WO2019236550A1 - Électrolytes pour électrodes au lithium métallique et batteries rechargeables les utilisant - Google Patents

Électrolytes pour électrodes au lithium métallique et batteries rechargeables les utilisant Download PDF

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WO2019236550A1
WO2019236550A1 PCT/US2019/035349 US2019035349W WO2019236550A1 WO 2019236550 A1 WO2019236550 A1 WO 2019236550A1 US 2019035349 W US2019035349 W US 2019035349W WO 2019236550 A1 WO2019236550 A1 WO 2019236550A1
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equal
electrode
electrolyte
less
separator
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PCT/US2019/035349
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Yet-Ming Chiang
Venkatasubramanian Viswanathan
Linsen Li
Vikram Pande
David Wang
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Massachusetts Institute Of Technology
Carnegie Mellon University
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Publication of WO2019236550A1 publication Critical patent/WO2019236550A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates generally to systems and methods for forming separators in electrochemical cells and healing defects in separators in electrochemical cells.
  • Lithium metal batteries are a promising technology because of the high specific energy of lithium.
  • many lithium metal batteries experience premature failure due to dendrite growth from the anode to the cathode.
  • Separators have been added to lithium metal batteries to arrest dendrite growth, but often use their utility once damaged by growing dendrites.
  • Methods and articles for formation and healing of separators in electrochemical cells are generally provided.
  • the subject matter of the present invention involves, in some cases, interrelated products, alternative solutions to a particular problem, and/or a plurality of different uses of one or more systems and/or articles.
  • a method may comprise holding a first electrode at a first voltage in a rechargeable electrochemical cell.
  • the electrochemical cell may comprise an electrolyte comprising a precursor for the separator in an amount of less than or equal to 1 mM and greater than or equal to 1 nM.
  • the first voltage causes the precursor for the separator to react to form a separator positioned between the first electrode and a second electrode.
  • a method may comprise holding a first electrode at a first voltage in a rechargeable electrochemical cell.
  • the rechargeable electrochemical cell may comprise a separator and an electrolyte comprising a precursor for the separator in an amount of less than or equal to 1 mM and greater than or equal to 1 nM.
  • the first voltage may cause the precursor for the separator to react to heal a defect in the separator.
  • Some embodiments are related to rechargeable electrochemical cells.
  • a rechargeable electrochemical cell comprises a first electrode, a second electrode, and an electrolyte.
  • the electrolyte may comprise a precursor for a separator that has a solubility in the electrolyte of less than or equal to 1 mM and greater than or equal to 1 nM.
  • a rechargeable electrochemical cell comprises a first electrode, a second electrode, and an electrolyte.
  • the electrolyte may comprise at least one of a first halide anion and a species that can react to form a first halide anion, and comprises at least one of a second halide anion and a species that can react to form a second halide anion.
  • a rechargeable electrochemical cell comprises a first electrode, a second electrode, and a separator.
  • the separator may comprise at least a first layer and a second layer, and the second layer may undergo oxidation at a higher voltage than the first layer.
  • a device for measuring lithium (Li) cycling efficiency comprises a first electrode configured to have a first thickness and areal capacity.
  • a second electrode is configured to have second thickness and areal capacity.
  • a separator is positioned between the first electrode and second electrode, the second thickness arranged to be larger than the first thickness.
  • the first electrode and the second electrode are configured to differentiate dendritic and non-dendritic behavior of Li deposited on the first electrode and evaluate the effect of additives in terms of dendrite suppression and improvement of Li cycling efficiency.
  • a method of measuring lithium (Li) cycling efficiency comprises arranging a first electrode to have a first thickness and areal capacity. Also, the method includes arranging a second electrode to have second thickness and areal capacity. Furthermore, the method includes positioning a separator between the first electrode and second electrode. The second thickness is arranged to be larger than the first thickness, In addition, the method includes differentiating dendritic and non-dendritic behavior of Li deposited on the first electrode and evaluate the effect of additives in terms of dendrite suppression and improvement of Li cycling efficiency.
  • FIG. 1 shows a rechargeable electrochemical cell comprising a first electrode, a second electrode, and an electrolyte comprising a precursor for a separator, according to some embodiments
  • FIG. 2 shows a rechargeable electrochemical cell comprising a first electrode, a second electrode, an electrolyte comprising a precursor for a separator, and a separator, according to some embodiments;
  • FIG. 3 shows a rechargeable electrochemical cell comprising a first electrode, a second electrode, an electrolyte, and a separator, according to some embodiments
  • FIG. 4 shows a rechargeable electrochemical cell comprising a first electrode, a second electrode, an electrolyte, and a separator comprising a first layer and a second layer, according to some embodiments;
  • FIG. 5A shows a rechargeable electrochemical cell comprising a first electrode, a second electrode, an electrolyte comprising a precursor for a separator, and a separator comprising a defect, in accordance with some embodiments;
  • FIG. 5B shows a method for repairing a defect in a rechargeable electrochemical cell, according to some embodiments
  • FIG. 6 shows a method for forming a lithium halide layer, in accordance with some embodiments
  • FIG. 7 is a plot showing various properties of various lithium halide salts, in accordance with some embodiments.
  • FIG. 8 shows self-healing in separators, according to some embodiments.
  • FIG. 9 shows a method for forming a passivation layer on an electrode, according to some embodiments.
  • FIG. 10 shows a method for forming a separator, according to some embodiments.
  • FIG. 11 shows calculated values of adsorption and formation energy for lithium halide salts, according to some embodiments.
  • FIG. 12 shows a solution phase diagram for G/I2/I3 , according to some embodiments.
  • FIGS. 13A-C show the measured impedance for various electrochemical cells, according to some embodiments.
  • FIGS. 14A-D show cyclic voltammetry measurements performed on various
  • electrochemical cells according to some embodiments.
  • FIGS. 15A-15B is a schematic diagram and graph of a Li-Li Asymmetric cell design and test results of such a cell design.
  • FIG. 16 is a graph of a Li-Li asymmetric cell cycling measurements.
  • FIGS. 17A-17B are SEM diagrams of the changes in electrolyte result in different Li deposit morphology.
  • FIG. 18 is a schematic diagram of the halogenated solvents used in accordance with some embodiments.
  • FIG. 19 is graph of lithium cobalt (LCO-Li) full cell tests using different electrolytes.
  • FIG. 20 is a schematic diagram of the fluorinated SEI-forming solvents used in accordance with some embodiments.
  • Certain articles and methods relate to forming and/or repairing a separator in a rechargeable electrochemical cell in situ.
  • a rechargeable electrochemical cell may lack a separator after assembly but a separator may form during electrochemical cell charging and/or discharging.
  • a rechargeable electrochemical cell may comprise an ex situ separator upon assembly and an in situ separator may form during electrochemical cell charging and/or discharging. Separators, such as those formed during electrochemical cell charging and/or discharging, may comprise one or more defects that may be repaired by one or more species present in the electrochemical cell.
  • Certain embodiments relate to rechargeable electrochemical cells that comprise one or more precursors for a separator.
  • the precursor for the separator may be a species that is capable of reacting to form a separator in an electrochemical cell and/or to repair a defect in a separator in an electrochemical cell.
  • the precursor for the separator may, in some embodiments, react to form a separator and/or to repair a defect in a separator when one or more electrodes are held at a voltage in the electrochemical cell.
  • a precursor for an electrochemical cell may comprise a halide or a species that comprises a halide.
  • a precursor for a separator may have a relatively low solubility in an electrolyte present in the rechargeable electrochemical cell, and/or may be present at a relatively low concentration in an electrolyte present in the rechargeable electrochemical cell.
  • separatator is given its ordinary meaning in the art. In one set of embodiments it is a solid or gel material that physically separates an anode from a cathode and prevents shorting.
  • a precursor of a separator is a substance which, by itself, is not as effective as a separator but, upon holding one of the electrodes at a set voltage, or cycling the electrode, or other implementation event as described herein, forms a separator.
  • FIG. 1 shows one non-limiting embodiment of a rechargeable electrochemical cell 100 that comprises first electrode 110, second electrode 120, and electrolyte 130 comprising precursor for a separator 140.
  • FIG. 1 shows one precursor for a separator, it should be understood that in some embodiments two, three, four, or more precursors for a separator may also be present in the electrolyte.
  • a rechargeable electrochemical cell may comprise a precursor for a separator that may undergo a reaction to form a separator. For example, holding a first electrode at a first voltage in a rechargeable electrochemical cell may result in the formation of a separator.
  • the reaction may be any suitable reaction, such as a redox reaction, a polymerization reaction, and/or crystallization reaction.
  • a reaction may comprise the crystallization on an electrochemical cell component (e.g., on a first electrode) of a solute dissolved in the electrolyte.
  • the first electrode may be held at the first voltage by any suitable means.
  • a voltage may be applied to the first electrode, such as, for example, by an external voltage source.
  • the first voltage may be a voltage that the first electrode inherently has when it is positioned in the rechargeable electrochemical cell. In some embodiments, the first voltage is greater than or equal to 0 V, greater than or equal to 1.5 V, greater than or equal to 2 V, greater than or equal to 2.5 V, greater than or equal to 3 V, greater than or equal to 3.5 V, greater than or equal to 4 V, greater than or equal to 4.5 V, greater than or equal to 5 V, or greater than or equal to 5.5 V.
  • the first voltage is less than or equal to 6 V, less than or equal to 5.5 V, less than or equal to 5 V, less than or equal to 4.5 V, less than or equal to 4 V, less than or equal to 3.5 V, less than or equal to 3 V, less than or equal to 2.5 V, less than or equal to 2 V, less than or equal to 1.5 V, less than or equal to 1 V, or less than or equal to 0.5 V. Combinations of the above- referenced ranges are also possible (e.g., greater than or equal to 0 V and less than or equal to 6 V). Other ranges are also possible.
  • the first voltage should be understood to be the voltage with respect to a Li + /Li reference potential.
  • FIG. 2 shows one embodiment in which precursor for a separator 140 undergoes a reaction to form separator 150 in rechargeable electrochemical cell 100.
  • the separator may form directly on the first electrode.
  • the separator may not form directly on the first electrode.
  • the separator may form on one or more intervening electrochemical cell components (e.g., one or more passivation layers, which will be described further below) disposed on the first electrode.
  • the separator may form (directly or indirectly) on the first electrode and on one or more of the second electrode, the electrolyte, and an ex situ separator.
  • one layer of a separator e.g., a second layer
  • Other configurations are also possible.
  • a rechargeable electrochemical cell component referred to as being“disposed on,” “disposed between,”“on,” or“adjacent” another rechargeable electrochemical cell component(s) means that it can be directly disposed on, disposed between, on, or adjacent the rechargeable electrochemical cell component (s), or an intervening rechargeable electrochemical cell component may also be present.
  • a rechargeable electrochemical cell component that is“directly adjacent,”“directly on,” or“in contact with,” another rechargeable electrochemical cell component means that no intervening electrochemical cell component is present.
  • a rechargeable electrochemical cell component when referred to as being “disposed on,”“disposed between,”“on,” or“adjacent” another rechargeable electrochemical cell component(s), it may be covered by, on or adjacent the entire rechargeable electrochemical cell component(s) or a part of the rechargeable electrochemical cell component(s).
  • a rechargeable electrochemical cell as described herein may initially lack a separator formed in situ, but may form a separator in situ during electrochemical cell cycling.
  • the separator may form during the first cycle, after greater than or equal to 1 cycle, greater than or equal to 2 cycles, or greater than or equal to 3 cycles.
  • the separator may form after less than or equal to 4 cycles, less than or equal to 3 cycles, less than or equal to 2 cycles, or less than or equal to 1 cycle. Combinations of the above-referenced ranges are also possible (e.g., during the first cycle and after less than or equal to 4 cycles). Other ranges are also possible.
  • the formation of the separator may be determined by using electron microscopy.
  • the rate of separator formation may be affected by one or more of the following factors: the identity and/or concentration of the precursor, the rate of cycling, the temperature at which cycling occurs, the voltage limits present during cycling, the composition of an electrolyte present during cycling, the identity and/or concentration of additives present during cycling, the electroactive material in the first and/or second electrodes, the identity of conductivity additives in the first and/or second electrode, the identity of a binder in the first and/or second electrodes, and the identity of any current collectors.
  • certain embodiments relate to electrochemical cells that comprise separators, such as electrochemical cells that comprise separators that are formed in situ.
  • FIG 3 shows one example of an electrochemical cell that includes a separator, where rechargeable electrochemical cell 100 includes first electrode 110, second electrode 120, electrolyte 130, and separator 150.
  • the separator is a separator that has formed in situ.
  • the electrolyte may comprise a precursor for a separator
  • the precursor for the separator may be a precursor for the separator present in the rechargeable electrochemical cell (i.e., it may be capable of undergoing a reaction to form a separator with substantially the same composition as the separator present in the electrochemical cell), or it may be a precursor for a separator different from the separator present in the rechargeable electrochemical cell (i.e., it may be capable of undergoing a reaction to form a separator with a different composition than the separator present in the rechargeable electrochemical cell).
  • the rechargeable electrochemical cell comprises an electrolyte that does not include a precursor for a separator.
  • the separator may be directly adjacent the first electrode. However, in other embodiments the separator may not be directly adjacent the first electrode.
  • the separator may be adjacent one or more intervening electrochemical cell components (e.g., one or more passivation layers, which will be described further below) disposed on the first electrode.
  • the separator may be directly or indirectly adjacent the first electrode and one or more of the second electrode, the electrolyte, and an ex situ separator. Other configurations are also possible.
  • a rechargeable electrochemical cell may comprise a separator including more than one layer.
  • FIG. 4 shows one non-limiting embodiment of a rechargeable electrochemical cell which includes a separator with two layers.
  • rechargeable electrochemical cell 100 comprises first electrode 110, second electrode 120, electrolyte 130, and separator 150.
  • Separator 150 comprises first layer 152 and second layer 154.
  • the first layer may be positioned closer to the first electrode than the second layer.
  • the second layer of the separator may have a substantially similar composition to the first layer of the separator, or the two layers may have different compositions. In some cases, the second layer of the separator may undergo oxidation at a higher voltage than the first layer.
  • the separator may include a first layer that comprises Lil (which may make up any suitable wt% of the first layer up to 100 wt%) and a second layer that comprises LiF (which may make up any suitable wt% of the second layer up to 100 wt%).
  • the outermost layer of the separator may be the layer within the separator that undergoes oxidation at the highest voltage because it may result in a separator in which the outermost layer is the layer that is most stable.
  • the stable top layer may prevent erosion and/or destruction of underlying layers that are less stable.
  • the first layer may have a high ion conductivity and/or for the second layer to have a relatively low solubility in the electrolyte (e.g., between 1 nM and 1 mm).
  • a precursor for an electrochemical cell may comprise at least a first layer and a second layer, and the second layer may undergoes oxidation at a voltage that is greater than or equal to 3% higher than the voltage at which the first layer undergoes oxidation, a voltage that is greater than or equal to 5% higher than the voltage at which the first layer undergoes oxidation, a voltage that is greater than or equal to 10% higher than the voltage at which the first layer undergoes oxidation, a voltage that is greater than or equal to 15% higher than the voltage at which the first layer undergoes oxidation, a voltage that is greater than or equal to 20% higher than the voltage at which the first layer undergoes oxidation, a voltage that is greater than or equal to 25% higher than the voltage at which the first layer undergoes oxidation, a voltage that is greater than or equal to 30% higher than the voltage at which the first layer undergoes oxidation, a voltage that is greater than or equal to 35% higher than the voltage at which the first layer undergoes
  • the second layer undergoes oxidation at a voltage that is less than or equal to 60% higher than the voltage at which the first layer undergoes oxidation, a voltage that is less than or equal to 55% higher than the voltage at which the first layer undergoes oxidation, a voltage that is less than or equal to 50% higher than the voltage at which the first layer undergoes oxidation, a voltage that is less than or equal to 45% higher than the voltage at which the first layer undergoes oxidation, a voltage that is less than or equal to 40% higher than the voltage at which the first layer undergoes oxidation, a voltage that is less than or equal to 35% higher than the voltage at which the first layer undergoes oxidation, a voltage that is less than or equal to 30% higher than the voltage at which the first layer undergoes oxidation, a voltage that is less than or equal to 25% higher than the voltage at which the first layer undergoes oxidation, a voltage that is less than or equal to 20% higher than the voltage at which the first layer undergo
  • the voltage at which a layer undergoes oxidation may be determined by cyclic voltammetry.
  • FIG. 4 shows a rechargeable electrochemical cell including a separator with only two layers, it should be understood that separators may comprise more than two layers.
  • a separator comprises greater than or equal to three layers, greater than or equal to four layers, or even more layers.
  • Each layer within the separator may have a substantially similar composition to each other layer in the separator, or one or more layers within the separator may have a different composition than one or more other layers within the separator.
  • FIG. 5A shows rechargeable electrochemical cell comprising first electrode 110, second electrode 120, electrolyte 130 comprising precursor for the separator 140, and separator 150 comprising defect 160.
  • precursor for the separator 140 undergoes a reaction to heal defect 160 so that the separator is no longer damaged, or damaged to a smaller degree.
  • one or more defect in the separator may be healed by the formation of a material in the defect with a substantially similar composition to the separator, as is shown in FIG.
  • a defect in the separator may be healed by the formation of a material in the defect with a different composition than the separator.
  • defects that may be healed include cracks, pits, pinholes, and the like.
  • a defect in a separator may be healed by holding the first electrode at a first voltage.
  • the a voltage may be applied to the first electrode, such as, for example, by an external voltage source.
  • the first voltage may be a voltage that the first electrode inherently has when it is positioned in the rechargeable electrochemical cell.
  • the first voltage is greater than or equal to 0 V, greater than or equal to 1.5 V, greater than or equal to 2 V, greater than or equal to 2.5 V, greater than or equal to 3 V, greater than or equal to 3.5 V, greater than or equal to 4 V, or greater than or equal to 4.5 V. In some embodiments, the first voltage is less than or equal to 5 V, less than or equal to 4.5 V, less than or equal to 4 V, less than or equal to 3.5 V, less than or equal to 3 V, less than or equal to 2.5 V, less than or equal to 2 V, less than or equal to 1.5 V, less than or equal to 1 V, or less than or equal to 0.5 V.
  • the first voltage should be understood to be the voltage with respect to a Li + /Li reference potential.
  • a precursor for a separator as described herein may have one or more properties that are beneficial for an electrochemical cell.
  • a rechargeable electrochemical cell may comprise a precursor for the separator that does not participate in a redox shuttle mechanism when the rechargeable electrochemical cell operates at a potential of greater than or equal to 2.5 V, greater than or equal to 3 V, 3.5 V, greater than or equal to 4 V, greater than or equal to 4.5 V, or greater than or equal to 5 V.
  • a redox shuttle mechanism is a process that happens in certain electrochemical cells in which a species is oxidized at the cathode, diffuses to the anode, and then is reduced at the anode. This results in an internal short circuit, and decreases the amount of power provided by and the roundtrip efficiency of the rechargeable electrochemical cell.
  • a rechargeable electrochemical cell may comprise a precursor for a separator that is relatively insoluble in an electrolyte that is also present in the rechargeable electrochemical cell.
  • the precursor for the separator may have a solubility in the electrolyte of less than or equal to 1 mM, less than or equal to 100 mM, less than or equal to 10 mM, less than or equal to 1 mM, less than or equal to 100 nM, or less than or equal to 10 nM.
  • the precursor for the separator may have a solubility in the electrolyte of greater than or equal to 1 nM, greater than or equal to 10 nM, greater than or equal to 100 nM, greater than or equal to 1 mM, greater than or equal to 10 mM, or greater than or equal to 100 mM. Combinations of the above- referenced ranges are also possible (e.g., greater than or equal to 1 nM and less than or equal to 1 mM). Other ranges are also possible.
  • a rechargeable electrochemical cell may comprise a precursor for a separator that is present in an electrolyte that is also present in the rechargeable electrochemical cell at a relatively low concentration.
  • the precursor for the separator may be present in the electrolyte at a concentration of less than or equal to 1 mM, less than or equal to 100 mM, less than or equal to 10 mM, less than or equal to 1 mM, less than or equal to 100 nM, or less than or equal to 10 nM.
  • the precursor for the separator may be present in the electrolyte at a concentration of greater than or equal to 1 nM, greater than or equal to 10 nM, greater than or equal to 100 nM, greater than or equal to 1 mM, greater than or equal to 10 mM, or greater than or equal to 100 mM. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1 nM and less than or equal to 1 mM). Other ranges are also possible.
  • a precursor for a separator described herein may comprise a species with one or more anions, such as a salt.
  • the precursor for the separator comprises a salt dissolved in an electrolyte.
  • the precursor for the separator may comprise one or more halide anions, such as one or more of a fluoride anion, a chloride anion, a bromide anion, and an iodide anion.
  • the precursor for the separator may comprise at least two halide anions, at least three halide anions, or more halide anions.
  • the precursor for the separator may comprise an anion that comprises one or more halogen atoms, such as a polyhalide anion.
  • the polyhalide anion may comprise only one type of halogen atom (such as, e.g., I 3 , which only comprises iodine) or ma may comprise two or more types of halogen atoms (such as, e.g., OBG 2 ).
  • the precursor for the separator may comprise a species that may undergo a reaction (e.g., a redox reaction, a chemical reaction) to form a halide anion and/or a polyhalide anion.
  • a reaction e.g., a redox reaction, a chemical reaction
  • Non-limiting examples of such species include LiPF 6 and LiBF 4 .
  • a precursor for a separator may comprise a species that does not comprise any halogen atoms.
  • the precursor for the separator may comprise a salt dissolved in an electrolyte that comprises an anion that does not include any halogen atoms.
  • Non-limiting examples of such anions include chlorate anions, perchlorate anions, nitrate anions, phosphate anions, bis(fluorosulfonyl)imide anions, and bis(trifluoromethane)sulfonimide anions.
  • a precursor for a separator may comprise a salt, such as a salt dissolved in an electrolyte.
  • suitable cations for the salt include alkali metal cations such as lithium and sodium, alkaline earth metal cations such as magnesium, and transition metal cations such as zinc and copper.
  • a rechargeable electrochemical cell as described herein may comprise a precursor for a separator that is not a salt or a component of a salt.
  • the rechargeable electrochemical cell may comprise a precursor for a separator that is a halogen with an oxidation state of zero, such as I 2 .
  • a rechargeable electrochemical cell may comprise at least two precursors for a separator, at least three precursors for a separator, or more precursors for a separator.
  • two or more of the precursors for the separator may be species that are halide anions or can react to form halide anions.
  • an electrochemical cell may comprise at least a first precursor for a separator that is at least one of a first halide anion and a species that can react to form a first halide anion and a second precursor for a separator that is at least one of a second halide anion and a species that can react to form a second halide anion.
  • the rechargeable electrochemical cell may comprise at least a first precursor for a separator that is at least one of a first halide anion and a species that can react to form a first halide anion and a second precursor for a separator that is not a halide anion or a species that can react to form a halide anion.
  • the separator may be a solid species that prevents the first electrode from contacting the second electrode, or a species that prevents or significantly retards the formation of a short circuit from the first electrode to the second electrode.
  • the separator may be a single ion conductor, or may be a solid electrolyte. For example, it may be capable of conducting cations but not anions.
  • the separator may have a relatively high ionic conductivity.
  • the ionic conductivity of the separator may be greater than or equal to 10 4 S/cm, greater than or equal to 10 3 S/cm, greater than or equal to 10 2 S/cm, greater than or equal to 10 1 S/cm, greater than or equal to 10° S/cm, or greater than or equal to 10 1 S/cm.
  • the ionic conductivity of the separator may be less than or equal to 10 2 S/cm, less than or equal to 10 1 S/cm, less than or equal to 10° S/cm, less than or equal to 10 1 S/cm, less than or equal to 10 2 S/cm, or less than or equal to 10 3 S/cm.
  • the ionic conductivity of the separator may be determined by electrochemical impedance spectroscopy.
  • a rechargeable electrochemical cell may comprise a separator with a relatively low area-specific impedance.
  • the area-specific impedance of the separator may be less than or equal to 100 Ohm*cm 2 , less than or equal to 50 Ohm*cm 2 , less than or equal to 20 Ohm*cm 2 , less than or equal to 10 Ohm*cm 2 , less than or equal to 5
  • the area-specific impedance of the separator may be greater than or equal to 0.5 Ohm* cm 2 , greater than or equal to 1 Ohm* cm 2 , greater than or equal to 2 Ohm* cm 2 , greater than or equal to 5 Ohm* cm 2 , greater than or equal to 10 Ohm* cm 2 , greater than or equal to 20 Ohm*cm 2 , or greater than or equal to 50 Ohm*cm 2 .
  • the area-specific impedance of the separator may be determined by electrochemical impedance spectroscopy.
  • a rechargeable electrochemical cell may comprise a separator that is stable at a relatively high voltage.
  • a separator is considered to be stable at a voltage if it does not undergo appreciable degradation such as dissolution, cracking, oxidation, and the like, when held at that voltage.
  • the separator may be stable at a voltage of greater than or equal to 2 V, greater than or equal to 2.5 V, greater than or equal to 3 V, 3.7 V, greater than or equal to 4.0 V, greater than or equal to 4.2 V, greater than or equal to 4.3 V, greater than or equal to 4.5 V, or greater than or equal to 4.7 V.
  • the separator may be stable at a voltage of less than or equal to 5 V, less than or equal to 4.7 V, less than or equal to 4.5 V, less than or equal to 4.3 V, less than or equal to 4.2 V, less than or equal to 4.0 V, less than or equal to 3.7 V, less than or equal to 3 V, or less than or equal to 2.5 V. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 2 V and less than or equal to 5 V, greater than or equal to 3.7 V and less than or equal to 5 V). Other ranges are also possible.
  • a rechargeable electrochemical cell may comprise a separator with a relatively high shear modulus.
  • separators that have a high shear modulus may be more resistant to dendrite growth and so may improve the cycle life of the rechargeable electrochemical cell.
  • the separator has a shear modulus of greater than or equal to 5 GPa, greater 7.5 GPa, greater than or equal to 10 GPa, greater than or equal to 12.5 GPa, greater than or equal to 15 GPa, or greater than or equal to 17.5 GPa.
  • the separator has a shear modulus of less than or equal to 20 GPa, less than or equal to 17.5 GPa, less than or equal to 15 GPa, less than or equal to 12.5 GPa, less than or equal to 10 GPa, or less than or equal to 5 GPa. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 5 GPa and less than or equal to 20 GPa). Other ranges are also possible.
  • the shear modulus of the separator may be determined by pulse echo ultrasonic methods.
  • a rechargeable electrochemical cell may comprise a separator with a relatively low linear coefficient of thermal expansion.
  • the linear coefficient of thermal expansion may be less than or equal to 0.0000105 K 1 , less than or equal to 10 5 K 1 , or less than or equal to lO ⁇ K 1 .
  • the linear coefficient of thermal expansion may be determined by thermomechanical analysis.
  • a separator may have any suitable thickness.
  • the thickness of the separator is greater than or equal to 1 nm, greater than or equal to 2 nm, greater than or equal to 5 nm, greater than or equal to 10 nm, greater than or equal to 20 nm, greater than or equal to 50 nm, greater than or equal to 100 nm, greater than or equal to 200 nm, greater than or equal to 500 nm, greater than or equal to 1 micron, greater than or equal to 2 microns, greater than or equal to 5 microns, greater than or equal to 10 microns, or greater than or equal to 20 microns.
  • the thickness of the separator is less than or equal to 50 microns, less than or equal to 20 microns, less than or equal to 10 microns, less than or equal to 5 microns, less than or equal to 2 microns, less than or equal to 1 micron, less than or equal to 500 nm, less than or equal to 200 nm, less than or equal to 100 nm, less than or equal to 50 nm, less than or equal to 20 nm, less than or equal to 10 nm, less than or equal to 5 nm, or less than or equal to 2 nm.
  • Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1 nm and less than or equal to 50 microns, or greater than or equal to 10 nm and less than or equal to 1 micron). Other ranges are also possible.
  • the thickness of the separator may be determined by electron microscopy.
  • the separator may have any suitable morphology and composition. In some embodiments,
  • the separator (or a precursor thereof) has a rock salt crystal structure, a fluorite crystal structure, or an R3m crystal structure.
  • the separator may comprise any of the precursors for the separator.
  • the separator may comprise one or more halide anions, one or more polyhalide anions, on more or species that may undergo a reaction to form a halide anion and/or a polyhalide anion, chlorate anions, perchlorate anions, nitrate anions, phosphate anions, alkali metal cations, alkaline earth metal cations, and/or halogen atoms as described above in reference to the precursors for the separator.
  • the separator may comprise an alkali halide salt that is doped with an alkaline earth cation, such as lithium iodide that is doped with magnesium.
  • suitable separator materials include LiF, LiCl, LiBr, Lil, LuFBr, Li 4 Br3l, Li 4 Br3Cl, LuChBr, and lithium oxyhalides such as L ⁇ OBr.
  • one or more lithium oxyhalides may form by abstracting an oxygen from a solvent molecule.
  • a rechargeable electrochemical cell comprises an electrolyte.
  • the electrolyte is a liquid electrolyte.
  • the electrolyte may comprise an organic solvent, such as a solvent comprising one or more of an ether group, a nitrile group, a cyanoester group, a fluoroester group, a tetrazole group, a fluorosulfonyl group, a chlorosulfonyl group, a nitro group, a carbonate group, a dicarbonate group, a nitrate group, a fluoroamide group, a dione group, an azole group, and a triazine group.
  • the electrolyte may comprise an alkyl carbonate, such as ethylene carbonate and/or dimethylene carbonate.
  • an electrolyte as described herein may comprise one or more salts to enhance the conductivity of the electrolyte.
  • suitable salts include LiPFe, LIBF 4 , LIFSI, LiTFSI, LiCl0 , LiBOB, and LiDFOB.
  • an electrolyte comprises a salt which enhances the conductivity of the electrolyte
  • the salt which enhances the conductivity of the electrolyte may be present at a concentration of greater than or equal to 0.01 M, greater than or equal to 0.02 M, greater than or equal to 0.05 M, greater than or equal to 0.1 M, greater than or equal to 0.2 M, greater than or equal to 0.5 M, greater than or equal to 1 M, or greater than or equal to 2 M.
  • the salt which enhances the conductivity of the electrolyte may be present at a concentration of less than or equal to 5 M, less than or equal to 2 M, less than or equal to 1 M, less than or equal to 0.5 M, less than or equal to 0.2 M, less than or equal to 0.1 M, less than or equal to 0.05 M, or less than or equal to 0.02 M. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.01 M and less than or equal to 5 M). Other ranges are also possible.
  • an electrolyte as described herein may comprise one or more additives that affects the solubility of a precursor for a separator in the electrolyte.
  • the electrolyte may comprise an additive that increases the solubility of a precursor for the separator in the electrolyte. That is, the precursor for the separator may have a higher solubility in the electrolyte in the presence of the additive than in an otherwise equivalent electrolyte that lacks the additive.
  • additives that increase the solubility of the precursor in the electrolyte include water, HF, and HNO3.
  • the additive may comprise one or more of a nitrile group, a fluorosulfonyl group, a chlorosulfonyl group, a nitro group, a nitrate group, a fluoroamide group, and a dione group.
  • the rechargeable electrochemical cell comprises at least a first electrode.
  • the first electrode is an anode.
  • the first electrode may comprise an alkali metal, such as lithium metal, sodium metal, and/or potassium metal.
  • the first electrode may comprise an alkaline earth metal, such as magnesium and/or calcium.
  • the first electrode comprises a transition metal (such as yttrium and/or zinc) and/or a post transition metal (such as aluminum).
  • a first electrode may have any suitable thickness.
  • the thickness of the first electrode is greater than or equal to 15 microns, greater than or equal to 20 microns, greater than or equal to 25 microns, greater than or equal to 30 microns, greater than or equal to 35 microns, greater than or equal to 40 microns, or greater than or equal to 45 microns.
  • the thickness of the first electrode may be less than or equal to 50 microns, less than or equal to 45 microns, less than or equal to 40 microns, less than or equal to 35 microns, less than or equal to 30 microns, less than or equal to 25 microns, or less than or equal to 20 microns. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 15 microns and less than or equal to 50 microns). Other ranges are also possible.
  • the thickness of the first electrode may be determined by electron microscopy.
  • a surface of a first electrode may be passivated.
  • a passivation layer may be disposed on the surface of the first electrode.
  • the passivation layer may comprise a precursor for a separator as described above, such as a halide anion.
  • the passivation layer comprises a polymer, such as poly(2 -vinyl pyridine).
  • the passivation layer may be formed by exposing the surface of the first electrode to a composition comprising a species that reacts with the surface of the first electrode to form the passivation layer.
  • the surface of the first electrode may be exposed to a composition comprising a halide salt, such as a lithium halide salt.
  • a passivation layer may be formed by exposing the surface of the first electrode first to poly(2- vinyl pyridine) and then to iodine vapor.
  • a passivation layer on a first electrode may have any suitable thickness.
  • the thickness of the passivation layer on the first electrode is greater than or equal to 1 nm, greater than or equal to 2 nm, greater than or equal to 5 nm, greater than or equal to 10 nm, greater than or equal to 20 nm, greater than or equal to 50 nm, greater than or equal to 100 nm, greater than or equal to 200 nm, greater than or equal to 500 nm, greater than or equal to 1 micron, greater than or equal to 2 microns, greater than or equal to 5 microns, greater than or equal to 10 microns, greater than or equal to 20 microns, or greater than or equal to 50 microns.
  • the thickness of the passivation layer on the first electrode is less than or equal to 100 microns, less than or equal to 50 microns, less than or equal to 20 microns, less than or equal to 10 microns, less than or equal to 5 microns, less than or equal to 2 microns, less than or equal to 1 micron, less than or equal to 500 nm, less than or equal to 200 nm, less than or equal to 100 nm, less than or equal to 50 nm, less than or equal to 20 nm, less than or equal to 10 nm, less than or equal to 5 nm, or less than or equal to 2 nm.
  • the thickness of the passivation layer may be determined by electron microscopy.
  • the rechargeable electrochemical cell comprises at least a first electrode and a second electrode.
  • the second electrode is a cathode.
  • the second electrode may comprise one or more of an intercalation compound such as a lithium ion intercalation compound, a conversion compound, an oxide, sulfur, a halide, and a chalcogenide.
  • suitable intercalation compounds include lithium cobalt oxide, lithium iron phosphate, lithium nickel cobalt manganese oxide, and lithium nickel cobalt aluminum oxide.
  • the rechargeable electrochemical cell is a metal-air cell, such as a lithium-air cell.
  • a second electrode may store a working ion present in the rechargeable electrochemical cell at any suitable potential.
  • a working ion is a species that is formed by oxidation of a metal species at the anode and intercalates into the cathode to provide electrical neutrality to the cathode when the cathode active species is reduced.
  • the second electrode stores the working ion at a voltage of greater than or equal to 2.0 V, greater than or equal to 2.5 V, greater than or equal to 3.0 V, greater than or equal to 3.5 V, greater than or equal to 4.0 V, or greater than or equal to 4.5 V.
  • the second electrode stores the working ion at a voltage of less than or equal to 5.0 V, less than or equal to 4.5 V, less than or equal to 4.0 V, less than or equal to 3.5 V, less than or equal to 3.0 V, or less than or equal to 2.5 V. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 2.5 V and less than or equal to 5 V). Other ranges are also possible.
  • the voltage at which the working ion is stored may be determined by cyclic voltammetry.
  • a rechargeable electrochemical cell may comprise a second electrode with a thickness of greater than or equal to 20 microns, greater than or equal to 50 microns, greater than or equal to 100 microns, or greater than or equal to 200 microns. In some embodiments, a rechargeable electrochemical cell may comprise a second electrode with a thickness of less than or equal to 500 microns, less than or equal to 200 microns, less than or equal to 100 microns, or less than or equal to 50 microns. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 20 microns and less than or equal to 50 microns). Other ranges are also possible.
  • the thickness of the second electrode may be determined by electron microscopy.
  • the first electrode and/or the second electrode may be disposed on a current collector.
  • the current collector may be in electrical communication with the electrode disposed on it, and may be capable of transmitting electrons from the electrode to an external component (e.g., a load).
  • suitable current collectors include copper, nickel, aluminum, titanium, chrome, graphite, and glassy carbon.
  • the current collector may be in the form of a foil, a mesh, and/or a foam.
  • a rechargeable electrochemical cell may comprise one or more ex situ separator(s), or a separator(s) that are added to the cell during the cell assembly process.
  • the ex situ separator(s) may have any suitable composition and structure.
  • suitable ex situ separators include porous materials, such as porous polymer membranes (e.g., cellulosic membranes), porous ceramic membranes, fiber mats (e.g., glass fiber mats), woven structures, and/or non-woven structures.
  • one or more ex situ separators present in a rechargeable electrochemical cell may comprise a coating.
  • each ex situ separator may independently have any, all, or none of the properties described herein.
  • a rechargeable electrochemical cell as described herein may have one or more advantageous properties, such as being free from short circuiting by metal dendrites after cycling.
  • the electrochemical cell may be free from short circuiting by metal dendrites after greater than or equal to 50 cycles, greater than or equal to 100 cycles, greater than or equal to 200 cycles, greater than or equal to 500 cycles, greater than or equal to 1000 cycles, or greater than or equal to 3000 cycles.
  • the electrochemical cell may be free from short circuiting by metal dendrites after less than or equal to 5000 cycles, less than or equal to 3000 cycles, less than or equal to 1000 cycles, less than or equal to 500 cycles, less than or equal to 200 cycles, or less than or equal to 200 cycles. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 50 cycles and less than or equal to 5000 cycles). Other ranges are also possible.
  • a rechargeable electrochemical cell may have a relatively high area capacity.
  • the area capacity of the rechargeable electrochemical cell may be greater than or equal to 2 mAh/cm 2 , greater than or equal to 3 mAh/cm 2 , greater than or equal to 4 mAh/cm 2 , greater than or equal to 5 mAh/cm 2 , greater than or equal to 6 mAh/cm 2 , greater than or equal to 7 mAh/cm 2 , greater than or equal to 8 mAh/cm 2 , greater than or equal to 9 mAh/cm 2 , greater than or equal to 10 mAh/cm 2 , greater than or equal to 11 mAh/cm 2 , greater than or equal to 12 mAh/cm 2 , greater than or equal to 13 mAh/cm 2 , greater than or equal to 14 mAh/cm 2 , greater than or equal to 15 mAh/cm 2 , greater than or equal to 16 mAh/cm 2 , greater than or equal to 17 mAh/cm 2
  • the area capacity of the rechargeable electrochemical cell may be less than or equal to 20 mAh/cm 2 , less than or equal to 19 mAh/cm 2 , less than or equal to 18 mAh/cm 2 , less than or equal to 17 mAh/cm 2 , less than or equal to 16 mAh/cm 2 , less than or equal to 15 mAh/cm 2 , less than or equal to 14 mAh/cm 2 , less than or equal to 13 mAh/cm 2 , less than or equal to 12 mAh/cm 2 , less than or equal to 11 mAh/cm 2 , less than or equal to 10 mAh/cm 2 , less than or equal to 9 mAh/cm 2 , less than or equal to 8 mAh/cm 2 , less than or equal to 7 mAh/cm 2 , less than or equal to 6 mAh/cm 2 , less than or equal to 5 mAh/cm 2 , less than or equal to 4 mAh/cm 2 , or less than or
  • Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 2 mAh/cm 2 and less than or equal to 20 mAh/cm 2 , or greater than or equal to 3 mAh/cm 2 and less than or equal to 10 mAh/cm 2 ). Other ranges are also possible.
  • a rechargeable electrochemical cell may have a relatively large cycle life.
  • the cycle life of the rechargeable electrochemical cell may be greater than or equal to 50 cycles, greater than or equal to 100 cycles, greater than or equal to 200 cycles, greater than or equal to 500 cycles, greater than or equal to 1000 cycles, or greater than or equal to 3000 cycles.
  • the cycle life of the rechargeable electrochemical cell may be less than or equal to 5000 cycles, less than or equal to 3000 cycles, less than or equal to 1000 cycles, less than or equal to 500 cycles, less than or equal to 200 cycles, or less than or equal to 100 cycles. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 50 cycles and less than or equal to 5000 cycles). Other ranges are also possible.
  • a rechargeable electrochemical cell may have a relatively large cycle life in comparison to an otherwise equivalent electrochemical cell lacking the separator and/or lacking the precursor for the separator.
  • the cycle life of the rechargeable electrochemical cell may be greater than or equal to 20% larger than an otherwise equivalent electrochemical cell, greater than or equal to 50% larger than an otherwise equivalent electrochemical cell, greater than or equal to 100% larger than an otherwise equivalent electrochemical cell, greater than or equal to 200% larger than an otherwise equivalent electrochemical cell, greater than or equal to 500% larger than an otherwise equivalent electrochemical cell, or greater than or equal to 1000% larger than an otherwise equivalent electrochemical cell.
  • the cycle life of the rechargeable electrochemical cell may be less than or equal to 2000% larger than an otherwise equivalent electrochemical cell, less than or equal to 1000% larger than an otherwise equivalent electrochemical cell, less than or equal to 500% larger than an otherwise equivalent electrochemical cell, less than or equal to 200% larger than an otherwise equivalent electrochemical cell, less than or equal to 100% larger than an otherwise equivalent
  • electrochemical cell or less than or equal to 50% larger than an otherwise equivalent
  • electrochemical cell Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 20% and less than or equal to 2000% larger than an otherwise equivalent electrochemical cell). Other ranges are also possible.
  • Lil has a formation potential (2.85V) higher than the Li-S reaction (2.5 V), corresponding to a more negative free energy of formation, hence it is expected that the SEI on the lithium metal will contain Lil.
  • Li metal anode were to be used with LiFeP0 4 cathode at cell voltage -3.45V
  • Lil solid electrolyte would not spontaneously form, but other halides such as LiBr, LiCl and LiF would. It is believed that mixed halides Li(I,Br,Cl,F) compositions, including graded solid electrolytes, can be produced by appropriate control of the reaction pathway.
  • Each of these metal halides preferentially crystallize in the rocksalt structure, which is further amenable to compositional tuning of its transport properties.
  • supervalent cation doping e.g., with alkaline earth iodides, can produce charge-compensating cation vacancies in the rocksalt lattice that enhance lithium ion conductivity.
  • Strategies for doping of the self-assembling lithium halide solid electrolytes can be evaluated through combined computation and experiment.
  • Self-healing functionality can be introduced by tuning the metal halide and the liquid electrolyte compositions to provide limited solubility of the halide in the liquid electrolyte.
  • Lithium metal that is exposed during battery cycling, for instance through cracking of the solid electrolyte film, may be able to be passivated upon exposure to the liquid.
  • the solubility of lithium halides in nonaqueous solvents varies, from high solubilities in ethereal solvents to low solubility in other solvents.
  • the wide range of formation potentials suggests that the choice of solvent and halogen allows a wide range of tuning to accomplish partial solubility. This area is especially amenable to thermodynamics-based computational search in order to guide experiments.
  • High electronic conductivity typically a material with band gap larger than 4 eV
  • solid electrolytes may have any of these features, all of these features, or none of these features.
  • the radar chart derived from certain lithium halide salts is presented in FIG. 7. It can be seen that for the case of pure halides, all the metrics are satisfied reasonably well except for ionic conductivity. However, the ionic conductivity is also reasonable for the doped Lil case.
  • the ionic conductivity may be improved by controlling the composition, including doping, of the in-situ formed solid halide electrolyte film.
  • the halides are high modulus inorganic solids with the ability to prevent Li dendrite penetration, as illustrated in FIG. 6.
  • these compounds may have a low fracture toughness. It may be possible to overcome this limitation by developing systems that are self-healing, such that exposure of Li metal that occurs during lithium metal stripping and deposition may be spontaneously and controllably passivated by new metal halide.
  • the ability to repair damage spontaneously, by, e.g., self-healing may be desirable for rechargeable batteries because electrochemical reactions in battery materials may result in structural changes (see FIG. 8).
  • Initial Passivation by Chemical Means There are numerous ways of forming an initial halide layer on Li metal, amongst the simplest of which may be dipping in a nonaqueous solvent containing a high concentration of Li + and X ions. Other methods include exposure to halogen vapor is another method, and deposition of a poly-2-vinylpyridine fdm followed by reaction with I 2 (see FIG. 9)
  • Li(X,Y) halides may then be deposited via control of the applied potential and speciation of the halides species in solution. All components are additives may be in the liquid electrolyte and the formation process may be carried out on the assembled cell. As shown above, deposition of the metal halides occurs with increasing potential in the order I, Br, Cl and F. Thus a
  • thermodynamics-based chronopotentiometric profde and the dissolved halides composition may work together to determine the composition of the solid halide film.
  • Electrochemical deposition mediated by another halogen ion in the solution may also be effective for the formation of conformal coatings of halides.
  • an LiCl layer can be mediated by a Br ion present in the solution phase.
  • the scheme may proceeds in the following sequence of steps:
  • LiX may be mediated by Y ions.
  • the anode need not be lithium metal but could also be any other material that oxidation releases Li + ions in solution; for example, the halide solid electrolyte could also be deposited on a cathode.
  • Controlling Solubility of Halides for Self-Healing The formation potentials of all the halides are large enough that exposed Li metal may be spontaneously passivated by at least a monolayer of LiX. If the LiX is completely insoluble in the electrolyte, then a substantial fraction or all X in solution may eventually be irreversibly“gettered” by exposed Li metal, and the ability of the solid iodide to passivate newly exposed Li metal against dendrite formation may eventually cease.
  • a persistent source of dissolved halides for self-healing of defects formed in a halide solid electrolyte during battery cycling may be advantageous.
  • thermodynamic description is that adsorption of halide species from liquid solution at sites of high Li activity may occur, and it may be beneficial to maintain an adequate source of halides in the liquid for self-healing and/or to control the composition and structure of the adsorbed layers that form on lithium metal.
  • the stability of the passivated Li metal surface against dendrite formation may be determined for relevant electrokinetic parameters such as the current density and
  • thickness/capacity of lithium metal that is reversibly plated It may be desirable to suppress dendrite formation at area capacities of 3 to 10 mAh/cm 2 , corresponding to Li metal thickness of 15 to 50 pm.
  • Mitigating dendrite growth Pure and mixed halides both show promising mechanical properties for the suppression of dendrite growth. Achieving selectivity in electrolyte fdm growth will allow the thickness and mechanical properties to be tuned for prevention of dendrites.
  • Adsorption energies are calculated by running DFT simulations with halides as adsorbed molecules on a four-atom-thick lithium slab. Three configurations - on top, bridge and hollow positions - are simulated and the lowest energy configuration is used for calculating the adsorption energy.
  • the adsorption energies are obtained as the formation energies of the adsorbed states, for which the energy of the lithium slab alone is obtained from DFT beforehand.
  • FIG. 11 shows the adsorption and formation energies of the LiF, LiCl, LiBr, Lil.
  • the adsorbed molecule is simulated similarly by replacing it with a molecule of the respective mixed/poly halide.
  • Solid electrolytes have the potential to significantly improving the safety and energy density of batteries. Solid electrolytes with suitable mechanical properties may suppress the growth of dendrites on lithium metal anodes, whose use can greatly enhance the energy density of the battery. Both of these perspectives call for carefully studying the mechanical properties of solid electrolytes.
  • DFT the following formalism is used to calculate the elastic moduli and mechanical properties of lithium and mixed halides.
  • the general stress-strain constitutive relation for anisotropic materials is used, wherein the stress is related to strain by an elastic 6x6 tensor.
  • density functional theory calculations of the strained halide structures the stress is calculated at a series of applied strains. The stresses and strains are then fitted to the general stress-strain relationship, and the components of the elastic tensor are recovered from the fitting parameters.
  • G Li+ depends on the Gutmann donor number of the solvent and the concentration of Li +
  • G x - depends on the Gutmann acceptor number of the solvent and the concentration of X- and G x is calculated from Density Functional Theory (DFT) calculations.
  • DFT Density Functional Theory
  • FIGS. 13A-C Results are shown in FIGS. 13A-C.
  • symmetric Li-Li cells have been subjected to cycling at 5 mA/cm 2 current density that reversibly strips and plates 10 pm of Li metal (2.05 mAh/cm 2 ).
  • the two Li electrodes are separated by a Whatman glass fiber mat, and the electrolyte is 1M LiPF 6 in EC:DMC (1 : 1), with and without 0.1 M addition of Lil.
  • the cells with Lil additive consistently showed both a lower initial impedance (FIG. 13 A) as well as a lower impedance growth rate (FIG. 13B) than the cells without Lil.
  • the proposed lithium halides scheme may have one or more advantages:
  • the self-forming process to make the protected electrode may be simple and scalable.
  • the mixed halide based formation process may be a step towards enabling three dimensional electrodes, which can enable very high energy density owing to a much higher surface area in comparison to the two dimensional electrodes.
  • the self-formed protected lithium electrode may not suffer from the issues faced by other additive approaches.
  • the self-healing function may be a unique aspect for the proposed scheme that has not been successfully and reliably demonstrated earlier.
  • thermodynamics of polyhalide speciation may be used to determine the stability range for these various polyhalide species under the operating potential.
  • Polyhalides have complex chemistry and can form X , X 3 , X 5 , X 7 , X 4 2 , etc., and the free energies may be calculated using first-principles density functional theory calculations within an implicit solvation framework.
  • the thermodynamics of polyhalides may change depending on the solvent. This analysis may provide an understanding of the active polyhalide species that will enable the self-assembling and self-healing processes and may be supplemented by half-cell and full cell testing.
  • the proposed self-assembling, self-limiting solid electrolytes may initially be formed on lithium metal via metal halide additives to liquid electrolytes.
  • a variety of two-electrode and three-electrode cell constructions may be used to systematically isolate and interrogate formation of solid halide films on lithium metal.
  • Cell designs may include“half cells” having a lithium working electrode and nonreactive metal counter-electrode, symmetric lithium-lithium cells, and“full cells” including Li-S and Li-intercalation cathode cells. Based on laboratory cell testing, down-selects may be performed and prototype full cells of >10 mAh capacity will be fabricated and delivered to DOE-specified laboratories for testing and evaluation.
  • a safe, long-lived rechargeable lithium metal anode (or metal alloy that is predominantly lithium metal, such as >50% by mole Li metal) is considered the“Holy Grail” for next- generation lithium-ion batteries due to its ultrahigh capacity (3860 mAh/g) and light weight.
  • replacing the industry-standard graphite anode with lithium metal will at least double the energy density of existing battery technology (currently ⁇ 250 Wh/kg at single-cell level).
  • lithium metal anodes suffer from dendrite/mossy formation and low cycling efficiency.
  • Lithium dendrites can penetrate through battery separators and cause short-circuit (i.e. sudden-death), leading to serious safety hazards.
  • fire and explosion accidents due to lithium dendrite formation led to the total collapse of the rechargeable Li metal battery industry (Li-MoS2, TiS2, or Mn02 batteries) in 1989, after which Li-ion batteries became mainstream (starting in 1991) only because the graphite anode was used instead of lithium metal.
  • the low cycling coulombic efficiency of lithium metal anode is caused by undesirable side reactions between the electrolyte and the highly reducing lithium metal, which leads to formation of a surface film commonly known as solid-electrolyte-interface (SEI).
  • SEI solid-electrolyte-interface
  • the invention provides a new approach to improving lithium cycling efficiency and suppressing dendrite formation simultaneously. It was discovered that fluorinated organic solvents, which are traditionally used as electrolyte additives at small volume fraction to help stabilize cathode-electrolyte interface (CEI) in batteries containing high-voltage cathode materials, can significantly change the crystal growth behavior of lithium metal during electrodeposition (charging) when they are used as the main solvents of the electrolyte.
  • CEI cathode-electrolyte interface
  • the invention includes developing a Li-Li asymmetric cell construction to measure the Li cycling (deposition/stripping) efficiency of different electrolytes, wherein one electrode has a small Li-excess ( ⁇ 140% excess). This is the most relevant condition for high energy-density Li metal rechargeable batteries.
  • the asymmetric cell 1500 include two Li metal electrodes 1502 and 1504 that have different thickness and areal capacity.
  • a separator 1506 is positioned between the Li metal electrodes 1502 and 1504.
  • the working electrode (WE) 1504 is a Li film coated on a copper foil (areal capacity -4.12 mAh/cm 2 ) having a thickness between 20 pm and 200 pm while the counter electrode (CE) 1502 is a Li foil having a thickness between 20 pm and 200 pm.
  • the two electrodes 1502 and 1504 are assembled into a CR2032-type coin-cell with a Tonen polyethylene separator 1506 and 40 pL electrolyte.
  • the cell 1500 is cycled at a current density of 0.6 mA/cm 2 and the cycling capacity is 3.0 mAh/cm 2 per deposition/stripping cycle, as shown in FIG. 15B.
  • the cell is cycled until the overpotential for Li-stripping reaches 0.5 V vs Li + /Li.
  • the cycling test begins with the deposition of a fixed amount of lithium, QT (3 mAh/cm 2 in our tests) on top of the pre-existing 20 pm-thick Li. Then the same 3 mAh/cm 2 of Li is stripped from this electrode. If there is an irreversible loss of Li due to the side reactions, the starting 20 pm-thick Li is partially consumed.
  • the Li-Li asymmetric cell test is a better test than the commonly used Li-Li symmetric cell test because the Li-Li symmetric cell test only shows polarization and its evolution, but cannot measure coulombic efficiency.
  • the Li-Li asymmetric cell test also measures Li cycling efficiency more accurately than does a Li-Cu asymmetric cell test, in which the remaining deposition products from previous cycles left on the Cu surface may impact Li deposition in subsequent cycles.
  • PC propylene carbonate
  • DOL 1, 3-dioxolane
  • DME l,2-Dimethoxyethane
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • FEC fluoroethylene carbonate
  • DFEC 4,5- difluoroethylene carbonate
  • THP tetrahydropyran
  • DMC dimethyl carbonate
  • 2-MeTHF 2-methyl tetrahydrofuran
  • CF3-EC tri-fluoromethyl ethylene carbonate
  • DTD 1, 3 ,2-dioxathiolan-2, 2-oxide.
  • the EC 1702 to FEC 1704 replacement changes the morphology of deposited lithium 1702, as shown in FIGs. 17A-17B.
  • the deposited lithium film 1704 when using 1 M LiPF 6 FEC-DMC electrolyte is denser, as shown in FIG. 17B, with tortuous and twisting morphology, compared to the less dense, straight fiber-like morphology from the 1 M FiPF 6 EC-DMC electrolyte, as shown in FIG. 17A.
  • CDFEA chlorodifluoroacetate
  • BFEA ethyl bromofluoroacetate
  • halogenated compounds have previously been used as additives in electrolytes for lithium ion batteries
  • the present invention concerns the use of halogenated solvents with metal or metal alloy negative electrodes.
  • halogenated compounds including FEC have previously been used in electrolyte formulations as additives at low concentration
  • the halogenated compound is used at a high concentration.
  • the volume percentage of the halogenated compound in the electrolyte is greater than 10 vol %.
  • the volume percentage of the halogenated compound in the electrolyte is greater than 20 vol %.
  • the volume percentage of the halogenated compound in the electrolyte is greater than 30 vol %.
  • the volume percentage of the halogenated compound in the electrolyte is greater than 40 vol %. According to one embodiment, the volume percentage of the halogenated compound in the electrolyte is greater than 50 vol %. According to one embodiment, the volume percentage of the halogenated compound in the electrolyte is greater than 60 vol %.
  • Fluorinated cyclic carbonates such FEC, DFEC, FVC etc. form LiF, LEO, LECCE and L1 2 C 2 O 4 but also decompose to lower organic SEI content and hence will have much higher lithium fluoride content as shown in FIG. 15 A.
  • some of the linear carbonates form LiF but with larger sized organic lithium salts leading to lower LiF content.
  • the sulfate and fluorosulfonate class solvents such as ethylene sulfate (DTD) and methyl fluorosulfonate form LiF through the decomposition of PF g ions along with formation LEO, LES or LESO 3 or LESO 4 on the surface and gaseous POF 5 .
  • PFg also reacts with Li and multiple DTD molecules to convert to LiF and L1 3 PO 4 .
  • LEO some LEO will convert to Li OH. Since all these compounds are inorganic lithium salts with poor electronic conductivity and small size, one can expect these to be good SEI components.
  • the fluorinated sulfate and fluorosulfonates lead to formation of even more LiF due to additional fluorine in the molecule.
  • the compounds include compounds where another halogen is substituted for fluorine.
  • said halogenated compound is used at a concentration greater than 0.01 volume %.
  • the volume percentage of the halogenated compound in the electrolyte is greater than 1 vol %.
  • the volume percentage of the halogenated compound in the electrolyte is greater than 5 vol %.
  • the volume percentage of the halogenated compound in the electrolyte is greater than 10 vol %. According to another embodiment, the volume percentage of the halogenated compound in the electrolyte is greater than 20 vol %. According to another embodiment, the volume percentage of the halogenated compound in the electrolyte is greater than 30 vol %. According to one embodiment, the volume percentage of the halogenated compound in the electrolyte is greater than 40 vol %. According to one embodiment, the volume percentage of the halogenated compound in the electrolyte is greater than 50 vol %. According to one embodiment, the volume percentage of the halogenated compound in the electrolyte is greater than 60 vol %.
  • Fluorinated versions of Epoxides in particular ethylene oxide, propylene oxide, oxetane, tetrahydrofuran, oxetene, furan can form good SEI layers.
  • Fluorine substituted dioxolanes specifically l,3-dioxolane, l,4-Dioxane, l,3-Dioxane, 1, 4-Dioxin are another class of compounds that can lead to desired SEI formation.
  • Fluorinated compounds of Lactones specifically, /le a-Propiolactone, gamma - B uty ro 1 acto n e and mono-fluorinated and di-fluorinated carbonates, specifically dimethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, trimethylene carbonate, vinylene carbonate, vinyl ethylene carbonate will lead to desired SEI layers.
  • Fluorinated Sulfones specifically sulfolane, Sulfolene, dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone and fluorinated sulfites, specifically ethylene sulfite, 1,3 -Propylene sulfite, 1, 2-Propyl enegly col sulfite, diethyl sulfite, dimethyl sulfite and fluorinated sulfates, specifically, ethylene sulfate, propylene sulfate, dimethyl sulfate, diethyl sulfate will lead to excellent SEI forming agents.
  • molecules with Pubchem ID: 17876702, 17876711, 18413638, 17876704, 17876708, 87509373, 17910933 can form good SEI layers.
  • inorganic compounds such as those given above (LEO, L1 2 CO 3 , L12SO3, L12SO4, L13PO4) have large formation energies and hence have a large thermodynamic driving force for formation.
  • electronegative elements such as F, O, S and P will be extracted from the solvent molecule during decomposition to form one of the inorganic lithium salts.
  • organic decomposition products such as alkanes, alkenes, alkynes, ethers and alcohols with fewer than 5 carbons are either gaseous or are highly volatile at room temperature. Accordingly, in one embodiment of the invention, a good SEI forming agent has five carbon atoms or less in the molecule.
  • molecules of the form C x H y F z O w and C x H y F z O w S v are included where x ⁇ 5 and z ⁇ 3 and at least one carbon in the molecule has a single fluorine atom bonded to it.
  • x ⁇ 5 and z ⁇ 3 at least one carbon in the molecule has a single fluorine atom bonded to it.
  • Acetals are organic compounds with the connectivity R 2 C(OR') 2 .
  • One embodiment of the invention comprises compounds with single fluorination of one or two of the organic chains.
  • the decomposition of mono-fluorinated cyclic acetal dioxalane starts with the abstraction of fluorine to form LiF.
  • the remaining cation then goes and chemically decomposes LiPF 6 to further form more LiF and PF 3 gas.
  • Another embodiment of the invention comprises fluorinated carbonates.
  • Alkyl carbonates are the most commonly used solvents in batteries.
  • FEC which is a fluorinated cyclic carbonate, decomposes with the abstraction of fluorine followed by ring opening to give lithium alkoxide and CO molecule adsorbed on lithium. Both of these compounds oxidize to give L1 2 CO 3 and CO2.
  • DMC di-fluorinated dimethyl carbonate
  • the decomposition of fluorinated butyrolactone which is a five membered cyclic ester leads to the formation of LiF and a cyclic lithium organic salt.
  • Another embodiment of the invention comprises fluorinated esters sulfones.
  • the decomposition of 3,4 difluorosulfolane, which is a di-fluorinated cyclic sulfone, proceeds via the abstraction of fluorines to form LiF and an oxosulfonium lithium salt which should hydrolyze to the salt of the corresponding sulfonic acid.
  • the decomposition of Methyl Fluorosulfonate which again starts by the abstraction of fluorine to from LiF. This is followed by the breaking of the S-0 bond leading to formation of SO2 adsorbed on Li and lithium methoxide.
  • SO2 with lithium can decompose to form L1 2 S and L1 2 O. It can also form L1 2 S 2 O 4 or L1 2 SO 4 .
  • the lithium methoxide will hydrolyze to form methanol and LiOH.
  • Another embodiment of the invention comprises fluorinated sulfites.
  • the decomposition of fluorinated ethylene sulfite is similar to flurosulfonate with abstraction of F to form LiF, followed by breaking of one S-0 sigma bond and the C-0 bond to give SO 2 adsorbed on Li and lithium ethoxide.
  • SO 2 with lithium can decompose to form L1 2 S and LLO. It can also form L1 2 S 2 O 4 or LhSCL.
  • the lithium ethoxide will hydrolyze to form ethanol and LiOH.
  • Another embodiment of the invention comprises fluorinated sulfates.
  • the decomposition of di-fluorinated dimethyl sulfate leads to formation of LiF followed by the breaking of the two S-0 sigma bonds to give SO2 adsorbed on the lithium and lithium methoxide.
  • SO 2 with lithium can decompose to form L1 2 S and L1 2 O. It can also form L1 2 S 2 O 4 or L1 2 SO 4 .
  • the lithium methoxide will hydrolyze to form methanol and LiOH.
  • any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the scope of the present invention. All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and/or ordinary meanings of the defined terms.
  • a reference to“A and/or B”, when used in conjunction with open-ended language such as“comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
  • “or” should be understood to have the same meaning as“and/or” as defined above.
  • “or” or“and/or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as“only one of’ or“exactly one of,” or, when used in the claims,“consisting of,” will refer to the inclusion of exactly one element of a number or list of elements.
  • the phrase“at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements.
  • This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase“at least one” refers, whether related or unrelated to those elements specifically identified.
  • “at least one of A and B” can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
  • Examples of such terms related to shape, orientation, and/or geometric relationship include, but are not limited to terms descriptive of: shape - such as, round, square, circular/circle, rectangular/rectangle, triangular/triangle, cylindrical/cylinder,
  • elliptical/ellipse (n)polygonal/(n)polygon, etc.; angular orientation - such as perpendicular, orthogonal, parallel, vertical, horizontal, collinear, etc.; contour and/or trajectory - such as, plane/planar, coplanar, hemispherical, semi-hemispherical, line/linear, hyperbolic, parabolic, flat, curved, straight, arcuate, sinusoidal, tangent/tangential, etc.; direction - such as, north, south, east, west, etc.; surface and/or bulk material properties and/or spatial/temporal resolution and/or distribution - such as, smooth, reflective, transparent, clear, opaque, rigid, impermeable, uniform(ly), inert, non-wettable, insoluble, steady, invariant, constant, homogeneous, etc.
  • a fabricated article that would described herein as being“ square” would not require such article to have faces or sides that are perfectly planar or linear and that intersect at angles of exactly 90 degrees (indeed, such an article can only exist as a mathematical abstraction), but rather, the shape of such article should be interpreted as approximating a“ square,” as defined

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Abstract

La présente invention concerne de manière générale des séparateurs destinés à être utilisés dans des batteries au lithium métallique, ainsi que des systèmes et des produits associés. Certains modes de réalisation concernent des séparateurs qui se forment ou sont réparés lorsqu'une électrode est maintenue à une tension. Selon certains modes de réalisation, une cellule électrochimique peut comprendre un électrolyte qui comprend un précurseur pour le séparateur.
PCT/US2019/035349 2018-06-04 2019-06-04 Électrolytes pour électrodes au lithium métallique et batteries rechargeables les utilisant WO2019236550A1 (fr)

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CN114868274A (zh) * 2019-12-20 2022-08-05 尤米科尔公司 锂二次蓄电池中的固体电解质中间相

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US20150093653A1 (en) * 2010-06-07 2015-04-02 Nexeon Ltd. Additive for lithium ion rechargeable battery cells
CA3016202A1 (fr) * 2016-03-04 2017-09-08 Broadbit Batteries Oy Cellules de sodium rechargeables pour l'utilisation de batterie a haute densite d'energie
CN107146911A (zh) * 2017-04-10 2017-09-08 珠海市赛纬电子材料股份有限公司 锂离子电池、非水锂离子电池电解液和氟代磺酸酐在制备非水锂离子电池电解液中的应用
KR20180013103A (ko) * 2016-07-28 2018-02-07 주식회사 엘지화학 침상 관통 안정성이 향상된 리튬 이차전지

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US20150093653A1 (en) * 2010-06-07 2015-04-02 Nexeon Ltd. Additive for lithium ion rechargeable battery cells
CA3016202A1 (fr) * 2016-03-04 2017-09-08 Broadbit Batteries Oy Cellules de sodium rechargeables pour l'utilisation de batterie a haute densite d'energie
KR20180013103A (ko) * 2016-07-28 2018-02-07 주식회사 엘지화학 침상 관통 안정성이 향상된 리튬 이차전지
CN107146911A (zh) * 2017-04-10 2017-09-08 珠海市赛纬电子材料股份有限公司 锂离子电池、非水锂离子电池电解液和氟代磺酸酐在制备非水锂离子电池电解液中的应用

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CN114868274A (zh) * 2019-12-20 2022-08-05 尤米科尔公司 锂二次蓄电池中的固体电解质中间相
CN114868274B (zh) * 2019-12-20 2024-01-16 尤米科尔公司 锂二次蓄电池中的固体电解质中间相

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