Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/134—Electrodes based on metals, Si or alloys
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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  • 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
  • H01M10/0566—Liquid materials
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  • 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
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
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  • 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
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
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  • 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
  • H01M10/0566—Liquid materials
  • H01M10/0569—Liquid materials characterised by the solvents
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/058—Construction or manufacture
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/44—Methods for charging or discharging
  • H01M10/446—Initial charging measures
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M12/00—Hybrid cells; Manufacture thereof
  • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0438—Processes of manufacture in general by electrochemical processing
  • H01M4/044—Activating, forming or electrochemical attack of the supporting material
  • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
  • H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/362—Composites
  • H01M4/366—Composites as layered products
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/381—Alkaline or alkaline earth metals elements
  • H01M4/382—Lithium
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/581—Chalcogenides or intercalation compounds thereof
  • H01M4/5815—Sulfides
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • H—ELECTRICITY
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  • 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
  • H01M2300/0025—Organic electrolyte
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  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0025—Organic electrolyte
  • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
• • H—ELECTRICITY
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/581—Chalcogenides or intercalation compounds thereof
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/90—Selection of catalytic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
  • H01M8/023—Porous and characterised by the material
  • H01M8/0234—Carbonaceous material
• • 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
• • 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
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the disclosure relates generally to batteries.
• the disclosure relates more specifically to protected anodes for batteries, and to methods for making such anodes.
• the combination of a metal, e.g., lithium, anode and a liquid electrolyte solution is problematic for rechargeable batteries because of the high reactivity of the active metal with any relevant polar aprotic solvent and/or salt anion in electrolyte solutions.
• a metal e.g., lithium
• electrolyte components can result in the formation of a mosaic structure of insoluble surface species at the solid electrolyte interphase (SEI), causing a loss of anode materials and leading to low cycling efficiency, gradual capacity loss, and poor cyclability.
• SEI solid electrolyte interphase
• a complex, uneven SEI results in non-uniform current distribution of a lithium electrode, which can induce an internal short circuit in, e.g., a lithium ion battery.
• One aspect of the disclosure is a method for preparing a protected anode, the method including
• a cathode comprising at least one transition metal dichalcogenide
• an anode comprising a metal
• an electrolyte in contact with the transition metal dichalcogenide of the cathode and the metal of the anode
• electrochemical cell is substantially free of water
• Another aspect of the disclosure is a method as described above, further including
• Another aspect of the disclosure is protected anode comprising a protective layer disposed on an anode comprising lithium metal, wherein the protective layer comprises U2CO3 in an amount of at least 50 atom% of the protective layer.
• Another aspect of the disclosure is a battery including a protected anode as described above, further comprising a cathode and an electrolyte in contact with the anode.
• Figure 1 is a graph of the performance of a lithium-air battery utilizing a protected anode prepared according to Example 1 over 800 charge-discharge cycles, as described in more detail in Example 2, below.
• Figure 2 is a graph showing the performance of an electrochemical cell utilizing protected anodes, prepared according to Example 1 as the working and counter electrodes, throughout the high rate cycling experiment, as described in more detail in Example 3, below.
• Figure 3 is a graph of the potential of the cell of Example 3 over the course of a low rate deep cycling experiment, performed after the high rate cycling experiment.
• Figure 4 is a representative XPS spectrum of the surface of a protected anode prepared according to Example 1 , highlighting the Li 1s region. The experiment is described in more detail in Example 4, below.
• Figure 5 is a representative XPS spectrum of the surface of a protected anode prepared according to Example 1 , highlighting the C 1s region. The experiment is described in more detail in Example 4, below.
• Figure 6 is a representative XPS spectrum of the surface of a protected anode prepared according to Example 1 , highlighting the O 1s region. The experiment is described in more detail in Example 4, below.
• Figure 7 is a graph of the cycle life and first cycle polarization gap of lithium-air batteries utilizing a protected anode, as a function of the number of anode protection cycles performed, as described in more detail in Example 5, below.
• Figure 8 is an electrochemical impedance spectroscopy (EIS) spectrum of lithium-air batteries utilizing protected anodes prepared with a varied number of anode protection cycles, as described in more detail in Example 6, below.
• EIS electrochemical impedance spectroscopy
• Figure 9 is a scanning electron microscopy (SEM) image of the surface of a protected anode prepared according to Example 1 , as described in more detail in Example 7, below.
• the scale bar is 1 ⁇ m.
• the inset image width is 500 nm.
• Figure 10 is a schematic of the lithium-air battery of Example 2.
• Ranges can be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
• each embodiment disclosed herein can comprise, consist essentially of or consist of its particular stated element, step, ingredient or component.
• the transition term “comprise” or “comprises” means includes, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts.
• the term "about” has the meaning reasonably ascribed to it by a person skilled in the art when used in conjunction with a stated numerical value or range, i.e. denoting somewhat more or somewhat less than the stated value or range, to within a range of ⁇ 20% of the stated value; ⁇ 19% of the stated value; ⁇ 18% of the stated value; ⁇ 17% of the stated value; ⁇ 16% of the stated value; ⁇ 15% of the stated value; ⁇ 14% of the stated value; ⁇ 13% of the stated value; ⁇ 12% of the stated value; ⁇ 11 % of the stated value; ⁇ 10% of the stated value; ⁇ 9% of the stated value; ⁇ 8% of the stated value; ⁇ 7% of the stated value; ⁇ 6% of the stated value; ⁇ 5% of the stated value; ⁇ 4% of the stated value; ⁇ 3% of the stated value; ⁇ 2% of the stated value; or ⁇ 1 % of the stated value.
• the disclosure relates to protected anodes prepared by discharging and charging an electrochemical cell comprising a cathode comprising at least one transition metal dichalcogenide, an anode comprising a metal, an electrolyte, and carbon dioxide, dissolved in the electrolyte.
• the disclosure demonstrates such protected anodes to have no adverse impact on battery performance while possessing a significantly increased cycle life.
• One aspect of the disclosure is a method of preparing a protected anode.
• the method includes providing an electrochemical cell comprising a cathode comprising at least one transition metal dichalcogenide, an anode comprising a metal, an electrolyte in contact with the transition metal dichalcogenide of the cathode and the metal of the anode, and carbon dioxide dissolved in the electrolyte.
• the method includes performing a discharge- charge cycle comprising discharging the electrochemical cell, and applying a voltage across the anode and the cathode for a time sufficient to charge the electrochemical cell.
• One or more chemical species formed in the discharge-charge cycle and dissolved in the electrolyte are deposited on the anode.
• the electrochemical cell of the method is substantially free of water.
• the electrochemical cell comprises water in an amount of less than 5 wt.% of the electrolyte, e.g., less than 4.5 wt.%, or less than 4 wt.%, or less than 3.5 wt.%, or less than 3 wt.%, or less than 2.5 wt.%, or less than 2 wt.%, or less than 1.5 wt.%, or less than 1 wt.%, or less than 0.75 wt.%, or less than 0.5 wt.% of the electrolyte.
• the electrochemical cell is substantially free of H 2 and 0 2 .
• the electrochemical cell comprises H 2 in an amount of less than about 5 wt.% of the electrolyte, e.g., less than about 4 wt.%, or less than about 3 wt.%, or less than about 2 wt.%, or less than about 1 wt.% of the electrolyte.
• the electrochemical cell comprises O2 in an amount of less than about 5 wt.% of the electrolyte, e.g., less than about 4 wt.%, or less than about 3 wt.%, or less than about 2 wt.%, or less than about 1 wt.% of the electrolyte.
• the electrochemical cell comprises 0 2 and H 2 in a combined about of less than about 10 wt.% of the electrolyte, e.g., less than about 9 wt.%, or less than about 8 wt.%, or less than about 7 wt.%, or less than about 6 wt.%, or less than about 5 wt.%, or less than about wt.%, or less than about 3 wt.%, or less than about 2 wt.%, or less than about 1 wt.% of the electrolyte.
• the method further comprises one or more additional discharge-charge cycles.
• the total number of discharge-charge cycles is from 2 to 25, e.g., from 2 to 24, or from 2 to 23, or from 2 to 22, or from 2 to 21 , or from 2 to 21 , or from 2 to 20, or from 2 to 19, or from 2 to 19, or from 2 to 18, or from 2 to 17, or from 2 to 16, or from 2 to 16, or from 2 to 15, or from 2 to 14, or from 2 to 13, or from 2 to 12, or from 2 to 11 , or from 2 to 10, of from 2 to 9, or from 2 to 8, or from 2 to 7, or from 2 to 6, or from 2 to 5, or from 3 to 25, or from 4 to 25, or from 5 to 25, or from 6 to 25, or from 7 to 25, or from 8 to 25, or from 9 to 25, or from 10 to 25, or from 11 to 25, or from 12 to 25, or from 13 to 25, or from 14 to 25, or from 15 to 25, or from 16 to 25, or from 17 to 25, or from 18 to 25, or
• the voltage applied is within the range of about 1 V to about 5 V, e.g., about 1.25 V to about 4.75 V, or about 1.5 V to about 4.5 V, or about 1.75 V to about 4.25 V, or about 2 V to about 4 V, or about 2.25 V to about 3.75 V, or about 2.5 V to about 3.5 V, or the voltage is about 1.5 V, or about 1.75 V, or about 2 V, or about 2.25 V, or about 2.5 V, or about 2.75 V, or about 3 V, or about 3.25 V, or about 3.5 V, or about 3.75 V, or about 4 V, or about 4.25 V, or about 4.5 V.
• the anode includes a metal.
• the anode can, for example, consist essentially of the metal (e.g., as a bar, plate, or other shape).
• the anode can be formed from an alloy of the metal, or can be formed as a deposit of the metal on a substrate (e.g., a substrate formed from a different metal, or from another conductive material).
• a substrate e.g., a substrate formed from a different metal, or from another conductive material.
• other materials that include the metal in its zero- valence state can be used.
• the metal can be provided as part of a compound metal oxide or carbonaceous material from which the metal can be reduced to provide metal ion and one or more electrons.
• the anode includes a metal and may be shaped as, for example, a bar, plate, chip, disc, etc.
• the person of ordinary skill in the art will appreciate that the anode may have a variety of different dimensions, for example, a chip with a thickness of 0.15 mm, 0.25 mm, 0.5 mm, 0.65 mm, etc.
• metals suitable for use in the anode of the disclosure include, but are not limited to alkaline metals such as lithium, sodium and potassium, alkaline-earth metals such as magnesium and calcium, group 13 elements such as aluminum, transition metals such as zinc, iron and silver, and alloy materials that contain any of these metals or materials that contain any of these metals.
• the metal is selected from one or more of lithium, magnesium, zinc, and aluminum. In other particular embodiments, the metal is lithium.
• a lithium-containing carbonaceous material an alloy that contains a lithium element, or a compound oxide, nitride or sulfide of lithium may be used.
• the alloy that contains a lithium element include, but are not limited to, lithium-aluminum alloys, lithium-tin alloys, lithium-lead alloys, and lithium-silicon alloys.
• lithium-containing compound metal oxides include lithium titanium oxide.
• lithium-containing compound metal nitrides include lithium cobalt nitride, lithium iron nitride and lithium manganese nitride.
• the cathode includes at least one transition metal dichalcogenide.
• transition metal dichalcogenkJes include those selected from the group consisting of TiX 2 , VX2, CrX 2 , ZrX 2 , NbX 2 , M0X2, HfX 2, WX 2, TaX2, TcX 2 , and ReX 2, wherein X is independently S, Se, or Te.
• each transition metal dichalcogenide is selected from the group consisting of T1X2, M0X2, and WX 2l wherein X is independently S, Se, or Te.
• each transition metal dichalcogenide is selected from the group consisting of TiS 2 , TiSe 2l M0S2, MoSe 2 , WS2 and WSe 2 .
• each transition metal dichalcogenide is TiS 2l M0S2, or WS 2 .
• each transition metal dichalcogenide is MoS 2 or MoSe 2 .
• the transition metal dichalcogenide may be MoS 2 in one embodiment.
• the at least one transition metal dichalcogenide itself can be provided in a variety of forms, for example, as a bulk material, in nanostructure form, as a collection of particles, and/or as a collection of supported particles.
• the transition metal dichalcogenide in bulk form may have a layered structure as is typical for such compounds.
• the transition metal dichalcogenide may have a nanostructure morphology, including but not limited to monolayers, nanotubes, nanoparticles, nanoflakes (e.g., multilayer nanoflakes), nanosheets, nanoribbons, nanoporous solids etc.
• the term “nanostructure” refers to a material with a dimension (e.g., of a pore, a thickness, a diameter, as appropriate for the structure) in the nanometer range (i.e., greater than 1 nm and less than 1 ⁇ m.).
• the transition metal dichalcogenide is layer-stacked bulk transition metal dichalcogenide with metal atom-terminated edges (e.g., MoS 2 with molybdenum-terminated edges).
• transition metal dichalcogenide nanoparticles e.g., MoS 2 nanoparticles
• transition metal dichalcogenide nanoflakes may be used in the devices and methods of the disclosure.
• Nanoflakes can be made, for example, via liquid exfoliation, as described in Coleman, J. N. et al. Two-dimensional nanosheets produced by liquid exfoliation of layered materials. Science 331 , 568-71 (2011) and Yasaei, P. et al. High- Quality Black Phosphorus Atomic Layers by Liquid-Phase Exfoliation. Adv. Mater. (2015) (doi:10.1002/adma.201405150), each of which is hereby incorporated herein by reference in its entirety.
• transition metal dichalcogenide nanoribbons e.g., nanoribbons of MoS 2
• TMDC nanosheets e.g., nanosheets of MoS 2
• the person of ordinary skill in the art can select the appropriate morphology for a particular device.
• the transition metal dichalcogenide nanostructures (e.g., nanoflakes, nanoparticles, nanoribbons, etc.) have an average size between about 1 nm and 1000 nm.
• the relevant size for a nanoparticle is its largest diameter.
• the relevant size for a nanoflake is its largest width along its major surface.
• the relevant size for a nanoribbon is its width across the ribbon.
• the relevant size for a nanosheet is its thickness.
• the transition metal dichalcogenide nanostructures have an average size between from about 1 nm to about 400 nm, or about 1 nm to about 350 nm, or about 1 nm to about 300 nm, or about 1 nm to about 250 nm, or about 1 nm to about 200 nm, or about 1 nm to about 150 nm, or about 1 nm to about 100 nm, or about 1 nm to about 80 nm, or about 1 nm to about 70 nm, or about 1 nm to about 50 nm, or 50 nm to about 400 nm, or about 50 nm to about 350 nm, or about 50 nm to about 300 nm, or about 50 nm to about 250 nm, or about 50 nm to about 200 nm, or about 50 nm to about 150 nm, or about 50 nm to about 100 nm, or about 10 nm to about 70 nm, or
• the transition metal dichalcogenide nanostructures have an average size between from about 1 nm to about 200 nm. In certain other embodiments, the transition metal dichalcogenide nanostructures have an average size between from about 1 nm to about 400 nm. In certain other embodiments, the transition metal dichalcogenide nanostructures have an average size between from about 400 nm to about 1000 nm. In certain embodiments, the transition metal dichalcogenide nanostructures are nanofiakes having an average size between from about 1 nm to about 200 nm. In certain other embodiments, the transition metal dichalcogenide nanofiakes have an average size between from about 1 nm to about 400 nm. In certain other embodiments, the transition metal dichalcogenide nanofiakes have an average size between from about 400 nm to about 1000 nm.
• transition metal dichalcogenide nanofiakes have an average thickness between about 1 nm and about 100 ⁇ (e.g., about 1 nm to about 10 ⁇ , or about 1 nm to about 1 ⁇ , or about 1 nm to about 1000 nm, or about 1 nm to about 400 nm, or about 1 nm to about 350 nm, or about 1 nm to about 300 nm, or about 1 nm to about 250 nm, or about 1 nm to about 200 nm, or about 1 nm to about 150 nm, or about 1 nm to about 100 nm, or about 1 nm to about 80 nm, or about 1 nm to about 70 nm, or about 1 nm to about 50 nm, or abou6t 50 nm to about 400 nm, or about 50 nm to about 350 nm, or about 50 nm to about 300
• the aspect ratio (largest major dimension:thickness) of the nanoflakes can be on average, for example, at least about 5:1 , at least about 10:1 or at least about 20:1.
• the transition metal dichalcogenide nanoflakes have an average thickness in the range of about 1 nm to about 1000 nm (e.g., about 1 nm to about 100 nm), average dimensions along the major surface of about 50 nm to about 10 ⁇ m., and an aspect ratio of at least about 5:1.
• the at least one transition metal dichalcogenide of the cathode may be provided in a variety of forms, provided that it is in contact with the electrolyte.
• the transition metal dichalcogenide can be disposed on a substrate.
• the transition metal dichalcogenide can be disposed on a porous member, which can allow gas (e.g., C0 2 ) to diffuse through the member to the TMDC.
• the porous member may be electrically-conductive. In cases where the porous member is not electrically conductive, the person of skill in the art can arrange for the electrical connection of the cathode to be made to some other part of the cathode.
• the substrate may be selected to allow C0 2 to be absorbed in a substantial quantity into the device and transmitted to the TMDC.
• the porous materials for the substrate include carbon-based materials, such as carbon as well as carbon blacks (e.g., Ketjen black, acetylene black, channel black, furnace black, and mesoporous carbon), activated carbon and carbon fibers.
• a carbon material with a large specific surface area is used.
• a material with a pore volume on the order of 1 mlJg can be used.
• a cathode can be prepared by mixing TMDC with conductive material (e.g.
• the TMDC-containing cathode material includes at least 10 wt%, at least 20 wt%, at least 50 wt%, at least 70 wt%, 10-99 wt%, 20- 99 wt%, 50-99 wt%, 10-95 wt%, 20-95 wt%, 50-95 wt%, 10-70 wt%, 20-70 wt%, 40-70 wt% or 70-99 wt% TMDC.
• TMDC-containing material can be coated onto a current collector or a porous member at any convenient thickness, e.g., in thicknesses up to 1000 ⁇ m. ⁇ .
• the overall cathode desirably has some porosity so that COz can be provided to the TMDC material.
• the electrolyte comprises at least 1 % of an ionic liquid.
• ionic liquid refers to an ionic substance (i.e., a combination of a cation and an anion) that is liquid at standard temperature and pressure (25 °C, 1 atm).
• the ionic liquid is a compound comprising at least one positively charged nitrogen, sulfur, or phosphorus group (for example, a phosphonium or a quaternary amine).
• the electrolyte comprises at least 10%, at least 20%, at least 50%, at least 70%, at least 85%, at least 90% or even at least 95% ionic liquid.
• ionic liquids include, but are not limited to, one or more of salts of: acetylcholines, alanines, aminoacetonitriles, methylammoniums, arginines, aspartic acids, threonines, chloroformamidiniums, thiouroniums, quinoliniums, pyrrolidinols, serinols, benzamidines, sulfamates, acetates, carbamates, inflates, and cyanides.
• salts that are in liquid form at standard temperature and pressure. These examples are meant for illustrative purposes only, and are not meant to limit the scope of the present disclosure.
• the ionic liquid of the disclosure may be an imidazolium salt, such as 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1- butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, or 1-butyl-3-methylimidazolium trifluoromethanesulfonate; a pyrrolidinium salt, such as 1-butyl-1-methylpyrrolidinium tetrafluoroborate, 1-butyH- methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, or 1-butyM-methylpyrrol
• imidazolium salt
• the ionic liquids of the disclosure include, but are not limited to imidazoliums, pyridiniums, pyrrolidiniums, phosphoniums, ammoniums, sulfoniums, prolinates, and methioninates salts.
• the anions suitable to form salts with the cations include, but are not limited to C 1 -C 6 alkylsulfate, tosylate, methanesulfonate, bis(trifluoromethylsulfonyl)imide, hexafluorophosphate, tetrafluoroborate, triflate, halkJe, carbamate, and sulfamate.
• the ionic liquid may be a salt of the cations selected from those illustrated below:
• the ionic liquid of the methods and devices of the disclosure is imidazolium salt of formula:
• R 3 are independently selected from the group consisting of hydrogen, linear aliphatic group, branched aliphatic group, and cyclic aliphatic C 1 -C 6 group.
• R 2 is hydrogen
• R 1 and R 3 are independently selected from linear or branched alkyl.
• the ionic liquid of the disclosure is an 1- ethyl-3-methylimidazolium salt.
• the ionic liquid of the disclosure is 1- ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4).
• a person of skill in the art can determine whether a given ionic liquid is a co-catalyst for a reaction (R) catalyzed by TMDC as follows:
• (k) calculate V2, which is the difference between the onset potential of the peak
• V2A which is the difference between the maximum potential of the peak associated with reaction and RHE.
• the ionic liquid is a co-catalyst for the reaction.
• the ionic liquid is present in the electrolyte within the range from about 50 weight % to about 100 weight %, or about 50 weight % to about 99 weight %, or about 50 weight % to about 98 weight %, or about 50 weight % to about 95 weight %, or about 50 weight % to about 90 weight %, or about 50 weight % to about 80 weight %, or about 50 weight % to about 70 weight %, or about 50 weight % to about 60 weight %, or about 80 weight % to about 99 weight %, from about 80 weight % to about 98 weight %, or about 80 weight % to about 95 weight %, or about 80 weight % to about 90 weight %, or about 70 weight % to about 99 weight %, from about 70 weight % to about 98 weight %, or about 70 weight % to about 95 weight %, or about 70 weight % to about 90 weight %, or about 70 weight % to about 80 weight %, or about 50 weight % to about 80 weight %, or
• the ionic liquid is present in the electrolyte within the range from about 75 weight % to about 100 weight %, or about 90 weight % to about 100 weight %. In some other embodiments, the ionic liquid is present in an electrolyte at about 90 weight %. In other embodiments, the electrolyte consists essentially of the ionic liquid.
• the electrolyte may further include a solvent, a buffer solution, an additive to a component of the system, or a solution that is bound to at least one of the catalysts in a system.
• the electrolyte may include an aprotic organic solvent.
• solvents include, but are not limited to dioxolane, dimethylsurfoxide (DMSO), diethylether, tetraethyleneglycol dimethylether (TEGDME), dimethyl carbonate (DMC), diethylcarbonate (DEC), dipropylcarbonate (DPC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), tetrahydrofuran (THF), butylene carbonate, lactones, esters, glymes, sulfoxides, sulfolanes, polyethylene oxide (PEO) and polyacrylnitrile (PAN), alone or in any combination.
• DMSO dimethylsurfoxide
• TEGDME tetraethyleneglycol dimethylether
• DMC diethylcarbonate
• DPC dipropylcarbonate
• EMC ethylmethylcarbonate
• EMC ethylmethylcarbonate
• EMC ethylmethylcarbonate
• non-ionic liquid organic solvents are present in an amount of less than about 40 weight %, less than about 30 weight %, less than about 20 weight %, less than about 10 weight %, less than about 5 weight %, or even less than about 1 weight %.
• the electrolyte is substantially free non-ionic liquid organic solvents.
• the electrolyte may further comprise other species, such as acids, bases, and salts.
• the electrolyte may include a metallic ion, e.g., lithium ion, magnesium ion, zinc ion, aluminum ion, etc.
• the electrolyte may include lithium ion.
• the electrolyte may include a salt of the metal of the anode (e.g., when the anode includes metallic lithium, the electrolyte may include a lithium salt, such as lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium hexafluorophosphate, lithium triflate, Lithium hexafluoroarsenate, etc.).
• the salt of the metal of the anode is present in a concentration in the range of about 0.005 M to about 5 M, about 0.01 M to about 1 M, or about 0.02 M to about 0.5 M. The inclusion of such other species would be evident to the person of ordinary skill in the art depending on the desired electrochemical and physicochemical properties to the electrolyte, and are not meant to limit the scope of the present disclosure.
• the electrochemical cell comprises carbon dioxide, dissolved in the electrolyte.
• the carbon dioxide is present in the electrolyte in a concentration of at least about 5% of the saturated concentration of carbon dioxide in the electrolyte, e.g., at least about 7.5%, or at least about 10%, or at least about 12.5%, or at least about 15%, or at least about 17.5%, or at least about 20%, or at least about 22.5%, or at least about 25%, or at least about 30%, or at least about 35%, or at least about 40%, or at least about 45%, or at least about 50%, or at least about 55%, or at least about 60%, or at least about 65%, or at leat about 70%, or at least about 75%, or at least about 80%, or at least about 85%, or at least about 90%, or at least about 95%, or at least about 96%, or at least about 97%, or at least about 98%, or at least about 99% of the saturated concentration
• the method further comprises removing the protected anode from the electrochemical cell after one or more discharge-charge cycles; and configuring a battery comprising the protected anode, a cathode, and an electrolyte in contact with the anode, and optionally with the metal of the anode.
• a protected anode made by a method as otherwise described herein.
• a protective anode comprising a protective layer disposed on an anode comprising lithium metal, wherein the protective layer comprises in an amount of at least 50 atom% of the protective layer.
• the protective layer has a thickness within the range of about 5 nm to about 5 ⁇ m., e.g., about 5 nm to about 40 ⁇ m.
• nm to about 5 ⁇ m. or about 20 nm to about 5 ⁇ m., or about 25 nm to about 5 ⁇ m., or about 50 nm to about 5 ⁇ m. ⁇ , or about 75 nm to about 5 ⁇ m., or about 100 nm to about 5 ⁇ m., or about 150 nm to about 5 ⁇ m., or about 200 nm to about 5 ⁇ m. ⁇ , or about 250 nm to about 5 ⁇ m., or about 300 nm to about 5 ⁇ m., or about 350 nm to about 5 ⁇ , or about 400 nm to about 5 ⁇ m., or about 450 nm to about 5 ⁇ m., or about 500 nm to about 5 ⁇ m., or about 600 nm to about 5 ⁇ m., or about 700 nm to about 5 ⁇ m., or about 800 nm to about 5 ⁇ m., or about 900 nm to about 5 ⁇ m., or about 1
• Another aspect of the disclosure is a battery comprising a protected anode described herein or made by a method as described herein, a cathode, and an electrolyte in contact with the anode, and optionally with the metal of the anode.
• the battery may be any battery in which the protected anode made by a method as described herein is suitable, e.g., a metal-sulfur better, a metal-air battery, or a metaHon battery.
• the battery is a metal-air battery.
• the battery is a metal-air battery wherein the cathode comprises at least one transition metal dichalcogenide.
• the battery is a metal-air battery described in WO2016/100204.
• the cathode of the battery does not comprise a transition metal dichalcogenide.
• the battery is a metal-air battery wherein the electrolyte comprises at least 50 wt.% of an ionic liquid.
• the battery cell comprises water, H 2, and/or O2 in an amount greater than the amount of water, H 2l and/or O 2 comprising the electrochemical cell of the method of producing a protected anode as otherwise described herein.
• Protected anodes were prepared by including the anode to be protected in an electrochemical battery cell also comprising a M0S2 nanoflake cathode and electrolyte.
• M0S2 nanoflakes were synthesized using a liquid exfoliation method in which 300 mg M0S2 powder (99%, Sigma-Aldrich) was dispersed in 60 ml. isopropyl alcohol (IPA) (>99.5%, Sigma-Aldrich). The solution was then exfoliated for 30 hrs and centrifuged for 1 hr to extract the nanoflakes from the unexfoliated powder.
• DLS Dynamic Light Scattering
• MoS 2 nanoflakes (0.2 mg) were coated onto a conductive substrate of a gas diffusion layer (GDL) (0.2 mm thickness, 80% porosity, Fuel Cells Etc.) with a surface area of 1 cm -2 .
• GDL gas diffusion layer
• Prepared cathodes were dried in a vacuum oven for 24 hrs at 85°C to stabilize the cathode and remove impurities. This procedure resulted in identically prepared cathode samples with a consistent catalyst loading of 0.2 mg/crrr 2 on GDL substrates.
• the anodes to be protected were prepared from pure lithium chips with a thickness of 0.25 mm (>99.9%, Sigma Aid rich).
• the electrolyte solution was prepared by dissolving 0.1 M Lithium Bis (Tnfluoromethanesulfonyl) ImkJe (LiTFSI) (>99.0%, Sigma-Aldrich) into a mixture of 25% 1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIM BF4) (HPLC, >99.0%, Sigma-Aldrich) and 75% dimethyl sulfoxide (DMSO) (Sigma-Aldrich).
• LiTFSI Lithium Bis (Tnfluoromethanesulfonyl) ImkJe
• EMIM BF4 1-Ethyl-3-methylimidazolium tetrafluoroborate
• HPLC >99.0%, Sigma-Aldrich
• DMSO dimethyl sulfoxide
• the assembled battery cell was first purged with pure C0 2 (99.99%, Praxair Inc.) in order to remove gas impurities and prevent parasitic reactions.
• the CO ⁇ filled battery was then connected to a potentiostat (MTI Corporation) for cycling measurements.
• a 0.1 mA/crrr 1 constant current was applied for 10 continuous cycles, each cycle consisting of a one hour charge process followed by a one hour discharge process. In-situ measurements of voltage as a function of time and capacity were recorded.
• a protected anode prepared according to Example 1 was incorporated into a lithium air battery configured as shown in Figure 10, wherein the protected anode and cathode were separated by a glass fiber filter wetted with electrolyte.
• the cathode and electrolyte were prepared according to Example 1.
• the assembled battery was first purged with an air mixture of ⁇ 21% Oxygen (0 2 ), ⁇ 79% Nitrogen (N 2 ), 500 ppm COz, and 45% relative humidity (RH) in order to remove gas impurities and prevent parasitic reactions.
• the air mixture was custom-made (Praxair Inc.) with an accuracy of ⁇ 1% for C0 2 and ⁇ 0.02% for O2. Humidity was added to the gas flow before introduction to the battery.
• the RH and temperature of the air flow were tracked during purging by a sensor (Silicon Labs SI 700 x) to maintain the RH at 45% and the temperature at 25°C 1 1°C (room temperature).
• the RH and temperature versus time were recorded (Si700x Evaluation software) continuously.
• the lithium-air battery was connected to a potentiostat for cycling measurements.
• a 0.1 mA/crrr 1 constant current was applied for 800 cycles, each cycle consisting of a one hour charge process followed by a one hour discharge process.
• In-situ measurements of voltage as a function of the cycle number and capacity were recorded (See, Figure 1). Through 800 cycles, there was negligible variation in battery performance.
• Qo is the theoretical lithium capacity of the electrode (10.2 mAh/cm 2 )
• Qr is the maximum capacity of the working electrode after deep cycling experiment (9.98 mAh/cm 2 )
• Q c is the capacity of the cell during high rate cycling (2 mA/cm 2 )
• N is the number of high rate cycles performed (51 cycles).
• X-ray photoelectron spectroscopy (XPS) experiments were carried out using a Thermo Scientific ESCALAB 250Xi instrument.
• the instrument was equipped with an electron flood and scanning ion gun.
• protected anodes were carefully rinsed with dimethyl carbonate (DMC) and dried under an argon flow before characterization.
• a mobile glove box filled with Ar was used for transferring the samples into the loading chamber of the instrument. All spectra were calibrated to the C1s binding energy of 284.8 eV.
• All data were processed by Thermo Avantage software, based on Scofield sensitivity factors. The background signal was removed by the Shirty method.
• the representative XPS spectra of the anode surface in the Li 1s, C 1s, and O 1s regions consistently showed that the protected layer on the anode surface was mainly U2CO3.
• the reference binding energies for U2CO3 in the Li 1s, C 1s, and O 1s regions are 55.15eV, 289.5eV, and 531.5eV, respectively.
• Elemental quantification results based on the surface area of the corresponding peak of each element further confirm the atomic ratio of Li 2 C0 3 as the main product on the surface of the lithium anode:
• LhC0 3 The physical and electronic properties of LhC0 3 provide for both ionic conduction and electronic insulation properties, which are two essential properties for any protective interphase utilized in, for example, secondary lithium batteries.
• the ionic conductivity of an L12CO3 layer may allow for Li* diffusion to or from an underlying anode, while the electronic insulativity prevents any poisoning of the anode.
• Figure 7 shows the cycle life of the lithium air battery and the first cycle polarization gap as a function of the number of protection cycles (which is correlated to the thickness of the protective layer).
• the cycle life of the battery was shown to be around 60 cycles after 5 anode protection cycles, and 800 cycles after 10 anode protection cycles.
• the opposite trend was observed for the polarization gap of the Li-air battery as a function of the number of anode protection cycles, wherein the smallest polarization gap was observed at 5 anode protection cycles.
• the polarization gap for the first cycle without anode protection was 1.366 V.
• the potential gap dropped to 0.4933 V for the battery comprising an anode after 5 protection cycles. Beyond 5 protection cycles, the first cycle polarization gap increased as the number of anode protection cycles increased, up to 20 cycles.
• Example 2 To investigate the effect of the thickness of the anode protective layer on the stability and efficiency of the cell, protected anodes were prepared according to Example 1 , but with a varying number of anode protection cycles (5, 10, and 15 cycles), and incorporated into lithium-air batteries prepared according to Example 2.
• EIS electrochemical impedance spectroscopy
• a fresh cathode with a known loading of catalyst and an identical electrolyte were used to avoid any contamination or external resistance in the system, in order to secure an independent study of the electrochemical properties of the protected anode.
• the battery cells were connected to a potentiostat (Volta Lab PGZ 100), and measurements were performed with a 700 mV overpotential at a frequency range of 10 Hz to 100 kHz.
• Figure 8 shows the EIS results with respect to the number of anode protection cycles.
• the charge transfer resistance (Ret) of the anode after 10 protection cycles was about 550 kohms, while it was about 160 and 1350 kohms after 5 and 15 cycles, respectively.
• the charge transfer resistance for an unprotected anode was 30 kohms.
• the increase in cell resistance may be attributed to the presence of L12CO3 on the anode surface.
• a thicker protective layer leads to more charge transfer resistance in the cell.
• the thickness of the protective layer after 5 anode protection cycles was not enough to protect the Li-Air battery for an extended amount time, while 15 anode protection cycles makes the resistance in the cell too high to be considered suitable for such a battery.

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