) and B (treated - annealed).
  • Figure 10 shows Raman spectra for Samples A and B prepared according to Example 2.
  • Figure 11 shows a plot of the survival electrochemical cells as a function of failure current density (mA/cm 2 ).
  • Figure 12 shows a plot Weibull cumulative failure as a function of current density.
  • Figure 13 shows an rectangular shape
  • Figure 14 shows a disc shape.
  • electrolytes is that researchers have had difficulty controlling the surface chemistry of for these electrolytes to operate in commercial devices.
  • surface contamination by L1 2 CO 3 and/or LiOH is thought to be detrimental to the performance of these electrolytes.
  • These species may block fast charge transfer kinetics at the surface of the electrolyte and lead to high interfacial resistance.
  • Other minor impurity phases at the surface, e.g. LiA10 2 may also lead to high interfacial resistance. See, for example, Sharafi, Asma, et al. Journal of Power Sources 302 (2016) 135-139.
  • “about 75 °C,” includes 75 °C as well 68 °C, 69 °C, 70 °C, 71 °C, 72 °C, 73 °C, 74 °C, 75 °C, 76 °C,
  • evaporating a solvent at about 80 ° C includes evaporating a solvent at 79 ° C, 80 ° C, or 81 ° C.
  • the phrase “about 10 ⁇ to about 100 ⁇ ” refers to the range 9 ⁇ -11 ⁇ to 90 ⁇ -110 ⁇ and the integer values therebetween.
  • the phrase “about 500 ° C to about 900 ° C,” refers to the range 450 ° C-550 ° C to 810 ° C-990 ° C and the integer temperature values therebetween.
  • Ra is a measure of surface roughness wherein Ra is an arithmetic average of absolute values of sampled surface roughness amplitudes.
  • Surface roughness measurements can be accomplished using, for example, a Keyence VK-X100 instrument that measures surface roughness using a laser.
  • Rt is a measure of surface roughness wherein Rt is the maximum peak height of sampled surface roughness amplitudes.
  • selected from the group consisting of refers to a single member from the group, more than one member from the group, or a combination of members from the group.
  • a member selected from the group consisting of A, B, and C includes, for example, A only, B only, or C only, as well as A and B, A and C, B and C, as well as A, B, and C.
  • the phrases “electrochemical cell” or “battery cell” shall mean a single cell including a positive electrode and a negative electrode, which have ionic communication between the two using an electrolyte. In some embodiments, the same battery cell includes multiple positive electrodes and/or multiple negative electrodes enclosed in one container.
  • a "binder” refers to a material that assists in the adhesion of another material. Binders useful in the present invention include, but are not limited to,
  • polypropylene PP
  • atactic polypropylene aPP
  • isotactive polypropylene iPP
  • ethylene propylene rubber EPR
  • ethylene pentene copolymer EPC
  • polyisobutylene PIB
  • styrene butadiene rubber SBR
  • polyolefins polyethylene-co-poly- 1-octene (PE-co-PO)
  • PE-co-PMCP PE-co-PMCP
  • stereoblock polypropylenes polypropylene polymethylpentene copolymer, acrylics, acrylates, polyvinyl butyral, vinyl family, cellulose family, polyethylene glycol, resins, polyvinyl alcohol, polymethyl methacrylate, polyvinyl pyrrolidone, polyacrylamide, polyethylene oxide (PEO), PEO block copolymers, silicone, and the like.
  • the term "surface” refers to material that is near or at an interface between two different phases, chemicals, or states of matter.
  • a thin film garnet membrane or separator when exposed to air has a surface described by the periphery or outside portion of the membrane or separator which contacts the air.
  • a top and a bottom surface which both individually have higher surface areas than each of the four side surfaces individually.
  • this rectangular membrane or separator example such as the example shown in Figure 13, there are also four side surfaces which have surface areas less than either or both of the top and bottom surfaces.
  • top and a bottom surface which both individually have higher surface areas than the circumference-side of the disc.
  • the top or bottom surface is the side or part of the membrane or separator which contacts the negative electrode (i.e., Li metal), which contacts the positive electrode (i.e. cathode or catholyte in cathode), and/or which contacts a layer or bonding agent disposed between the membrane or separator and the positive electrode.
  • a surface has larger x- and y-axis physical dimensions that it does z-axis physical dimensions, wherein the z-axis is the axis perpendicular to the surface.
  • the depth or thickness of a surface can be of molecular order of magnitude or up to 1 micron.
  • Oxide surfaces can include dangling bonds, excess hydroxyl groups, bridging oxides, or a variety of other species which result in the oxide surface having a chemical composition that may be
  • the bulk is characterized by a chemical formula of Li x La 7 Zr 2 0i 2 Al 2 0 3 and the surface is characterized by a chemical formula of Li y La 7 Zr 2 0i 2 Al 2 0 3 , wherein, in this paragraph, x is greater than y.
  • the term "bulk,” refers to a portion or part of a material that is extended in space in three-dimensions by at least 1 micron.
  • the bulk refers to the portion or part of a material which is exclusive of its surface, as defined above.
  • cathode and anode refer to the electrodes of a battery.
  • Li ions leave the cathode and move through an electrolyte and to the anode.
  • electrons leave the cathode and move through an external circuit to the anode.
  • Li ions migrate towards the cathode through an electrolyte and from the anode.
  • electrons leave the anode and move through an external circuit to the cathode.
  • a "catholyte” refers to an ion conductor that is intimately mixed with, or that surrounds, or that contacts the positive electrode active material.
  • Catholytes suitable with the embodiments described herein include, but are not limited to, catholytes having the common name LPS, LXPS, LXPSO, where X is Si, Ge, Sn, As, Al, LATS, or also Li-stuffed garnets, or combinations thereof, and the like.
  • Catholytes may also be liquid, gel, semi- liquid, semi-solid, polymer, and/or solid polymer ion conductors known in the art.
  • Catholytes include those catholytes set forth in US Patent Application Publication No. 2015-0171465, which published on June 18, 2015, entitled SOLID STATE CATHOLYTE OR
  • Catholytes include those catholytes set forth in US Patent Application Publication No. 2015/0099190, published on April 9, 2015, entitled GARNET MATERIALS FOR LI SECONDARY
  • solid state catholyte refers to an ion conductor that is intimately mixed with, or surrounded by, a cathode (i.e., positive electrode) active material (e.g., a metal fluoride optionally including lithium).
  • a cathode i.e., positive electrode
  • active material e.g., a metal fluoride optionally including lithium
  • the catholyte may include a gel electrolyte such as, but not limited to, the electrolyte compositions set forth in U. S. Patent Nos. 5,296,318, entitled RECHARGEABLE LITHIUM INTERCALATION BATTERY WITH HYBRID POLYMERIC ELECTROLYTE; also 5,460,904; also 5,456,000, to Gozdz, et al., or those compositions set forth in US Patent Application No. 20020192561, entitled SEPARATORS FOR WINDING-TYPE LITHIUM SECONDARY BATTERIES HAVING GEL-TYPE POLYMER ELECTROLYTES AND MANUFACTURING METHOD FOR THE SAME, which published December 19, 2002.
  • a gel electrolyte such as, but not limited to, the electrolyte compositions set forth in U. S. Patent Nos. 5,296,318, entitled RECHARGEABLE LITHIUM INTERCALATION BATTERY WITH HYBRID POLYMERIC ELECTROLYTE;
  • the phrase "current collector” refers to a component or layer in a secondary battery through which electrons conduct, to or from an electrode in order to complete an external circuit, and which are in direct contact with the electrode to or from which the electrons conduct.
  • the current collector is a metal (e.g., Al, Cu, or Ni, steel, alloys thereof, or combinations thereof) layer which is laminated to a positive or negative electrode.
  • the current collector moves in the opposite direction to the flow of Li ions and pass through the current collector when entering or exiting an electrode.
  • electrolyte refers to a material that allows ions, e.g., Li+, to migrate therethrough but which does not allow electrons to conduct therethrough.
  • Electrolytes are useful for electrically isolating the cathode and anodes of a secondary battery while allowing ions, e.g., Li + , to transmit through the electrolyte. Electrolytes are ionically conductive and electrically insulating material. Electrolytes are useful for electrically insulating the positive and negative electrodes of a secondary battery while allowing for the conduction of ions, e.g., Li + , through the electrolyte.
  • d 50 diameter or “median diameter (d 50 )” refers to the median size, in a distribution of sizes, measured by microscopy techniques or other particle size analysis techniques, such as, but not limited to, scanning electron microscopy or dynamic light scattering.
  • D 50 describes a characteristic dimension of particles at which 50% of the particles are smaller than the recited size.
  • diameter (d 90 ) refers to the size, in a distribution of sizes, measured by microscopy techniques or other particle size analysis techniques, including, but not limited to, scanning electron microscopy or dynamic light scattering.
  • D 90 includes the characteristic dimension at which 90% of the particles are smaller than the recited size.
  • diameter (di 0 ) refers to the size, in a distribution of sizes, measured by microscopy techniques or other particle size analysis techniques, including, but not limited to, scanning electron microscopy or dynamic light scattering. Di 0 includes the characteristic dimension at which 10% of the particles are smaller than the recited size.
  • the term “rational number” refers to any number which can be expressed as the quotient or fraction (e.g., p/q) of two integers (e.g., p and q), with the denominator (e.g., q) not equal to zero.
  • Example rational numbers include, but are not limited to, 1, 1.1, 1.52, 2, 2.5, 3, 3.12, and 7.
  • free-standing thin film refers to a film that is not adhered or supported by an underlying substrate.
  • free-standing thin film is a film that is self-supporting, which can be mechanically manipulated or moved without need of substrate adhered or fixed thereto.
  • the molar ratios unless specified to the contrary, describe the ratio of constituent elements as batched in the reaction used to make the described material.
  • a "thickness" by which is film is characterized refers to the distance, or median measured distance, between the top and bottom faces of a film.
  • the top and bottom faces refer to the sides of the film having the largest surface areas.
  • film thickness refers to the distance, or median measured distance, between the top and bottom faces of a film.
  • top and bottom faces refer to the sides of the film having the largest surface areas.
  • the word “thickness” in the phrase “a thin electrolyte membrane, having top and bottom surfaces and a thickness therebetween” refers to the distance, or median measured distance, between the top and bottom surfaces of a film.
  • the top and bottom surfaces refer to the sides of the film having the largest surface areas.
  • electrolyte separator or membrane thickness is measured by cross- sectional scanning electron microscopy.
  • active electrode material refers to a material that is suitable for use as a Li rechargeable battery and which undergoes a chemical reaction during the charging and discharging cycles.
  • active cathode material includes a metal fluoride that converts to a metal and lithium fluoride during the discharge cycle of a Li rechargeable battery.
  • active anode material refers to an anode material that is suitable for use in a Li rechargeable battery that includes an active cathode material as defined above.
  • the active material is Lithium metal.
  • the sintering temperatures are high enough to melt the Lithium metal used as the active anode material.
  • free-standing thin film refers to a film that is not adhered or supported by an underlying substrate. In some examples, free-standing thin film is a film that is self-supporting, which can be mechanically manipulated or moved without need of substrate adhered or fixed thereto.
  • Density as determined by geometric measurements refers to measurements of density obtained by physical mass and volume measurements. Density is determined by the ratio of measured mass to the measured volume. Customary techniques including the Archimedes method have been employed for such determinations.
  • the phrase "current collector” refers to a component or layer in a secondary battery through which electrons conduct, to or from an electrode in order to complete an external circuit, and which are in direct contact with the electrode to or from which the electrons conduct.
  • the current collector is a metal (e.g., Al, Cu, or Ni, steel, alloys thereof, or combinations thereof) layer which is laminated to a positive or negative electrode.
  • the current collector moves in the opposite direction to the flow of Li ions and pass through the current collector when entering or exiting an electrode.
  • slot casting refers to a deposition process whereby a substrate is coated, or deposited, with a solution, liquid, slurry, or the like by flowing the solution, liquid, slurry, or the like, through a slot or mold of fixed dimensions that is placed adjacent to, in contact with, or onto the substrate onto which the deposition or coating occurs.
  • slot casting includes a slot opening of about 1 to 100 ⁇ .
  • the term “laminating” refers to the process of sequentially depositing a layer of one precursor specie, e.g., a lithium precursor specie, onto a deposition substrate and then subsequently depositing an additional layer onto an already deposited layer using a second precursor specie, e.g., a transition metal precursor specie. This laminating process can be repeated to build up several layers of deposited vapor phases.
  • the term “laminating” also refers to the process whereby a layer comprising an electrode, e.g., positive electrode or cathode active material comprising layer, is contacted to a layer comprising another material, e.g., garnet electrolyte.
  • the laminating process may include a reaction or use of a binder which adheres of physically maintains the contact between the layers which are laminated.
  • green film refers to an unsintered film including at least one member selected from garnet materials, precursors to garnet materials, calcined garnet materials, binder, solvent, carbon, dispersant, or combinations thereof.
  • providing an unsintered thin film refers to the provision of, generation or, presentation of, or delivery of an unsintered thin film or a green film defined above.
  • providing an unsintered thin film refers to the process of making an unsintered thin film available, or delivering an unsintered thin film, such that the unsintered thin film can be used as set forth in a method described herein.
  • the phrase "unsintered thin film,” refers to a thin film, including the components and materials described herein, but which is not sintered by a sintering method set forth herein.
  • Thin refers, for example, to a film that has an average thickness dimensions of about 10 nm to about 100 ⁇ . In some examples, thin refers to a film that is less than about 1 ⁇ , 10 ⁇ or 50 ⁇ in thickness.
  • the phrase "evaporating the cathode current collector,” refers to a process of providing or delivering a metal, such as, but not limited to, copper, nickel, aluminum, or an combination thereof, in vapor or atomized form such that the metal contacts and forms an adhering layer to the cathode, catholyte, or combinations thereof or to the anode, anolyte, or combinations thereof. This process results in the formation of a metal layer on a cathode or anode such that the metal layer and the cathode or anode are in electrical communication.
  • a metal such as, but not limited to, copper, nickel, aluminum, or an combination thereof
  • making refers to the process or method of forming or causing to form the object that is made.
  • making an energy storage electrode includes the process, process steps, or method of causing the electrode of an energy storage device to be formed.
  • the end result of the steps constituting the making of the energy storage electrode is the production of a material that is functional as an electrode.
  • energy storage electrode refers to, for example, an electrode that is suitable for use in an energy storage device, e.g., a lithium rechargeable battery or Li-secondary battery. As used herein, such an electrode is capable of conducting electrons and Li ions as necessary for the charging and discharging of a rechargeable battery.
  • the phrase “electrochemical device” refers to an energy storage device, such as, but not limited to a Li-secondary battery that operates or produces electricity or an electrical current by an electrochemical reaction, e.g., a conversion chemistry reaction such as 3Li + FeF 3 ⁇ 3LiF + Fe.
  • the phrase “providing” refers to the provision of, generation or, presentation of, or delivery of that which is provided.
  • lithium stuffed garnet refers to oxides that are characterized by a crystal structure related to a garnet crystal structure.
  • Lithium-stuffed garnets include compounds having the formula Li A La B M' c M" D Zr E 0 F , Li A La B M'cM" D Ta E O F , or
  • Li A La B M'cM" D Nb E O F wherein 4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 2, 10 ⁇ F ⁇ 13, and M' and M" are each, independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta, or Li a La b Zr c Al d Me" e O f , wherein 5 ⁇ a ⁇ 7.7; 2 ⁇ b ⁇ 4; 0 ⁇ c ⁇ 2.5; 0 ⁇ d ⁇ 2; 0 ⁇ e ⁇ 2, 10 ⁇ f ⁇ 13 and Me" is a metal selected from Nb, Ta, V, W, Mo, or Sb and as described herein.
  • Garnets as used herein, also include those garnets described above that are doped with A1 2 0 3 . Garnets, as used herein, also include those garnets described above that are doped so that Al 3+ substitutes for Li + .
  • garnet used herein includes, but is not limited to, Li x La 3 Zr 2 0i 2 + yAl 2 0 3 , wherein x ranges from 5.5 to 9; and y ranges from 0 to 1.
  • x is 7 and y is 1.0.
  • x is 7 and y is 0.35.
  • x is 7 and y is 0.7.
  • x is 7 and y is 0.4.
  • garnets as used herein include, but are not limited to, Li x La 3 Zr 2 0i 2 + yAl 2 0 3 .
  • garnet does not include YAG-garnets (i.e., yttrium aluminum garnets, or, e.g., Y 3 Al 5 0i 2 ).
  • garnet does not include silicate-based garnets such as pyrope, almandine, spessartine, grossular, hessonite, or cinnamon-stone,
  • Garnets herein do not include nesosilicates having the general formula X 3 Y 2 (Si0 4 ) 3 wherein X is Ca, Mg, Fe, and, or, Mn; and Y is Al, Fe, and, or, Cr.
  • garnet precursor chemicals or "chemical precursor to a Garnet-type electrolyte” refers to chemicals which react to form a lithium stuffed garnet material described herein.
  • These chemical precursors include, but are not limited to lithium hydroxide (e.g., Li OH), lithium oxide (e.g., Li 2 0), lithium carbonate (e.g., LiC0 3 ), zirconium oxide (e.g., Zr0 2 ), lanthanum oxide (e.g., La 2 0 3 ), aluminum oxide (e.g., A1 2 0 3 ), aluminum (e.g., Al), aluminum nitrate (e.g., A1N0 3 ), aluminum nitrate nonahydrate, niobium oxide (e.g., Nb 2 05), tantalum oxide (e.g., Ta 2 0 5 ).
  • lithium hydroxide e.g., Li OH
  • lithium oxide e.g., Li 2 0
  • lithium carbonate e.
  • the phrase "garnet-type electrolyte,” refers to an electrolyte that includes a garnet or lithium stuffed garnet material described herein as the ionic conductor.
  • the phrase "doped with alumina” means that A1 2 0 3 is used to replace certain components of another material, e.g., a garnet.
  • a lithium stuffed garnet that is doped with A1 2 0 3 refers to garnet wherein aluminum (Al) substitutes for an element in the lithium stuffed garnet chemical formula, which may be, for example, Li or Zr.
  • aluminum reaction vessel refers to a container or receptacle into which precursor chemicals are placed in order to conduct a chemical reaction to produce a product, e.g., a lithium stuffed garnet material.
  • high conductivity refers to a conductivity, such as ionic conductivity, that is greater than 10 "5 S/cm at room temperature. In some examples, high conductivity includes a conductivity greater than 10 "5 S/cm at room temperature.
  • Zr is partially replaced by a higher valence species
  • a higher valence species refers to the substitution of Zr 4+ with a species that has, for example, a 5 + or 6 + charge.
  • Nb 5+ can reside in a lattice position in a garnet crystal structure where a Zr atom resides and in doing so substitute for Zr 4+ , then Zr is partially replaced by Nb. This is also referred to as niobium doping.
  • the phrase "subscripts and molar coefficients in the empirical formulas are based on the quantities of raw materials initially batched to make the described examples” means the subscripts, (e.g., 7, 3, 2, 12 in Li 7 La 3 Zr 2 0i 2 and the coefficient 0.35 in 0.35Al 2 O 3 ) refer to the respective elemental ratios in the chemical precursors (e.g., LiOH, La 2 0 3 , Zr0 2 , A1 2 0 3 ) used to prepare a given material, (e.g., Li 7 La 3 Zr 2 Oi 2 0.35Al 2 O 3 ).
  • the term "grains” refers to domains of material within the bulk of a material that have a physical boundary which distinguishes the grain from the rest of the material. For example, in some materials both crystalline and amorphous components of a material, often having the same chemical composition, are distinguished from each other by the boundary between the crystalline component and the amorphous component. The approximate diameter or maximum dimensions of the boundaries of a crystalline component, or of an amorphous component, is referred herein as the grain size.
  • active electrode material refers to a material that is suitable for use as a Li rechargeable battery and which undergoes a chemical reaction during the charging and discharging cycles.
  • active cathode material includes a metal fluoride that converts to a metal and lithium fluoride during the discharge cycle of a Li rechargeable battery.
  • active anode material refers to an anode material that is suitable for use in a Li rechargeable battery that includes an active cathode material as defined above.
  • the active material is Lithium metal.
  • the sintering temperatures are high enough to melt the Lithium metal used as the active anode material.
  • conductive additive refers to a material that is mixed with the cathode active material in order to improve the conductivity of the cathode. Examples includes, but are not limited to, carbon and the various forms of carbon, e.g., ketjen black, VGCF, acetylene black, graphite, graphene, nanotubes, nanofibers, the like, and combinations thereof.
  • the phrase "casting a film,” refers to the process of delivering or transferring a liquid or a slurry into a mold, or onto a substrate, such that the liquid or the slurry forms, or is formed into, a film. Casting may be done via doctor blade, meyer rod, comma coater, gravure coater, microgravure, reverse comma coater, slot dye, slip and/or tape casting, and other methods known to those skilled in the art.
  • applying a pressure refers to a process whereby an external device, e.g., a calender, induces a pressure in another material.
  • the phrase "burning the binder or calcining the unsintered film,” refers to the process whereby a film that includes a binder is heated, optionally in an environment that includes an oxidizing specie, e.g., 0 2 , in order to burn the binder or induce a chemical reaction that drives off, or removes, the binder, e.g., combustion, or which causes a film having a binder to sinter, to become more dense or less porous.
  • an oxidizing specie e.g., 0 2
  • composite electrode refers to an electrode that is composed of more than one material.
  • a composite electrode may include, but is not limited to, an active cathode material and a garnet-type electrolyte in intimate mixture or ordered layers or wherein the active material and the electrolyte are interdigitated.
  • inert setter plates refer to plates, which are normally flat, and which are unreactive with a material that is sintered.
  • Inert setter plates can be metallic or ceramic, and, optionally, these setter plates can be porous to provide for the diffusion of gases and vapors therethrough when a sintered material is actually sintered.
  • Inert setter plates are exemplified in U.S. Provisional Patent Application No. 62/148,337, filed April 16, 2015.
  • free-standing thin film refers to a film that is not adhered or supported by an underlying substrate.
  • free-standing thin film is a film that is self-supporting, which can be mechanically manipulated or moved without need of substrate adhered or fixed thereto.
  • the phrase "wherein either the top or bottom surface is characterized as having substantially no layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof,” refers to a material set forth herein where the material's top or bottom surface is not observed to have a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof when analyzed by Raman, FT-IR, or XPS spectroscopy.
  • a thin electrolyte separator having top and bottom surfaces and a thickness therebetween, wherein the top or bottom surface length or width is greater than the thickness by a factor of ten (10) or more, and the thickness is from about 10 nm to about 100 ⁇ .
  • the electrolyte bulk is characterized by the chemical formula Li x La 3 Zr 2 0i 2 y(Al 2 0 3 ), wherein 3 ⁇ x ⁇ 8 and 0 ⁇ y ⁇ l .
  • the top or bottom surface is characterized as having a layer thereupon, greater than 1 nm and less than 1 ⁇ , comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • a thin electrolyte separator having top and bottom surfaces and a thickness therebetween, wherein the top or bottom surface length or width is greater than the thickness by a factor of ten (10) or more, and the thickness is from about 10 nm to about 100 ⁇ .
  • the electrolyte bulk is characterized by the chemical formula LixLa3Zr2012 y(A1203), wherein 3 ⁇ x ⁇ 8 and 0 ⁇ y ⁇ l .
  • either the top or bottom surface is characterized as having substantially no layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • either the top or bottom surface is characterized as having substantially no layer thereupon comprising a lithium carbonate. In certain examples, either the top or bottom surface is characterized as having substantially no layer thereupon comprising a lithium hydroxide. In certain examples, either the top or bottom surface is characterized as having substantially no layer thereupon comprising a lithium oxide. In certain examples, either the top or bottom surface is characterized as having substantially no layer thereupon comprising a lithium peroxide. In certain examples, either the top or bottom surface is characterized as having substantially no layer thereupon comprising a hydrate of any of the aforementioned. In certain examples, either the top or bottom surface is characterized as having substantially no layer thereupon comprising a peroxide of any of the aforementioned. In certain examples, either the top or bottom surface is characterized as having substantially no layer thereupon comprising an oxide of any of the aforementioned.
  • the electrolyte separator has a top or bottom surface length or width is from about 100 ⁇ to 100 cm.
  • the electrolyte separator has an x as 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, or 8.
  • the electrolyte separator bulk is characterized by the chemical formula Li 3 La 3 Zr 2 O h 0.2(Al 2 O 3 ), Li 3 La3Zr 2 O h 0.25(Al 2 O3), Li 3 La 3 Zr 2 O h 0.3(Al 2 O 3 ),
  • Li 3 La 3 Zr 2 O h 0.5(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 3 La 3 Zr 2 O h 0.6(Al 2 O 3 ),
  • Li 5 La 3 Zr 2 O h 0.5(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.6(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.7(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.75(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.8(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.85(Al 2 O 3 ), Li 5 La 3 Zr 2 O h 0.9(Al 2 O 3 ),
  • Li 6 La 3 Zr 2 O h 0.6(Al 2 O 3 ), Li 6 La 3 Zr 2 O ll 0.55(Al 2 O 3 ), Li 6 La 3 Zr 2 O ll 0.7(Al 2 O 3 ),
  • Li 7 La 3 Zr 2 O h 0.5(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.6(Al 2 O 3 ),
  • Li 7 La 3 Zr 2 O h 0.5(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.55(Al 2 O 3 ), Li 7 La 3 Zr 2 O h 0.6(Al 2 O 3 ),
  • Li 8 La 3 Zr 2 O h 0.8(Al 2 O 3 ), Li 8 La 3 Zr 2 Oi 1 0.85(Al 2 O 3 ), Li 8 La 3 Zr 2 Oi 1 0.8(Al 2 O 3 ),
  • Li 8 La 3 Zr 2 O h (Al 2 O 3 ), Li 8 La 3 Zr 2 O ll 0.3(Al 2 O 3 ), Li 8 La 3 Zr 2 O ll 0.35(Al 2 O 3 ),
  • Li 8 La 3 Zr 2 O h 0.8(Al 2 O 3 ), Li 8 La 3 Zr 2 Oi 1 0.85(Al 2 O 3 ), Li 8 La 3 Zr 2 Oi 1 0.8(Al 2 O 3 ),
  • subscript h is a number selected so that the chemical characterized by the formula is charge neutral. Subscript h can be any rational number greater than 0 or less than 15 as required to maintain charge neutrality.
  • h is 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, or 15.
  • h is 9, 10, 11, 12, or 13.
  • h is 10, 11, or 12.
  • h is 11 or 12.
  • h is 12 or 13.
  • h is 12.
  • the electrolyte separator bulk is characterized by the chemical formula LisLasZ ⁇ O O ⁇ A ⁇ Os), Li 3 La3Zr2Oi20.25(Al 2 O3), Li3La3Zr 2 Oi 2 0.3(Al 2 O3), Li3La3Zr2Oi20.35(Al2O3), Li3La3Zr2Oi20.4(Al2O3), Li3La3Zr 2 Oi20.45(Al2O3),
  • Li3La3Zr 2 Oi 2 0.5(Al 2 O3), Li3La3Zr 2 Oi 2 0.55(Al 2 O3), Li 3 La3Zr 2 Oi20.6(Al 2 O3),
  • the electrolyte separator electrolyte bulk is characterized by a chemical formula different from the top or bottom surface of the electrolyte separator.
  • the electrolyte separator electrolyte bulk is characterized by the chemical formula Li x iLa 3 Zr 2 0i 2 y(Al 2 0 3 ), wherein 3 ⁇ xl ⁇ 8 and 0 ⁇ y ⁇ l ;
  • top or bottom surface or both is/are characterized by the chemical formula y(Al 2 0 3 ), wherein 3 ⁇ xl ⁇ 8 and 0 ⁇ y ⁇ l, wherein x2 is less than xl .
  • the electrolyte separator has either the top or bottom surface as characterized as having less than a 0.5 ⁇ thick layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • either the top or bottom surface is characterized as having less than a 0.35 ⁇ thick layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • either the top or bottom surface is characterized as having less than a 0.25 ⁇ thick layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • either the top or bottom surface is characterized as having less than a 0.15 ⁇ thick layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • either the top or bottom surface is characterized as having less than a 0.1 ⁇ thick layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • either the top or bottom surface is characterized as having less than a 0.05 ⁇ thick layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • both the top and bottom surfaces are characterized as having a similar thickness layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • both the top and bottom surfaces are characterized as having no detectable presence of lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, or a combination thereof as detected by XPS or FT-IR.
  • both the top and bottom surfaces are characterized as having no secondary phases present on the top or bottom surface, wherein secondary phases are selected from LiA10 2 , Li 2 Zr0 3 , LaA10 3 , Li 5 A104, Li 6 Zr 2 0 7 , La 2 (Li x Ali -x )04, wherein x is from 0 to 1, or combinations thereof.
  • both the top and bottom surfaces are characterized as having the same thickness layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • the separator a Li-metal interface area specific resistance between 0 and 15 Qcm 2 at 60°C. In some examples, the Li -metal interface area specific resistance is less than 2 Qcm 2 at 60 °C. In other examples, the Li-metal interface area specific resistance is less than 2 Qcm 2 at 25 °C. In certain examples, the Li-metal interface area specific resistance is less than 20 Qcm 2 at -25 °C.
  • the separator is a pellet, a film, free-standing film, or a monolith.
  • the lithium carbonate is characterized by Li x (C0 3 ) y and x is from 0 to 2, and y is from 0 to 1.
  • the lithium hydroxide is characterized by Li x (OH) y and x and y are each, independently, from 0 to 1.
  • the lithium oxide is characterized by Li x O y and x and y are each, independently, from 0 to 2.
  • the electrolyte separator is characterized by an EPR spectrum substantially as shown in FIG. 4.
  • the top or bottom surface of the electrolyte membrane or separator is characterized by an FT-IR spectrum substantially as shown in FIG. 9
  • the top or bottom surface is characterized by a Raman spectrum substantially as shown in FIG. 10.
  • electrolyte separators or membranes characterized by the chemical formula Li x La 3 Zr 2 0i 2 + yAl 2 0 3 , wherein 3 ⁇ x ⁇ 8 and 0 ⁇ y ⁇ l and having a top or bottom surface that has less than 5 atomic % of an amorphous material comprising carbon and oxygen.
  • the top or bottom surface is in direct contact with Li-metal.
  • the top or bottom surface that has a carbon concentration at the surface of less than 5 atomic %.
  • the top or bottom surface that has a hydrogen concentration at the surface of less than 5 atomic %.
  • the atomic % of carbon is measured by XPS.
  • the atomic % of hydrogen is measured by SIMS.
  • the electrolyte separator or membrane has an Oxygen (O) vacancy concentration characterized by an EPR signal spin density of 1 x 10 "18 /cm 3 to l l0- 20 /cm 3 .
  • the electrolyte separator or membrane has a spin density equal to about l x lO "19 /cm 3 .
  • compositions and methods set forth herein include a Garnet- type electrolyte material selected from Li x La 3 Zr 2 O z yAl 2 0 3 , wherein x is from 5 to 7.5; z is from 1 1 to 12.25; and y is from 0 to 1.
  • Li A LaBM'cM”DTa E OF Li A La B M'cM” D Nb E 0 F , wherein 4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 2, 10 ⁇ F ⁇ 14, and M' and M' are each, independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta, or Li a La b Zr c Al d Me" e O f , wherein 5 ⁇ a ⁇ 7.7; 2 ⁇ b ⁇ 4; 0 ⁇ c ⁇ 2.5; 0 ⁇ d ⁇ 2; 0 ⁇ e ⁇ 2, 10 ⁇ f ⁇ 14 and Me" is a metal selected from Nb, Ta, V, W, Mo, or Sb, or combinations thereof.
  • the methods set forth herein include a Garnet-type electrolyte material selected from Li A La B M' c M" D Zr E OF, Li A LaBM'cM' D Ta E OF, Li A La B M'cM' D Nb E OF, wherein 4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 2, 10 ⁇ F ⁇ 14, and M' and M" are each, independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta, or Li a La Zr c Al d Me"eO f , wherein 5 ⁇ a ⁇ 7.7; 2 ⁇ b ⁇ 4; 0 ⁇ c ⁇ 2.5; 0 ⁇ d ⁇ 2; 0 ⁇ e ⁇ 2, 10 ⁇ f ⁇ 14 and Me" is a metal selected from Nb, Ta, V, W, Mo, or Sb, or combinations thereof.
  • a Garnet-type electrolyte material selected from Li A La
  • the methods set forth herein include a Garnet-type electrolyte material selected from Li A La B M' c M" D Zr E OF, Li A La B M'cM” D Ta E OF, Li A La B M'cM” D Nb E OF, wherein 4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 2, 10 ⁇ F ⁇ 13, and M* and M" are each, independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta, or Li a La b Zr c Al d Me" e O f , wherein 5 ⁇ a ⁇ 7.7; 2 ⁇ b ⁇ 4; 0 ⁇ c ⁇ 2.5; 0 ⁇ d ⁇ 2; 0 ⁇ e ⁇ 2, 10 ⁇ f ⁇ 13 and Me" is a metal selected from Nb, Ta, V, W, Mo, or Sb, or combinations thereof.
  • a Garnet-type electrolyte material selected
  • the methods set forth herein include a Garnet-type electrolyte selected from Li A La B M' c M" D Nb E 0 F , wherein 4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 2, 10 ⁇ F ⁇ 14, and M' and M" are each, independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta, or combinations thereof.
  • the methods set forth herein include a Garnet-type electrolyte selected from Li A La B M'cM" D Nb E O F , wherein 4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 2, 10 ⁇ F ⁇ 13, and M' and M" are each, independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta.
  • the methods set forth herein include a Garnet-type electrolyte selected from Li a La Zr c Al d Me" e O f , wherein 5 ⁇ a ⁇ 7.7; 2 ⁇ b ⁇ 4; 0 ⁇ c ⁇ 2.5; 0 ⁇ d ⁇ 2; 0 ⁇ e ⁇ 2, 10 ⁇ f ⁇ 14 and Me" is a metal selected from Nb, Ta, V, W, Mo, or Sb.
  • the methods set forth herein include a Garnet-type electrolyte selected from Li a La Zr c Al d Me" e O f , wherein 5 ⁇ a ⁇ 7.7; 2 ⁇ b ⁇ 4; 0 ⁇ c ⁇ 2.5; 0 ⁇ d ⁇ 2; 0 ⁇ e ⁇ 2, 10 ⁇ f ⁇ 13 and Me" is a metal selected from Nb, Ta, V, W, Mo, or Sb.
  • the garnet material described herein is used as an electrolyte.
  • the garnet has the formula Li x La 3 Zr 2 0i 2 y1 ⁇ 2Al 2 0 3 ; wherein 5.0 ⁇ x ⁇ 9 and 0.1 ⁇ y ⁇ 1.5.
  • the electrolyte is Li x La 3 Zr 2 Oi 2 0.35Al 2 O 3 . In other of these examples, the electrolyte is Li 7 La 3 Zr 2 Oi 2 0.35Al 2 O 3 .
  • the garnet does not include any Nb, Ta, W or Mo, which is used herein to mean that the concentration of those elements (e.g., Nb, Ta, W, or Mo) is 10 parts per million (ppm) or lower. In some examples, the concentration of those elements (e.g., Nb, Ta, W, or Mo) is 1 parts per million (ppm) or lower. In some examples, the concentration of those elements (e.g., Nb, Ta, W, or Mo) is 0.1 parts per million (ppm) or lower.
  • the Lithium stuffed garnet set forth herein can be represented by the general formula Li x A 3 B 2 0i 2 , wherein 5 ⁇ x ⁇ 7.
  • A is a large ion occupying an 8-fold coordinated lattice site.
  • A is La, Sr, Ba, Ca, or a combination thereof.
  • B is a smaller more highly charged ion occupying an octahedral site.
  • B is Zr, Hf, Nb, Ta, Sb, V, or a combination thereof.
  • the composition is doped with 0.3 to 1 molar amount of Al per Li x A 3 B 2 0i 2 . In certain of these examples, the composition is doped with 0.35 molar amount of Al per Li x A 3 B 2 0i 2 .
  • the lithium stuffed garnet is Li 7 La 3 Zr 2 0i 2 (LLZ) and is doped with alumina.
  • the LLZ is doped by adding A1 2 0 3 to the reactant precursor mix that is used to make the LLZ.
  • the LLZ is doped by the aluminum in an aluminum reaction vessel that contacts the LLZ.
  • the alumina doped LLZ has a high conductivity, e.g., greater than 10 "4 S/cm at room temperature.
  • a higher conductivity is observed when some of the Zr is partially replaced by a higher valence species, e.g., Nb, Ta, Sb, or combinations thereof. In some examples, the conductivity reaches as high as 10 "3 S/cm at room temperature.
  • a higher valence species e.g., Nb, Ta, Sb, or combinations thereof.
  • the conductivity reaches as high as 10 "3 S/cm at room temperature.
  • the composition set forth herein is Li x A 3 B 2 0i 2 doped with 0.35 molar amount of Al per Li x A 3 B 2 0i 2 .
  • x is 5. In certain other examples, x is 5.5. In yet other examples, x is 6.0. In some other examples, x is 6.5. In still other examples, x is 7.0. In some other examples, x is 7.5.
  • the garnet-based composition is doped with 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 1 molar amount of Al per Li x A 3 B 2 0i 2 .
  • the garnet-based composition is doped with 0.35 molar amount of
  • the instant disclosure provides a composition including a lithium stuffed garnet and A1 2 0 3 .
  • the lithium stuffed garnet is doped with alumina.
  • the lithium-stuffed garnet is characterized by the empirical formula Li A La B M' c M" D Zr E O F , wherein 4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 2, 10 ⁇ F ⁇ 13, and M' and M" are, independently in each instance, either absent or are each independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; and wherein the molar ratio of Garnet: A1 2 0 3 is between 0.05 and 0.7.
  • the instant disclosure provides a composition including a lithium stuffed garnet and A1 2 0 3 .
  • the lithium stuffed garnet is doped with alumina.
  • the lithium-stuffed garnet is characterized by the empirical formula Li A La B M' c M" D Zr E O F , wherein 4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 2, 10 ⁇ F ⁇ 13, and M' and M" are, independently in each instance, either absent or are each independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; and wherein the molar ratio of Li:Al is between 0.05 and 0.7.
  • the instant disclosure provides a composition including a lithium stuffed garnet and A1 2 0 3 .
  • the lithium stuffed garnet is doped with alumina.
  • the lithium-stuffed garnet is characterized by the empirical formula Li A La B M' c M" D Zr E O F , wherein 2 ⁇ A ⁇ 10, 2 ⁇ B ⁇ 6, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 3, 8 ⁇ F ⁇ 14, and M' and M" are, independently in each instance, either absent or are each independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; and wherein the molar ratio of Garnet: A1 2 0 3 is between 0.01 and 2.
  • the instant disclosure provides a composition including a lithium stuffed garnet and A1 2 0 3 .
  • the lithium stuffed garnet is doped with alumina.
  • the lithium-stuffed garnet is characterized by the empirical formula Li A La B M' c M" D Zr E O F , wherein 2 ⁇ A ⁇ 10, 2 ⁇ B ⁇ 6, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 3, 8 ⁇ F ⁇ 14, and M' and M" are, independently in each instance, either absent or are each independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; and wherein the molar ratio of Li:Al is between 0.01 and 2.
  • the lithium stuffed garnet is Li A La B ZrcM' D M" E Oi 2 and 5 ⁇ A ⁇ 7.7, 2 ⁇ B ⁇ 4, 0 ⁇ C ⁇ 2.5
  • M' comprises a metal dopant selected from a material including Al and 0 ⁇ D ⁇ 2
  • M" comprises a metal dopant selected from a material including Nb, Ta, V, W, Mo, Sb, and wherein 0 ⁇ e ⁇ 2.
  • the lithium stuffed garnet is a lithium stuffed garnet set forth in U.S. Provisional Patent Application No. 61/887,451, entitled METHOD AND SYSTEM FOR FORMING GARNET MATERIALS WITH SINTERING PROCESS, filed October 7, 2013, the entire contents of which are herein incorporated by reference in its entirety for all purposes.
  • A is 6. In some other examples, A is 6.5. In other examples, A is 7.0. In certain other examples, A is 7.5. In yet other examples, A is 8.0.
  • B is 2. In some other examples, B is 2.5. In other examples, B is 3.0. In certain other examples, B is 3.5. In yet other examples, B is 3.5. In yet other examples, B is 4.0.
  • C is 0.5. In other examples C is 0.6. In some other examples, C is 0.7. In some other examples C is 0.8. In certain other examples C is 0.9. In other examples C is 1.0. In yet other examples, C is 1.1. In certain examples, C is 1.2. In other examples C is 1.3. In some other examples, C is 1.4. In some other examples C is 1.5. In certain other examples C is 1.6. In other examples C is 1.7. In yet other examples, C is 1.8. In certain examples, C is 1.9. In yet other examples, C is 2.0. In other examples C is 2.1. In some other examples, C is 2.2. In some other examples C is 2.3. In certain other examples C is 2.4. In other examples C is 2.5. In yet other examples, C is 2.6. In certain examples, C is 2.7. In yet other examples, C is 2.8. In other examples C is 2.9. In some other examples, C is 3.0.
  • D is 0.5. In other examples D is 0.6. In some other examples, D is 0.7. In some other examples D is 0.8. In certain other examples D is 0.9. In other examples D is 1.0. In yet other examples, D is 1.1. In certain examples, D is 1.2. In other examples D is 1.3. In some other examples, D is 1.4. In some other examples D is 1.5. In certain other examples D is 1.6. In other examples D is 1.7. In yet other examples, D is 1.8. In certain examples, D is 1.9. In yet other examples, D is 2.0. In other examples D is 2.1. In some other examples, D is 2.2. In some other examples D is 2.3. In certain other examples D is 2.4. In other examples D is 2.5. In yet other examples, D is 2.6. In certain examples, D is 2.7. In yet other examples, D is 2.8. In other examples D is 2.9. In some other examples, D is 3.0.
  • E is 0.5. In other examples E is 0.6. In some other examples, E is 0.7. In some other examples E is 0.8. In certain other examples E is 0.9. In other examples E is 1.0. In yet other examples, E is 1.1. In certain examples, E is 1.2. In other examples E is 1.3. In some other examples, E is 1.4. In some other examples E is 1.5. In certain other examples E is 1.6. In other examples E is 1.7. In yet other examples, E is
  • E is 1.9. In yet other examples, E is 2.0. In other examples E is 2.1. In some other examples, E is 2.2. In some other examples E is 2.3. In certain other examples E is 2.4. In other examples E is 2.5. In yet other examples, E is 2.6. In certain examples, E is 2.7. In yet other examples, E is 2.8. In other examples E is 2.9. In some other examples, E is 3.0.
  • F is 11.1. In other examples F is 11.2. In some other examples, F is 11.3. In some other examples F is 11.4. In certain other examples F is
  • F is 11.6. In yet other examples, F is 11.7. In certain examples, F is 11.8. In other examples F is 11.9. In some other examples, F is 12. In some other examples F is 12.1. In certain other examples F is 12.2. In other examples F is 12.3. In yet other examples, F is 12.3. In certain examples, F is 12.4. In yet other examples, F is 12.5. In other examples F is 12.6. In some other examples, F is 12.7. In some other examples F is 12.8. In certain other examples E is 12.9. In other examples F is 13.
  • a composition characterized by the empirical formula Li x La 3 Zr 2 0 12 -y1 ⁇ 2Al 2 0 3 ; wherein 5.0 ⁇ x ⁇ 9 and 0. l ⁇ y ⁇ l .5.
  • x is 5.
  • x is 5.5.
  • x is 6.
  • x is 6.5.
  • x is 7.
  • x is 7.5.
  • x is 8.
  • y is 0.3.
  • y is 0.35.
  • y 0.4.
  • y 0.45.
  • y is 0.5. In other examples, y is 0.55.
  • y is 0.6. In other examples y is 0.7. In some examples, y is 0.75. In other examples, y is 0.8. In some examples, y is 0.85. In other examples y is 0.9. In some examples, y is 0.95. In other examples, y is 1.0.
  • composition characterized by the empirical formula Li 7 0 La3(Zr t i + >t2 + Tac)Oi 2 + 0.35Al 2 O3.
  • tl+t2+t3 subscript 2 so that the molar ratio of La to the combined amount of (Zr + Nb + Ta) is 3 :2.
  • composition is characterized by the empirical formula Li 7 La 3 Zr 2 Oi 2 0.35Al 2 O3.
  • A is 5, 6, 7, or 8. In certain examples, wherein A is 7.
  • M' is Nb and M" is Ta.
  • E is 1, 1.5, or 2. In certain examples, E is 2.
  • C and D are 0.
  • the Li:Al ratio is between 7:0.2 to 7: 1.3. In some examples, the Li:Al ratio is between 7:0.3 to 7: 1.2. In some examples, the Li:Al ratio is between 7:0.3 to 7: 1.1. In some examples, the Li:Al ratio is between 7:0.4 to 7: 1.0. In some examples, the Li:Al ratio is between 7:0.5 to 7:0.9. In some examples, the Li:Al ratio is between 7:0.6 to 7:0.8. In some examples, the Li:Al ratio is about 7:0.7. In some examples, the Li:Al ratio is 7:0.7.
  • composition wherein the molar ratio of Garnet:Al 2 03 is between 0.15 and 0.55.
  • composition wherein the molar ratio of Garnet: A1 2 0 3 is between 0.25 and 0.45.
  • composition wherein the molar ratio of Garnet: AI2O3 is 0.35.
  • composition wherein the molar ratio of Al to garnet is 0.35.
  • composition wherein the lithium-stuffed garnet is characterized by the empirical formula Li 7 La3Zr 2 0i 2 and is doped with aluminum.
  • the lithium stuffed garnet is Li 7 La 3 Zr 2 0i 2 (LLZ) and is doped with alumina.
  • the LLZ is doped by adding A1 2 0 3 to the reactant precursor mix that is used to make the LLZ.
  • the LLZ is doped by the aluminum in an aluminum reaction vessel that contacts the LLZ.
  • conductive holes are introduced which increases the conductivity of the lithium stuffed garnet. In some examples, this increased conductivity is referred to as increased ionic (e.g., Li + ) conductivity.
  • Catholyte materials suitable for use with the components, devices, and methods set forth herein include, without limitation, a garnet material selected from Li A LaBM' c M"DZr E OF, Li A LaBM'cM”DTa E OF, Li ALaeM ' cM " oNb EOF, wherein 4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 2, 10 ⁇ F ⁇ 14, and M' and M" are each, independently in each instance selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta, or Li a La b Zr c Al d Me" e O f , wherein 5 ⁇ a ⁇ 7.7; 2 ⁇ b ⁇ 4; 0 ⁇ c ⁇ 2.5; 0 ⁇ d ⁇ 2; 0 ⁇ e ⁇ 2, 10 ⁇ f ⁇ 14 and Me" is a metal selected from Nb, Ta, V, W, Mo, or Sb.
  • the garnet material is LiALaBM' c M" D Zr E OF. In some other embodiments, the garnet material is LiALaBM'cM" D TaEOF. In other embodiments, the garnet material is LiALaBM'cM" D NbEOF.
  • the subscript value (4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 2, 10 ⁇ F ⁇ 14) characterize the ratio of reactants used to make the garnet material. Certain deviations from these reactant ratios may be present in the garnet products.
  • precursors to Garnet refers to the reactants used to produce or to synthesize the Garnet.
  • the subscript value (e.g., 4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4, 0 ⁇ C ⁇ 2, 0 ⁇ D ⁇ 2; 0 ⁇ E ⁇ 2, 10 ⁇ F ⁇ 13) characterize the ratio of reactants used to make the garnet material. Certain deviations from these reactant ratios may be present in the garnet products.
  • precursors to Garnet refers to the reactants used to produce Garnet.
  • the subscript values may also include 4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4,
  • C is equal to 1.99 or less.
  • the subscript values may also include 4 ⁇ A ⁇ 8.5, 1.5 ⁇ B ⁇ 4,
  • C is equal to 1.99 or less.
  • the garnet is a lithium-stuffed garnet.
  • the garnet is characterized Li a La b Zr c Al d Me" e O f , wherein the subscripts are characterized by the values noted above.
  • the lithium-stuffed garnet is a lithium lanthanum zirconium oxide that is mixed with aluminum oxide.
  • the lithium lanthanum zirconium oxide is characterized by the formula Li 7 oLa 3 Zr 2 Oi 2 + 0.35Al 2 O 3 , wherein the subscript and coefficients represent molar ratios that are determined based on the reactants used to make the garnet.
  • the ratio of La:Zr is 3 :2.
  • the garnet is Li x La 3 Zr 2 0i 2 + yAl 2 0 3 , wherein x ranges from 5.5 to 9; and y ranges from 0 to 1. In some examples x is 7 and y is 0.35.
  • the catholytes set forth herein include, in some embodiments, a hierarchical structure with a lithium conducting garnet scaffold filled with carbon electron conductive additive, lithium conductive polymer binder, and active material.
  • the active material loading can be greater than 50 volume percent to enable high energy density.
  • the garnet is sintered and retains >70% porosity to allow for the volume of the other components.
  • the disclosures herein overcomes several problems associated with the assembly of a solid energy storage device, for example, but not limited to, sintering composite electrodes having well developed contact points between particles and reduced particle-particle electrical resistance, which permits higher current flow without a significant voltage drop; also preparing methods for making entire device (electrodes, and electrolyte) in one step; also preparation methods for making solid state energy storage devices which eliminate the need to use a flammable liquid electrolyte, which is a safety hazard in some instances; and methods for FAST sintering films to reduce the process time and expense of making electrochemical devices; and methods for making FAST sintering and densifying components of electrode composites without significant interdiffusion or detrimental chemical reaction,
  • the disclosure sets forth herein a free-standing thin film Garnet- type electrolyte prepared by the method set forth herein.
  • Exemplary free-standing thin films are found, for example, in US Patent Application Publication No. 2015/0099190, published on April 9, 2015, entitled GARNET MATERIALS FOR LI SECONDARY BATTERIES AND METHODS OF MAKING AND USING GARNET MATERIALS, and filed October 7, 2014, the contents of which are incorporated by reference in their entirety.
  • a free-standing thin film Garnet-type electrolyte prepared by a method set forth herein.
  • the thickness of the free-standing film is less than 50 ⁇ . In certain embodiments, the thickness of the film is less than 40 ⁇ . In some embodiments, the thickness of the film is less than 30 ⁇ . In some other embodiments, the thickness of the film is less than 20 ⁇ . In other embodiments, the thickness of the film is less than 10 ⁇ . In yet other embodiments, the thickness of the film is less than 5 ⁇ .
  • the thickness of the film is less than 45 ⁇ . In certain embodiments, the thickness of the film is less than 35 ⁇ . In some embodiments, the thickness of the film is less than 25 ⁇ . In some other embodiments, the thickness of the film is less than 15 ⁇ . In other embodiments, the thickness of the film is less than 5 ⁇ . In yet other embodiments, the thickness of the film is less than 1 ⁇ .
  • the thickness of the film is about ⁇ to about 50 ⁇ . In certain embodiments, the thickness of the film about 10 ⁇ to about 50 ⁇ . In some embodiments, the thickness of the film is about 20 ⁇ to about 50 ⁇ . In some other embodiments, the thickness of the film is about 30 ⁇ to about 50 ⁇ . In other embodiments, the thickness of the film is about 40 ⁇ to about 50 ⁇ .
  • the thickness of the film is about ⁇ to about 40 ⁇ . In certain embodiments, the thickness of the film about ⁇ to about 40 ⁇ . In some embodiments, the thickness of the film is about 20 ⁇ to about 40 ⁇ . In some other embodiments, the thickness of the film is about 30 ⁇ to about 40 ⁇ . In other embodiments, the thickness of the film is about 20 ⁇ to about 30 ⁇ .
  • a thin and free standing sintered garnet film wherein the film thickness is less than 50 ⁇ and greater than 10 nm, and wherein the film is substantially flat; and wherein the garnet is optionally bonded to a current collector (CC) film comprising a metal or metal powder on at least one side of the film.
  • CC current collector
  • the thin and free standing sintered garnet film has thickness is less than 20 ⁇ or less than 10 ⁇ . In some examples, the thin and free standing sintered garnet film has a surface roughness of less than 5 ⁇ . In some examples, the thin and free standing sintered garnet film has a surface roughness of less than 4 ⁇ . In some examples, the thin and free standing sintered garnet film has a surface roughness of less than 2 ⁇ . In some examples, the thin and free standing sintered garnet film has a surface roughness of less than 1 ⁇ . In certain examples, the garnet has a median grain size of between 0.1 ⁇ to 10 ⁇ . In certain examples, the garnet has a median grain size of between 2.0 ⁇ to 5.0 ⁇ .
  • the films set forth herein include a film that is bound to a substrate that is selected from a polymer, a glass, or a metal.
  • the substrate adhered to or bound to the film is a current collector (CC).
  • the CC film includes a metal selected from the group consisting of Nickel (Ni), Copper (Cu), steel, stainless steel, combinations thereof, and alloys thereof.
  • the film is bonded to a metal current collector (CC) on one side of the film.
  • the CC is positioned between, and in contact with, two garnet films,
  • the thin films set forth herein are less than 50 ⁇ in thickness. In some other examples, the thin films set forth herein are less than 45 ⁇ in thickness. In certain examples, the thin films set forth herein are less than 40 ⁇ in thickness. In still other examples, the thin films set forth herein are less than 35 ⁇ in thickness. In some examples, the thin films set forth herein are less than 30 ⁇ in thickness. In some other examples, the thin films set forth herein are less than 25 ⁇ in thickness. In certain examples, the thin films set forth herein are less than 20 ⁇ in thickness. In still other examples, the thin films set forth herein are less than 15 ⁇ in thickness. In some examples, the thin films set forth herein are less than 10 ⁇ in thickness.
  • the thin films set forth herein are less than 5 ⁇ in thickness. In certain examples, the thin films set forth herein are less than 0.5 ⁇ in thickness. In still other examples, the thin films set forth herein are less than 0.1 ⁇ in thickness.
  • the thickness is 50 ⁇ .
  • the thickness is 40 ⁇ .
  • the thickness is 30 ⁇ .
  • the thickness is 20 ⁇ .
  • the thickness is 10 ⁇ .
  • the thickness is 5 ⁇ .
  • the thickness is 1 ⁇ .
  • the thickness is 0.5 ⁇ .
  • the films are 1 mm in length. In some other of these examples, the films are 5 mm in length. In yet other examples, the films are 10 mm in length. In still other examples, the films are 15 mm in length. In certain examples, the films are 25 mm in length. In other examples, the films are 30 mm in length. In some examples, the films are 35 mm in length. In some other examples, the films are 40 mm in length. In still other examples, the films are 45 mm in length. In certain examples, the films are 50 mm in length. In other examples, the films are 30 mm in length. In some examples, the films are 55 mm in length. In some other examples, the films are 60 mm in length.
  • the films are 65 mm in length. In still other examples, the films are 70 mm in length. In certain examples, the films are 75 mm in length. In other examples, the films are 80 mm in length. In some examples, the films are 85 mm in length. In some other examples, the films are 90 mm in length. In still other examples, the films are 95 mm in length. In certain examples, the films are 100 mm in length. In other examples, the films are 30 mm in length.
  • the films are 1 cm in length. In some other examples, the films are 2 cm in length. In other examples, the films are 3 cm in length. In yet other examples, the films are 4 cm in length. In some examples, the films are 5 cm in length. In other examples, the films are 6 cm in length. In yet other examples, the films are 7 cm in length. In some other examples, the films are 8 cm in length. In yet other examples, the films are 9 cm in length. In still other examples, the films are 10 cm in length. In some examples, the films are 11 cm in length. In some other examples, the films are 12 cm in length. In other examples, the films are 13 cm in length. In yet other examples, the films are 14 cm in length. In some examples, the films are 15 cm in length.
  • the films are 16 cm in length. In yet other examples, the films are 17 cm in length. In some other examples, the films are 18 cm in length. In yet other examples, the films are 19 cm in length. In still other examples, the films are 20 cm in length. In some examples, the films are 21 cm in length. In some other examples, the films are 22 cm in length. In other examples, the films are 23 cm in length. In yet other examples, the films are 24 cm in length. In some examples, the films are 25 cm in length. In other examples, the films are 26 cm in length. In yet other examples, the films are 27 cm in length. In some other examples, the films are 28 cm in length. In yet other examples, the films are 29 cm in length. In still other examples, the films are 30 cm in length.
  • the films are 31 cm in length. In some other examples, the films are 32 cm in length. In other examples, the films are 33 cm in length. In yet other examples, the films are 34 cm in length. In some examples, the films are 35 cm in length. In other examples, the films are 36 cm in length. In yet other examples, the films are 37 cm in length. In some other examples, the films are 38 cm in length. In yet other examples, the films are 39 cm in length. In still other examples, the films are 40 cm in length. In some examples, the films are 41 cm in length. In some other examples, the films are 42 cm in length. In other examples, the films are 43 cm in length. In yet other examples, the films are 44 cm in length. In some examples, the films are 45 cm in length.
  • the films are 46 cm in length. In yet other examples, the films are 47 cm in length. In some other examples, the films are 48 cm in length. In yet other examples, the films are 49 cm in length. In still other examples, the films are 50 cm in length. In some examples, the films are 51 cm in length. In some other examples, the films are 52 cm in length. In other examples, the films are 53 cm in length. In yet other examples, the films are 54 cm in length. In some examples, the films are 55 cm in length. In other examples, the films are 56 cm in length. In yet other examples, the films are 57 cm in length. In some other examples, the films are 58 cm in length. In yet other examples, the films are 59 cm in length.
  • the films are 60 cm in length. In some examples, the films are 61 cm in length. In some other examples, the films are 62 cm in length. In other examples, the films are 63 cm in length. In yet other examples, the films are 64 cm in length. In some examples, the films are 65 cm in length. In other examples, the films are 66 cm in length. In yet other examples, the films are 67 cm in length. In some other examples, the films are 68 cm in length. In yet other examples, the films are 69 cm in length. In still other examples, the films are 70 cm in length. In some examples, the films are 71 cm in length. In some other examples, the films are 72 cm in length. In other examples, the films are 73 cm in length.
  • the films are 74 cm in length. In some examples, the films are 75 cm in length. In other examples, the films are 76 cm in length. In yet other examples, the films are 77 cm in length. In some other examples, the films are 78 cm in length. In yet other examples, the films are 79 cm in length. In still other examples, the films are 80 cm in length. In some examples, the films are 81 cm in length. In some other examples, the films are 82 cm in length. In other examples, the films are 83 cm in length. In yet other examples, the films are 84 cm in length. In some examples, the films are 85 cm in length. In other examples, the films are 86 cm in length. In yet other examples, the films are 87 cm in length.
  • the films are 88 cm in length. In yet other examples, the films are 89 cm in length. In still other examples, the films are 90 cm in length. In some examples, the films are 91 cm in length. In some other examples, the films are 92 cm in length. In other examples, the films are 93 cm in length. In yet other examples, the films are 94 cm in length. In some examples, the films are 95 cm in length. In other examples, the films are 96 cm in length. In yet other examples, the films are 97 cm in length. In some other examples, the films are 98 cm in length. In yet other examples, the films are 99 cm in length. In still other examples, the films are 100 cm in length. In some examples, the films are 101 cm in length.
  • the films are 102 cm in length. In other examples, the films are 103 cm in length. In yet other examples, the films are 104 cm in length. In some examples, the films are 105 cm in length. In other examples, the films are 106 cm in length. In yet other examples, the films are 107 cm in length. In some other examples, the films are 108 cm in length. In yet other examples, the films are 109 cm in length. In still other examples, the films are 110 cm in length. In some examples, the films are 111 cm in length. In some other examples, the films are 112 cm in length. In other examples, the films are 113 cm in length. In yet other examples, the films are 114 cm in length. In some examples, the films are 115 cm in length.
  • the films are 116 cm in length. In yet other examples, the films are 117 cm in length. In some other examples, the films are 118 cm in length. In yet other examples, the films are 119 cm in length. In still other examples, the films are 120 cm in length.
  • the garnet-based films are prepared as a monolith useful for a lithium secondary battery cell.
  • the form factor for the garnet-based film is a film with a top surface area of about 10 cm 2 . In certain cells, the form factor for the garnet-based film with a top surface area of about 100 cm 2 .
  • the films set forth herein have a Young's Modulus of about 130- 150 GPa. In some other examples, the films set forth herein have a Vicker's hardness of about 5-7 GPa.
  • the films set forth herein have a porosity less than 20%. In other examples, the films set forth herein have a porosity less than 10%. In yet other examples, the films set forth herein have a porosity less than 5%. In still other examples, the films set forth herein have a porosity less than 3%.
  • an electrochemical cell having a positive electrode, a negative electrode, and an electrolyte between the positive and negative electrode, wherein the electrolyte comprises an electrolyte separator or membrane set forth herein.
  • set forth herein is an electrochemical cell having an electrolyte separator set forth herein, wherein the electrochemical cell further includes a gel electrolyte.
  • set forth herein is an electrochemical cell having an electrolyte separator set forth herein, wherein the electrochemical cell further includes a gel electrolyte between the positive electrode active material and the electrolyte separator.
  • gel comprises a solvent, a lithium salt, and a polymer.
  • the solvent is ethylene carbonate, propylene carbonate, diethyl ene carbonate, methylene carbonate, or a combination thereof.
  • the lithium salt is LiPF 6 , LiBOB, or LFTSi.
  • the polymer is PVDF-HFP.
  • the gel includes PVDF with the solvent dioxolane and the salt, lithium bis(trifluoromethane)sulfonimide (LiTFSI), at 1M concentration.
  • LiTFSI lithium bis(trifluoromethane)sulfonimide
  • the polymer is polypropylene (PP), atactic polypropylene (aPP), isotactive polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), polyolefins, polyethylene-co-poly- 1-octene (PE-co-PO), PE-co-poly(m ethylene cyclopentane) (PE-co- PMCP), poly methyl-methacrylate (and other acrylics), acrylic, polyvinylacetacetal resin, polyvinylbutylal resin, PVB, polyvinyl acetal resin, stereoblock polypropylenes,
  • polypropylene polymethylpentene copolymer polyethylene oxide (PEO), PEO block copolymers, silicone, or the like.
  • the gel acetonitrile as a solvent and a 1M concentration of a lithium salt, such as LiPF 6 .
  • the gel includes a dioxolane solvent and a 1M concentration of a Lithium salt, such as LiTFSI or LiPF 6 .
  • a Lithium salt such as LiTFSI or LiPF 6 .
  • the gel includes PVDF polymer, dioxolane solvent and 1M concentration of LiFTSI or LiPF 6 .
  • the gel includes PVDF polymer, acetonitrile (ACN) solvent and 1M concentration of LiFTSI or LiPF 6 .
  • the gel has a EC:PC solvent and a 1M concentration of a Lithium salt, such as LiTFSI or LiPF 6 .
  • the composite and the gel show a low impedance of about 10 Qcm 2 .
  • the gel is a composite electrolyte which includes a polymer and a ceramic composite with the polymer phase having a finite lithium conductivity.
  • the polymer is a single ion conductor (e.g., Li + ).
  • the polymer is a multi-ion conductor (e.g., Li + and electrons). The following non-limiting combinations of polymers and ceramics may be included in the composite electrolyte.
  • the composite electrolyte may be selected from polyethyleneoxide (PEO) coformulated with LiCF 3 S0 3 and Li 3 N, PEO with LiA10 2 and Li 3 N, PEO with L1CIO4, PEO : LiBF4-Ti0 2 , PEO with LiBF 4 -Zr0 2 .
  • the composite in addition to the polymers, includes an additive selected from Li 3 N; A1 2 0 3 , LiA10 3 ; Si0 2 , SiC, (P0 4 ) 3" , Ti0 2 ; Zr0 2 , or zeolites in small amounts.
  • the additives can be present at from 0 to 95 % w/w.
  • the additives include Al 2 0 3 , Si0 2 , Li 2 0, Al 2 0 3 , Ti0 2 , P 2 0 5, Lii 3 Tii 7 Alo.3(P0 4 ) 3 , or (LTAP).
  • the polymer present is polyvinylidenefluoride at about 10 % w/w.
  • the composite includes an amount of a solvent and a lithium salt (e.g., LiPF 6 ).
  • the solvent is ethyl carbonate/dimethyl carbonate (EC/DMC) or any other solvent set forth herein.
  • the composite includes a solvent useful for dissolving lithium salts.
  • the polymer serves several functions.
  • the polymer has the benefit of ameliorating interface impedance growth in the solid electrolyte even if the polymer phase conductivity is much lower than the ceramic.
  • the polymer reinforces the solid electrolyte mechanically.
  • this mechanical reinforcement includes coformulating the solid electrolyte with a compliant polymer such as poly paraphenylene terephthal amide.
  • a compliant polymer such as poly paraphenylene terephthal amide.
  • set forth herein is method of surface treating an electrolyte separator, which includes providing chemical precursors to the electrolyte; calcining the chemical precursors to form a calcined electrolyte; providing a slurry comprising the calcined electrolyte; casting a film from the slurry; sintering the film to form a sintered electrolyte separator; and surface treating the sintered electrolyte separator in a reducing atmosphere.
  • surface treating comprises laser ablating, polishing, polishing in dry room atmosphere, annealing, etching, acid washing, plasma abating, and ozone treating.
  • set forth herein is a method of annealing an electrolyte separator, including providing chemical precursors to the electrolyte separator; calcining the chemical precursors in an oxidizing atmosphere to form a calcined electrolyte; providing a slurry comprising the calcined electrolyte; casting a film from the slurry; sintering the film in a reducing or inert atmosphere to form a sintered electrolyte separator; and annealing the sintered electrolyte separator in a reducing or inert atmosphere.
  • the methods further include milling or mixing the chemical precursors before the calcining step.
  • the methods include an oxidizing atmosphere as Air.
  • the sintering step in the methods herein becomes the annealing step by controlling or changing the reducing or inert atmosphere.
  • the sintering step in the methods herein becomes the annealing step by changing temperature of the sintered electrolyte separator.
  • the chemical precursors are garnet chemical precursors.
  • the annealing comprises heating the sintered electrolyte from 200°C to 1000°C.
  • the heating is to 210°, 220°, 230°, 240°, 250°, 260°, 270°, 280°, 290°, 300°, 310°, 320°, 330°, 340°, 350°, 360°, 370°, 380°, 390°, 300°, 410°, 420°, 430°, 440°, 450°, 460°, 470°, 480°, 490°, 400°, 510°, 520°, 530°, 540°, 550°, 560°, 570°, 580°, 590°, 500°, 210°, 620°, 630°, 640°, 650°, 660°, 670°, 680°, 690°, 700°, 710°, 720°, 730°, 740°, 750
  • the annealing comprises heating the sintered electrolyte from 500°C to 800°C. In some examples, the annealing comprises heating the sintered electrolyte from 600°C to 800°C. In some examples, the annealing comprises heating the sintered electrolyte from 700°C to 800°C. In some examples, the annealing comprises heating the sintered electrolyte from 500°C to 700°C. In some examples, the annealing comprises heating the sintered electrolyte from 500°C to 600°C. In some examples, the annealing comprises heating the sintered electrolyte from 550°C to 650°C. The method of claim 39, wherein the annealing comprises heating the sintered electrolyte from 600°C to 700°C.
  • the methods further include laser ablation of the electrolyte surface in a(n) Ar, N 2 , He, and/or 0 2 atmosphere.
  • the methods include plasma ablation in Ar, N 2 , H 2 , He and/or 0 2 environment.
  • the methods include heating the sintered electrolyte from 200°C to 1000°C in an inert atmosphere selected from the group consisting of He, Ne, Ar, Xe, N 2 , and combinations thereof.
  • the methods include heating the sintered electrolyte from 200°C to 1000°C in an inert atmosphere selected from He, Ne, Ar, Xe, or N 2 .
  • the methods include heating the sintered electrolyte from 200°C to 1000°C in an inert atmosphere selected from He:H 2 , Ne:H 2 , Ar:H 2 , Xe:H 2 , or N 2 :H 2 .
  • the ratio of the two gases is 100:0 to 50:50 v/v.
  • the ratio of Ar:H 2 is 100:0 to 50:50 v/v.
  • the annealing includes heating the sintered electrolyte from 200°C to 1000°C in an Argon:H 2 atmosphere until the top or bottom surface of the electrolyte does not have a layer thereupon comprising a lithium carbonate, lithium hydroxide, lithium oxide, lithium peroxide, a hydrate thereof, an oxide thereof, or a combination thereof.
  • the annealing further includes cooling the electrolyte at least 10°C/min, in an Air atmosphere to room temperature after the calcining step.
  • the methods herein further include comprising depositing
  • Li metal onto the polished surface within 2 days of the annealing step Li metal onto the polished surface within 2 days of the annealing step.
  • Lithium-Stuffed Garnet Powder Calcined lithium-stuffed garnet powder was produced by the following series of steps. First, lithium hydroxide (LiOH), aluminum nitrate [A1(N03)39H 2 0], zirconia (Zr0 2 ), and lanthanum oxide (La 2 0 3 ) were massed (i.e., weighed) and mixed into a combination wherein the molar ratio of the constituent elements was Li 7 La 3 Zr 2 Oi 2 0.5Al 2 O 3 . This combination was mixed and milled, using wet-milling techniques and Zr0 2 milling media, until the combination had a d 50 particle size of 100 nm - 5 ⁇ .
  • LiOH lithium hydroxide
  • Zr0 2 zirconia
  • La 2 0 3 lanthanum oxide
  • RhodalineTM dispersant also included with the milling media was a RhodalineTM dispersant.
  • the milled combination of reactants was separated from the milling media after milling to the d 5 o particle size.
  • the separated milled reactants was then placed in an alumina crucible and calcined at about nine-hundred degrees Celsius (900 °C) for approximately six (6) hours in an oven with a controlled oxidizing atmosphere in contact with the calcining reactants.
  • the calcination process burned and/or combusted residual solvents as well as the dispersant, binder, and surfactant.
  • the calcination caused the inorganic reactants to react to form the lithium-stuffed garnet.
  • the calcined product was removed from the alumina crucibles after it cooled to room temperature.
  • the product is characterized by a variety of analytical techniques, including x- ray powder diffraction (XRD) and scanning electron microscopy. This product is referred to as calcined lithium-stuffed garnet and has an empirical formula of approximately
  • the slurry mixture was then tape cast using a doctor blade setting of 20-400 ⁇ to produce 10-200 ⁇ thin films of calcined but unsintered lithium-stuffed garnet in combination with surfactants, binders, plasticizers, and dispersants.
  • the tape cast thin films were allowed to dry. These dry calcined by unsintered thin films are referred to as green films.
  • the green films were sintered at a temperature selected from 1100 °C,
  • the sintered films were, for some samples, then stored in an Argon-filled glove box, and, for other samples, were stored in air.
  • a lithium stuffed garnet electrolyte separator was made according to Example 1 and then subsequently annealed to remove surface species which result in an increased ionic impedance in the separator.
  • a different sample of a lithium stuffed garnet electrolyte separator was made according to Example 1 but not subsequently annealed to remove surface species and instead was exposed to air at room temperature for two hours after being made according to Example 1.
  • the sample which was not annealed is referred to herein as Sample A.
  • the sample which was annealed is referred to herein as Sample B.
  • the separator was placed in nickel crucible in a tubular furnace with a controlled atmosphere in contact with the annealing separator.
  • the controlled atmosphere included a gas phase protection environment. Suitable gas phase protection environments used were Ar, He, Kr, N 2 , H 2 and mixtures in both static and flowing conditions. The pressure was maintained at 1 atmosphere.
  • Electrolyte samples were prepared using a FEI Helio Focused Ion Beam (FIB) electron microscope.
  • the sample had a thickness less 200 nm for TEM imaging.
  • the sample was stored in an air-tight (i.e., hermetically sealed) container for transfer to the TEM for imaging and without exposure to air.
  • a FEI Tecnai G2 F20 Transmission electron microscope (TEM) was used for sample imaging for both bright field and dark field imaging.
  • Attenuated Total Reflection Fourier Transformed Infrared Resonance (ATR- FTIR) spectrum was collected on a Bruker Alpha FTIR spectrometer. Diamond Optics were used for sample mounting.
  • X-ray photo-electron spectroscopy was conducted a PHI-5600 System, equipped with Al-K X-ray sources. After sample preparation, the sample was stored in an air-tight (i.e., hermetically sealed) container for transfer to the XPS instrument for analysis. Annealed samples were not exposed to air prior to analysis.
  • Electron Microscope SEM The cross-section was prepared by fracturing specimen and followed by a thin layer of Au coating.
  • Sample A included an electrolyte separator
  • the annealed sample B does not have L1 2 CO 3 on the surface.
  • the untreated (i.e., unannealed) sample A shows a L1 2 CO 3 coating on the surface of the electrolyte separator.
  • Sample B is approximately in the order of 1 x 10 "19 /cm 3 .
  • Sample A which was not annealed, shows Raman stretches characteristic of the garnet crystal structure and can be associated with Zr0 6 , La0 8 and Li0 4 chemical units.
  • Sample B which was annealed, shows Raman stretches characteristic of the garnet crystal structure and can be associated with Zr0 6 , La0 8 and L1O 4 chemical units and additional peaks at 515, 531 cm “1 and 711 cm "1 .
  • the additional peaks show enhanced surface features in Sample B which are observable on account of the removal of the surface species through the annealing methods in Example 2.
  • a two (2) ⁇ thick metallic Li layer was evaporated on both side of the electrolyte separator to create electrodes.
  • the electrolyte having Li layer(s) thereupon was assembled into an electrochemical cell housing.
  • EIS Nyquist plots were collected using a Biologic VMP-300 potential-stat using a frequency range of lMHz - lHz. The bulk and interfacial impedances were determined by the Nyquist plot
  • Figure 7 shows an EIS Nyquist plot of a Li-garnet-Li cell for two
  • FIG. 6 is a magnified imagine of the low impedance (high frequency) portion of the EIS signal. This plot shows that the annealed sample, Sample B, has a resistance which is much lower than Sample A, which was not annealed.
  • ASR values were extrapolated from the EIS measurement at as function of the testing conditions. ASR measurements at both 50°C and 80°C confirmed that interfacial ASR was significantly reduced in those cells having Sample B electrolyte separators.
  • the lateral ionic conductivity at ambient temperature was also improved by two orders of magnitude on average for those cells having Sample B electrolytes as compared to those cells having Sample A electrolytes.
  • Sample B membranes also have a more uniform ionic conductivity across the electrolyte's top or bottom surface as compared to Sample A membranes.
  • the results herein show that at the same current density and testing conditions, Sample A (unannealed) electrolytes have a higher total impedance and also have voltage instability.
  • the results herein show that at the same current density and testing conditions, Sample B (annealed) electrolytes have voltage stability and cycle performance.
  • a cell is constructed with two lithium electrodes, one on either side of the solid state electrolyte which in one sample is a Sample A electrolyte and in another sample is a Sample B electrolyte.
  • a constant current was applied across the cell for a predetermined amount of time and then reversed for an equal duration.
  • the cells were then cycled at 130 °C at a current density of 2m A/cm 2 with a charge throughput of
  • the cell which included the annealed Sample B as the electrolyte membrane was observed to have a high conductance as evidenced by the total overpotential of about 25mV at a current density of 2m A/cm 2 . This demonstrates a total resistance of 12.5Qcm 2 . This same cell was also observed to have a symmetric and flat voltage profile. This shows that the Sample B electrolyte membrane was cycled reversibly and in a stable condition at a high current density of 2mA/cm 2 .

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Abstract

L'invention concerne des pastilles, des films minces et des monolithes d'électrolytes à grenat remplis au lithium, ayant des surfaces travaillées. Ces surfaces travaillées ont différentes propriétés avantageuses telles que, entre autres, une faible résistance de surface, une conductivité élevée des ions Li +, une tendance à la formation de dendrites de lithium dans ou sur ces surfaces qui reste faible lorsque les électrolytes sont utilisés dans une cellule électrochimique. D'autres avantages sont la stabilité de tension et une longue durée de vie lors d'une utilisation dans des cellules électrochimiques comme séparateurs ou comme membranes entre les électrodes positive et négative. L'invention concerne également des procédés de fabrication de ces électrolytes comprenant, entre autres, des procédés de recuit de ces électrolytes sous atmosphère contrôlée. L'invention concerne également des procédés d'utilisation de ces électrolytes dans des cellules électrochimiques et des dispositifs. La présente invention comprend en outre des cellules électrochimiques qui contiennent les électrolytes à grenat remplis au lithium décrits ici.
EP16888407.0A 2016-01-27 2016-01-27 Séparateurs d'électrolyte à grenat recuit Pending EP3411914A4 (fr)

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